CN112978739A - Synthesis method of uniform symmetrical or asymmetrical nanoparticles, large-size and modified nanoparticles - Google Patents

Synthesis method of uniform symmetrical or asymmetrical nanoparticles, large-size and modified nanoparticles Download PDF

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CN112978739A
CN112978739A CN202110279570.9A CN202110279570A CN112978739A CN 112978739 A CN112978739 A CN 112978739A CN 202110279570 A CN202110279570 A CN 202110279570A CN 112978739 A CN112978739 A CN 112978739A
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聂志鸿
张艳
易成林
吴琪
陶晶
沈晓雪
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Fudan University
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    • C01B33/113—Silicon oxides; Hydrates thereof
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Abstract

The invention provides a method for synthesizing uniform symmetrical or asymmetrical nanoparticles, and relates to the technical field of nanoparticle synthesis. The synthesis method provided by the invention comprises the following steps: dissolving a copolymer in an organic solvent to obtain a copolymer solution; mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid; mixing the polymer single-chain nanoparticle seed dispersion liquid with a nanoparticle precursor, and carrying out sol-gel reaction to obtain uniform symmetrical or asymmetrical nanoparticles; the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene. The invention can obtain uniform symmetrical or asymmetrical nano particles by controlling the structure and the composition of the copolymer, has simple and convenient operation steps, is suitable for large-scale production, does not introduce organic impurities in the synthesis process, and is convenient for later application.

Description

Synthesis method of uniform symmetrical or asymmetrical nanoparticles, large-size and modified nanoparticles
Technical Field
The invention relates to the technical field of nanoparticle synthesis, in particular to a synthesis method of uniform symmetrical or asymmetrical nanoparticles and large-size and modified nanoparticles.
Background
Amorphous silica nanoparticles are of great interest due to their wide range of applications in the fields of cosmetics, paints, pharmaceuticals, dentistry and electronics. In many applications, uniform silica nanoparticles of controllable size, shape and morphology are desired. In particular, silica nanoparticles with asymmetric structures have become a novel class of materials useful for drug delivery, nanoreactors, optics, and catalysis. Currently, monodisperse spherical silica nanoparticles can be synthesized by various wet chemistry strategies, for example
Figure BDA0002978206530000011
Methods, soft template methods, and reverse microemulsion techniques. Compared with the one-step synthesis of symmetric silica nanoparticles, the preparation of asymmetric silica nanoparticles is usually based on the induction effect of a directing agent, and the asymmetric nucleation and growth of silica are controlled on the surface of synthesized seed nanoparticles. Currently, this method has been used to prepare asymmetric silica nanoparticles with different morphologies, e.g., Janus-like nanoparticles (e.g., polymer/SiO) composed of different organic or inorganic components2，Au/SiO2，Fe3O4/SiO2Up-conversion nanoparticles/SiO2) And multi-cavity silica nanoparticles having different shapes (branched and badminton, daisy, multi).
Organic surfactants have been widely used as structure inducers to prepare porous or nonporous silica nanoparticles with a synthesized template. Commonly used surfactants include cationic surfactants (e.g., cetyl trimethylammonium bromide) and commercially available copolymers (e.g., Pluronic F127, P124, and F108), and laboratory-synthesized copolymers (e.g., PEO-b-PS, PEO-b-PMMA, and PAA-b-PMMA). Although the synthesis conditions are slightly changed, the core of all template synthesis methods is that the molecular surfactant is firstly self-assembled into nano-micelle, and then the inorganic precursor of the silicon dioxide is controllably hydrolyzed around the micelle template. The morphological diversity of surfactant micelles allows a high degree of flexibility in the manipulation of silica nanoparticle structure. However, this synthetic method requires a relatively high concentration of surfactant, i.e., above its Critical Micelle Concentration (CMC), resulting in increased cost for large-scale production. In addition, the use of micelle templates leads to the introduction of a certain amount of organic impurities in the silica nanoparticles and, after selective removal of the micelle templates, leads to the generation of porous structures inside the silica nanoparticles, which have prevented their use without the need for pores or organic substances.
Disclosure of Invention
The invention aims to provide a synthesis method of uniform symmetrical or asymmetrical nanoparticles and large-size and modified nanoparticles, which is suitable for preparing various nanoparticles, is simple and convenient in operation steps, is suitable for large-scale production, does not introduce organic impurities in the synthesis process, and is convenient for later application.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a synthesis method of uniform symmetrical or asymmetrical nano particles, which comprises the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
mixing the polymer single-chain nanoparticle seed dispersion liquid with a nanoparticle precursor, and carrying out sol-gel reaction to obtain uniform symmetrical or asymmetrical nanoparticles;
the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene.
The invention also provides a method for synthesizing large-size uniform symmetrical or asymmetrical nanoparticles, which comprises the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution; the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
and mixing the polymer single-chain nanoparticle seed dispersion liquid with the nanoparticle precursor, carrying out sol-gel reaction, and carrying out secondary growth by using the obtained system as a seed template to obtain large-size uniform symmetrical or asymmetrical nanoparticles.
The invention also provides a synthetic method of the modified uniform symmetrical or asymmetrical nano particles, which comprises the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution; the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
and mixing the polymer single-chain nanoparticle seed dispersion liquid and the nanoparticle precursor, carrying out sol-gel reaction, and mixing the obtained system and the organosilicate precursor to obtain the modified uniform symmetrical or asymmetrical nanoparticles.
Preferably, the random copolymer is poly (acrylic monomer-r-styrene).
Preferably, the block-random copolymer is a block-poly (acrylic monomer-r-styrene) and the block-random copolymer midblock comprises polystyrene, polyethylene oxide, polypropylene oxide, or poly-t-butylstyrene.
Preferably, the acrylic monomer comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-butylacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isooctyl methacrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-diethylaminoethyl methacrylate, glycidyl methacrylate, n-octyl methacrylate, t-butyl acrylate or t-butyl methacrylate.
Preferably, the concentration of the copolymer solution is 0.0001-50.0 mg/mL; the volume ratio of the ammonia water to the organic solvent is 7-126: 1000; the mass concentration of the ammonia water is 25%.
Preferably, the organic solvent comprises tetrahydrofuran, toluene, dichloromethane, chloroform, ethyl acetate, trichloroethylene, cyclohexane, methyl isobutyl ketone, methyl isopropyl ketone, xylene, dimethyl ether, dimethyl sulfoxide, benzene, 2-butanone, acetone, N-dimethylformamide, ethanol, methanol or N-butanol.
Preferably, the molar ratio of the acrylic monomer in the nanoparticle precursor and the copolymer is 5-1000: 1.
Preferably, the organosilicate precursor comprises propyltrimethoxysilane, 7-octenyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, dodecyltriethoxysilane, octadecyltriethoxysilane or octadecyltrimethoxysilane.
The invention provides a synthesis method of uniform symmetrical or asymmetrical nano particles, which comprises the following steps: dissolving a copolymer in an organic solvent to obtain a copolymer solution; mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid; mixing the polymer single-chain nanoparticle seed dispersion liquid with a nanoparticle precursor, and carrying out sol-gel reaction to obtain uniform symmetrical or asymmetrical nanoparticles; the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene. In the invention, the copolymer is dissolved in an organic solvent, ammonia water is added to deprotonate acrylic monomers in the copolymer to obtain copolymer molecules with negative charges, the solubility of the acrylic monomers in the copolymer solution is reduced, and due to the electrostatic repulsion between charged segments, the copolymer molecules with negative charges collapse to form ultra-small single-chain nanoparticles instead of larger aggregates or micelles; meanwhile, the shielding of the solvent-philic styrene segment on the acrylic monomer segment can prevent the copolymer from associating into a micelle with a plurality of chains, thereby forming the polymer single-chain nano particle. The polymer single-chain nano particles are used as seed templates for hydrolyzing nano particle precursors, and the nano particle precursors nucleate and grow on the polymer single-chain nano particle seed templates under the catalysis of ammonia water to perform sol-gel reaction to obtain uniform symmetrical or asymmetrical nano particles. The invention can obtain uniform symmetrical or asymmetrical nano particles by controlling the structure and the composition of the copolymer, has simple and convenient operation steps, is suitable for large-scale production, does not introduce organic impurities in the synthesis process, and is convenient for later application.
Drawings
FIG. 1 is a schematic diagram of the synthesis and structure of silica nanoparticles prepared in example 2;
FIG. 2 is a TEM photograph (a-c) and a size distribution chart (d) of silica nanoparticles of examples 1 to 3;
FIG. 3 is a schematic diagram of the synthesis and structure of Janus-like polymer/silica hybrid nanoparticles.
Detailed Description
The invention provides a synthesis method of uniform symmetrical or asymmetrical nano particles, which comprises the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
mixing the polymer single-chain nanoparticle seed dispersion liquid with a nanoparticle precursor, and carrying out sol-gel reaction to obtain uniform symmetrical or asymmetrical nanoparticles;
the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene.
The copolymer is dissolved in an organic solvent to obtain a copolymer solution. In the present invention, the copolymer includes a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene.
In the invention, the random copolymer is preferably poly (acrylic monomer-r-styrene), and the mole percentage of the acrylic monomer in the random copolymer is preferably 10-90%, more preferably 10-60%, and even more preferably 20-50%; the random copolymer has an acrylic monomer-r-styrene as a unit, and the number of repeating units is preferably 10 to 1000, more preferably 10 to 700, and further preferably 30 to 298.
In the present invention, the acrylic monomer preferably includes acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-butylacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isooctyl methacrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-diethylaminoethyl methacrylate, glycidyl methacrylate, n-octyl methacrylate, t-butyl acrylate or t-butyl methacrylate.
In the present invention, the block-random copolymer is preferably a block-poly (acrylic monomer-r-styrene); the structure and composition of the poly (acrylic monomer-r-styrene) in the block-random copolymer are the same as those in the random copolymer described above, and are not described herein again. In the present invention, the block-random copolymer midblock preferably comprises polystyrene, polyethylene oxide, polypropylene oxide or poly-t-butylstyrene. In the present invention, the number of repeating units in the block portion of the block-random copolymer is preferably 50 to 5000, and more preferably 250 to 413.
In the present invention, when the copolymer is a random copolymer, the resulting nanoparticles are uniform symmetric nanoparticles: i.e., the random copolymer is dissolved in an organic solvent, and the addition of aqueous ammonia deprotonates the acrylic monomer in the copolymer, thereby reducing the solubility of the acrylic monomer fragments in solution. Due to the electrostatic repulsion between the charged segments, the negatively charged random copolymer collapses in the molecule to form ultra-small single-chain nanoparticles rather than larger aggregates or micelles, and the shielding of the solvent-philic styrene segment on the acrylic monomer segment can prevent the association between the copolymers to form micelles with multiple chains, thereby forming the polymer single-chain nanoparticles. The ultra-small single-chain nano particles are used as seed template nano particle precursors to be hydrolyzed, the nano particle precursors nucleate and grow on the copolymer single-chain seed template under the catalysis of ammonia water, and spherical nano particles, namely uniform symmetrical nano particles, are obtained after sol-gel reaction. By controlling the structure and the composition of the polymer, when the copolymer is a block-random copolymer, a random part forms an ultra-small single-chain nanoparticle as a seed template like the random copolymer to form a spherical nanoparticle, and a block part is dissolved in a solvent and finally embedded at one side of the spherical nanoparticle to obtain the asymmetric nanoparticle.
In the present invention, the organic solvent preferably includes tetrahydrofuran, toluene, dichloromethane, chloroform, ethyl acetate, trichloroethylene, cyclohexane, methyl isobutyl ketone, methyl isopropyl ketone, xylene, dimethyl ether, dimethyl sulfoxide, benzene, 2-butanone, acetone, N-dimethylformamide, ethanol, methanol or N-butanol, more preferably 2-butanone or tetrahydrofuran.
In the present invention, the concentration of the copolymer solution is preferably 0.0001 to 50.0mg/mL, more preferably 0.001 to 25mg/mL, and still more preferably 0.01 to 10 mg/mL.
After the copolymer solution is obtained, the copolymer solution is mixed with ammonia water to obtain the polymer single-chain nano particle seed dispersion liquid. In the present invention, the mass concentration of the ammonia water is preferably 25%. In the invention, the ammonia water can deprotonate carboxyl in the copolymer to obtain copolymer molecules with negative charges, and the copolymer molecules with negative charges collapse to form ultra-small single-chain nano particle seeds under the electrostatic repulsion action between the charged segments.
In the present invention, the volume ratio of the ammonia water to the organic solvent is preferably 7 to 126:1000, more preferably 14 to 77:1000, and further preferably 21: 500. The invention limits the dosage ratio to control the obtained polymer single-chain nano particles and the hydrolysis rate of the nano particle precursor.
In a specific embodiment of the present invention, it is preferable to mix the copolymer solution and ammonia water in an alcohol solvent to reduce the viscosity of the nanoparticle precursor forming sol. In the present invention, the alcohol solvent is preferably ethanol. In a specific embodiment of the present invention, the volume ratio of the ammonia water to the ethanol is preferably 1: 1.
In the invention, the method for mixing the copolymer solution and the ammonia water is preferably ultrasonic mixing, and the power of the ultrasonic mixing is preferably 20-100W, and more preferably 40-70W; the time for the ultrasonic mixing is preferably 20s to 1 hour, more preferably 20s to 0.5 hour, and still more preferably 20s to 10 min. The invention can fully and uniformly mix the solution by controlling the power and time of ultrasonic mixing.
In the invention, the single-chain nanoparticle seeds in the polymer single-chain nanoparticle seed dispersion liquid are ultra-small single-chain nanoparticle seeds, and the size is preferably 2-10 nm, and more preferably 2-5 nm. Compared with the traditional surfactant micelle template, the single-chain nanoparticle seed does not need a surfactant with relatively high concentration, so that the cost of large-scale production is reduced, the introduction of organic impurities in the nanoparticle is reduced, and the generation of a porous structure in the nanoparticle is avoided.
After the polymer single-chain nanoparticle seed dispersion liquid is obtained, the polymer single-chain nanoparticle seed dispersion liquid and a nanoparticle precursor are mixed to carry out sol-gel reaction, so that uniform symmetrical or asymmetrical nanoparticles are obtained. In the present invention, the nanoparticle precursor is preferably a silica precursor, a titanium dioxide precursor, a phenolic precursor, a polydopamine precursor, or an iron oxide precursor. In the invention, the silicon dioxide precursor is preferably tetraethoxysilane or methyl orthosilicate; the titanium dioxide precursor is preferably n-butyl titanate; the phenolic aldehyde precursor is preferably resorcinol and formaldehyde solution, and the mass concentration of the formaldehyde solution is preferably 37%; the mass ratio of the resorcinol to the formaldehyde solution is preferably 1-12: 7, and more preferably 4-8: 7; the polydopamine precursor is preferably dopamine hydrochloride; the ferric oxide precursor is preferably ferric chloride hexahydrate.
In the present invention, the molar ratio of the acrylic monomer in the nanoparticle precursor to the acrylic monomer in the copolymer is preferably 5 to 1000:1, more preferably 5 to 500:1, and still more preferably 20 to 100: 1. The size of the obtained nanoparticles can be regulated and controlled by controlling the molar ratio of the acrylic monomers in the nanoparticle precursor and the copolymer, and when the molar ratio of the acrylic monomers in the nanoparticle precursor and the copolymer is in the range, the average diameter of the obtained uniform symmetrical or asymmetrical nanoparticles is 10-100 nm.
In the invention, the method for mixing the polymer single-chain nanoparticle seed dispersion liquid and the nanoparticle precursor is preferably ultrasonic mixing, and the power of the ultrasonic mixing is preferably 20-100W, and more preferably 40-70W; the time for the ultrasonic mixing is preferably 20s to 1 hour, more preferably 20s to 0.5 hour, and still more preferably 20s to 10 min. The invention can fully and uniformly mix the solution by controlling the power and time of ultrasonic mixing.
In the invention, the sol-gel reaction is preferably carried out under a standing condition, the temperature of the sol-gel reaction is preferably normal temperature, and the time is preferably 7-48 h, and more preferably 24-36 h. In the sol-gel reaction process, under the catalysis of ammonia water, a nanoparticle precursor nucleates and grows on a single-chain nanoparticle seed to obtain uniform symmetrical or asymmetrical nanoparticles. In the invention, the average diameter of the uniform symmetrical or asymmetrical nanoparticles is preferably 10-100 nm, and the coefficient of variation is less than 8.0%. In the present invention, the yield of the uniform symmetric or asymmetric nanoparticles is preferably 5%.
In the present invention, when asymmetric nanoparticles are produced, it is preferable to add water to the system obtained by standing to obtain asymmetric nanoparticles. In the present invention, the amount of water added is preferably 1 vol% to 50 vol%, more preferably 10 vol%, based on the amount of the organic solvent. In the invention, the effect of adding water is to collapse the polymer of the block part in the block-random copolymer, so that different phase regions of the asymmetric nanoparticles can be observed more easily.
The synthesis method provided by the invention has simple and convenient operation steps, is carried out under the normal temperature condition, does not need stirring, and can be carried out by standing; in addition, the uniform symmetrical or asymmetrical nano particles prepared by the invention are dispersed in an organic solvent, so that later-stage modification and application are facilitated.
The invention also provides a method for synthesizing large-size uniform symmetrical or asymmetrical nanoparticles, which comprises the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution; the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
and mixing the polymer single-chain nanoparticle seed dispersion liquid with the nanoparticle precursor, carrying out sol-gel reaction, and carrying out secondary growth by using the obtained system as a seed template to obtain large-size uniform symmetrical or asymmetrical nanoparticles.
In the present invention, the preparation method of the system obtained by the sol-gel reaction is the same as the synthesis method of the uniform symmetric or asymmetric nanoparticles described above, and the details are not repeated here.
In the present invention, the method of secondary growth preferably includes the steps of:
mixing a system obtained by sol-gel reaction with an organic solvent to obtain a nano particle solution;
mixing the nano particle solution with ammonia water to obtain nano particle seed dispersion liquid;
and mixing the nanoparticle seed dispersion liquid and the nanoparticle precursor, and carrying out secondary sol-gel reaction to obtain uniform symmetrical or asymmetrical nanoparticles.
In the present invention, the reagents used in the secondary growth process, the mixing method of each step, and the process parameters of the secondary sol-gel reaction are the same as those of the above-mentioned synthesis method of uniform symmetric or asymmetric nanoparticles, and are not described herein again.
According to the invention, large-size nanoparticles can be obtained through secondary growth, and the average diameter of the nanoparticles obtained through secondary growth is preferably 100-500 nm.
The invention also provides a synthetic method of the modified uniform symmetrical or asymmetrical nano particles, which comprises the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution; the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
and mixing the polymer single-chain nanoparticle seed dispersion liquid and the nanoparticle precursor, carrying out sol-gel reaction, mixing the obtained system and the organosilicate precursor, and carrying out secondary sol-gel reaction to obtain the modified uniform symmetrical or asymmetrical nanoparticles.
In the present invention, the preparation method of the system obtained by the sol-gel reaction is the same as the synthesis method of the uniform symmetric or asymmetric nanoparticles described above, and the details are not repeated here.
In the present invention, the organosilicate precursor preferably comprises propyltrimethoxysilane, 7-octenyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, dodecyltriethoxysilane, octadecyltriethoxysilane or octadecyltrimethoxysilane. In the present invention, the molar ratio of the organosilicate precursor to the nanoparticle precursor is preferably 1:3 to 100, and more preferably 1:12 to 60. The invention can obtain nano particles with different surface properties by utilizing the organic silicate precursor, for example, functional groups such as hydrophobic groups, amino groups, carbon-carbon double bonds and the like are introduced on the surface of the nano particles.
In the invention, the mixing method of the system obtained by the sol-gel reaction and the organic silicate precursor is preferably ultrasonic mixing, and the power of the ultrasonic mixing is preferably 20-100W, and more preferably 40-70W; the time for the ultrasonic mixing is preferably 20s to 1 hour, more preferably 20s to 0.5 hour, and still more preferably 20s to 10 min.
In the invention, the secondary sol-gel reaction is preferably carried out under a standing condition, the temperature of the secondary sol-gel reaction is preferably normal temperature, and the time is preferably 7-48 h, and more preferably 24-36 h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
With poly (r-styrene-methacrylic acid) (P (MAA)0.2-r-St0.8)100) Synthesizing silicon dioxide nano particles with the diameter of 38nm for the seed template; p (MAA)0.2-r-St0.8)100The mole percentage of methacrylic acid (MAA) is 20%, and P (MAA)0.2-r-St0.8)100The number of repeating units of (2) is 100.
500mg of P (MAA)0.2-r-St0.8)100Dissolving in 500mL of 2-butanone, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 100W power, adding 28.5mL of methyl orthosilicate, performing ultrasonic dispersion for 20s under the condition of 100W power, standing the reaction solution for 24h under the condition of room temperature, and finishing the sol-gel reaction to obtain the monodisperse silica nanoparticles. The average diameter of the monodisperse silicon dioxide nano particles is 38 by test and characterizationnm。
Example 2
With poly (acrylic acid-r-styrene) (P (AA)0.3-r-St0.7)80) Synthesizing silica nanoparticles with the diameter of 53nm for a seed template; p (AA)0.3-r-St0.7)80The mole percentage of Acrylic Acid (AA) is 30 percent, and P (AA)0.3-r-St0.7)80The number of repeating units of (2) is 80.
500mg of P (AA)0.3-r-St0.7)80Dissolving in 500mL of Tetrahydrofuran (THF), adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 20W power, adding 35.7mL of tetraethoxysilane, performing ultrasonic dispersion for 20s under the condition of 20W power, standing the reaction solution for 24h at room temperature, and finishing the sol-gel reaction to obtain the monodisperse silica nanoparticles. The test shows that the average diameter of the monodisperse silicon dioxide nano particles is 53 nm.
Example 3
With poly (methyl acrylate-r-styrene) (P (MA)0.5-r-St0.5)70) Synthesizing silica nanoparticles with the diameter of 23nm for the seed template; p (MA)0.5-r-St0.5)70The molar percentage of Methyl Acrylate (MA) in the composition is 50%, P (MA)0.5-r-St0.5)70The number of repeating units of (a) is 70.
500mg of P (MA)0.5-r-St0.5)70Dissolving in 500mL of tetrahydrofuran, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 40W, adding 3.5mL of tetraethoxysilane, performing ultrasonic dispersion for 20s under the condition of 40W, standing the reaction solution for 24h under the condition of room temperature, and finishing the sol-gel reaction to obtain the monodisperse silicon dioxide nanoparticles. The test shows that the average diameter of the monodisperse silicon dioxide nano particles is 23 nm.
Example 4
With polystyrene-b-poly (methyl acrylate-r-styrene) (PSt)250-b-P(MA0.5-r-St0.5)70) Synthesis of Janus-like polymer/silica hybrid nanoparticles for seed templates，PSt250-b-P(MA0.5-r-St0.5)70The number of polystyrene repeating units of the midblock portion was 250.
100mg of PSt250-b-P(MA0.5-r-St0.5)70Dissolving the mixture in 100mL of 2-butanone, adding 4.2mL of 25% ammonia water and 4.2mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 70W power, adding 3.5mL of tetraethoxysilane, performing ultrasonic dispersion for 20s under the condition of 70W power, standing the reaction solution for 24h at room temperature, finishing sol-gel reaction, adding 10 vol% of water, and performing test characterization to obtain the Janus-shaped polymer/silicon dioxide hybrid nanoparticles, wherein the size of a silicon dioxide phase region is 23nm, and the size of a Polymer (PS) phase region is 34 nm.
Example 5
With polystyrene-b-poly (acrylic acid-r-styrene) (PSt)413-b-P(AA0.5-r-St0.5)50) Synthesis of Janus-like Polymer/silica hybrid nanoparticles, PSt, for seed templates413-b-P(AA0.5-r-St0.5)50The number of polystyrene repeating units of the midblock portion was 413.
500mg of PSt413-b-P(AA0.5-r-St0.5)50Dissolving in 500mL of tetrahydrofuran, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 70W power, adding 2.9mL of tetraethoxysilane, performing ultrasonic dispersion for 20s under the condition of 70W power, standing the reaction solution for 24h under the condition of room temperature, finishing the sol-gel reaction, adding 10 vol% of water, and performing test characterization to obtain the Janus-shaped polymer/silicon dioxide hybrid nanoparticles, wherein the size of a silicon dioxide phase region is 28nm, and the size of a PS phase region is 41 nm.
Example 6
With polystyrene-b-poly (acrylic acid-r-styrene) (PSt)250-b-P(AA0.3-r-St0.7)298) Janus-like polymer/silica hybrid nanoparticles were synthesized for the seed template.
500mg of PSt250-b-P(AA0.3-r-St0.7)298Dissolved in 500mL of tetrahydrofuran, and 21mL of tetrahydrofuran was addedAfter 25% of ammonia water and 21mL of ethanol are used, performing ultrasonic dispersion for 20s under the condition of 100W power, adding 5.7mL of ethyl orthosilicate, performing ultrasonic dispersion for 20s under the condition of 100W power, standing the reaction solution for 24h at room temperature, finishing the sol-gel reaction, adding 10 vol% of water, and performing test characterization to obtain the Janus-shaped polymer/silicon dioxide hybrid nanoparticles, wherein the size of a silicon dioxide phase region is 38nm, and the size of a PS phase region is 49 nm.
Example 7
With polystyrene-b-poly (acrylic acid-r-styrene) (PSt)250-b-P(AA0.3-r-St0.7)298) Janus-like polymer/silica hybrid nanoparticles were synthesized for the seed template.
500mg of PSt250-b-P(AA0.3-r-St0.7)298Dissolving in 500mL of tetrahydrofuran, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 100W power, adding 7.8mL of tetraethoxysilane, performing ultrasonic dispersion for 20s under the condition of 100W power, standing the reaction solution for 24h under the condition of room temperature, finishing the sol-gel reaction, adding 10 vol% of water, and performing test characterization to obtain the Janus-shaped polymer/silicon dioxide hybrid nanoparticles, wherein the size of a silicon dioxide phase region is 41nm, and the size of a PS phase region is 38 nm.
Example 8
Secondary growth synthesis of 130nm silica nanoparticles:
taking 10mL of THF solution of the 50nm silica nanoparticles prepared in example 2, adding 10mL of THF to dilute the solution, adding 0.42mL of 25% ammonia water and 0.42mL of ethanol, performing ultrasonic treatment for 20s under the condition of 100W power, adding 2mL of ethyl orthosilicate, performing ultrasonic treatment for 20s under the condition of 70W power, standing the reaction solution for 24h at room temperature, and finishing the sol-gel reaction to obtain the monodisperse silica nanoparticles. The test shows that the average diameter of the monodisperse silicon dioxide nano particles is 130 nm.
Example 9
And (3) secondary growth synthesis of 200nm silicon dioxide nanoparticles:
taking 5mL of THF solution of the 50nm silica nanoparticles prepared in example 2, adding 10mL of THF to dilute the solution, adding 0.42mL of 25% ammonia water and 0.42mL of ethanol, performing ultrasonic treatment for 20s under the condition of 40W power, adding 2mL of ethyl orthosilicate, performing ultrasonic treatment for 20s under the condition of 100W power, standing the reaction solution for 24h at room temperature, and finishing the sol-gel reaction to obtain the monodisperse silica nanoparticles. The test shows that the average diameter of the monodisperse silicon dioxide nano particles is 200 nm.
Example 10
Preparation of hydrophobic silica nanoparticles:
500mg of P (MAA)0.3-r-St0.7)100Dissolving the mixture in 500mL of 2-butanone, adding 21mL of 25 mass percent ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 40W power, adding 37.7mL of methyl orthosilicate, performing ultrasonic dispersion for 20s under the condition of 40W power, standing the reaction solution for 24h at room temperature, adding 2mL of octadecyl triethoxysilane, and standing for 24h at room temperature to obtain the hydrophobic silicon dioxide nanoparticles.
The hydrophobic silica nanoparticles are added into toluene, and centrifuged at 4000rpm for 20min, so that the silica nanoparticles are uniformly dispersed in the toluene, which shows that the silica nanoparticles prepared in the embodiment have hydrophobicity.
Example 11
Preparation of hydrophobic silica nanoparticles:
500mg of P (AA)0.3-r-St0.7)80Dissolving in 500mL of tetrahydrofuran, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 100W power, adding 35.7mL of ethyl orthosilicate, performing ultrasonic dispersion for 20s under the condition of 100W power, standing the reaction solution for 24h at room temperature, adding 3.2mL of 7-octenyltrimethoxysilane, and standing for 24h at room temperature to obtain the hydrophobic silicon dioxide nanoparticles.
The hydrophobic silica nanoparticles are added into toluene, and centrifuged at 5000rpm for 20min, so that the silica nanoparticles are uniformly dispersed in the toluene, which shows that the silica nanoparticles prepared in this embodiment have hydrophobicity.
Example 12
With P (MAA)0.3-r-St0.7)100Synthesizing titanium dioxide nano particles with the diameter of 50nm for the seed template:
500mg of P (MAA)0.3-r-St0.7)100Dissolving the titanium dioxide nanoparticles in 500mL of 2-butanone, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 70W power, adding 20mL of n-butyl titanate, performing ultrasonic dispersion for 20s under the condition of 70W power, standing the reaction solution for 24h at room temperature, and finishing the sol-gel reaction to obtain the monodisperse titanium dioxide nanoparticles. The test shows that the average diameter of the monodisperse titanium dioxide nano particles is 50 nm.
Example 13
With P (AA)0.3-r-St0.7)80Synthesizing phenolic aldehyde nano particles with the diameter of 70nm for a seed template:
500mg of P (AA)0.3-r-St0.7)80Dissolving in 500mL of tetrahydrofuran, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 70W power, adding 20g of resorcinol and 25mL of 37% formaldehyde solution, performing ultrasonic dispersion for 20s under the condition of 70W power, standing the reaction solution for 24h at room temperature, and finishing sol-gel to obtain the monodisperse phenolic nanoparticles. The test shows that the average diameter of the monodisperse phenolic aldehyde nano particles is 50 nm.
Example 14
With P (MA)0.5-r-St0.5)70Synthesizing polydopamine nano particles with the diameter of 50nm for a seed template:
500mg of P (MA)0.5-r-St0.5)70Dissolving in 500mL of tetrahydrofuran, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the power condition of 100W, adding 37g of dopamine hydrochloride, performing ultrasonic dispersion for 20s under the power condition of 100W, standing the reaction solution for 24h under the room temperature condition, and finishing the sol-gel reaction to obtain the monodisperse poly-dopamine nanoparticles. The average diameter of the monodisperse polydopamine nano-particles is 50nm through test characterization.
Example 15
With P (AA)0.3-r-St0.7)30Synthesizing iron oxide nanoparticles with the diameter of 30nm for the seed template:
500mg of P (AA)0.3-r-St0.7)30Dissolving in 500mL of tetrahydrofuran, adding 21mL of 25% ammonia water and 21mL of ethanol, performing ultrasonic dispersion for 20s under the condition of 70W power, adding 20g of ferric trichloride hexahydrate, performing ultrasonic dispersion for 20s under the condition of 70W power, standing the reaction solution for 24h under the condition of room temperature, and finishing the sol-gel reaction to obtain the monodisperse iron oxide nanoparticles. The average diameter of the monodisperse iron oxide nanoparticles is 30nm according to the test.
And (4) result characterization:
FIG. 1 is a schematic diagram of synthesis and structure of silica nanoparticles prepared in example 2, wherein a in FIG. 1 is a schematic diagram of the synthesis process; b in fig. 1 is a powder of silica nanoparticles and an optical photograph in a tetrahydrofuran solution. As can be seen in FIG. 1, the random copolymer is dissolved in an organic solvent and the addition of aqueous ammonia deprotonates the acrylic monomer in the copolymer, thereby reducing the solubility of the polyacrylic monomer fragments in solution. Due to electrostatic repulsion between the charged segments, the negatively charged random copolymer collapses intramolecularly to form ultra-small single-stranded nanoparticles, rather than larger aggregates or micelles. The ultra-small single-chain nano particles are used as a seed template nano particle precursor for hydrolysis, the nano particle precursor nucleates and grows on the copolymer single-chain seed template under the catalysis of ammonia water, and the spherical nano particles can be obtained through sol-gel reaction.
FIG. 2 is a TEM photograph (a-c) and a size distribution (d) of silica nanoparticles of examples 1 to 3, with a scale bar of 100 nm; wherein a in fig. 2 represents the silica nanoparticles having a diameter of 23.0 ± 1.8nm prepared in example 3, b in fig. 2 represents the silica nanoparticles having a diameter of 38.3 ± 1.5nm prepared in example 1, and c in fig. 2 represents the silica nanoparticles having a diameter of 53.2 ± 1.8nm prepared in example 2. It can be seen from d in fig. 2 that the silica nanoparticles have good monodispersity with a coefficient of variation of less than 8.0%.
FIG. 3 is a schematic diagram of the synthesis and structure of Janus-like polymer/silica hybrid nanoparticles; wherein a in fig. 3 represents a schematic diagram of a synthesis process of the Janus-like polymer/silica hybrid nanoparticles; FIG. 3 b is a TEM image of the nanoparticles before water is added after the completion of the sol-gel reaction in example 5; FIG. 3 c is a TEM image of the nanoparticles after the completion of the sol-gel reaction in example 5 and after the addition of water; d in fig. 3 represents STEM photograph and EDX element mapping photograph of Janus-like polymer/silica hybrid nanoparticles; e in fig. 3 represents TEM photograph of the synthesized Janus-like polymer/silica hybrid nanoparticles of example 6; FIG. 3 shows TEM photographs of Janus-like polymer/silica hybrid nanoparticles synthesized in example 7 at f, and FIG. 3 at e and f show the use of PS at different molar ratios of ethyl orthosilicate and acrylic acid250-b-P(AA0.3-r-St0.7)298TEM photograph of synthesized Janus-like polymer/silica hybrid nanoparticles: (e) RTEOS/AA-50; (f) RTEOS/AA 80. The dimensions of the scales in fig. 3 b, c, e and f are 100nm and the scale in d is 10 nm.
As can be seen from the above examples, compared with the prior art, the invention realizes the large-scale preparation of the nanoparticles with the diameter within 100nm in the organic phase, and opens up a new way for the large-scale preparation of the nanoparticles with simple or complex morphology; the organic silicate precursor is introduced in the later stage of the reaction, so that the nano particles with different surface chemical properties can be easily obtained. In addition, compared with the existing multi-step synthesis of asymmetric nanoparticles, the technical scheme can synthesize the Janus-like anisotropic hybrid nanoparticles consisting of a silicon dioxide phase region and a polymer phase region in one step by designing the copolymer with a specific structure.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for synthesizing uniform symmetrical or asymmetrical nanoparticles is characterized by comprising the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
mixing the polymer single-chain nanoparticle seed dispersion liquid with a nanoparticle precursor, and carrying out sol-gel reaction to obtain uniform symmetrical or asymmetrical nanoparticles;
the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene.
2. A method for synthesizing large-size uniform symmetrical or asymmetrical nanoparticles is characterized by comprising the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution; the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
and mixing the polymer single-chain nanoparticle seed dispersion liquid with the nanoparticle precursor, carrying out sol-gel reaction, and carrying out secondary growth by using the obtained system as a seed template to obtain large-size uniform symmetrical or asymmetrical nanoparticles.
3. A synthetic method of modified uniform symmetrical or asymmetrical nanoparticles is characterized by comprising the following steps:
dissolving a copolymer in an organic solvent to obtain a copolymer solution; the copolymer comprises a random copolymer or a block-random copolymer; the copolymer comprises acrylic monomers and styrene;
mixing the copolymer solution with ammonia water to obtain a polymer single-chain nanoparticle seed dispersion liquid;
and mixing the polymer single-chain nanoparticle seed dispersion liquid and the nanoparticle precursor, carrying out sol-gel reaction, and mixing the obtained system and the organosilicate precursor to obtain the modified uniform symmetrical or asymmetrical nanoparticles.
4. A synthesis process according to any one of claims 1 to 3, characterised in that the random copolymer is poly (acrylic monomer-r-styrene).
5. The method for synthesizing the copolymer according to any one of claims 1 to 3, wherein the block-random copolymer is block-poly (acrylic monomer-r-styrene), and the block-random copolymer comprises polystyrene, polyethylene oxide, polypropylene oxide or poly-tert-butyl styrene.
6. The method of any one of claims 1 to 3, wherein the acrylic monomer comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, 2-butylacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, isooctyl methacrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-diethylaminoethyl methacrylate, glycidyl methacrylate, n-octyl methacrylate, t-butyl acrylate, or t-butyl methacrylate.
7. The method of any one of claims 1 to 3, wherein the concentration of the copolymer solution is 0.0001 to 50.0 mg/mL; the volume ratio of the ammonia water to the organic solvent is 7-126: 1000; the mass concentration of the ammonia water is 25%.
8. The method according to any one of claims 1 to 3, wherein the organic solvent comprises tetrahydrofuran, toluene, dichloromethane, chloroform, ethyl acetate, trichloroethylene, cyclohexane, methyl isobutyl ketone, methyl isopropyl ketone, xylene, dimethyl ether, dimethyl sulfoxide, benzene, 2-butanone, acetone, N-dimethylformamide, ethanol, methanol or N-butanol.
9. A synthesis method according to any one of claims 1 to 3, characterized in that the molar ratio of acrylic monomers in the nanoparticle precursor and copolymer is 5-1000: 1.
10. The method of claim 3, wherein the organosilicate precursor comprises propyltrimethoxysilane, 7-octenyltrimethoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, dodecyltriethoxysilane, octadecyltriethoxysilane or octadecyltrimethoxysilane.
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