WO2012145868A1

WO2012145868A1 - Polymer nanofiber and its functional materials, preparation method and use thereof

Info

Publication number: WO2012145868A1
Application number: PCT/CN2011/001097
Authority: WO
Inventors: 杨振忠; 倪伟; 梁福鑫; 刘继广
Original assignee: 中国科学院化学研究所
Priority date: 2011-04-28
Filing date: 2011-07-01
Publication date: 2012-11-01
Also published as: CN102758264A; CN102758264B

Abstract

A polymer nanofiber and its functional materials, preparation method and use thereof are provided. The polymer nanofiber is composed of core and shell which surrounds the core, or only comprises shell, the polymer nanofiber is synthesized by polymerization of monomer in the presence of initiator and solvent, and this preparation method may extensively reduce costs and be easy to carry out batch production of polymer nanotubes and core-shell nanowires. The polymer nanofiber has potential applications in organic solvent adsorption, high performance ion exchange, functional template, etc.

Description

Polymer nanofiber and functionalized material thereof, and preparation method and application thereof

Technical field

The present invention relates to polymeric nanofibers and functionalized/hybrid materials thereof, as well as methods for their preparation and use.

Background technique

Organic polymer one-dimensional nanomaterials have many potential applications in many aspects such as organic solvent adsorption, high-efficiency ion exchange, functional template or carrier due to their large specific surface area and variable functional adjustability (R. Dersch, M. Steinhart, U. Boudriot, A. Greiner, JH Wendorff, Polym. Adv. Technol. 2005, 16, 276-282). However, current preparation methods are mostly limited to electrospinning (D. Li, Y. Xia, Adv. Mater.

2004, 16, 1 151-1 170; A. Greiner, JH Wendorff, Angew. Chem. Int. Ed. 2007, 46, 5670-5703 ) or template method (M. Steinhart, JH Wendorff, A. Greiner, RB Wehrspohn , K. Nielsch, J. Schilling, J. Choi, U. Gosele, Science 2002, 296, 1997) and self-assembly methods (H. Fenniri, B. Deng, AE Ribbe, K. Hallenga, J. Jacob, P. Thiyagarajan, Proc. Natl. Acad. Sci. USA 2002, 99, 6487-6492; T. Shimizu, M. Masuda, H. Minamikawa, Chem. Rev.

2005, 105, 1401-1444) and so on. Due to its high cost and limited production, as well as solvent resistance or poor thermal and mechanical properties, its application is greatly limited.

Invention disclosure

It is an object of the present invention to provide polymeric nanofibers, as well as functionalized and hybrid materials thereof, and methods for their preparation and use.

The polymer nanofiber provided by the present invention is any one of the following two structures: consisting of a core layer and a shell layer surrounding the core layer or only a shell layer; constituting the core layer The material is the same as or different from the material constituting the shell layer; the polymer nanofiber has a diameter of 10 nm to 10 μm and a length of 500 nm to 50 mm.

The above polymer nanofibers preferably have a diameter of 50 to 500 nm and a length of 500 nm to 10 mm. The polymer nanofibers are hollow, solid or hollow-solid alternating (like bamboo-like and braided) structures in which functional groups, organic compounds and functional substances are gradient-distributed or interpenetrated. Network structure.

The method for preparing the above polymer nanofibers provided by the present invention is the following method or method 2, wherein the method 1 comprises the following steps: polymerizing a monomer and an initiator in a solvent, and completing the reaction to obtain the Polymer nanofibers;

The method 2 includes the steps of dissolving the initiator in a polar solvent to obtain a polar solution of the initiator, and dissolving the monomer in a non-polar solvent to obtain a non-polar solution of the monomer, and then The polar solution of the initiator is mixed with the non-polar solution of the monomer to carry out a reaction, and the reaction is completed to obtain the polymer nanofiber; in the method 1 and the method 2, the monomer is selected from the group consisting of At least one of a cationic polymerization monomer, an anionic polymerization monomer, a radical polymerization monomer, and a sol-gel reaction monomer; the initiators are each selected from a radical initiator, a cationic initiator, an anionic initiator, and a solvent. At least one of a gel reaction catalyst, the initiation The particle size of the agent is from 10 nm to 10 μm, preferably from 50 to 500 nm. In the first method and the second method, the cationic polymerization monomer is selected from the group consisting of styrene, methyl styrene, α-methyl styrene, methyl styrene, methoxy styrene, and divinyl benzene (DVB). ), butadiene, isoprene, isobutylene, 3-methyl-1-butene, 4-methyl-1-pentene, alkyl vinyl ether, chloromethylstyrene (or benzyl chloride) Styrene, VBC, ), bromomethylstyrene, iodomethylstyrene, halogenated styrene, oxetane derivative, tetrahydrofuran, trioxane, formaldehyde, alkylene oxide, epoxy coupling At least one of the agent and the ethylene sulfide; wherein the alkyl vinyl ether is isobutyl vinyl ether, methyl vinyl ether or divinyl ether; the halogenated styrene is chlorostyrene, P-chloromethylstyrene or 4-bromostyrene; the oxetane derivative is a butoxy ring or a 3,3'-bis(chloromethylene)butoxy ring; the alkylene oxide is Ethylene oxide or propylene oxide; the epoxy coupling agent is an epoxy silane coupling agent or an epoxy titanate coupling agent;

The anionic polymerizable monomers are each selected from the group consisting of α-methylstyrene, styrene, butadiene, isoprene, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, methyl ketene. , nitroethylene, diethyl methylene malonate, α-cyanoacrylate, ethyl α-cyano-2,4-hexadienoate, dicyanoethylene, formaldehyde, ethylene oxide, epoxy At least one of an alkane, ethylene sulfide, and ε-caprolactam;

The radical polymerizable monomers are all vinyl monomers; the vinyl monomer is selected from at least one of divinylbenzene (DVB), styrene, acrylonitrile, acrylamide, and vinyl acetate;

The sol-gel reactive monomers are all hydrolyzed compounds; the hydrolyzed compounds are selected from the group consisting of silicates, titanates, tin halides, trichloromethylsilanes, tetrachlorosilanes, titanium trichloride and titanium tetrachloride. At least one type;

The radical initiators are each selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, ammonium persulfate, ammonium persulfate or a mixture of hydrogen peroxide and ferrous chloride (molar ratio 1-2: 2- 1, preferably 1; 1), a mixture of potassium permanganate and oxalic acid, a mixture of ammonium cerium nitrate and ethanol (molar ratio 1-2: 2-1, preferably 1:1), from diphenyl peroxide a mixture of an acyl group and a hydrazine, dimethyl aniline, a mixture of dibenzoyl peroxide and cuprous naphthalate, and at least one of a mixture of dibenzoyl peroxide and triethylaluminum; The cationic initiator is selected from at least one of protonic acid, Lewis acid and iodine; wherein the protic acid is selected from at least one of concentrated sulfuric acid, phosphoric acid, perchloric acid and trichloroacetic acid; The Lewis acid is selected from the group consisting of BF ₃ , boron trifluoride diethyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride methanol complex, boron trifluoride acetate complex, and boron trifluoride ethylamine. At least one of a compound, A1C1 ₃ , TiCl ₄ and SnCl ₄ ;

The anion initiator is selected from the group consisting of an alkali metal, an organometallic compound or a tertiary amine; wherein the alkali metal is at least one selected from the group consisting of sodium and potassium, and the organometallic compound is selected from the group consisting of metal amino compounds and metal alkyl groups. At least one of a compound and a Grignard reagent; the tertiary amine is at least one selected from the group consisting of trimethylamine, triethylamine, and pyridine; wherein the metal amino compound is preferably a NaNH ₂ or KM-liquid ammonia system (the In the KM-liquid ammonia system, the mass ratio of KH _{2 to} liquid ammonia is 1:10-1:1000, preferably 1:50-1:500), and the metal alkyl compound is preferably butyl lithium, ethyl sodium or benzene. Isopropyl potassium; the Grignard reagent is of the formula RMgX (R- alkane group having a total of 1-8 carbon atoms, phenyl or benzyl group, X is a halogen), such as benzyl magnesium chloride;

The sol-gel reaction catalyst is an acid or a base; wherein the acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid and nitric acid; and the base is at least one selected from the group consisting of ammonia water, sodium hydroxide and potassium hydroxide. The mass percentage of the ammonia water is 1-28%, preferably 5-20%;

In the method 1, the solvent is selected from the group consisting of a total of 5-10 carbon atoms, cyclohexane, halogenated alkane, At least one of petroleum ether, gasoline and liquid paraffin, preferably at least one of n-pentane, n-hexane and n-heptane; the mass ratio of the initiator to the solvent is from 0.001 to 10:100, preferably 0.02- 2: 100; The mass ratio of the monomer to the solvent is 0.0001-50: 100, preferably 0.05-10: 100; in the polymerization step, the temperature is -60°. ~100, preferably -20 ° C ~ 60 ° C, the time is 5 seconds ~ 12 hours, preferably 10 seconds ~ 15 minutes;

In the second method, the non-polar solvent is selected from at least one of a total of 5-10 carbon atoms, cyclohexane, petroleum ether, gasoline and liquid paraffin, preferably n-pentane, n-hexane and n-glycan. At least one of the alkane; the polar solvent is selected from at least one of hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, dimethyl sulfoxide, and water; The mass ratio of the polar solvent to the polar solvent is from 0.001 to 10:100, preferably from 0.02 to 2:100; the mass ratio of the monomer to the non-polar solvent is from 0.0001 to 50:100, preferably from 0.05 to 10:100. In the polymerization step, the temperature is -60 to 100, preferably -20 ° C to 60 ° C, and the time is 5 seconds to 12 hours, preferably 10 seconds to 15 minutes.

In the above two methods, the polymerization reaction can be terminated by adding a terminator according to a conventional method; wherein the terminator of the cationic polymerization may be an alcohol (including methanol, ethanol, propanol, ethylene glycol, glycerin, etc.), an amine (including monoamine, diamine, polyamine, etc.), at least one of water and lye, preferably ethanol; an anionic polymerization terminator is at least one of water, an alcohol, an acid, preferably ethanol; radical polymerization Terminators of benzoquinone, nitro compounds, oxygen, sulfur, 1, 1-diphenyl-2-trinitrophenylhydrazine (DPPH), aromatic amines, phenols, ferric chloride and copper chloride At least one is preferably oxygen. Further, in the above two methods, the reactants may be mixed by various conventional means such as mechanical stirring (including magnetic stirring), mechanical oscillation, artificial oscillation or ultrasonic vibration. The method can adjust the morphology of the polymer fiber by adjusting the concentration of different monomers and the concentration of the initiator, for example, completely hollow, completely solid, bamboo-like, braided and hollow single-hole spherical regulation.

On the basis of synthesizing the above-mentioned original polymer fibers, the related hybrid materials can be further functionalized and prepared; the main means of functionalization is activation reaction to generate related functional groups such as sulfonic acid groups, maleic anhydride groups and carboxylic acid groups. , quaternary ammonium salt or quaternary ammonium salt base; the main means of hybridization is to prepare surface-related epithelial shells by post-treatment to prepare related nanocomposites, such as polyaniline, metal particles, etc. as shell layer, and other carbonization And other means to prepare nanocomposites and the like.

The method for preparing the functionalized polymer nanofiber provided by the present invention is any one of the following methods 1 to 4;

The method 1 includes the following steps: mixing the polymer nanofibers with a sulfonating agent to carry out a reaction, and completing the reaction to obtain the functionalized polymer nanofibers (specifically, strong acid cation exchange fibers); The method comprises the following steps: mixing the polymer nanofibers in a solvent with a comonomer and an initiator to carry out a reaction, and completing the reaction to obtain the functionalized polymer nanofibers (specifically, weakly acidic cation exchange fibers);

The method 3 includes the following steps: the polymer nanofiber obtained by using the cationic polymerization monomer provided above is at least one selected from the group consisting of chloromethylstyrene, bromomethylstyrene and iodomethylstyrene in a solvent The reaction is carried out by mixing with an aqueous solution of a tertiary amine and a strong base, and the reaction is completed to obtain the functionalized polymer nanofiber (specifically, a strongly basic anion exchange fiber);

The method 4 includes the steps of: the cationically polymerizable monomer provided above is selected from the group consisting of chloromethylbenzene The polymer nanofiber obtained by using at least one of alkene, bromomethylstyrene and iodomethylstyrene in a solvent, adding a polymerization monomer, a catalyst and a ligand to carry out a living graft polymerization reaction, and the reaction is completed. Functionalized polymer nanofibers.

In the first method, the sulfonating agent is at least one selected from the group consisting of sulfur trioxide, concentrated sulfuric acid, fuming sulfuric acid and chlorosulfonic acid; and the mass ratio of the polymer nanofiber to the sulfonating agent is 1-100. 100, preferably 1: 10; in the reaction step, the temperature is 20-100 ° C, preferably 20 ° C, the time is 1 minute ~ 10 hours, preferably 10 minutes ~ 2 hours;

In the second method, the solvent is selected from the group consisting of toluene, methanol, an alkane having a total carbon number of 5-127, preferably 5-18, and at least one of ethanol, the comonomer being maleic anhydride; the initiator And at least one selected from the group consisting of azobisisobutyronitrile and benzoyl peroxide; the mass ratio of the polymer nanofiber, the solvent, the comonomer and the initiator is 1-20: 100 -1000: 0.1-20: 0.1-5, preferably 10: 250: 10: 1; in the reaction step, the temperature is 50-100 ° C, preferably 70 ° C, and the time is 1-24 hours, preferably 4-12 Hour

In the third method, the tertiary amine is at least one selected from the group consisting of trimethylamine and triethylamine; the strong base is at least one selected from the group consisting of sodium hydroxide and potassium hydroxide; and the quality of the aqueous solution of the tertiary amine The percentage concentration is 0.1-30%, preferably 1-10%; the mass ratio of the polymer nanofiber, the solvent, the aqueous solution of the tertiary amine and the strong base is 0.1-10: 20-1000: 1-100 : 0.5-50, preferably 1: 100: 10: 5; in the reaction step, the temperature is 20-80 ° C, preferably 30 ° C, the time is 1-24 hours, preferably 2-6 hours;

In the fourth method, the polymerization monomer is selected from the group consisting of α-methylstyrene, styrene, butadiene, isoprene, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, Methyl ketene, nitroethylene, diethyl methylene malonate, α-cyanoacrylate, ethyl α-cyano-2,4-hexadienoate, dicyanoethylene, formaldehyde, epoxy B At least one of an alkane, an alkylene oxide, an ethylene sulfide, and an ε-caprolactam, preferably methyl methacrylate; the catalyst is cuprous chloride; the ligand is pentamethyldiethylenetriamine or 2,2 '-bipyridyl; the catalyst, ligand, polymer nanofiber, polymerizable monomer and the solvent are used in an amount of 0.1-100 g: 0.1-10 g: l-100 g: l-1000 g: 10-5000 mL, preferably 0.4 g: 0.5 g: 1.5 g: 30 g: 100 mL; in the reactive graft polymerization step, the temperature is 50-100 ° C, preferably 80 ° C, and the time is 2-24 hours, preferably 4-12 hours.

The functionalized polymer nanofibers prepared according to the above methods are also within the scope of the present invention. The method for preparing a hybrid polymer nanofiber provided by the present invention is any one of the following methods 1 to 4; wherein the method 1 comprises the following steps: magnetic nanoparticles, the monomer, the initiation The polymerization is carried out in the solvent, and the reaction is completed to obtain the hybrid polymer nanofiber (specifically, a magnetic polymer one-dimensional nano material);

The method 2 includes the following steps: after adsorbing the functionalized polymer nanofibers and the conductive polymer monomer, reacting the obtained polymer nanofibers with an oxidant solution to obtain the hybrid polymer nanofibers (specifically Conductive polymer one-dimensional nanocomposite);

The method 3 includes the following steps: after the functionalized polymer nanofibers are adsorbed with an ethanol solution of an oxide, the obtained polymer nanofibers are reacted with an aqueous solution of an acid or a base, and the reaction is completed to obtain the polymer nanofibers. (Specifically, the inorganic oxide/polymer one-dimensional nanocomposite is prepared by a swelling polymerization method); the method 4 includes the following steps: water of the functionalized polymer nanofiber and the metal salt precursor After the solution is adsorbed, the obtained polymer nanofibers are hydrolyzed or reacted with a reducing agent to obtain the hybrid polymer nanofibers (specifically, metal/polymer one-dimensional nanocomposites).

In the first method, the magnetic nanoparticles are at least one selected from the group consisting of triiron tetroxide, γ-iron oxide, and magnetic rare earth alloy nanoparticles; and the magnetic nanoparticles have a particle diameter of 1-1000 nm, preferably 10 -100 nm; the amount of the magnetic nanoparticles, the monomer, the initiator and the solvent is 0.1-10: 0.5-200: 0.01-20: 10-10 ⁵ , preferably 1: 50: 2 : 2000; in the reaction step, the temperature is -60~120 ° C, preferably 0-60 ° C, the time is 0.1-60 minutes, preferably 2-15 minutes;

In the second method, the conductive polymer monomer is at least one selected from the group consisting of aniline, pyrrole, thiophene and thiophene derivatives; in the oxidizing agent solution, the solute is selected from the group consisting of ammonium persulfate, potassium persulfate and trichlorination. At least one of iron, the solvent is selected from at least one of water, ethanol and acetone; the functionalized polymer nanofiber, the conductive polymer monomer and the oxidizing agent are used in an amount of 0.1-10: 0.1 -5: 0.01-10, preferably 1: 0.5: 1; in the adsorption step, the time is from 1 to 24 hours, preferably from 12 to 24 hours; in the reaction step, the temperature is from -20 to 80 ° C, preferably 0. °C, the time is 10 minutes to 6 hours, preferably 1-4 hours;

In the third method, in the ethanol solution of the oxide, the oxide is selected from the group consisting of ethyl orthosilicate, tetrabutyl titanate, trichloromethylsilane, tetrachlorosilane, titanium trichloride and tetrachlorochloride. At least one of titanium oxide; the ethanol solution of the oxide has a mass percentage of 0.1-80%, preferably 1-50%; and the acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid and hydrobromic acid, The base is selected from at least one of ammonia water, potassium hydroxide and sodium hydroxide; the aqueous solution of the acid or base has a mass percentage of 0.1 to 10%, preferably 1-5%; The nanofiber, the mass ratio of the oxide to the acid or base is 0.1-10: 0.02-100: 0.1-100, preferably 1: 1:0.5; in the adsorption step, the time is 1-24 hours, Preferably, in the reaction step, the temperature is -20 to 100 ° C, preferably 10 to 40 ° C, and the time is 0.5 to 12 hours, preferably 2 to 6 hours;

In the fourth method, in the aqueous solution of the metal salt precursor, the metal salt precursor is at least one selected from the group consisting of silver nitrate and nickel acetate; and the reducing agent is at least selected from the group consisting of hydrazine, hydrazine hydrate and glucose. a ratio of the functionalized polymer nanofiber, the metal salt precursor and the reducing agent is 0.1-10: 0.01-100: 0.1-100, preferably 1: 10: 5; in the adsorption step, The time is 1-24 hours, preferably 12-24 hours; in the reaction step, the temperature is 0-100 ° C, preferably 20-70 ° C, and the time is 1 minute to 12 hours, preferably 5 minutes to 4 hours.

Hybrid polymer nanofibers prepared according to the above method are also within the scope of the present invention. DRAWINGS

Fig. 1 is a scanning electron microscope and transmission electron micrograph of a (hollow bamboo-like) polymer nanofiber synthesized in Example 3.

Figure 2 is a scanning electron microscopy and transmission electron micrograph of a (completely hollow) polymer nanofiber synthesized in Example 1.

Fig. 3 is a scanning electron microscope and transmission electron micrograph of the (hollow braided) polymer nanofiber synthesized in Example 2.

4 is a scanning electron microscope and transmission electron micrograph of the (solid) polymer nanofiber synthesized in Example 7. Figure 5 is a chemical modification of the polymer one-dimensional nanomaterial in Example 3: macroscopic morphology (original, moderately sulfonated and highly sulfonated polymer nanotubes) and electron micrograph (highly sulfonated cation exchanged nanoparticle) Aggregation Fiber).

Figure 6 is an infrared characterization of typical polymer nanofibers and their chemically modified products synthesized in Examples 3, 17, 21 and 24: a) original polystyrene based polymer fibers; b) sulfonated fibers; c) the fiber copolymerized with benzyl chloride; d) the maleated anhydride fiber; e) the quaternary amine salted fiber.

Figure 7 is a graph showing the carbonation characterization (scanning electron microscopy and transmission electron micrographs) of a typical polymer nanofiber synthesized in Example 3.

Figure 8 is a polymer one-dimensional nanohybrid material synthesized in Example 29: macroscopic morphology and electron micrograph (conductive polyaniline hybrid polymer nanotubes).

Figure 9 is a magnetic polymer nanofiber synthesized in Example 27 and its magnetic behavior. a) a transmission photograph of the magnetized polymer nanofiber; b) a photo of the magnetic field induced enrichment effect of the magnetic polymer nanofiber.

Figure 10 is a graphical representation of the thermal properties of typical polymer nanofibers synthesized in Examples 3, 17, 21 and 29: a) raw polystyrene based polymer fibers; b) sulfonated fibers; c) maleic anhydride The fiber; d) conductive polyaniline hybrid nanofiber.

The best way to implement the invention

The method for preparing polymer nanofibers and nanotubes provided by the invention is to disperse the droplets of the initiator into nano droplets, and the surrounding reactive monomer is quickly materialized by the movement of the nanodroplet initiator to form a length. And the one-dimensional polymer nanotubes and nanofibers with adjustable diameters, the original polymer nanotubes/fibers provided by the invention are obtained, and further post-treated to obtain the nanotubes/fibers with special structure and function provided by the invention.

The invention is further illustrated by the following specific examples, but the invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The materials are commercially available from the public unless otherwise stated. The boron trifluoride diethyl ether complex, the boron trifluoride tetrahydrofuran complex, the boron trifluoride methanol complex, the boron trifluoride acetate complex, and the boron trifluoride ethylamine complex are all purchased from A. Latin Reagent Co., Ltd., article number 1098744, 1130297, 1104633, 1134519, 1104634.

Example 1. Preparation of Polymer Nanofibers by Method One

The O. lg divinylbenzene (DVB) monomer was dissolved in 125 g of n-hexane to prepare a solution, and the temperature of the solution was adjusted to 0 °C. O. lg boron trifluoride diethyl ether initiator was added dropwise and placed in a constant temperature water bath at 0 ° C for 30 minutes to obtain a reddish brown flake precipitate. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber had a diameter of 10 to 200 nm and a length of ΙΟμηη or more.

The polymer nanofiber scanning electron microscope and transmission electron micrograph are shown in Fig. 1.

Example 2. Preparation of polymer nanofibers by method one

20 g of divinylbenzene (DVB) monomer was dissolved in 125 g of cyclohexane to prepare a solution, and the temperature of the solution was adjusted to 50 °C. The lg boron trifluoride diethyl ether initiator was added dropwise and placed in a constant temperature water bath at 50 ° C for 1 minute to obtain a reddish brown wooly precipitate. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 50 to 500 nm and a length of 0.5 to 20 μm.

The polymer nanofiber scanning electron microscope and transmission electron micrograph are shown in Fig. 2.

Example 3: Using Method 1 to prepare polymer nanofibers

10 g of divinylbenzene (DVB) monomer was dissolved in 125 g of cyclohexane to prepare a solution, and the temperature of the solution was adjusted to 25 °C. 0.5 g of boron trifluoride diethyl ether initiator was added dropwise, and placed in a constant temperature water bath at 25 ° C for 15 minutes to obtain Reddish brown fleece precipitate. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 50 to 200 nm and a length of ΙΟμηη or more.

The SEM and TEM photographs of the polymer nanofibers are shown in Fig. 3 and Fig. 5. The infrared characterization spectrum is shown in Fig. 6. The carbonization characterization is shown in Fig. 7, and the thermal performance is shown in Fig. 10.

Example 4, using method 1 to prepare polymer nanofibers

Divinylbenzene (DVB) and p-chloromethylstyrene (VBC) monomers (each O.lg) were dissolved in 125 g of cyclohexane to prepare a solution, and the temperature of the solution was adjusted to 25 °C. O. lg boron trifluoride diethyl ether initiator was added dropwise and placed in a constant temperature water bath at 25 ° C for 15 minutes to obtain a reddish brown wooly precipitate. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 10 to 200 nm and a length of Ιμηη or more.

Example 5: Preparation of polymer nanofibers by method one

Divinylbenzene (DVB) and p-chloromethylstyrene (VBC) monomers (10 g each) were dissolved in 125 g of cyclohexane to prepare a solution, and the temperature of the solution was adjusted to 50 °C. Add lg of boron trifluoride diethyl ether initiator to 50 °. The reaction was carried out for 1 minute in a constant temperature water bath to obtain a reddish brown flake precipitate. Thereafter, the reaction was terminated with ethanol, and a white cotton-like product was obtained by filtration. The obtained fiber has a diameter of 50 to 500 nm and a length of Ιμηη or more.

Example 6. Preparation of Polymer Nanofibers by Method One

Divinylbenzene (DVB) and p-chloromethylstyrene (VBC) monomers (each lg) were dissolved in 125 g of cyclohexane to prepare a solution, and the temperature of the solution was adjusted to 25 °C. 0.5 g of boron trifluoride diethyl ether initiator was added dropwise and placed at 25 °. The reaction was carried out for 15 minutes in a constant temperature water bath to obtain a reddish brown flake precipitate. Thereafter, the reaction was terminated with ethanol, and a white cotton-like product was obtained by filtration. The obtained fiber has a diameter of 50 to 200 nm and a length of ΙΟμηη or more.

Example 7. Preparation of Polymer Nanofibers by Method One

The lg DVB monomer was dissolved in 1250 g of cyclohexane solvent to form a solution, and then the monomer solution and lg boron trifluoride diethyl ether initiator were pumped at a flow rate of 1 ml/s into a tubular reactor having a diameter of 0.5 cm at 0 ° C. In the middle, a reddish brown fleece precipitate was obtained at the end of the tube. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 10 to 200 nm and a length of ΙΟμηη or more.

The polymer nanofiber scanning electron microscope and transmission electron micrograph are shown in Fig. 4.

Example 8. Preparation of Polymer Nanofibers by Method One

200 g of DVB monomer was dissolved in 1250 g of cyclohexane solvent to prepare a solution, and then the monomer solution and 10 g of boron trifluoride diethyl ether initiator were pumped at a flow rate of 5 L/s into a tubular reactor having a diameter of 10 cm at 80 ° C. A reddish brown fleece precipitate was obtained at the end of the tube. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 50 to 500 nm and a length of Ιμηη or more.

Example 9. Preparation of Polymer Nanofibers by Method One

100 g of DVB monomer was dissolved in 1250 g of cyclohexane solvent to form a solution, and then the monomer solution and 5 g of boron trifluoride diethyl ether initiator were pumped into a 40 ° C diameter 5 cm tubular reactor at a flow rate of 2 L/s. A reddish brown fleece precipitate was obtained at the end of the tube. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 20 to 500 nm and a length of Ιμηη or more.

Example 10: Preparation of polymer nanofibers by method one

1 mg of n-butyllithium initiator was dissolved in 125 g of cyclohexane to form a dispersion, and the temperature of the solution was adjusted to 0 °C. DVB and styrene (each O. lg) monomer were added dropwise, and placed in a constant temperature water bath at 0 ° C for 60 minutes to obtain red brown A woolly precipitate. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 50 to 200 nm and a length of Ιμηη or more.

Example 11. Preparation of Polymer Nanofibers by Method One

A 100 mg of n-butyllithium initiator was dissolved in 125 g of cyclohexane to form a dispersion, and the temperature of the solution was adjusted to 50 °C. The monomer of DVB and styrene (2.5 g each) was added dropwise and placed in a constant temperature water bath at 50 ° C for 5 minutes to obtain a reddish brown wooly precipitate. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 50 to 500 nm and a length of Ιμηη or more.

Example 12: Preparation of Polymer Nanofibers by Method One

500 mg of n-butyllithium initiator was dissolved in 125 g of cyclohexane to form a dispersion, and the temperature of the solution was adjusted to 25 V. DVB and styrene (1.3 g each) were added dropwise and placed in a constant temperature water bath at 25 ° C for 30 minutes to obtain a reddish brown flake precipitate. The reaction was then quenched with ethanol and filtered to give a white cotton. The obtained fiber has a diameter of 50 to 200 nm and a length of ΙΟμηη or more.

Example 13. Preparation of Polymer Nanofibers by Method 2

The 0.1AIBN initiator was dissolved in 10 g of DMF to form a solution, and then the solution was added to 100 g of a 0.1% DVB n-heptane solution, and placed in a constant temperature water bath at 70 ° C for 12 hours to obtain a white precipitate which was filtered to give a white product. The obtained fiber has a diameter of 50 to 200 nm and a length of ΙΟμηη or more.

Example 14. Preparation of Polymer Nanofibers by Method 2

The lg AIBN initiator was dissolved in 10 g of DMF to prepare a solution, and then the solution was added to 100 g of a 10% DVB n-heptane solution, and placed in a 95 ° C constant temperature water bath for 1 hour to obtain a white precipitate, which was filtered to give a white product. The obtained fiber has a diameter of 50 to 500 nm and a length of Ιμηη or more.

Example 15. Preparation of Polymer Nanofibers by Method 2

0.5 g of AIBN initiator was dissolved in 10 g of DMF to prepare a solution, and then the solution was added to 100 g of 5% DVB in n-heptane solution, and placed in a constant temperature water bath at 80 ° C for 6 hours to obtain a white precipitate, which was filtered to obtain a white product. . The obtained fiber has a diameter of 20 to 200 nm and a length of Ιμηη or more.

Example 16. Preparation of Functionalized Polymer Nanofibers by Method One

The product obtained in Example 3 (4 g) was mixed with 10 ml of concentrated sulfuric acid having a 50% by mass concentration, and reacted at room temperature for 6 hours to obtain a brown suspension which was suction-filtered to obtain a brown powdery product, i.e., a strongly acidic cation exchange fiber. The obtained fiber has a diameter of 50 to 200 nm and a length of Ιμηη or more.

Example 17. Preparation of Functionalized Polymer Nanofibers by Method One

The product obtained in Example 3 (4 g) was mixed with 100 ml of a concentrated sulfuric acid having a 98% by mass concentration, and reacted at room temperature for 0.5 hour to obtain a brown suspension which was suction-filtered to obtain a brown powdery product, i.e., a strongly acidic cation exchange fiber. The obtained fiber has a diameter of 50 to 200 nm and a length of Ιμηη or more.

Example 18: Using Method 1 to Prepare Functionalized Polymer Nanofibers

The product obtained in Example 3 (4 g) was mixed with 50 ml of concentrated sulfuric acid having a mass concentration of 75%, and reacted at room temperature for 3 hours to obtain a brown suspension which was suction-filtered to obtain a brown powdery product, i.e., a strongly acidic cation exchange fiber. The obtained fiber has a diameter of 50 to 200 nm and a length of Ιμηη or more.

Example 19: Preparation of Functionalized Polymer Nanofibers by Method 2

The product obtained in Example 3 (8 g) was dispersed in 50 g of toluene, and lg maleic anhydride comonomer was added. After reacting with an Ig AIBN initiator at 50 ° C for 12 hours, a white suspension was obtained, which was filtered under suction to obtain a white powdery product, that is, a maleated nanofiber, which was further hydrolyzed to obtain a weakly acidic cation exchange fiber. The obtained fiber has a diameter of 50 to 200 nm and a length of Ιμηη or more.

Example 20, using method 2 to prepare functionalized polymer nanofibers

The product obtained in Example 3 (8 g) was dispersed in 500 g of toluene, 10 g of maleic anhydride comonomer and 10 g of AIBN initiator were added, and reacted at 90 ° C for 2 hours to obtain a white suspension, which was suction filtered to give a white powdery product. That is, the maleic anhydride nanofibers are further hydrolyzed to obtain weakly acidic cation exchange fibers. The obtained fiber has a diameter of 50 to 200 nm and a length of Ιμηη or more.

Example 21: Using Method 2 to Prepare Functionalized Polymer Nanofibers

The product obtained in Example 3 (8 g) was dispersed in 250 g of toluene, 5 g of maleic anhydride comonomer and 5 g of AIBN initiator were added, and reacted at 70 ° C for 6 hours to obtain a white suspension, which was suction filtered to give a white powdery product. That is, the maleic anhydride nanofibers are further hydrolyzed to obtain weakly acidic cation exchange fibers. The obtained fiber has a diameter of 50 to 200 nm and a length of Ιμηη or more.

Example 22. Preparation of Functionalized Polymer Nanofibers by Method Three

The chloromethylstyrene (VBC) obtained in Example 6 and the copolymerized polymer nanofiber (polystyrene-co-chloromethylstyrene, 4 g) of DVB were dispersed in 50 g of ethanol, and lg 30% aqueous solution of trimethylamine was added. After reacting with O. lg sodium hydroxide at 50 ° C for 6 hours, a white suspension was obtained, which was suction filtered to give a white powdery product, that is, a strongly basic anion exchange fiber. The obtained fiber has a diameter of 50 to 200 nm and a length of ΙΟμηη or more.

Example 23, Preparation of Functionalized Polymer Nanofibers by Method Three

The chloromethylstyrene (VBC) obtained in Example 6 and the copolymerized polymer nanofiber (polystyrene-co-chloromethylstyrene, 4 g) of DVB were dispersed in 500 g of ethanol, and 20 g of a 30% aqueous solution of trimethylamine was added. After reacting with 10 g of sodium hydroxide at 80 ° C for 2 hours, a white suspension was obtained, which was suction filtered to give a white powdery product, that is, a strongly basic anion exchange fiber. The obtained fiber has a diameter of 50 to 200 nm and a length of ΙΟμηη or more.

Example 24: Preparation of Functionalized Polymer Nanofibers by Method Three

The chloromethylstyrene (VBC) obtained in Example 6 and the copolymerized polymer nanofiber (polystyrene-co-chloromethylstyrene, 4 g) of DVB were dispersed in 250 g of ethanol, and 10 g of a 30% aqueous solution of trimethylamine was added. After reacting with 5 g of sodium hydroxide at 25 ° C for 12 hours, a white suspension was obtained, which was suction filtered to give a white powdery product, that is, a strongly basic anion exchange fiber. The obtained fiber has a diameter of 50 to 200 nm and a length of ΙΟμηη or more.

Example 25, using method 1 to prepare hybrid polymer nanofibers

5 g of divinylbenzene (DVB) monomer was dissolved in 50 g of n-hexane solvent to form a solution, and O. lg diameter lOnm magnetic ferroferric oxide nanoparticles were added, followed by dropwise addition of 50 mg of boron trifluoride diethyl ether initiator, and placed 0 °. The reaction was carried out for 1 hour in a constant temperature water bath to obtain a brown fluffy precipitate. The reaction was quenched by the addition of 5 ml of ethanol and filtered to give a brown cotton. The obtained fiber has a diameter of 10 to 200 nm and a length of Ιμηη or more.

Example 26, using method 1 to prepare hybrid polymer nanofibers

5g of divinylbenzene (DVB) monomer was dissolved in 500g of cyclohexane solvent to form a solution, 5g of magnetic iron tetraoxide nanoparticles with a diameter of 100nm was added, and then 500mg of boron trifluoride diethyl ether initiator was added dropwise, and put into 50 The reaction was carried out for 15 minutes in a constant temperature water bath to obtain a brown fluffy precipitate. The reaction was quenched by the addition of 20 ml of ethanol and filtered to give a brown cotton. The obtained fiber has a diameter of 10 to 500 nm and a length of Ιμηη or more. Example 27, using method 1 to prepare hybrid polymer nanofibers

5g of divinylbenzene (DVB) monomer was dissolved in 250g of cyclohexane solvent to form a solution, 2.5g of magnetic nanometer ferroferric oxide nanoparticles were added, and then 250mg of boron trifluoride diethyl ether initiator was added dropwise. The reaction was carried out for 0.5 hour in a constant temperature water bath at 25 ° C to obtain a brown wooly precipitate. The reaction was quenched by the addition of 15 ml of ethanol and filtered to give a brown cotton. The obtained fiber has a diameter of 20 to 400 nm and a length of Ιμηη or more.

Figure 9 shows the magnetic polymer nanofibers synthesized in this example and their magnetic behavior. a) a transmission photograph of the magnetized polymer nanofiber; b) a photo of the magnetic field induced enrichment effect of the magnetic polymer nanofiber.

Example 28, using method 2 to prepare hybrid polymer nanofibers

The strongly acidic cation exchange fiber lg obtained in Example 17 was dispersed in 5 g of aniline for adsorption for 12 hours, and then the adsorbed saturated nanofiber was extracted with 10 g of water, and 50 ml of a 1% ammonium persulfate hydrochloric acid solution was added thereto, and the reaction was carried out at room temperature. After a few hour, a dark green suspension was obtained which was filtered to give the product. The obtained fiber has a diameter of 100 to 500 nm and a length of Ιμηη or more.

Example 29: Preparation of Hybrid Polymer Nanofibers by Method 2

The strongly acidic cation exchange fiber lg obtained in Example 17 was dispersed in 20 g of aniline for adsorption for 12 hours, and then the adsorbed saturated nanofiber was extracted with 50 g of water, and 50 ml of a 5% ammonium persulfate hydrochloric acid solution was added thereto, and the reaction was carried out at room temperature. After a few hour, a dark green suspension was obtained which was filtered to give the product. The obtained fiber has a diameter of 100 to 500 nm and a length of Ιμηη or more.

Fig. 8 is a macroscopic morphology and an electron micrograph (conductive polyaniline hybridized polymer nanotube) of the polymer one-dimensional nanohybrid material synthesized in this example, and its thermal performance is characterized as shown in Fig. 10.

Example 30, Preparation of Hybrid Polymer Nanofibers by Method 2

The strongly acidic cation exchange fiber lg obtained in Example 17 was dispersed in 12 g of aniline for adsorption for 12 hours, and then the adsorbed saturated nanofiber was extracted with 30 g of water, and 50 ml of a 3% ammonium persulfate hydrochloric acid solution was added thereto, and the reaction was carried out at room temperature. After a few hour, a dark green suspension was obtained which was filtered to give the product. The obtained fiber has a diameter of 100 to 500 nm and a length of Ιμηη or more.

Example 31, Preparation of Hybrid Polymer Nanofibers by Method Three

The strongly acidic cation exchange fiber lg obtained in Example 17 was dispersed in 5 ml of 50% tetrabutyl titanate in ethanol, stirred for 6 hours to reach a saturated adsorption state, and 5 ml of a 5% aqueous hydrochloric acid solution was added to the product obtained by filtration. After reacting at room temperature for 2 hours, a white suspension was obtained, which was filtered to give a product. The obtained fiber has a diameter of 100 to 500 nm and a length of Ιμηη or more.

Example 32, Preparation of Hybrid Polymer Nanofibers by Method Three

The strongly acidic cation exchange fiber lg obtained in Example 17 was dispersed in 50 ml of 50% tetrabutyl titanate in ethanol, stirred for 6 hours to reach a saturated adsorption state, and 50 ml of a 5% aqueous hydrochloric acid solution was added to the product obtained by filtration. After reacting for 12 hours at room temperature, a white suspension was obtained, which was filtered to give a product. The obtained fiber has a diameter of 100 to 500 nm and a length of Ιμηη or more.

Example 33, Preparation of Hybrid Polymer Nanofibers by Method Three

The strongly acidic cation exchange fiber lg obtained in Example 17 was dispersed in 25 ml of 50% tetrabutyl titanate in ethanol, stirred for 6 hours to reach a saturated adsorption state, and 25 ml of a 5% aqueous hydrochloric acid solution was added to the product obtained by filtration. After reacting at room temperature for 6 hours, a white suspension was obtained, which was filtered to give a product. Fiber obtained The diameter is 100-500 nm and the length is above Ιμιη.

Example 34, Preparation of Hybrid Polymer Nanofibers by Method 4

The strongly acidic cation exchange fiber lg obtained in Example 18 was dispersed in 100 ml of 0.1% silver nitrate aqueous solution for adsorption for 24 hours, and the nanofibers obtained by filtration and saturated adsorption of the precursor were added to 5 ml of 10% aqueous glucose solution at 20 ° C. After reacting for 2 hours, a black dispersion was obtained, which was filtered to give a product. The obtained fiber has a diameter of 100 to 500 nm and a length of Ιμηη or more.

Example 35, Preparation of Hybrid Polymer Nanofibers by Method 4

The strongly acidic cation exchange fiber lg obtained in Example 18 was dispersed in 100 ml of a 5% silver nitrate aqueous solution for adsorption for 12 hours, and the nanofibers obtained by filtration and saturated adsorption of the precursor were added to 50 ml of 10% aqueous glucose solution at 90 ° C. After 12 hours of reaction, a black dispersion was obtained, which was filtered to give a product. The obtained fiber has a diameter of 100 to 500 nm and a length of Ιμηη or more.

Example 36, Preparation of Hybrid Polymer Nanofibers by Method 4

The strongly acidic cation exchange fiber lg obtained in Example 18 was dispersed in 100 ml of a 2.5% silver nitrate aqueous solution for adsorption for 12 hours, and the nanofibers obtained by filtration and saturated adsorption of the precursor were added to 25 ml of 10% aqueous glucose solution at 55 ° C. After 7 hours of reaction, a black dispersion was obtained, which was filtered to give a product. The obtained fiber has a diameter of 100 to 500 nm and a length of Ιμηη or more.

Example 37. Using Method 4 to Prepare Functionalized Polymer Nanofibers

The chloromethylstyrene (VBC) obtained in Example 6 and the copolymerized polymer nanofiber (polystyrene-co-chloromethylstyrene, 1.5 g) of DVB were dispersed in 100 ml of anisole, and 0.43 g of a catalyst was added. Copper chloride (CuCl), 0.51g ligand pentamethyldiethylenetriamine (PMDETA) and 30g of polymerized monomer methyl methacrylate (MMA), reactive graft polymerization at 95 °C under argon protection 1 After an hour, the product was obtained by rinsing with acidic ethanol. The obtained fiber has a diameter of 50 to 500 nm and a length of Ιμηη or more.

Example 38. Preparation of Functionalized Polymer Nanofibers by Method 4

The chloromethylstyrene (VBC) obtained in Example 6 and the copolymerized polymer nanofiber (polystyrene-co-chloromethylstyrene, 1.5 g) of DVB were dispersed in 100 ml of anisole, force B 0.43 g CuCl, 0.51g

PMDETA and 30 g of MMA were subjected to reactive graft polymerization at 95 °C for 6 hours under argon atmosphere, and then filtered with an acid ethanol to obtain a product. The obtained fiber has a diameter of 50 to 500 nm and a length of Ιμηη or more.

Example 39. Using Method 4 to Prepare Functionalized Polymer Nanofibers

PMDETA and 30 g of butyl acrylate (BA) were subjected to reactive graft polymerization at 95 °C for 6 hours under argon atmosphere, and then filtered with acidic ethanol to obtain a product. The obtained fiber has a diameter of 50 to 500 nm and a length of more than Ιμηη.

Industrial application

The product synthesized by the method is a white or light yellow cotton-like block or powder, and the microscopic fiber diameter is in the range of 10 nm to 10 μm, and may be completely hollow, the bamboo-like portion is hollow or completely solid; the microscopic fiber length is adjustable, and The diameter and length are controllable. The resulting product can be further chemically modified and prepared with nanocomposites, and is expected to have more excellent properties and be used in many fields. For example, sulfonation is obtained by chemical modification. And carboxylation and quaternization of cationic and anionic nanofibers, can be used in the fields of catalysis, ion exchange and the like. A surface-coated polyaniline conductive layer and a nano-fiber hybrid material having magnetic responsiveness were prepared by a swelling polymerization method and a dispersion polymerization method. Related carbon nanotube or nanowire materials can be obtained by further high temperature carbonization of functionalized nanofibers. Through the further exploration of the polymerization conditions and the improvement of the polymerization equipment and process, the tubular volume preparation is realized, which is suitable for efficient batch preparation of related polymer nano materials.

The invention realizes simple and batch preparation of polymer nanotubes or nanowires by a new method. This non-traditional and simple method can be used to prepare polymer nanotubes or nanofibers on a large scale and low cost, and to prepare related functionalized nanowires/tubes and hybrid nanowires/tubes or even carbon nanomaterials by modification. A discovery will greatly advance related industries and products, such as super-hydrophobic, high-efficiency oil-absorbing materials, high performance liquid chromatography, ion exchange resins, water treatment, heterogeneous separability catalysis, nanosensors, battery separators and electrodes, thermal insulation materials, Development of sound damping materials, phase change energy storage materials, and the like.

Claims

Rights request

A polymer nanofiber, which is any one of the following two structures: consisting of a core layer and a shell layer surrounding the core layer or only a shell layer; constituting the core layer The material is the same as or different from the material constituting the shell layer; the polymer nanofiber has a diameter of 10 nm to 10 μm and a length of 500 nm to 50 mm.

The nanofiber according to claim 1, wherein the polymer nanofiber has a diameter of 50 to 500 nm and a length of 500 nm to 5 mm.

The nanofiber according to claim 1 or 2, wherein the polymer nanofiber is produced by the method according to any one of claims 4 or 5.

A method for producing the polymer nanofiber according to any one of claims 1 or 2, which is the following method 1 or method 2,

Wherein the method 1 comprises the steps of: polymerizing a monomer and an initiator in a solvent, and obtaining the polymer nanofiber after the reaction;

The method 2 includes the steps of dissolving the initiator in a polar solvent to obtain a polar solution of the initiator, and dissolving the monomer in a non-polar solvent to obtain a non-polar solution of the monomer, and then The polar solution of the initiator is mixed with the non-polar solution of the monomer to carry out a reaction, and the reaction is completed to obtain the polymer nanofiber; in the method 1 and the method 2, the monomer is selected from the group consisting of At least one of a cationically polymerizable monomer, an anionic polymerizable monomer, a radical polymerizable monomer, and a sol-gel reactive monomer; the initiators are each selected from the group consisting of a radical initiator, a cationic initiator, an anionic initiator, and a solvent. At least one of the gum reaction catalysts has a particle diameter of from 10 nm to 10 μm, preferably from 50 to 500 nm.

The method according to claim 4, wherein in the method 1 and the method 2, the cationic polymerization monomer is selected from the group consisting of styrene, methyl styrene, α-methyl styrene, and methyl group. Styrene, methoxystyrene, divinylbenzene, butadiene, isoprene, isobutylene, 3-methyl-1-butene, 4-methyl-1-pentene, alkyl vinyl ether , chloromethylstyrene, bromomethylstyrene, iodomethylstyrene, halogenated styrene, oxetane derivative, tetrahydrofuran, trioxane, formaldehyde, alkylene oxide, epoxy coupling At least one of the agent and the ethylene sulfide; wherein the alkyl vinyl ether is isobutyl vinyl ether, methyl vinyl ether or divinyl ether; the halogenated styrene is chlorostyrene, a p-chloromethylstyrene or a 4-bromostyrene; the oxetane derivative is a butoxy ring or a 3,3'-bis(chloromethylene)butoxy ring; the alkylene oxide is Ethylene oxide or propylene oxide; the epoxy coupling agent is an epoxy silane coupling agent or an epoxy titanate coupling agent;

The radical polymerizable monomers are all vinyl monomers; the vinyl monomer is at least one selected from the group consisting of divinylbenzene, styrene, acrylonitrile, acrylamide, and vinyl acetate;

The sol-gel reactive monomers are all hydrolyzed compounds; the hydrolyzed compounds are selected from the group consisting of silicates, titanates, At least one of a tin halide, a trichloromethylsilane, a tetrachlorosilane, a titanium trichloride, and a titanium tetrachloride;

The free radical initiator is selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, ammonium persulfate, ammonium persulfate or a mixture of hydrogen peroxide and ferrous chloride, and consists of potassium permanganate and oxalic acid. Mixture, a mixture of ammonium cerium nitrate and ethanol, a mixture of dibenzoyl peroxide and hydrazine, dimethyl aniline, a mixture of dibenzoyl peroxide and cuprous naphthalate and by peroxidation At least one of a mixture of dibenzoyl and triethylaluminum;

The cationic initiator is selected from at least one of protonic acid, Lewis acid and iodine; wherein the protic acid is selected from at least one of concentrated sulfuric acid, phosphoric acid, perchloric acid and trichloroacetic acid; The Lewis acid is selected from the group consisting of BF ₃ , boron trifluoride diethyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride methanol complex, boron trifluoride acetate complex, and boron trifluoride ethylamine. At least one of a compound, A1C1 ₃ , TiCl ₄ and SnCl ₄ ; the concentrated sulfuric acid has a mass percent concentration of 20-150%, preferably 50-98%;

The anion initiator is selected from the group consisting of an alkali metal, an organometallic compound or a tertiary amine; wherein the alkali metal is at least one selected from the group consisting of sodium and potassium, and the organometallic compound is selected from the group consisting of metal amino compounds and metal alkyl groups. At least one of a compound and a Grignard reagent; the tertiary amine is at least one selected from the group consisting of trimethylamine, triethylamine, and pyridine; wherein the metal amino compound is preferably a NaNH ₂ or KM-liquid ammonia system. The metal alkyl compound is preferably butyl lithium, ethyl sodium or phenyl isopropyl potassium; the Grignard reagent has the structural formula of RMgX, wherein R is an alkane group having a total number of carbon atoms of 1-8, a phenyl group. Or a benzyl group, X is a halogen, preferably benzyl magnesium chloride; the sol-gel reaction catalyst is an acid or a base; wherein the acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid and nitric acid; At least one of sodium hydroxide and potassium hydroxide; the mass percentage of the ammonia water is 1-28%, preferably 5-20%;

In the first method, the solvent is at least one selected from the group consisting of a total of 5-10 carbon atoms, cyclohexane, alkyl halide, petroleum ether, gasoline and liquid paraffin, preferably n-pentane, n-hexane and n-heptane. At least one of the initiator; the mass ratio of the initiator to the solvent is from 0.001 to 10: 100, preferably from 0.02 to 2: 100; the mass ratio of the monomer to the solvent is from 0.0001 to 50: 100, preferably 0.05-10: 100; in the polymerization step, the temperature is -60°. 〜100, preferably -20 ° C ~ 60 ° C, the time is 5 seconds ~ 12 hours, preferably 10 seconds ~ 15 minutes;

6. A method for preparing a functionalized polymer nanofiber, which is any one of the following methods 1 to 4;

The method 1 includes the following steps: mixing the polymer nanofiber according to any one of claims 1-3 with a sulfonating agent, and reacting to obtain the functionalized polymer nanofiber;

The method 2 includes the following steps: the polymer nanofiber according to any one of claims 1 to 3 in a solvent and The comonomer and the initiator are mixed to carry out a reaction, and the reaction is completed to obtain the functionalized polymer nanofiber; the method 3 includes the following steps: the cationically polymerizable monomer according to any one of claims 1 to 3 is selected from a chloromethyl group. The polymer nanofiber obtained by mixing at least one of styrene, bromomethylstyrene and iodomethylstyrene is mixed with a tertiary amine aqueous solution and a strong base in a solvent to complete the reaction to obtain the functionalized polymer nanometer. The method 4 includes the following steps: when the cationically polymerizable monomer according to any one of claims 1 to 3 is at least one selected from the group consisting of chloromethylstyrene, bromomethylstyrene, and iodomethylstyrene The polymer nanofibers are mixed with a polymerization monomer, a catalyst and a ligand to carry out a living graft polymerization reaction in a solvent, and the functionalized polymer nanofibers are obtained by completion of the reaction.

7. The method of claim 6 wherein:

In the second method, the solvent is selected from at least one of toluene and ethanol, the comonomer is maleic anhydride; and the initiator is selected from the group consisting of azobisisobutyronitrile and benzoyl peroxide. At least one; the mass ratio of the polymer nanofiber, the solvent, the comonomer, and the initiator is 1-20: 100-1000: 0.1-20: 0.1-5, preferably 10: 250: 10: 1; in the reaction step, the temperature is 50-100 ° C, preferably 70 ° C, the time is 1-24 hours, preferably 4-12 hours;

In the third method, the tertiary amine is at least one selected from the group consisting of trimethylamine and triethylamine; the solvent is at least one selected from the group consisting of ethanol, anisole and methanol, preferably ethanol; From at least one of sodium hydroxide and potassium hydroxide; the tertiary amine aqueous solution has a mass percent concentration of 0.1-30%, preferably 1-10%; the polymer nanofiber, the solvent, the tertiary amine The mass ratio of the aqueous solution to the strong base is 0.1-10: 20-1000: 1-100: 0.5-50, preferably 1: 100: 10: 5; in the reaction step, the temperature is 20-80 ° C, preferably 30 ° C, time is 1-24 hours, preferably 2-6 hours;

In the fourth method, the polymerization monomer is selected from the group consisting of α-methylstyrene, styrene, butadiene, isoprene, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, Methyl ketene, nitroethylene, diethyl methylene malonate, α-cyanoacrylate, ethyl α-cyano-2,4-hexadienoate, dicyanoethylene, formaldehyde, epoxy B At least one of an alkane, an alkylene oxide, an ethylene sulfide, and an ε-caprolactam, preferably methyl methacrylate; the catalyst is cuprous chloride; the solvent is selected from at least one of ethanol, anisole and methanol Preferred is anisole; the ligand is selected from the group consisting of pentamethyldiethylenetriamine or 2,2'-bipyridine; the catalyst, ligand, polymer nanofiber, polymerizable monomer and the solvent The dosage ratio is 0.1-100 g: 0.1-10 g: l-100 g: l-1000 g: 10-5000 mL, preferably 0.4 g: 0.5 g: 1.5 g: 30 g: lOOmL; in the living graft polymerization step, the temperature It is 50-100 ° C, preferably 80 ° C, and the time is 2-24 hours, preferably 4-12 hours.

8. A functionalized polymeric nanofiber prepared as claimed in any one of claims 6 or 7.

A method for preparing a hybrid polymer nanofiber, which is any one of the following methods 1 to 4; wherein the method 1 comprises the following steps: magnetic nanoparticles, according to any one of claims 4 or 5. The monomer, the initiator according to any one of claims 4 or 5 is subjected to polymerization in a solvent according to any one of claims 4 or 5, and the reaction is completed to obtain the hybrid polymer nanofiber; The method 2 includes the following steps: after the functionalized polymer nanofiber of claim 8 is adsorbed with a conductive polymer monomer, the obtained polymer nanofiber is reacted with an oxidant solution to obtain the hybrid polymer nanometer. fiber;

The method 3 includes the following steps: after the functionalized polymer nanofiber of claim 8 is adsorbed with an ethanol solution of an oxide, the obtained polymer nanofiber is reacted with an aqueous solution of an acid or a base, and the reaction is completed. Polymer nanofibers;

The method 4 includes the following steps: after the functionalized polymer nanofiber of claim 8 is adsorbed with an aqueous solution of a metal salt precursor, the obtained polymer nanofiber is hydrolyzed or reacted with a reducing agent, and the reaction is completed. Hybrid polymer nanofibers.

The method according to claim 9, wherein in the method 1, the magnetic nanoparticles are at least one selected from the group consisting of triiron tetroxide, γ-iron oxide, and magnetic rare earth alloy nanoparticles; The magnetic nanoparticles have a particle diameter of 1 to 1000 nm, preferably 10 to 100 nm; the magnetic nanoparticles, the monomer according to any one of claims 4 or 5, and the initiator according to any one of claims 4 or 5. And the solvent according to any one of claims 4 or 5 is used in an amount of 0.1-10: 0.5-200: 0.01-20: 100-10 ⁵ , preferably 1: 50: 2: 2000; in the reaction step, the temperature is -60 to 120 ° C, preferably 0-60 ° C, time is 0.1-60 minutes, preferably 2-15 minutes;

In the second method, the conductive polymer monomer is at least one selected from the group consisting of aniline, pyrrole, thiophene and thiophene derivatives; in the oxidizing agent solution, the solute is selected from the group consisting of ammonium persulfate, potassium persulfate and trichlorination. At least one of iron, the solvent is selected from at least one of water, ethanol, and acetone; the functionalized polymer nanofiber of claim 8, the conductive polymer monomer, and a solute in the oxidant solution The dosage ratio is 0.1-10: 0.1-5: 0.01-10, preferably 1: 0.5: 1; in the adsorption step, the time is 1-24 hours, preferably 12-24 hours; in the reaction step, the temperature is - 20 to 80 ° C, preferably 0 ° C, the time is 10 minutes to 6 hours, preferably 1-4 hours;

In the third method, in the ethanol solution of the oxide, the oxide is selected from the group consisting of ethyl orthosilicate, tetrabutyl titanate, trichloromethylsilane, tetrachlorosilane, titanium trichloride and tetrachlorochloride. At least one of titanium oxide; the ethanol solution of the oxide has a mass percentage of 0.1-80%, preferably 1-50%; and the acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid and hydrobromic acid, The base is selected from at least one of ammonia water, potassium hydroxide and sodium hydroxide; the aqueous solution of the acid or base has a mass percentage of 0.1-10%, preferably 1-5%; The mass ratio of the functionalized polymer nanofiber, the oxide to the acid or base is 0.1-10: 0.02-100: 0.1-100, preferably 1: 1: 0.5; in the adsorption step, the time is 1-24 hours, preferably 12-24 hours; in the reaction step, the temperature is -20~100 ° C, preferably 10-40 ° C, the time is 0.5-12 hours, preferably 2-6 hours; In the aqueous solution of the metal salt precursor, the metal salt precursor is at least one selected from the group consisting of silver nitrate and nickel acetate; The agent is at least one selected from the group consisting of hydrazine, hydrazine hydrate and glucose; and the ratio of the functionalized polymer nanofiber, metal salt precursor and the reducing agent according to claim 8 is 0.1-10: 0.01-100 : 0.1-100, preferably 1: 10: 5; in the adsorption step, the time is 1-24 hours, preferably 12-24 hours; in the reaction step, the temperature is 0-100 ° C, preferably 20-70 ° C, the time is from 1 minute to 12 hours, preferably from 5 minutes to 4 hours.

11. A hybrid polymer nanofiber prepared by the method of any of claims 9 or 10.