CN108543505B - Composite particle with multiple core-shell structures and preparation method thereof - Google Patents
Composite particle with multiple core-shell structures and preparation method thereof Download PDFInfo
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a composite particle with a multiple core-shell structure, which takes inorganic silicon dioxide nano particles as an inner core, organic acrylate polymers as a middle layer and a carbon nano tube adsorption layer as an outer shell. The invention also discloses a preparation process of the composite particle, which comprises the following steps of
The method is used for synthesizing nano silicon dioxide, then acrylic ester polymer layer coating is carried out on the surface of the nano silicon dioxide based on a dispersion polymerization method, and the polymer coating and the charge modification of the surface of the nano silicon dioxide are further realized by using a hydrolysable ionized initiator, and then the carbon nano tube is further adsorbed directly through electrostatic self-assembly. The invention provides a composite particle with a multiple core-shell structure and a preparation method thereof, the preparation process is green and efficient, complex functional modification is not needed, and the prepared composite particle has excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of multifunctional nano composite particles, in particular to a composite particle with a multi-core-shell structure and a preparation method thereof.
Background
With the continuous development of science and technology, nano materials play more and more important roles in the development process of new materials. Due to low density (40-200 kg/m)3) High specific surface area (400-1500 m)2(g) and low thermal conductivity (0.02W/m/K), and the nano silica particles have been widely used in the fields of high-efficiency insulating materials, high-strength materials, gas adsorbing materials, and the like. Also, since their discovery by japanese scientist Iijima in 1991, carbon nanotubes have been receiving much attention from researchers as a new one-dimensional functional material. The carbon nano tube has high length-diameter ratio and hollow structure, excellent conductivity, extremely high mechanical strength and good flexibility, can be used as a super fiber, and plays a role in enhancing a composite material.
However, due to the special structural features of the nano-materials, the nano-materials still have great challenges in industrial application: on one hand, the nano materials have high surface energy, and strong van der Waals force and pi-pi conjugation often exist among the nano materials, so that the nano materials are easy to agglomerate; on the other hand, when the nano material is filled with a modified matrix material, the phenomenon that the compatibility is poor, the nano material is easy to precipitate out in a disordered state and the comprehensive performance of the composite material is deteriorated often exists.
In order to solve the problems of the application of the nano material and improve the dispersibility and compatibility of the nano material in a polymer matrix, many researches are carried out to synthesize inorganic/organic nano composite particles, especially core-shell structure composite particles through design. For example, in chinese patent publication No. CN 106517215 a, it is proposed that graphene is uniformly coated on the surface of silica to synthesize a core-shell structure material, so that agglomeration of silica and graphene is effectively avoided, and a material with excellent properties such as regular structure, high porosity and low density is prepared. However, the core-shell structure is easily damaged by a strong shearing force in the molding process, and the nanoparticles are exposed and reunited, so that the performance improvement and the long-term stability of the composite material are greatly influenced. A great deal of research shows that the problem can be well solved by coating the surfaces of the nanoparticles with the polymer. For example, chinese patent publication No. CN 102199259A discloses a nano modified epichlorohydrin resin with a core-shell structure and a preparation method thereof, and a polymerization coating method is used to perform nano modification on the epichlorohydrin resin, so as to solve the problem of agglomeration of nanoparticles to the greatest extent and achieve good dispersion of nanoparticles in a polymer.
The liquid phase method is the most commonly used method for preparing the core-shell structure polymer coated nanoparticle composite material, but the development and the application of the core-shell structure composite particles are limited by the problems of solvent pollution, complex process, complex post-treatment and the like in the conventional method. Meanwhile, as the demand of people for high-performance materials increases, compared with a core-shell structure material with a single function, the preparation of the multi-core-shell multifunctional material becomes unsmooth. In the design synthesis of the core-shell structure nanocomposite, the shell material not only serves as a 'barrier' for preventing the agglomeration of core particles, but also has unique properties of the shell material. In order to realize the preparation of the multifunctional multiple core-shell structure, a multi-step modification process is generally required. For example, Wuchao et al functionalize the surface of the polymer matrix and the surface of graphene respectively, and then construct multiple core-shells. However, impurities are often introduced and damage the graphene structure of the modified layer is easily caused, the interface resistance of the conductive material is increased, the final performance is affected, and the synthesis efficiency is low.
Therefore, how to construct multifunctional highly-ordered inorganic/organic composite particles, which can be realized in a green, high-efficiency, simple and easily-industrialized manner, remains a difficult problem to be solved.
Disclosure of Invention
The invention provides the composite particles with the multiple core-shell structures and the preparation method thereof for solving the technical problems, the preparation process is green and efficient, complex functional modification is not needed, and the prepared composite particles have excellent comprehensive performance.
The specific technical scheme is as follows:
the composite particle with multiple core-shell structures takes inorganic silicon dioxide nano particles as an inner core, organic acrylate polymers as an intermediate layer and a carbon nano tube adsorption layer as an outer shell.
The novel composite particle disclosed by the invention has a three-layer structure, and the inner core is an inorganic silicon dioxide nano particle, so that the novel composite particle has excellent mechanical property and size stability; the middle layer is an organic acrylate polymer, which not only can effectively reduce the agglomeration among silicon dioxide particles, but also can improve the toughness of the matrix polymer; the carbon nanotube-adsorbed layer of the shell can provide good electrical conductivity and mechanical properties.
Preferably, the particle size of the inner core is 70-300 nm, the thickness of the middle layer is 5-300 nm, and the thickness of the outer shell is 0.1-5 nm.
Preferably, the composite particles having a multiple core-shell structure comprise, in mass percent:
60-85 wt% of inorganic silica nanoparticles;
5 to 37 wt% of an organic acrylic polymer;
3-10 wt% of carbon nano tube.
The organic acrylic ester polymer is at least one selected from polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polyethyl methacrylate and polybutyl methacrylate.
The invention also discloses a preparation method of the composite particle with the multiple core-shell structure, which comprises the following steps:
(1) by using
Synthesizing nano silicon dioxide by the method, and carrying out surface modification by a silane coupling agent to obtain the productTo a surface pre-modified silica powder;
(2) mixing the surface pre-modified silicon dioxide powder prepared in the step (1) with an ethanol-water solution, adding a stabilizer, uniformly mixing, adding an initiator and an acrylate monomer, and carrying out polymerization reaction to obtain a polymer surface coating modified silicon dioxide suspension;
the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile and 2,2' -azobisisobutylamidine dihydrochloride;
(3) and (3) acidifying and modifying the carbon nano tube to obtain an acidified carbon nano tube aqueous solution, mixing the polymer surface coating modified silicon dioxide suspension prepared in the step (2) with the acidified carbon nano tube aqueous solution, stirring, standing, and performing electrostatic self-assembly to obtain the composite particle with the multiple core-shell structure.
The preparation process disclosed by the invention comprises the following steps of
The method is used for synthesizing nano silicon dioxide, then acrylic ester polymer layer coating is carried out on the surface of the nano silicon dioxide based on a dispersion polymerization method, and the polymer coating and the charge modification of the surface of the nano silicon dioxide are further realized by using a hydrolysable ionized initiator, and then the carbon nano tube is further adsorbed directly through electrostatic self-assembly.
The initiator adopted by the invention can generate cations after being hydrolyzed and ionized, and the cations are mutually adsorbed with the carbon nano tube which is acidized and has anions on the surface, such as carboxyl, hydroxyl and the like, and the surface of the polymer coating layer is further coated with the carbon nano tube adsorption layer through electrostatic self-assembly.
The preparation process does not need to carry out further modification treatment on the polymer coating layer, and does not damage the mechanical property of the polymer coating layer or further introduce impurities.
Preferably, in step (1):
said adoption of
The method for synthesizing the nano silicon dioxide specifically comprises the following steps:
mixing absolute ethyl alcohol, ammonia water and tetraethoxysilane, stirring at the rotating speed of 300-700 revolutions per minute at the temperature of 20-50 ℃ for 15-30 hours, and then centrifugally purifying by using deionized water until the pH value is 7-8 to obtain a nano silicon dioxide suspension;
the volume ratio of the ammonia water to the absolute ethyl alcohol is 1: 7-15, and the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 1: 10-30;
the concentration of the prepared nano silicon dioxide suspension is 5-10 g/L.
Preferably, in the step (1), the silane coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane;
the surface modification specifically comprises the following steps:
mixing the nano silicon dioxide suspension with a silane coupling agent, stirring for 2-5 hours at room temperature at 200-500 rpm, continuing to stir for 2-3 hours at 70-100 ℃, performing centrifugal purification on ethanol at a rotating speed of 3500-4500 rpm, performing single treatment for 15-25 minutes at 2-5 times, and performing vacuum drying on a purified product at 25-40 ℃ for 15-30 hours to obtain surface pre-modified silicon dioxide powder;
the mass ratio of the solid content in the nano silicon dioxide suspension to the silane coupling agent is 10-50: 1.
Preferably, in step (2):
the mass ratio of the surface pre-modified nano silicon dioxide to the ethanol-water solution is 1: 20-50;
in the ethanol-water solution, the volume ratio of water to ethanol is 4: 1-18;
the stabilizer is selected from polyvinylpyrrolidone or polyvinyl alcohol, and the addition amount of the stabilizer is 5-15% of the mass of the acrylate monomer;
the addition amount of the initiator is 0.3-0.8% of the mass of the acrylate monomer;
the acrylic ester monomer is selected from at least one of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate;
the polymerization reaction is carried out in a nitrogen atmosphere, the reaction temperature is 60-90 ℃, the stirring reaction is carried out for 15-20 hours, and the stirring rotation speed is 100-200 r/min;
the concentration of the prepared polymer surface coating modified silicon dioxide suspension is 5-15 g/L.
Preferably, in step (3):
the carbon nano tube is subjected to acidification modification, and the method specifically comprises the following steps:
mixing the multi-walled carbon nano-tube with concentrated sulfuric acid and concentrated nitric acid, ultrasonically dispersing for 1-2 hours, heating to 40-70 ℃, and mechanically stirring for 2-4 hours; slowly adding deionized water, settling for 10-15 hours, and then carrying out centrifugal purification by using the deionized water as a solvent until the pH value of the solution is neutral to obtain an acidified carbon nanotube aqueous solution;
the diameter of the multi-walled carbon nanotube is 5-30 nm, and the length of the multi-walled carbon nanotube is 10-35 mu m;
the mass ratio of the multi-walled carbon nanotubes to concentrated sulfuric acid is 1: 60-90, and the mass ratio of the multi-walled carbon nanotubes to concentrated nitric acid is 1: 5-30;
the concentration of the prepared acidified carbon nano tube aqueous solution is 1-10 g/L.
Preferably, in the step (3), the mass ratio of the solid content in the acidified carbon nanotube aqueous solution to the solid content in the polymer surface coating modified silica suspension is 1: 10-20.
Preferably, in the step (3), the rotation speed of the stirring is 100-150 rpm, and the time is 3-5 hours; then standing for 1-2 hours to promote the static self-assembly;
and centrifuging the mixture subjected to electrostatic self-assembly at the rotating speed of 4000-7000 rpm for 20-30 minutes to remove the upper-layer liquid, centrifuging and purifying the mixture by using water as a solvent until the upper-layer liquid is not turbid any more, and freeze-drying the mixture to obtain the composite particles with the multiple core-shell structures.
Compared with the prior art, the invention has the following advantages:
in the preparation process of the invention, the preparation method firstly passes
The method synthesizes the nano silicon dioxide, and then coats the surface of the nano silicon dioxide with an acrylate polymer layer based on a dispersion polymerization method, and prepares composite particles with different polymer coating efficiencies on the surface only by changing the proportion of ethanol and water, thereby avoiding using a large amount of surfactant; and the special initiator capable of hydrolyzing and ionizing to obtain cationic groups is used to further realize the polymer coating and the charged modification on the surface of the synthesized nano silicon dioxide, and then the carbon nano tubes are further adsorbed by directly electrostatic self-assembly, so that the complicated chemical grafting modification is avoided, and the thickness of the carbon nano tube adsorption layer can be regulated and controlled by changing the content of the initiator. The preparation process is simple, controllable, green and efficient.
The composite particles prepared by the invention have a multiple core-shell structure, and simultaneously meet the comprehensive properties of high thermal stability and dimensional stability, good matrix compatibility, certain flexibility and excellent conductivity.
Drawings
FIG. 1 is a scanning electron microscopy topography of the nanosilica prepared in example 1;
FIG. 2 is a transmission electron microscope image of the PMMA coated nano silica particles with core-shell structure prepared in example 1;
fig. 3 is a transmission electron microscope morphology of the nano silica/polymethyl methacrylate/carbon nanotube composite particles with multiple core-shell structures prepared in example 1.
Detailed Description
The materials and the preparation method thereof are described in detail by the following examples, which are only used for further illustration of the present invention and do not limit the protection scope of the present invention.
Example 1
(1) And (3) synthesis of nano silicon dioxide:
140mL of absolute ethanol, 20mL of ammonia water and 14mL of ethyl orthosilicate were poured into a three-necked flask, and stirred at 500 rpm for 20 hours at 30 ℃. And then centrifugally purifying with deionized water until the pH value is 7, adding a proper amount of deionized water to obtain a nano-silica suspension with the concentration of 10g/L, wherein the particle size of the nano-silica is 250nm, and the shape of the obtained nano-silica in a scanning electron microscope is shown in figure 1.
(2) Pretreating the surface of the nano silicon dioxide:
to 100mL of the nanosilica suspension (10 g/L) was added 0.05g of gamma- (methacryloyloxy) propyltrimethoxysilane, and after stirring at 200 rpm for 4 hours at room temperature, stirring was continued at 90 ℃ for 2 hours. And (3) carrying out ethanol centrifugal purification on the modified nano silicon dioxide (the rotating speed is 4000 revolutions per minute, the single time is 15 minutes, and the times are 3 times), and carrying out vacuum drying on the obtained product at the temperature of 30 ℃ for 25 hours to obtain the silicon dioxide powder with the pre-modified surface.
(3) Coating the nano silicon dioxide surface with a polymer:
20g of the silane coupling agent modified nano-silica and 0.1g of polyvinylpyrrolidone are added into 400mL of ethanol/water solution, and the volume ratio of ethanol to water is 1: 1. And introducing nitrogen for 2-4 hours, adding 1mL of methyl methacrylate monomer containing 5mg of 2,2' -azobisisobutylamidine dihydrochloride initiator, and immediately heating and refluxing, wherein the reaction temperature is controlled to be 60-70 ℃, the reaction time is 20-30 hours, and the stirring speed is 150 rpm. After the reaction is finished, deionized water is used for washing and centrifuging for many times, a proper amount of deionized water is added to obtain the polymethyl methacrylate coated nano silicon dioxide suspension with the core-shell structure (the concentration is 10g/L), the electron microscope morphology of the obtained polymethyl methacrylate coated nano silicon dioxide particles with the core-shell structure is shown in figure 2, and the thickness of the polymethyl methacrylate coating layer is about 200 nm.
(4) Acidifying the multi-wall carbon nano tube: sequentially adding 2.5g of multi-walled carbon nanotubes, 62.5mL of concentrated nitric acid and 187.5mL of concentrated sulfuric acid into a single-neck flask, and carrying out ultrasonic treatment for 1-2 hours; heating the mixture subjected to ultrasonic treatment in an oil bath to 40-70 ℃, and mechanically stirring for 2-4 hours; slowly adding deionized water, settling for 10-15 hours, then taking the deionized water as a solvent, carrying out centrifugal purification until the pH value of the solution is neutral, and adding a proper amount of deionized water to obtain an acidified carbon nanotube aqueous solution (the concentration is 2 g/L).
(5) Preparing nano silicon dioxide/polymethyl methacrylate/carbon nano tube composite particles with multiple core-shell structures:
mixing 500mL of polymethyl methacrylate surface-coated modified silica suspension (with the concentration of 10g/L) and 150mL of acidified carbon nanotube aqueous solution (with the concentration of 2g/L) in a beaker, and stirring for 3-5 hours at the stirring speed of 100-150 revolutions per minute. And then standing for 1-2 hours to promote the adsorption of the two. Centrifuging the mixture at the rotating speed of 4000-7000 revolutions per minute for 20-30 minutes to remove the upper liquid, centrifuging and purifying the mixture by using water as a solvent until the upper liquid is not turbid any more, and freeze-drying the mixture to obtain the nano-silica/polymethyl methacrylate/carbon nano tube composite particles with the multiple core-shell structures, wherein the shape transmission diagram of the particles is shown in fig. 3.
Claims (9)
1. A composite particle with a multiple core-shell structure is characterized in that inorganic silicon dioxide nano particles are used as an inner core, an organic acrylate polymer is used as a middle layer, and a carbon nano tube adsorption layer is used as an outer shell;
the preparation method of the composite particle with the multiple core-shell structure comprises the following steps:
(1) by using
Synthesizing nano silicon dioxide by the method, and carrying out surface modification by a silane coupling agent to obtain surface pre-modified silicon dioxide powder;
(2) mixing the surface pre-modified silicon dioxide powder prepared in the step (1) with an ethanol-water solution, adding a stabilizer, uniformly mixing, adding an initiator and an acrylate monomer, and carrying out polymerization reaction to obtain a polymer surface coating modified silicon dioxide suspension;
the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile and 2,2' -azobisisobutylamidine dihydrochloride;
(3) and (3) acidifying and modifying the carbon nano tube to obtain an acidified carbon nano tube aqueous solution, mixing the polymer surface coating modified silicon dioxide suspension prepared in the step (2) with the acidified carbon nano tube aqueous solution, stirring, standing, and performing electrostatic self-assembly to obtain the composite particle with the multiple core-shell structure.
2. The composite particle having a multiple core-shell structure according to claim 1, wherein the particle diameter of the core is 70 to 300nm, the thickness of the intermediate layer is 5 to 300nm, and the thickness of the shell is 0.1 to 5 nm.
3. The composite particle having a multiple core-shell structure according to claim 1, comprising, in mass percent:
60-85 wt% of inorganic silica nanoparticles;
5 to 37 wt% of an organic acrylic polymer;
3-10 wt% of carbon nanotubes;
the organic acrylic ester polymer is at least one selected from polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polyethyl methacrylate and polybutyl methacrylate.
4. The composite particle having a multiple core-shell structure according to claim 1, wherein in step (1):
said adoption of
The method for synthesizing the nano silicon dioxide specifically comprises the following steps:
mixing absolute ethyl alcohol, ammonia water and tetraethoxysilane, stirring at the rotating speed of 300-700 revolutions per minute at the temperature of 20-50 ℃ for 15-30 hours, and then centrifugally purifying by using deionized water until the pH value is 7-8 to obtain a nano silicon dioxide suspension;
the volume ratio of the ammonia water to the absolute ethyl alcohol is 1: 7-15, and the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 1: 10-30;
the concentration of the prepared nano silicon dioxide suspension is 5-10 g/L.
5. The composite particle having a multiple core-shell structure according to claim 1, wherein in the step (1), the silane coupling agent is at least one selected from the group consisting of γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, and γ - (methacryloyloxy) propyltrimethoxysilane;
the surface modification specifically comprises the following steps:
mixing the nano silicon dioxide suspension with a silane coupling agent, stirring for 2-5 hours at room temperature at 200-500 rpm, continuing to stir for 2-3 hours at 70-100 ℃, performing centrifugal purification on ethanol at a rotating speed of 3500-4500 rpm, performing single treatment for 15-25 minutes at 2-5 times, and performing vacuum drying on a purified product at 25-40 ℃ for 15-30 hours to obtain surface pre-modified silicon dioxide powder;
the mass ratio of the solid content in the nano silicon dioxide suspension to the silane coupling agent is 10-50: 1.
6. The composite particle having a multiple core-shell structure according to claim 1, wherein in step (2):
the mass ratio of the surface pre-modified nano silicon dioxide to the ethanol-water solution is 1: 20-50;
in the ethanol-water solution, the volume ratio of water to ethanol is 4: 1-18;
the stabilizer is selected from polyvinylpyrrolidone or polyvinyl alcohol, and the addition amount of the stabilizer is 5-15% of the mass of the acrylate monomer;
the addition amount of the initiator is 0.3-0.8% of the mass of the acrylate monomer;
the acrylic ester monomer is selected from at least one of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate;
the polymerization reaction is carried out in a nitrogen atmosphere, the reaction temperature is 60-90 ℃, the stirring reaction is carried out for 15-20 hours, and the stirring rotation speed is 100-200 r/min;
the concentration of the prepared polymer surface coating modified silicon dioxide suspension is 5-15 g/L.
7. The composite particle having a multiple core-shell structure according to claim 1, wherein in step (3):
the carbon nano tube is subjected to acidification modification, and the method specifically comprises the following steps:
mixing the multi-walled carbon nano-tube with concentrated sulfuric acid and concentrated nitric acid, ultrasonically dispersing for 1-2 hours, heating to 40-70 ℃, and mechanically stirring for 2-4 hours; slowly adding deionized water, settling for 10-15 hours, and then carrying out centrifugal purification by using the deionized water as a solvent until the pH value of the solution is neutral to obtain an acidified carbon nanotube aqueous solution;
the diameter of the multi-walled carbon nanotube is 5-30 nm, and the length of the multi-walled carbon nanotube is 10-35 mu m;
the mass ratio of the multi-walled carbon nanotubes to concentrated sulfuric acid is 1: 60-90, and the mass ratio of the multi-walled carbon nanotubes to concentrated nitric acid is 1: 5-30;
the concentration of the prepared acidified carbon nano tube aqueous solution is 1-10 g/L.
8. The composite particle with a multiple core-shell structure according to claim 1, wherein in the step (3), the mass ratio of the solid content in the acidified carbon nanotube aqueous solution to the solid content in the polymer surface coating modified silica suspension is 1: 10-20.
9. The composite particle with multiple core-shell structures according to claim 1, wherein in the step (3), the rotation speed of stirring is 100-150 rpm for 3-5 hours; then standing for 1-2 hours to promote the static self-assembly;
and centrifuging the mixture subjected to electrostatic self-assembly at the rotating speed of 4000-7000 rpm for 20-30 minutes to remove the upper-layer liquid, centrifuging and purifying the mixture by using water as a solvent until the upper-layer liquid is not turbid any more, and freeze-drying the mixture to obtain the composite particles with the multiple core-shell structures.
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