CN114644823B - PH responsive composite Janus nano-particle and preparation method thereof - Google Patents
PH responsive composite Janus nano-particle and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a pH responsive composite Janus nano particle and a preparation method thereof, wherein the material is a pH responsive magnetic polymer/inorganic composite Janus nano particle, and comprises a magnetic inorganic nano particle core and a polymer shell layer covering the core; the polymer shell layer includes an outer shell layer comprising a hydrophilic polymer and an inner shell layer comprising a pH-responsive polymer. The material has multiple functions including magnetism, pH responsiveness, janus characteristics and the like, can be applied to the fields of oil-water separation, sewage treatment, drug controlled release and the like, and has wide application prospect. The invention also provides a corresponding preparation method, and the preparation method has the advantages of high solid content, mass preparation and the like.
Description
Technical Field
The invention relates to the technical field of preparation and application of polymer composite nano materials, in particular to a pH-responsive magnetic polymer/inorganic composite Janus nano particle and a preparation method thereof.
Background
Since de Gennes first described particles with surfaces having different chemical properties with Janus, material research with surfaces having multiple properties has become a research hotspot in the field of materials. The Janus particles with the surface having dual properties simultaneously provide an effective way for solving the functionalization and dispersibility of the nano material, and the dual-property integration can generate new properties, so that the Janus particles have important practical significance for promoting the development of new materials. As a result of the combination of different components and properties, janus materials have attracted increasing attention and have found wide application in various fields (LIANG F, ZHANG C, YANG Z.ratio design and synthesis of Janus composites [ J ]. Adv Mater,2014,26 (40): 6944-6949). Janus materials have shown excellent performance and attractive application prospects in the fields of solid particle emulsifiers, assembly, optical probes, catalysis and the like.
The polymer/inorganic composite Janus nano material can have the unique properties of both polymer and inorganic material, and has wide application prospect. Those skilled in the art will appreciate the development of more Janus nanomaterials that have utility.
Disclosure of Invention
The invention aims to provide a pH-responsive magnetic polymer/inorganic composite Janus nano particle and a preparation method thereof, and the material has multiple functions including magnetism, pH responsiveness, janus characteristics and the like, and can be applied to the fields of oil-water separation and drug controllable release. In addition, the preparation method provided by the invention has the advantages of high solid content and mass preparation.
To this end, in a first aspect, the present invention provides a pH-responsive magnetic polymer/inorganic composite Janus nanoparticle comprising a core and a polymer shell layer covering the core; the core is a magnetic inorganic nano particle; the polymer shell layer includes an outer shell layer comprising a hydrophilic polymer and an inner shell layer comprising a pH-responsive polymer.
According to the technical scheme, the magnetic inorganic nano-particles are used as cores, so that the composite Janus nano-particles have magnetism, can be controlled by an external magnetic field, and can be enriched efficiently by simple modes such as magnet traction.
Further, the particle size of the magnetic inorganic nano particles is 10 nm-300 nm; preferably 10-50nm, for example 10nm, 20nm, 30nm, 40nm, 50nm, etc.
Further, the magnetic inorganic nanoparticles are ferroferric oxide nanoparticles.
Further, the hydrophilic polymer is polyethylene glycol, and the molecular weight of the hydrophilic polymer is 500-1000.
Further, the pH-responsive polymer is a class of polymers having different hydrophilicity and hydrophobicity under different pH conditions.
In some embodiments, the pH-responsive polymer is a diethylaminoethyl methacrylate having a molecular weight of 500 to 5000. The pH responsiveness of the diethylaminoethyl methacrylate is expressed as follows: at a pH greater than 7.2, the diethylaminoethyl methacrylate exhibits hydrophobicity; at a pH of less than 7.2, the diethylaminoethyl methacrylate exhibits hydrophilicity.
According to the technical scheme of the invention, when the pH is more than 7.2, the inner shell layer of the polymer shell layer shows hydrophobicity, the outer shell layer shows hydrophilicity, and the different hydrophilicity and hydrophobicity of the inner shell layer and the outer shell layer can realize the selective adsorption of hydrophobic substances, such as oily organic solvents, oily medicaments, oily dyes and the like; when the pH is less than 7.2, the outer shell polymer is still hydrophilic, the inner shell polymer becomes hydrophilic, and the hydrophobic substances originally adsorbed by the inner shell polymer are released.
According to the technical scheme of the invention, the magnetic polymer/inorganic composite Janus nano particles have the functions of magnetic operability and controllable adsorption and release of pH excited hydrophobic substances.
A second aspect of the present invention provides a method for preparing a pH-responsive magnetic polymer/inorganic composite Janus nanoparticle, comprising:
(1) Treating the magnetic inorganic nano-particles by using an aminosilane coupling agent to obtain the magnetic inorganic nano-particles with the surfaces containing amino groups;
(2) Sequentially polymerizing a 4- (vinylphenyl) -1-butene (VSt) monomer and a 4-chloromethyl styrene (VBC) monomer by cationic polymerization to obtain PVSt-b-PVBC two-block cationic living polymer chains;
(3) Grafting a plurality of PVSt-b-PVBC diblock cationic active polymer chains onto the surface of the magnetic inorganic nanoparticle containing the amino group on the surface to obtain a composite nanoparticle;
(4) Adding polyethylene glycol with a sulfhydryl group at the end group into the composite nano-particles, so that the polyethylene glycol performs click reaction with double bonds on PVSt chain segments to prepare modified composite nano-particles; then, adding pH responsive monomers into the modified composite nano particles by taking benzyl chloride on PVBC chain segments as an initiator to carry out atom transfer radical polymerization reaction, so as to introduce pH responsive polymers; namely, the pH-responsive magnetic polymer/inorganic composite Janus nano-particles are prepared.
Further, in the step (1), the aminosilane coupling agent is 3-aminopropyl triethoxysilane.
Further, in the step (1), the magnetic inorganic nanoparticle is a magnetic ferroferric oxide nanoparticle, and the magnetic inorganic nanoparticle is prepared by a solvothermal method.
Further, in the step (2), the initiator of cationic polymerization is boron trifluoride diethyl etherate, and the addition amount thereof is 5-20% of the volume of the added monomer VSt.
Further, in the step (2), the solvent for cationic polymerization is methylene dichloride, and the volume of the solvent is 5-30 times of the volume of the monomer VSt.
Further, in the step (2), the temperature condition of the cationic polymerization is-10 to 20 ℃, preferably-5 to 10 ℃.
Further, in the step (2), the polymerization time of the VSt monomer and the polymerization time of the VBC monomer are each independently selected from 1 to 60min, preferably 10 to 30min.
Further, in step (2), the volume of VBC monomer is 1 to 5 times the volume of VSt monomer.
Further, in the step (3), before the grafting step, the method further comprises the steps of: dispersing the magnetic inorganic nano particles with the amino groups on the surfaces in methylene dichloride to prepare particle dispersion liquid with the solid content of 10-200 mg/mL.
According to the technical scheme, in the step (4), hydrophilic modification is realized by carrying out a sulfhydryl-vinyl click reaction between a carbon-carbon double bond on PVSt and a sulfhydryl polyethylene glycol polymer; the click reaction has high yield and no byproducts.
In step (4), the solvent for the click reaction is one or more selected from dichloromethane, alcohols (such as methanol), and N, N-dimethylformamide.
In step (4), the catalyst for click reaction may be azo catalyst (such as azobisisobutyronitrile) or photocatalyst (such as benzoin dimethyl ether, which reacts under ultraviolet irradiation).
Further, in the step (4), the reaction time of the click reaction is 1 to 4 hours, preferably 1 hour.
Further, in step (4), the pH-responsive monomer is diethylaminoethyl methacrylate (DEAEMA).
Further, in the step (4), the mass ratio of the composite nano particles to diethylaminoethyl methacrylate is 1:0.5-2.
Further, in the step (4), the solvent for the atom transfer radical polymerization is N, N-dimethylformamide.
Further, in the step (4), the catalyst for atom transfer radical polymerization is cuprous bromide (CuBr).
Further, in step (4), the ligand of the atom transfer radical polymerization is selected from the group consisting of tris [2- (dimethylamino) ethyl ]]Amine (Me) 6 TREN) and one or both of N, N ', N,' N "-Pentamethyldiethylenetriamine (PMDETA).
Further, in the step (4), the reaction temperature of the atom transfer radical polymerization is 50 to 100 ℃, preferably 60 to 80 ℃; the reaction time is 4 to 12 hours, preferably 6 to 8 hours.
In a third aspect, the invention provides application of the pH-responsive magnetic polymer/inorganic composite Janus nano particles in oil-water separation, sewage treatment or drug controlled release.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The invention provides a pH responsive magnetic polymer/inorganic composite Janus nano particle, wherein the magnetic inorganic nano particle has magnetic responsiveness and can be controlled by an external magnetic field; the pH-responsive polymer may have different hydrophilicity and hydrophobicity with changes in external pH. The invention combines the magnetic inorganic nano particles and the pH responsive polymer to prepare the composite Janus nano material, so that the material has the functions of magnetic control and controllable adsorption and release of the pH-excited hydrophobic substance.
(2) The pH responsive magnetic polymer/inorganic composite Janus nano particle provided by the invention has a wide application prospect, and can be applied to the fields of oil-water separation, sewage treatment, drug controllable release and the like.
(3) The preparation method provided by the invention has the advantages of high solid content, mass preparation and the like.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. In the drawings:
FIG. 1 is a schematic diagram of a preparation method provided by the invention;
wherein 1 is a magnetic inorganic nanoparticle with an amino group on the surface, 2 is PVSt-b-PVBC two-block cationic active polymer chains, 3 is a magnetic polymer/inorganic composite nanoparticle, and 4 is a pH-responsive magnetic polymer/inorganic composite Janus nanoparticle; wherein the inner layer of the polymer layer is polyethylenimine methacrylate, and the outer layer is polyethylene glycol;
FIG. 2 is a schematic representation of PVSt-b-PVBC two-block cationically active polymer chains;
FIG. 3 is a transmission electron micrograph of the pH-responsive magnetic polymer/inorganic composite Janus nanoparticle prepared in example 1.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Example 1
The embodiment provides a pH-responsive magnetic polymer/inorganic composite Janus nanoparticle, which is prepared by the following steps:
(1) Preparation of magnetic inorganic nanoparticles containing amino groups on the surface
Firstly, preparing ferroferric oxide nano particles by a solvothermal method. 50mL of 0.2M aqueous sodium oleate was slowly added dropwise to 50mL of 0.2M aqueous ferric chloride solution under stirring to give a red precipitate. Washing the precipitate with distilled water for multiple times, and vacuum drying to obtain viscous ferric oleate complex. The iron oleate complex is dissolved in oleic acid and diluted with ethanol (iron oleate complex: oleic acid: ethanol=1:20:1 wt/wt). The ethanol diluted solution was transferred to a tetrafluoroethylene lined autoclave and heated to 180 ℃ for reaction for 5h. And (3) cooling the autoclave to room temperature, and washing the autoclave with ethanol for multiple times to obtain the magnetic ferroferric oxide nano particles with the particle size of about 10nm.
Then, the obtained magnetic ferroferric oxide nanoparticles were dispersed in n-hexane at a concentration of 0.5mg/mL, 3-aminopropyl triethoxysilane (0.5% vol/vol) was slowly added dropwise with stirring, and a trace amount of acetic acid (0.01% vol/vol) was further added. After stirring at room temperature for 24 hours, the product was separated with a magnet and washed with n-hexane several times to obtain magnetic inorganic nanoparticles having amino groups on the surface.
(2) Preparation of PVSt-b-PVBC two-block cationic living Polymer chain solution
To 15mL of overdry dichloromethane, 50. Mu.L of 1- (4-methoxyphenyl) ethanol and 50. Mu.L of boron trifluoride-diethyl ether complex were added, and the solution turned dark red. Slowly dripping 0.5mL of 4- (vinylphenyl) -1-butene (VSt) monomer into the solution at the temperature of 0 ℃, stirring and reacting for 30min, then completely reacting the VSt monomer, slowly dripping 1mL of 4-chloromethyl styrene (VBC) monomer, stirring and reacting for 30min, and obtaining the dark red PVSt-b-PVBC two-block cationic active polymer chain solution, wherein the molecular weight of the polymer is 8100k. A schematic representation of the PVSt-b-PVBC diblock cationically active polymer chain is shown in FIG. 2.
(3) Preparation of magnetic Polymer/inorganic composite nanoparticles
100mg of the magnetic inorganic nano particles with the amino groups on the surfaces, which are prepared in the step (1), are dispersed in 10mL of ultra-dry dichloromethane, and the magnetic inorganic nano particle dispersion liquid is prepared. Slowly dripping the PVSt-b-PVBC diblock cationic active polymer chain solution prepared in the step (2) into the magnetic inorganic nanoparticle dispersion liquid under the condition of ultrasound until the system presents light pink. Separating by using a magnet and washing for multiple times by using dichloromethane to obtain the magnetic polymer/inorganic compound nano particles.
(4) Preparation of pH-responsive magnetic Polymer/inorganic composite Janus nanoparticles
Firstly, adding 5mL of N, N-dimethylformamide solvent, 30mg of the magnetic polymer/inorganic compound nano-particles prepared in the step (3), 0.01mg of Azodiisobutyronitrile (AIBN) initiator and 4mg of polyethylene glycol polymer with a mercapto end group (molecular weight is 1000) into a reaction tube in sequence, charging nitrogen for protection, and reacting at 70 ℃ for 1h to obtain the modified compound nano-particles by grafting hydrophilic polyethylene glycol polymer on the PVSt chain segment on the outer layer.
Then 30mg of the modified composite nanoparticle and 5mg of tris [2- (dimethylamino) ethyl were sequentially added into a polymerization tube]Amine (Me) 6 TREN), 5mL of ultra-dry N, N-dimethylformamide and 15mg of diethylaminoethyl methacrylate (DEAEMA) monomer, freezing and pumping three times by using a double-row pipe, adding 5mg of cuprous bromide (CuBr) under the protection of freezing and nitrogen, and sealing a polymerization pipe by filling nitrogen after freezing and pumping circulation once again. The polymerization tube was left to react at 70℃for 8h. And after the reaction is finished, washing with dichloromethane and collecting with a magnet to obtain the pH-responsive magnetic polymer/inorganic composite Janus nano particles. The transmission electron micrograph is shown in figure 3.
The pH-responsive magnetic polymer/inorganic composite Janus nano particles provided by the invention have multiple functions, including magnetic operability and pH-activated hydrophobic substance controllable adsorption and release functions, and can be applied to the fields of oil-water separation, sewage treatment, drug controllable release and the like.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (18)
1. The preparation method of the pH-responsive magnetic polymer/inorganic composite Janus nano particle is characterized by comprising the following steps of:
(1) Treating the magnetic inorganic nano-particles by using an aminosilane coupling agent to obtain the magnetic inorganic nano-particles with the surfaces containing amino groups;
(2) Sequentially polymerizing a 4- (vinyl phenyl) -1-butene monomer and a 4-chloromethyl styrene monomer through cationic polymerization to obtain PVSt-b-PVBC two-block cationic active polymer chains;
(3) Grafting a plurality of PVSt-b-PVBC diblock cationic active polymer chains onto the surface of the magnetic inorganic nanoparticle containing the amino group on the surface to obtain a composite nanoparticle;
(4) Adding polyethylene glycol with a sulfhydryl group at the end group into the composite nano-particles, so that the polyethylene glycol and double bonds on a poly 4- (vinyl phenyl) -1-butene chain segment perform click reaction to prepare modified composite nano-particles; then, benzyl chloride on a poly-4-chloromethyl styrene chain segment is used as an initiator, and a pH responsive monomer is added into the modified composite nano particles to carry out atom transfer radical polymerization reaction, so that a pH responsive polymer is introduced; namely, the pH-responsive magnetic polymer/inorganic composite Janus nano-particles are prepared.
2. The method of claim 1, wherein in step (1), the aminosilane coupling agent is 3-aminopropyl triethoxysilane.
3. The method of claim 1, wherein in step (1), the magnetic inorganic nanoparticles are magnetic ferroferric oxide nanoparticles prepared by a solvothermal method.
4. The process according to claim 1, wherein in the step (2), the cationic polymerization initiator is boron trifluoride diethyl etherate in an amount of 5 to 20% by volume of the 4- (vinylphenyl) -1-butene monomer.
5. The process according to claim 1, wherein the cationically polymerized solvent is methylene chloride, the volume of which is 5 to 30 times the volume of the 4- (vinylphenyl) -1-butene monomer.
6. The process according to claim 1, wherein the cationic polymerization is carried out at a temperature of-10 to 20 ℃.
7. The process according to claim 1, wherein the polymerization time of the 4- (vinylphenyl) -1-butene monomer and the polymerization time of the 4-chloromethylstyrene monomer are each independently selected from 1 to 60 minutes.
8. The process according to claim 1, wherein the volume of the 4-chloromethylstyrene monomer is 1 to 5 times the volume of the 4- (vinylphenyl) -1-butene monomer.
9. The method of claim 1, wherein in step (3), before the grafting step, further comprising the steps of: dispersing the magnetic inorganic nano particles with the amino groups on the surfaces in methylene dichloride to prepare particle dispersion liquid with the solid content of 10-200 mg/mL.
10. The method according to claim 1, wherein the solvent for the click reaction is one or more selected from the group consisting of methylene chloride, alcohols, and N, N-dimethylformamide.
11. The method according to claim 1, wherein the click reaction catalyst is azo catalyst or photocatalyst.
12. The method of claim 1, wherein the click reaction time is 1 to 4 hours.
13. The method of claim 1, wherein in step (4), the pH-responsive monomer is diethylaminoethyl methacrylate.
14. The method of claim 13, wherein the mass ratio of the composite nanoparticle to diethylaminoethyl methacrylate is 1:0.5-2.
15. The method of claim 1, wherein the solvent for atom transfer radical polymerization is N, N-dimethylformamide.
16. The method of claim 1, wherein the catalyst for atom transfer radical polymerization is cuprous bromide.
17. The method of claim 1, wherein the atom transfer radical polymerization ligand is selected from one or both of tris [2- (dimethylamino) ethyl ] amine and N, N ', N, ' N ' -pentamethyldiethylenetriamine.
18. The method according to claim 1, wherein the reaction temperature of the atom transfer radical polymerization is 50 to 100 ℃; the reaction time is 4-12 h.
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