CN114455592B - Hollow mesoporous silica modified by sym-triazinyl, and preparation method and application thereof - Google Patents
Hollow mesoporous silica modified by sym-triazinyl, and preparation method and application thereof Download PDFInfo
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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Abstract
The invention relates to a hollow mesoporous silica modified by s-triazinyl, and a preparation method and application thereof, comprising the following steps: (1) Preparing solid silica nanospheres by adopting a stoner method; (2) A mesoporous silica shell is modified on the surface of the solid silica nanospheres by adopting a sol-gel method; (3) Preparing the surface modified amino hollow mesoporous silica nanoparticle by adopting an etching method; (4) Mixing cyanuric chloride with the mixture to react to prepare the hollow mesoporous silica modified by the sym-triazinyl. When the product is used as a carrier to load the perfume, the problems of instability, volatility and too fast perfume release of the perfume are solved, the perfume is high in loading rate, uniform and slow in perfume release, and the perfume is long in fragrance retention time, more importantly, the perfume can be covalently combined with chemical groups on the surfaces of substrates such as silk, leather and leather, the perfume attaching efficiency of the nano perfume is improved, the perfume is not easy to fall off, and the long-term use is facilitated.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, relates to hollow mesoporous silica and a preparation method and application thereof, and in particular relates to s-triazinyl modified hollow mesoporous silica and a preparation method and application thereof.
Background
With the progress of social civilization, people's life quality is improved, and aromatic smell is gradually promoted by people. Fragrances have been widely used in the fields of cosmetics silk, leather and the like. The perfume is mainly a volatile micromolecular compound, the components are unstable and volatile, most of the perfume is combined with various base materials in a physical adsorption mode, the combination efficiency is low, the perfume is easy to fall off, the fragrance is not durable enough, and therefore the realization of the slow release effect of the perfume and the enhancement of the combination of the perfume and the perfume-attached base materials are technical problems to be solved.
CN109518463B discloses a pH-responsive controlled release polymer nano perfume, and preparation method and application thereof, comprising the following steps: firstly preparing a pH response amphiphilic block copolymer through a RAFT reaction; then, preparing a cationic pH response amphiphilic block copolymer through an acid ammonium condensation reaction with a cationic surfactant; finally loading the cationic amphiphilic block copolymer with perfume to obtain the pH response controlled release polymer nanometer perfume. Although the invention solves the problems of unstable, volatile and uncontrollable perfume releasing process, the combination of perfume and perfume-attached base material can not be enhanced.
CN109504537a discloses a temperature-controlled slow-release mesoporous silica nano perfume and a preparation method thereof, comprising: firstly, preparing nano mesoporous silica spheres by a sol-gel method; then modifying temperature-sensitive polymer poly (N-isopropyl acrylamide) on the surface of the nano mesoporous silica sphere by an atom transfer radical polymerization method to obtain a temperature-sensitive nano mesoporous silica sphere; finally, the temperature-sensitive mesoporous silica spheres are loaded with perfume, so that the temperature-controlled slow-release mesoporous silica nano perfume is obtained. Although the invention can solve the problems of unstable, volatile and uncontrollable perfume releasing process, the combination of perfume and perfume-attached base material can not be enhanced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide hollow mesoporous silica and a preparation method and application thereof, in particular to hollow mesoporous silica modified by s-triazinyl and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of s-triazinyl modified hollow mesoporous silica, the preparation method comprising the following steps:
(1) Preparing solid silica nanospheres by adopting a stoner method;
(2) Using a silane coupling agent with terminal amino groups as a silane coupling agent, and adopting a sol-gel method to modify a layer of mesoporous silica shell on the surface of the solid silica nanospheres obtained in the step (1) to obtain double-layer silica nanoparticles with the amino groups modified on the surfaces;
(3) Preparing the double-layer silicon dioxide nano particles with the surface modified amino groups obtained in the step (2) into hollow mesoporous silicon dioxide nano particles with the surface modified amino groups by adopting an etching method;
(4) Mixing cyanuric chloride with the hollow mesoporous silica nanoparticles with the amino groups modified on the surfaces, which are obtained in the step (3), and reacting to obtain the hollow mesoporous silica modified by the sym-triazinyl.
The invention creatively designs and prepares the s-triazinyl modified hollow mesoporous silica carrier, the hollow inside of the hollow mesoporous silica carrier improves the material storage capacity of the carrier, the existence of the mesoporous silica surface can prolong the time for releasing the stored material from the inside to the outside, and the hollow mesoporous silica carrier can be covalently combined with chemical groups on the surfaces of substrates such as silk, leather and the like due to the existence of the s-triazinyl serving as a surface active group, improves the attaching efficiency of the hollow mesoporous silica carrier, is not easy to fall off, and is beneficial to long-term use.
Preferably, the specific method of step (1) comprises: and mixing silicate, ethanol, water and alkali for reaction to obtain the solid silica nanospheres.
Preferably, the silicate comprises ethyl orthosilicate.
Preferably, the silicate to water volume ratio is (0.5-0.7): 1, e.g. 0.5:1, 0.55:1, 0.6:1, 0.65:1 or 0.7:1, etc.
Preferably, the volume ratio of ethanol to water is (6-8): 1, e.g., 6:1, 6.5:1, 7:1, 7.5:1, or 8:1, etc.
Preferably, the base comprises aqueous ammonia.
Preferably, the temperature of the mixing reaction is 15-35 ℃, e.g. 15 ℃,20 ℃,25 ℃,30 ℃ or 35 ℃, etc., for a time of 0.5-2 hours, e.g. 0.5 hours, 0.8 hours, 1 hour, 1.2 hours, 1.5 hours or 2 hours, etc.
Other specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
And (3) carrying out solid-liquid separation after the step (1) is finished, and washing and drying the solid.
Preferably, the specific method of step (2) comprises: mixing solid silica nanospheres, a surfactant, alkali, water and ethanol, and then adding silicate and a silane coupling agent with terminal amino groups for reaction to obtain double-layer silica nanoparticles with surface modified amino groups.
Preferably, the surfactant comprises cetyltrimethylammonium bromide.
Preferably, the base comprises aqueous ammonia.
Preferably, the mass to volume ratio of the surfactant to the water is (3-6): 1mg/mL, e.g., 3:1mg/mL, 4:1mg/mL, 4.2:1mg/mL, 4.5:1mg/mL, 4.8:1mg/mL, 5:1mg/mL, 6:1mg/mL, etc.
Preferably, the volume ratio of the base to the water is (0.01-0.04): 1, e.g. 0.01:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1 or 0.04:1 etc.
Preferably, the volume ratio of the base to the ethanol is (0.01-0.05): 1, e.g., 0.01:1, 0.02:1, 0.03:1, 0.035:1, 0.04:1, 0.045:1, or 0.05:1, etc.
Preferably, the temperature of the mixing is 15-35 ℃, e.g. 15 ℃,20 ℃,25 ℃,30 ℃ or 35 ℃, etc., for a time of 0.5-1h, e.g. 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1h, etc.
Preferably, the silicate and the silane coupling agent having a terminal amino group are added with stirring in a total volume to volume ratio of the water of (0.005-0.01): 1, for example 0.005:1, 0.006:1, 0.007:1, 0.008:1, 0.0085:1, 0.009:1, 0.0095:1 or 0.01:1, etc.
Preferably, the temperature of the reaction is 15-35 ℃, e.g. 15 ℃,20 ℃,25 ℃,30 ℃ or 35 ℃, etc., for a period of 6-10 hours, e.g. 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, etc.
Other specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
And (3) carrying out solid-liquid separation after the step (2) is finished, and washing and drying the solid.
Preferably, the specific method of step (3) comprises: mixing the double-layer silica nanoparticles with the surface modified amino groups with an alkali solution for reaction to obtain the hollow mesoporous silica nanoparticles with the surface modified amino groups.
Preferably, the alkaline solution comprises an aqueous sodium carbonate solution.
Preferably, the temperature of the reaction is 60-72 ℃, e.g. 60 ℃, 62 ℃,65 ℃, 67 ℃,70 ℃ or 72 ℃, etc., for a period of 8-12 hours, e.g. 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc.
Other specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
Preferably, the surfactant remained on the surface of the product is also removed after the reaction in the step (3), and the removing method is an extraction method.
Preferably, the extraction method comprises: mixing the product with solvent and acid, reacting, separating solid from liquid, and drying.
Preferably, the solvent comprises ethanol.
Preferably, the acid comprises hydrochloric acid, the concentration of which is 0.8-4%, e.g. 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5% or 4%, etc.
Preferably, the mass to volume ratio of the product to the solvent is (10-20): 1mg/mL, e.g., 10:1mg/mL, 12:1mg/mL, 15:1mg/mL, 18:1mg/mL, or 20:1mg/mL, etc.
Preferably, the volume ratio of the acid to the solvent is (0.01-0.05): 1, e.g. 0.01:1, 0.02:1, 0.03:1, 0.04:1 or 0.05:1, etc.
Preferably, the reaction is carried out under reflux conditions for a reaction time of 12-48 hours, for example 12, 15, 20, 24, 36, 42 or 48 hours, etc.
Other specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
And (3) carrying out solid-liquid separation after the step (3) is finished, and washing and drying the solid.
Preferably, the mass ratio of the cyanuric chloride to the hollow mesoporous silica nanoparticles with the amino groups modified on the surface in the step (4) is (2-5): 1, such as 2:1, 3:1, 4:1 or 5:1.
Preferably, the reaction of step (4) is carried out in a solvent comprising tetrahydrofuran.
Preferably, the mass to volume ratio of the surface modified amino hollow mesoporous silica nanoparticle to the solvent is (10-50): 1mg/mL, e.g., 10:1mg/mL, 15:1mg/mL, 20:1mg/mL, 25:1mg/mL, 30:1mg/mL, 35:1mg/mL, 40:1mg/mL, 45:1mg/mL, 50:1mg/mL, etc.
Preferably, the reaction of step (4) is carried out under the catalysis of a catalyst comprising N, N-diisopropylethylamine.
Preferably, the temperature of the reaction in step (4) is from-10 to 0 ℃, e.g. from-10 ℃, -8 ℃, -5 ℃, -3 ℃ or 0 ℃ etc., for a period of time of from 12 to 24 hours, e.g. 12 hours, 15 hours, 17 hours, 20 hours, 22 hours, 23 hours or 24 hours etc.
Other specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
And (3) carrying out solid-liquid separation after the step (4) is finished, and washing and drying the solid.
In the present invention, the solid-liquid separation method used in steps (1) to (5) is preferably centrifugation, but is not limited to centrifugation, and other solid-liquid separation methods that can achieve the object of the product are also applicable to the present invention.
As a preferred technical scheme of the invention, the preparation method of the s-triazinyl modified mesoporous hollow silica specifically comprises the following steps:
(1) Mixing silicate, ethanol, water and alkali at 15-35 ℃ for reaction for 0.5-2h to obtain solid silica nanospheres; the volume ratio of silicate to water is (0.5-0.7): 1; the volume ratio of the ethanol to the water is (6-8) 1;
(2) Mixing solid silica nanospheres, a surfactant, alkali, water and ethanol for 0.5-1h at 15-35 ℃, then adding silicate and a silane coupling agent with terminal amino groups under stirring, and reacting for 6-10h at 15-35 ℃ to obtain double-layer silica nanoparticles with surface modified amino groups; the mass volume ratio of the surfactant to the water is (3-6) 1mg/mL; the volume ratio of the alkali to the water is (0.01-0.04): 1; the volume ratio of the alkali to the ethanol is (0.01-0.05): 1; the ratio of the total volume of the silicate and the silane coupling agent having a terminal amino group to the volume of the water is (0.005-0.01): 1;
(3) Mixing the surface-modified amino double-layer silica nanoparticles with an alkali solution at 60-72 ℃ for reaction for 8-12h to obtain surface-modified amino hollow mesoporous silica nanoparticles; then mixing the mixture with a solvent and acid, reacting for 12-48 hours under the reflux condition, separating solid from liquid, and drying to obtain the catalyst; the mass volume ratio of the hollow mesoporous silica nanoparticle with the surface modified amino to the solvent is (10-20): 1mg/mL; the volume ratio of the acid to the solvent is (0.01-0.05): 1;
(4) Mixing cyanuric chloride with the hollow mesoporous silica nanoparticles with the amino groups modified on the surfaces, which are obtained in the step (3), in a solvent under the catalysis of a catalyst at the temperature of-10-0 ℃ for reaction for 12-24 hours to obtain the hollow mesoporous silica modified by the s-triazinyl; the mass ratio of the cyanuric chloride to the hollow mesoporous silica nanoparticles with the amino groups modified on the surfaces is (2-5) 1; the mass volume ratio of the hollow mesoporous silica nanoparticle with the surface modified amino to the solvent is (10-50) 1mg/mL.
In a second aspect, the invention provides the s-triazinyl modified mesoporous hollow silica prepared by the preparation method of the s-triazinyl modified mesoporous hollow silica.
In a third aspect, the present invention provides a s-triazinyl modified mesoporous hollow silica nanoflava comprising a s-triazinyl modified mesoporous hollow silica as described above and a perfume encapsulated therein.
When the mesoporous hollow silica modified by the sym-triazinyl is used as a carrier for loading the perfume, the problems of instability, easy volatilization and too fast perfume release of the perfume are solved, the perfume loading rate is high, the perfume release is uniform and slow, the perfume retention time is long, more importantly, the mesoporous hollow silica modified by the sym-triazinyl can be covalently combined with chemical groups on the surfaces of substrates such as silk, leather and leather, the perfume attaching efficiency of the nano perfume is improved, the nano perfume is not easy to fall off, and the long-term use is facilitated. The nanometer perfume has the advantages of convenient use and simple preparation method, and can be widely applied to various fields of daily chemicals, textiles, leather and the like. According to the invention, through accurate self-assembly, the perfume is nanocrystallized, the perfume carrying rate is improved, the perfume is endowed with chemical active groups, the carrying between the nano perfume and the base material is improved through a chemical bond combination mode, and the volatility of the perfume is improved.
In a fourth aspect, the present invention provides a method for preparing the s-triazinyl modified mesoporous hollow silica nano perfume described above, the method comprising: mixing the mesohole hollow silica modified by the sym-triazinyl with a spice solution, and carrying out solid-liquid separation and drying after soaking to obtain the mesohole hollow silica nano spice modified by the sym-triazinyl.
Preferably, the perfume solution has a mass concentration of 80-99%, for example 80%, 82%, 85%, 88%, 90%, 95% or 99% etc.
Preferably, the soaking time is not less than 24 hours, such as 24 hours, 28 hours, 30 hours, 32 hours, 36 hours, 40 hours, 42 hours, or the like.
Other specific point values within the above numerical ranges are all selectable, and will not be described in detail herein.
Compared with the prior art, the invention has the following beneficial effects:
the invention creatively designs and prepares the s-triazinyl modified hollow mesoporous silica carrier, the hollow inside of the hollow mesoporous silica carrier improves the material storage capacity of the carrier, the existence of the mesoporous silica surface can prolong the time for releasing the stored material from the inside to the outside, and the hollow mesoporous silica carrier can be covalently combined with chemical groups on the surfaces of substrates such as silk, leather and the like due to the existence of the s-triazinyl serving as a surface active group, improves the attaching efficiency of the hollow mesoporous silica carrier, is not easy to fall off, and is beneficial to long-term use.
When the mesoporous hollow silica modified by the sym-triazinyl is used as a carrier for loading the perfume, the problems of instability, easy volatilization and too fast perfume release of the perfume are solved, the perfume loading rate is high, the perfume release is uniform and slow, the perfume retention time is long, more importantly, the mesoporous hollow silica modified by the sym-triazinyl can be covalently combined with chemical groups on the surfaces of substrates such as silk, leather and leather, the perfume attaching efficiency of the nano perfume is improved, the nano perfume is not easy to fall off, and the long-term use is facilitated. The nanometer perfume has the advantages of convenient use and simple preparation method, and can be widely applied to various fields of daily chemicals, textiles, leather and the like.
According to the invention, through accurate self-assembly, the perfume is nanocrystallized, the perfume carrying rate is improved, the perfume is endowed with chemical active groups, the carrying between the nano perfume and the base material is improved through a chemical bond combination mode, and the volatility of the perfume is improved.
Drawings
FIG. 1 is a TEM image of solid silica nanospheres prepared in example 1;
FIG. 2 is a TEM image of surface-modified amino bilayer silica nanoparticles prepared in example 1;
FIG. 3 is a TEM image of the s-triazinyl-modified hollow mesoporous silica prepared in example 1;
FIG. 4 is a TEM image of the solid silica nanospheres prepared in example 2;
FIG. 5 is a TEM image of surface-modified amino bilayer silica nanoparticles prepared in example 2;
FIG. 6 is a TEM image of the s-triazinyl-modified hollow mesoporous silica prepared in example 2;
FIG. 7 is a TEM image of solid silica nanospheres prepared in example 3;
FIG. 8 is a TEM image of surface-modified amino bilayer silica nanoparticles prepared in example 3;
FIG. 9 is a TEM image of the s-triazinyl-modified hollow mesoporous silica prepared in example 3;
FIG. 10 is an SEM image of blank leather used in application example 1;
FIG. 11 is an SEM image of a hollow mesoporous silica having no s-triazinyl modifying groups supported on a blank leather used in application example 1;
FIG. 12 is an SEM image of hollow mesoporous silica loaded with s-triazinyl modifying groups for blank leather used in application example 1;
FIG. 13 is an SEM image of blank leather used in application example 2;
FIG. 14 is an SEM image of a hollow mesoporous silica having no s-triazinyl modifying groups supported on a blank leather used in application example 2;
FIG. 15 is an SEM image of hollow mesoporous silica loaded with s-triazinyl modifying groups for blank leather used in application example 2;
FIG. 16 is an SEM image of the control group of application example 3 and the group of example 3 after stirring in water for 2 days;
FIG. 17 is an SEM image of the control group of application example 3 and the group of example 3 after stirring in water for 4 days;
fig. 18 is an SEM image of the control group in application example 3 and the group in example 3 after stirring in water for 6 days.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a hollow mesoporous silica nano perfume modified by s-triazinyl, and the preparation method thereof is as follows:
(1) Preparation of solid silica nanospheres: 74mL of ethanol, 10mL of water and 3.15mL of ammonia water are mixed and stirred for 5min, 6mL of tetraethoxysilane is rapidly added, the mixture is vigorously stirred for 2h at 25 ℃, the mixture is filtered, the product is washed three times with water and ethanol, and vacuum drying is carried out for 12h, thus obtaining solid silica nanospheres (sSiO) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Solid silica nanospheres (sSiO) prepared by transmission electron microscope 2 ) Characterization was performed, and the results are shown in fig. 1;
(2) Preparation of double-layer silica nanoparticles with surface modified amino groups: 300mg of sSiO 2 Dissolving in 50mL of water, performing ultrasonic treatment for 20min to uniformly disperse the mixture, adding the mixture into a solution containing 400mg of cetyltrimethylammonium bromide, 75mL of water, 75mL of ethanol and 1.375mL of ammonia water, vigorously stirring the mixture for 1h, rapidly adding 125 mu L N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and 600 mu L of tetraethoxysilane, continuously stirring the mixture at 25 ℃ for 6h, separating solid and liquid of the product after the reaction is finished, and performing vacuum drying for 12h to obtain double-layer silica nanoparticles (sSiO) with amino groups modified on the surface 2 @mSiO 2 ) The method comprises the steps of carrying out a first treatment on the surface of the sSiO prepared by using transmission electron microscope pair 2 @mSiO 2 Characterization was performed, and the results are shown in fig. 2;
(3) Preparation of hollow mesoporous silica nanoparticles with amino groups modified on the surfaces: weighing 60mg of sSiO 2 @mSiO 2 Added to 10mL of 0.3M aqueous sodium carbonate, sonicated for 15min, etched for 12h at 70℃and centrifuged, the product washed three times with ethanol and water and dried overnight in vacuo. Removing residual surfactant by an extraction method: adding 1g of a product collected by the first reaction into 100mL of ethanol solution, adding 1mL of hydrochloric acid, refluxing at 75 ℃ for 12h, extracting three times, centrifuging, washing three times with ethanol and ultrapure water respectively, and vacuum drying for 12h to obtain hollow mesoporous silica nanoparticles with amino modified surfaces;
(4) Preparation of s-triazinyl modified hollow mesoporous silica: mixing 100mg of the hollow mesoporous silica nanoparticle with the amino modified on the surface, which is obtained in the step (3), 500mg of cyanuric chloride and 10mL of tetrahydrofuran, adding 500 mu L N and N-diisopropylethylamine, stirring at 0 ℃ for reaction for 24 hours, centrifuging, washing the product thoroughly with dichloromethane, acetone, methanol and dichloromethane in sequence, and vacuum drying to obtain the hollow mesoporous silica nanoparticle with the triazinyl modified; the prepared triazinyl modified hollow mesoporous silica nanoparticle is characterized by utilizing a transmission electron microscope, the result is shown in a figure 3, and the particle size of the obtained product is about 200 nm;
(5) Preparation of a symtriazinyl modified hollow mesoporous silica nano perfume: mixing the 100mg triazinyl modified hollow mesoporous silica nano particles obtained in the step (4) with 10mL 90% linalool solution, soaking for 24 hours under stirring, centrifuging, and drying in vacuum to obtain the symtriazinyl modified hollow mesoporous silica nano perfume.
Example 2
The embodiment provides a hollow mesoporous silica nano perfume modified by s-triazinyl, and the preparation method thereof is as follows:
(1) Preparation of solid silica nanospheres: 60mL of ethanol, 10mL of water and 3.15mL of ammonia water are mixed and stirred for 5min, 5mL of tetraethoxysilane is rapidly added, the mixture is vigorously stirred for 1h at 30 ℃, the mixture is filtered, the product is washed three times by water and ethanol, and the mixture is dried in vacuum for 12h, so that solid silica nanospheres (sSiO 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Solid silica nanospheres (sSiO) prepared by transmission electron microscope 2 ) Characterization was performed, and the results are shown in fig. 4;
(2) Preparation of double-layer silica nanoparticles with surface modified amino groups: 300mg of sSiO 2 Dissolving in 50mL of water, performing ultrasonic treatment for 20min to uniformly disperse the mixture, adding the mixture into a solution containing 400mg of cetyltrimethylammonium bromide, 75mL of water, 75mL of ethanol and 1.375mL of ammonia water, vigorously stirring the mixture for 0.5h, rapidly adding 125 mu L N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and 600 mu L of tetraethoxysilane, continuously stirring the mixture for 9h at 20 ℃, separating solid and liquid of the product after the reaction is finished, and performing vacuum drying for 12h to obtain double-layer silica nanoparticles (sSiO) with amino groups modified on the surface 2 @mSiO 2 ) The method comprises the steps of carrying out a first treatment on the surface of the sSiO prepared by using transmission electron microscope pair 2 @mSiO 2 Characterization was performed, and the results are shown in fig. 5;
(3) Preparation of hollow mesoporous silica nanoparticles with amino groups modified on the surfaces: weighing 60mg of sSiO 2 @mSiO 2 Added to 10mL of 0.3M aqueous sodium carbonate, sonicated for 15min, etched for 8h at 72℃and centrifuged, the product washed three times with ethanol and water and dried overnight in vacuo. Removing residual surfactant by an extraction method: adding 2g of the product collected by the first reaction into 100mL of ethanol solution, adding 5mL of hydrochloric acid, refluxing at 75 ℃ for 24 hours, extracting three times, centrifuging, washing three times by ethanol and ultrapure water respectively, and vacuum drying for 12 hours to obtain hollow mesoporous silica nanoparticles with amino modified surfaces;
(4) Preparation of s-triazinyl modified hollow mesoporous silica: mixing 100mg of the hollow mesoporous silica nanoparticle with the amino modified on the surface, 300mg of cyanuric chloride and 5mL of tetrahydrofuran, adding 500 mu L N and N-diisopropylethylamine, stirring at the temperature of minus 5 ℃ for reaction for 24 hours, centrifuging, washing the product thoroughly with dichloromethane, acetone, methanol and dichloromethane in sequence, and vacuum drying to obtain the hollow mesoporous silica nanoparticle with the triazinyl modified; the prepared triazinyl modified hollow mesoporous silica nanoparticle is characterized by using a transmission electron microscope, and the result is shown in figure 6;
(5) Preparation of a symtriazinyl modified hollow mesoporous silica nano perfume: mixing the hollow mesoporous silica nanoparticle with the concentration of 200mg of triazinyl modified hollow mesoporous silica nanoparticles obtained in the step (4) with 20mL of 90% linalool solution, soaking for 24 hours under stirring, centrifuging, and drying in vacuum to obtain the sym-triazinyl modified hollow mesoporous silica nano perfume.
Example 3
The embodiment provides a hollow mesoporous silica nano perfume modified by s-triazinyl, and the preparation method thereof is as follows:
(1) Preparation of solid silica nanospheres: 80mL of ethanol, 10mL of water and 3.15mL of ammonia water are mixed and stirred for 5min, 7mL of tetraethoxysilane is rapidly added, and the mixture is vigorously stirred for 0.5h at 35 ℃, filtered, and the product is washed three times with water and ethanol and dried in vacuum for 12h to obtain solid silica nanospheres (sSiO) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Solid silica nanospheres (sSiO) prepared by transmission electron microscope 2 ) Characterization was performed and the results are shown in fig. 7;
(2) Preparation of double-layer silica nanoparticles with surface modified amino groups: 300mg of sSiO 2 Dissolving in 50mL of water, performing ultrasonic treatment for 20min to uniformly disperse the mixture, adding the mixture into a solution containing 400mg of cetyltrimethylammonium bromide, 75mL of water, 75mL of ethanol and 1.375mL of ammonia water, vigorously stirring the mixture for 0.5h, rapidly adding 125 mu L N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and 600 mu L of tetraethoxysilane, continuously stirring the mixture at 30 ℃ for 7h, separating solid and liquid of the product after the reaction is finished, and performing vacuum drying for 12h to obtain the double-layer dioxide of the surface modified aminoSilicon nanoparticles (sSiO) 2 @mSiO 2 ) The method comprises the steps of carrying out a first treatment on the surface of the sSiO prepared by using transmission electron microscope pair 2 @mSiO 2 Characterization was performed, and the results are shown in fig. 8;
(3) Preparation of hollow mesoporous silica nanoparticles with amino groups modified on the surfaces: weighing 60mg of sSiO 2 @mSiO 2 Added to 10mL of 0.3M aqueous sodium carbonate, sonicated for 15min, etched for 12h at 65℃and centrifuged, the product washed three times with ethanol and water and dried overnight in vacuo. Removing residual surfactant by an extraction method: adding 2g of the product collected by the first reaction into 100mL of ethanol solution, adding 5mL of hydrochloric acid, refluxing at 75 ℃ for 24 hours, extracting three times, centrifuging, washing three times by ethanol and ultrapure water respectively, and vacuum drying for 12 hours to obtain hollow mesoporous silica nanoparticles with amino modified surfaces;
(4) Preparation of s-triazinyl modified hollow mesoporous silica: mixing 100mg of the hollow mesoporous silica nanoparticle with the amino modified on the surface, which is obtained in the step (3), 200mg of cyanuric chloride and 3mL of tetrahydrofuran, adding 500 mu L N and N-diisopropylethylamine, stirring at the temperature of minus 10 ℃ for reaction for 24 hours, centrifuging, washing the product thoroughly with dichloromethane, acetone, methanol and dichloromethane in sequence, and vacuum drying to obtain the hollow mesoporous silica nanoparticle with the triazinyl modified; the prepared triazinyl modified hollow mesoporous silica nanoparticle is characterized by using a transmission electron microscope, and the result is shown in figure 9;
(5) Preparation of a symtriazinyl modified hollow mesoporous silica nano perfume: mixing the hollow mesoporous silica nanoparticle with the concentration of 200mg of triazinyl modified hollow mesoporous silica nanoparticles obtained in the step (4) with 20mL of 90% linalool solution, soaking for 24 hours under stirring, centrifuging, and drying in vacuum to obtain the sym-triazinyl modified hollow mesoporous silica nano perfume.
Application example 1
Leather sample (25 cm) 2 ) The solution was immersed in the sym-triazinyl modified hollow mesoporous silica nano perfume solution prepared in example 1 above and stirred for 12 hours at 25 ℃, wherein the stirring rate was 1200rpm. And linalool concentration was 1mg/mL. The leather was then placed in an oven at 40 ℃ for 1 hour to dry. Leather is prepared by soaking perfume solutionAs a blank, the adsorption effect of the perfume was observed by a transmission electron microscope using a hollow mesoporous silica nano perfume solution immersed in a surface-unmodified s-triazinyl group as a control (the difference from the preparation of example 1 is only that step (4)) as shown in fig. 10 to 12 (fig. 10 is a blank, fig. 11 is a control, and fig. 12 is a example 1), it is known that: compared with the leather adsorption of blank leather and surface-unmodified nano particles, the leather adsorption effect of the surface-modified s-triazinyl nano perfume is very obvious, and the hollow mesoporous silica nano perfume prepared in the embodiment 1 has the advantages that the surface active group s-triazinyl can be covalently combined with chemical groups on the surface of a leather substrate due to the existence of the surface active group s-triazinyl, so that the perfume attaching efficiency of the nano perfume is greatly improved, the nano perfume is not easy to fall off, and long-term use is facilitated.
Application example 2
Leather sample (25 cm) 2 ) The solution was immersed in the sym-triazinyl modified hollow mesoporous silica nano perfume solution prepared in example 2 above and stirred for 12 hours at 25 ℃, wherein the stirring rate was 1200rpm. And linalool concentration was 1mg/mL. The leather was then placed in an oven at 40 ℃ for 1 hour to dry. The result of observation of the adsorption effect of the perfume by a transmission electron microscope using the leather soaked with the perfume solution as a blank control group and the hollow mesoporous silica nano perfume solution soaked in the surface-unmodified s-triazinyl as a control group (the preparation of example 2 is different from that of example 2 only in omitting step (4)) is shown in fig. 13 to 15 (fig. 13 is a blank control group, fig. 14 is a control group, and fig. 15 is an example 2 group), it is known that: compared with the leather adsorption of blank leather and surface-unmodified nano particles, the leather adsorption effect of the surface-modified s-triazinyl nano perfume is very obvious, and the hollow mesoporous silica nano perfume prepared in the embodiment 2 has the advantages that the surface active group s-triazinyl can be covalently combined with chemical groups on the surface of a leather substrate due to the existence of the surface active group s-triazinyl, so that the perfume attaching efficiency of the nano perfume is greatly improved, the nano perfume is not easy to fall off, and long-term use is facilitated.
Application example 3
Leather sample (25 cm) 2 ) Soaking the hollow mesoporous two modified by the sym-triazinyl group prepared in the embodiment 2The silica nano-perfume solution was stirred at 25 ℃ for 12 hours, wherein the stirring rate was 1200rpm. And linalool concentration was 1mg/mL. The leather was then placed in an oven at 40 ℃ for 1 hour to dry. The adsorption effect of the perfume was observed with a transmission electron microscope using the leather impregnated with the perfume solution as a blank control group and the hollow mesoporous silica nano perfume solution impregnated with the surface-unmodified s-triazinyl as a control group (the preparation of example 3 is different from that of example 3 only in omitting step (4)), as follows: compared with the leather adsorption of blank leather and surface-unmodified nano particles, the leather adsorption effect of the surface-modified s-triazinyl nano perfume is very obvious, and the hollow mesoporous silica nano perfume prepared in the embodiment 3 has the advantages that the surface active group s-triazinyl can be covalently combined with chemical groups on the surface of a leather substrate, so that the perfume attaching efficiency of the nano perfume is greatly improved, the nano perfume is not easy to fall off, and long-term use is facilitated.
And placing the dried leather sample into a beaker filled with water, continuously stirring, taking out one piece every two days (2 days, 4 days and 6 days), and airing for SEM characterization. The hollow mesoporous silica nano perfume solution soaked in the surface unmodified s-triazinyl is used as a control group. The results are shown in fig. 16-18 (the results of fig. 16 are the results of 2 days of characterization, the results of fig. 17 are the results of 4 days of characterization and the results of fig. 18 are the results of 6 days of characterization), and the results show that the s-triazinyl modified hollow mesoporous silica according to the invention significantly improves the bonding fastness of the nano perfume on leather.
The applicant states that the invention is illustrated by the above examples of a hollow mesoporous silica modified by s-triazinyl group and a method for preparing the same and application thereof, but the invention is not limited to the above examples, i.e. it is not meant that the invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Claims (32)
1. The preparation method of the s-triazinyl modified hollow mesoporous silica is characterized by comprising the following steps of:
(1) Preparing solid silica nanospheres by adopting a stoner method;
(2) Using a silane coupling agent with terminal amino groups as a silane coupling agent, and adopting a sol-gel method to modify a layer of mesoporous silica shell on the surface of the solid silica nanospheres obtained in the step (1) to obtain double-layer silica nanoparticles with the amino groups modified on the surfaces;
(3) Preparing the double-layer silicon dioxide nano particles with the surface modified amino groups obtained in the step (2) into hollow mesoporous silicon dioxide nano particles with the surface modified amino groups by adopting an etching method;
(4) Mixing cyanuric chloride with the hollow mesoporous silica nanoparticles with the amino groups modified on the surfaces, which are obtained in the step (3), and reacting to obtain the hollow mesoporous silica modified by the s-triazinyl;
the specific method of the step (1) comprises the following steps: mixing silicate, ethanol, water and alkali for reaction to obtain solid silica nanospheres;
the silicate comprises ethyl orthosilicate, the volume ratio of the silicate to water is (0.5-0.7): 1, the volume ratio of the ethanol to the water is (6-8): 1, the temperature of the mixing reaction is 15-35 ℃ and the time is 0.5-2 h.
2. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 1, wherein the base comprises aqueous ammonia.
3. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 1, wherein the specific method in the step (2) comprises: mixing solid silica nanospheres, a surfactant, alkali, water and ethanol, and then adding silicate and a silane coupling agent with terminal amino groups for reaction to obtain double-layer silica nanoparticles with surface modified amino groups.
4. A method for preparing the s-triazinyl modified hollow mesoporous silica according to claim 3, wherein said surfactant comprises cetyltrimethylammonium bromide.
5. A method for preparing a s-triazinyl-modified hollow mesoporous silica according to claim 3, wherein said base comprises aqueous ammonia.
6. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 3, wherein the mass-to-volume ratio of the surfactant to the water is (3-6): 1mg/mL.
7. A process for the preparation of s-triazinyl-modified hollow mesoporous silica according to claim 3, wherein the volume ratio of said base to said water is from (0.01 to 0.04): 1.
8. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 3, wherein the volume ratio of said base to said ethanol is (0.01-0.05): 1.
9. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 3, wherein the mixing temperature is 15-35 ℃ and the mixing time is 0.5-1 h.
10. The method for preparing a s-triazinyl-modified hollow mesoporous silica according to claim 3, wherein said silicate and said silane coupling agent having a terminal amino group are added with stirring in a volume ratio of (0.005-0.01) to the volume of said water of 1.
11. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 3, wherein the reaction temperature is 15-35 ℃ and the reaction time is 6-10 h.
12. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 1, wherein the specific method in the step (3) comprises: mixing the double-layer silica nanoparticles with the surface modified amino groups with an alkali solution for reaction to obtain the hollow mesoporous silica nanoparticles with the surface modified amino groups.
13. The method for preparing a s-triazinyl-modified hollow mesoporous silica according to claim 12, wherein said alkaline solution comprises an aqueous sodium carbonate solution.
14. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 12, wherein the reaction temperature is 60-72 ℃ and the reaction time is 8-12 h.
15. The method for preparing the s-triazinyl modified hollow mesoporous silica according to claim 12, wherein the surfactant remaining on the surface of the product after the reaction in the step (3) is removed by an extraction method.
16. The method for preparing the s-triazinyl modified hollow mesoporous silica according to claim 15, wherein said extraction method comprises: mixing the product with solvent and acid, reacting, separating solid from liquid, and drying.
17. The method for preparing a s-triazinyl modified hollow mesoporous silica according to claim 16, wherein said solvent comprises ethanol.
18. The method for preparing a s-triazinyl-modified hollow mesoporous silica according to claim 16, wherein said acid comprises hydrochloric acid, and the concentration of said hydrochloric acid is from 0.8% to 4%.
19. The method for preparing a s-triazinyl-modified hollow mesoporous silica according to claim 16, wherein the mass to volume ratio of said product to said solvent is (10-20): 1mg/mL.
20. The method for preparing a s-triazinyl-modified hollow mesoporous silica according to claim 16, wherein the volume ratio of said acid to said solvent is from (0.01 to 0.05): 1.
21. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 16, wherein said reaction is carried out under reflux conditions for a reaction time of from 12 to 48 h.
22. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 1, wherein the mass ratio of the cyanuric chloride to the hollow mesoporous silica nanoparticles with the surface modified amino groups in the step (4) is (2-5): 1.
23. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 1, wherein said reaction of step (4) is carried out in a solvent comprising tetrahydrofuran.
24. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 23, wherein the mass to volume ratio of the hollow mesoporous silica nanoparticle with the surface modified amino groups to the solvent is (10-50): 1mg/mL.
25. The method for preparing the s-triazinyl-modified hollow mesoporous silica according to claim 1, wherein the reaction in the step (4) is performed under the catalysis of a catalyst, and the catalyst comprisesN,N-Diisopropylethylamine.
26. The method for preparing the s-triazinyl modified hollow mesoporous silica according to claim 1, wherein the reaction temperature in the step (4) is-10-0 ℃ and the reaction time is 12-24 h.
27. The method for preparing the s-triazinyl modified hollow mesoporous silica according to claim 1, comprising the following steps:
(1) Mixing silicate, ethanol, water and alkali at 15-35 ℃ for reaction of 0.5-2h to obtain solid silica nanospheres; the volume ratio of silicate to water is (0.5-0.7): 1; the volume ratio of the ethanol to the water is (6-8) 1;
(2) Mixing solid silica nanospheres, a surfactant, alkali, water and ethanol at 15-35 ℃ for 0.5-1h, adding silicate and a silane coupling agent with terminal amino groups under stirring, and reacting at 15-35 ℃ for 6-10h to obtain double-layer silica nanoparticles with surface modified amino groups; the mass volume ratio of the surfactant to the water is (3-6) 1: 1mg/mL; the volume ratio of the alkali to the water is (0.01-0.04): 1; the volume ratio of the alkali to the ethanol is (0.01-0.05): 1; the ratio of the total volume of the silicate and the silane coupling agent having a terminal amino group to the volume of the water is (0.005-0.01): 1;
(3) Mixing the surface-modified amino double-layer silica nanoparticles with an alkali solution at 60-72 ℃ for reaction of 8-12h to obtain surface-modified amino hollow mesoporous silica nanoparticles; then mixing the mixture with a solvent and acid, reacting under reflux condition for 12-48 and h, separating solid from liquid, and drying to obtain the final product; the mass volume ratio of the hollow mesoporous silica nanoparticle with the surface modified amino to the solvent is (10-20): 1mg/mL; the volume ratio of the acid to the solvent is (0.01-0.05): 1;
(4) Mixing cyanuric chloride with the hollow mesoporous silica nanoparticles with the amino groups modified on the surfaces, which are obtained in the step (3), in a solvent under the catalysis of a catalyst at the temperature of-10-0 ℃ for reaction of 12-24h to obtain the hollow mesoporous silica modified by the s-triazinyl; the mass ratio of the cyanuric chloride to the hollow mesoporous silica nanoparticles with the amino groups modified on the surfaces is (2-5) 1; the mass volume ratio of the hollow mesoporous silica nanoparticle with the surface modified amino to the solvent is (10-50): 1mg/mL.
28. The s-triazinyl-modified hollow mesoporous silica prepared by the method for preparing a s-triazinyl-modified hollow mesoporous silica according to any one of claims 1 to 27.
29. An s-triazinyl-modified hollow mesoporous silica nano perfume, comprising the s-triazinyl-modified hollow mesoporous silica of claim 28 and a perfume encapsulated therein.
30. The method for preparing a s-triazinyl modified hollow mesoporous silica nano perfume according to claim 29, wherein said method comprises: and mixing the hollow mesoporous silica modified by the sym-triazinyl with a spice solution, and carrying out solid-liquid separation and drying after soaking to obtain the hollow mesoporous silica nano spice modified by the sym-triazinyl.
31. The method for preparing a s-triazinyl modified hollow mesoporous silica nano perfume according to claim 30, wherein the mass concentration of the perfume solution is 80-99%.
32. The method for preparing a s-triazinyl modified hollow mesoporous silica nano perfume according to claim 30, wherein the soaking time is not less than 24 h.
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