CN114455592A - S-triazinyl modified hollow mesoporous silica and its preparation method and use - Google Patents
S-triazinyl modified hollow mesoporous silica and its preparation method and use Download PDFInfo
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Abstract
The invention relates to s-triazinyl modified hollow mesoporous silica and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) preparing solid silicon dioxide nanospheres by a stober method; (2) modifying a layer of mesoporous silica shell on the surface of the solid silica nanosphere by adopting a sol-gel method; (3) preparing the amino-modified hollow mesoporous silica nanoparticles from the amino-modified double-layer silica nanoparticles by an etching method; (4) cyanuric chloride is mixed with cyanuric chloride to react to prepare the s-triazinyl modified hollow mesoporous silica. When the product is used as a carrier to load the spice, the problems of instability, volatility and over-quick spice release of the spice are solved, the loading rate of the spice is high, the fragrance is uniformly and slowly released, the fragrance-retaining time is long, more importantly, the product can be covalently combined with chemical groups on the surfaces of base materials such as silk, leather and leather, the fragrance-attaching efficiency of the nano spice is improved, the nano spice is not easy to drop, and the nano spice is favorable for long-term use.
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 particularly relates to s-triazinyl modified hollow mesoporous silica and a preparation method and application thereof.
Background
With the progress of social civilization, the quality of life of people is improved, and aromatic odor is gradually worried by people. Perfumes have been widely used in the fields of cosmetics such as silk, leather and leather. The perfume is mainly a volatile small molecular compound, the components are unstable and volatile, most perfumes are combined with various base materials in a physical adsorption mode, the combination efficiency is low, and the perfume is easy to fall off, so that the fragrance is not durable, and therefore the technical problems to be solved are to realize the slow release effect of the perfume and to strengthen the combination of the perfume and the fragrance-attached base materials.
CN109518463B discloses a polymer nano perfume with pH response and sustained and controlled release, a preparation method and an application thereof, comprising the following steps: firstly, preparing a pH response amphiphilic block copolymer through RAFT reaction; then, carrying out ammonium condensation reaction with a cationic surfactant to prepare a cationic pH response amphiphilic block copolymer; and finally, loading the cationic amphiphilic block copolymer with perfume to obtain the pH-responsive controlled-release polymer nano perfume. The invention solves the problems of instability, volatility and uncontrollable release process of the perfume, but can not strengthen the combination of the perfume and the perfume-attached base material.
CN109504537A discloses a temperature-controlled slow-release mesoporous silica nano perfume and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, preparing a nano mesoporous silica sphere by a sol-gel method; then modifying temperature-sensitive high molecular poly (N-isopropylacrylamide) on the surface of the nano mesoporous silica spheres by an atom transfer radical polymerization method to obtain temperature-sensitive nano mesoporous silica spheres; finally, perfume is loaded on the temperature-sensitive nano mesoporous silica spheres to obtain the temperature-controlled slow-release mesoporous silica nano perfume. Although the invention can solve the problems of instability, volatility and uncontrollable release process of the perfume, the invention can not strengthen the combination of the perfume and the perfume base material.
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, and particularly provides s-triazinyl modified hollow mesoporous silica and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of s-triazinyl modified hollow mesoporous silica, which comprises the following steps:
(1) preparing solid silicon dioxide nanospheres by a stober method;
(2) modifying a layer of mesoporous silica shell on the surface of the solid silica nanosphere obtained in the step (1) by using a sol-gel method by taking a silane coupling agent with terminal amino as the silane coupling agent to obtain double-layer silica nanoparticles with surface modified amino;
(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) and (4) carrying out mixing reaction on cyanuric chloride and the hollow mesoporous silica nanoparticles with the surface modified with amino groups obtained in the step (3) to obtain the s-triazinyl modified hollow mesoporous silica.
The invention creatively designs and prepares the s-triazine modified hollow mesoporous silica carrier, the material storage capacity of the carrier is improved due to the hollow inside, the time for releasing a stored material from the inside to the outside can be prolonged due to the existence of the surface mesoporous of the silica, and due to the existence of the surface active group s-triazine, the hollow mesoporous silica carrier can be covalently combined with chemical groups on the surfaces of base materials such as silk, leather and leather, the attachment efficiency of the hollow mesoporous silica carrier is improved, the hollow mesoporous silica carrier is not easy to fall off, and the hollow mesoporous silica carrier is beneficial to long-term use.
Preferably, the specific method in step (1) comprises the following steps: mixing silicate ester, ethanol, water and alkali for reaction to obtain the solid silicon dioxide nanospheres.
Preferably, the silicate comprises ethyl orthosilicate.
Preferably, the volume ratio of silicate to water is (0.5-0.7):1, such as 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, such as 6:1, 6.5:1, 7:1, 7.5:1 or 8:1, etc.
Preferably, the base comprises ammonia.
Preferably, the mixing reaction is carried out at a temperature of 15 to 35 ℃, e.g., 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃ and the like, for a time of 0.5 to 2 hours, e.g., 0.5 hour, 0.8 hour, 1 hour, 1.2 hour, 1.5 hour or 2 hours and the like.
Other specific point values within the above numerical range can be selected, and are not described in detail herein.
And (2) after the step (1) is finished, carrying out solid-liquid separation, and washing and drying the solid.
Preferably, the step (2) comprises the following steps: mixing the solid silica nanospheres, a surfactant, alkali, water and ethanol, and then adding silicate ester and a silane coupling agent with terminal amino groups for reaction to obtain the double-layer silica nanoparticles with surface modified amino groups.
Preferably, the surfactant comprises cetyltrimethylammonium bromide.
Preferably, the base comprises 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, such as 0.01:1, 0.02:1, 0.025:1, 0.03:1, 0.035:1, or 0.04:1, and the like.
Preferably, the volume ratio of the base to the ethanol is (0.01-0.05):1, such as 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 mixing is carried out at a temperature of 15-35 deg.C, such as 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C or 35 deg.C, and for a time of 0.5-1h, such as 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 volume ratio of total volume to the water of (0.005-0.01):1, e.g., 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 reaction is carried out at a temperature of 15-35 deg.C, such as 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C or 35 deg.C, and for a time of 6-10h, such as 6h, 7h, 8h, 9h or 10 h.
Other specific point values within the above numerical range can be selected, and are not described in detail herein.
And (3) after the step (2) is finished, carrying out solid-liquid separation, and washing and drying the solid.
Preferably, the step (3) comprises the following steps: mixing the double-layer silicon dioxide nano particles with the surface modified with amino groups with an alkaline solution for reaction to obtain the hollow mesoporous silicon dioxide nano particles with the surface modified with amino groups.
Preferably, the alkali solution comprises an aqueous solution of sodium carbonate.
Preferably, the reaction is carried out at a temperature of 60-72 deg.C, such as 60 deg.C, 62 deg.C, 65 deg.C, 67 deg.C, 70 deg.C or 72 deg.C, and for a period of 8-12h, such as 8h, 9h, 10h, 11h or 12 h.
Other specific point values within the above numerical range can be selected, and are not described in detail herein.
Preferably, the surfactant remaining 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 a solvent and an acid for reaction, carrying out solid-liquid separation, and drying to obtain the catalyst.
Preferably, the solvent comprises ethanol.
Preferably, the acid comprises hydrochloric acid at a concentration of 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, such as 0.01:1, 0.02:1, 0.03:1, 0.04:1, or 0.05:1, and the like.
Preferably, the reaction is carried out under reflux conditions for a reaction time of 12 to 48h, e.g., 12h, 15h, 20h, 24h, 36h, 42h, or 48h, etc.
Other specific point values within the above numerical range can be selected, and are not described in detail herein.
And (4) after the step (3) is finished, carrying out solid-liquid separation, and washing and drying the solid.
Preferably, the mass ratio of the cyanuric chloride to the hollow mesoporous silica nanoparticles with amino groups modified on the surface in the step (4) is (2-5) to 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 group hollow mesoporous silica nanoparticles to the solvent is (10-50):1mg/mL, such as 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, or the like.
Preferably, the reaction of step (4) is carried out under catalysis of a catalyst comprising N, N-diisopropylethylamine.
Preferably, the reaction in step (4) is carried out at-10-0 ℃, such as-10 ℃, -8 ℃, -5 ℃, -3 ℃ or 0 ℃ and the like, for 12-24h, such as 12h, 15h, 17h, 20h, 22h, 23h or 24h and the like.
Other specific point values within the above numerical range can be selected, and are not described in detail herein.
And (4) after the step (4) is finished, carrying out solid-liquid separation, and washing and drying the solid.
In the present invention, the solid-liquid separation method used in steps (1) to (5) is preferably centrifugal separation, 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 ester, ethanol, water and alkali at 15-35 deg.C, and reacting for 0.5-2h to obtain solid silicon dioxide nanospheres; the volume ratio of the silicate ester to the water is (0.5-0.7) to 1; the volume ratio of the ethanol to the water is (6-8) to 1;
(2) mixing solid silicon dioxide nanospheres, a surfactant, alkali, water and ethanol at 15-35 ℃ for 0.5-1h, adding silicate ester and a silane coupling agent with terminal amino under stirring, and reacting at 15-35 ℃ for 6-10h to obtain double-layer silicon dioxide nanoparticles with surface modified amino; the mass-volume ratio of the surfactant to the water is (3-6) to 1 mg/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) to 1; the volume ratio of the total volume of the silicate and the silane coupling agent having a terminal amino group to the water is (0.005-0.01): 1;
(3) mixing and reacting the double-layer silica nanoparticles with the surface modified amino groups with an alkali solution at 60-72 ℃ for 8-12h to obtain hollow mesoporous silica nanoparticles with the surface modified amino groups; then mixing the mixed solution with a solvent and an acid, reacting for 12-48h under the reflux condition, carrying out solid-liquid separation, and drying to obtain the product; the mass-volume ratio of the hollow mesoporous silica nanoparticles with the surface modified amino groups to the solvent is (10-20):1 mg/mL; the volume ratio of the acid to the solvent is (0.01-0.05): 1;
(4) carrying out mixed reaction on cyanuric chloride and the hollow mesoporous silica nanoparticles with the surface modified with amino groups obtained in the step (3) for 12-24h at the temperature of-10-0 ℃ under the catalysis of a catalyst in a solvent to obtain the s-triazine modified hollow mesoporous silica; the mass ratio of the cyanuric chloride to the hollow mesoporous silica nanoparticles with the surface modified amino groups is (2-5) to 1; the mass-volume ratio of the hollow mesoporous silica nanoparticles with the surface modified amino groups to the solvent is (10-50):1 mg/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 invention provides an s-triazinyl-modified mesoporous hollow silica nano-perfume, which comprises the above-mentioned s-triazinyl-modified mesoporous hollow silica and a perfume coated therein.
When the s-triazinyl modified mesoporous hollow silica is used as a carrier to load the spice, the problems of instability, volatility and over-quick spice release are solved, the loading rate of the spice is high, the fragrance is uniformly and slowly released, the fragrance retaining time is long, more importantly, the nano-triazinyl modified mesoporous hollow silica can be covalently combined with chemical groups on the surfaces of base materials such as silk, leather and leather, the fragrance attaching efficiency of the nano-spice is improved, the nano-triazinyl modified mesoporous hollow silica is not easy to fall off, and the nano-triazinyl modified mesoporous hollow silica is favorable for long-term use. And the nano perfume is convenient to use, has a simple preparation method, and can be widely applied to various fields of daily use chemicals, textiles, leather and the like. According to the invention, through accurate self-assembly, the perfume is subjected to nanocrystallization, the perfume loading rate is increased, chemical active groups are endowed to the perfume, the loading between the nano perfume and the base material is increased through a chemical bond combination mode, and the volatility of the perfume is improved.
In a fourth aspect, the present invention provides a preparation method of the s-triazinyl-modified mesoporous hollow silica nano-perfume, wherein the preparation method comprises: mixing the s-triazinyl modified mesoporous hollow silica with a perfume solution, and performing solid-liquid separation and drying after soaking to obtain the s-triazinyl modified mesoporous hollow silica nano perfume.
Preferably, the perfume solution has a mass concentration of 80-99%, such as 80%, 82%, 85%, 88%, 90%, 95%, or 99%, etc.
Preferably, the soaking time is not less than 24h, such as 24h, 28h, 30h, 32h, 36h, 40h or 42h and the like.
Other specific point values within the above numerical range can be selected, and are not described in detail herein.
Compared with the prior art, the invention has the following beneficial effects:
the invention creatively designs and prepares the s-triazine modified hollow mesoporous silica carrier, the material storage capacity of the carrier is improved due to the hollow interior of the hollow silica carrier, the time for releasing a stored material from the interior to the outside can be prolonged due to the existence of the surface mesoporous of the silica, and due to the existence of the surface active group s-triazine, the hollow mesoporous silica carrier can be covalently combined with chemical groups on the surfaces of substrates such as silk, leather and leather, the attachment efficiency of the hollow mesoporous silica carrier is improved, the hollow mesoporous silica carrier is not easy to fall off, and the hollow mesoporous silica carrier is favorable for long-term use.
When the s-triazinyl modified mesoporous hollow silica is used as a carrier to load the spice, the problems of instability, volatility and over-quick spice release are solved, the loading rate of the spice is high, the fragrance is uniformly and slowly released, the fragrance retaining time is long, more importantly, the nano-triazinyl modified mesoporous hollow silica can be covalently combined with chemical groups on the surfaces of base materials such as silk, leather and leather, the fragrance attaching efficiency of the nano-spice is improved, the nano-triazinyl modified mesoporous hollow silica is not easy to fall off, and the nano-triazinyl modified mesoporous hollow silica is favorable for long-term use. And the nano perfume is convenient to use, has a simple preparation method, and can be widely applied to various fields of daily use chemicals, textiles, leather and the like.
According to the invention, through accurate self-assembly, the perfume is subjected to nanocrystallization, the perfume loading rate is increased, chemical active groups are endowed to the perfume, the loading between the nano perfume and the base material is increased 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 the surface-modified amino group-containing double-layered 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 solid silica nanospheres prepared in example 2;
FIG. 5 is a TEM image of the surface-modified amino double-layered 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 double-layered 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 a blank leather used in application example 1;
FIG. 11 is an SEM image of a blank leather used in application example 1 loaded with a hollow mesoporous silica having no s-triazinyl modifying group;
fig. 12 is an SEM image of a blank leather used in application example 1 carrying a hollow mesoporous silica having an s-triazinyl modifying group;
fig. 13 is an SEM image of a blank leather used in application example 2;
fig. 14 is an SEM image of a blank leather used in application example 2 loaded with hollow mesoporous silica without s-triazinyl modifying group;
FIG. 15 is an SEM image of a blank leather used in application example 2 carrying a hollow mesoporous silica having an s-triazinyl modifying group;
FIG. 16 is SEM pictures of the control group and the group of example 3 in application example 3 after stirring in water for 2 days;
FIG. 17 is an SEM photograph of a control group and example 3 group in application example 3 after stirring in water for 4 days;
fig. 18 is SEM images of the control group and the example 3 group in application example 3 after stirring in water for 6 days.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an s-triazinyl modified hollow mesoporous silica nano perfume, and the preparation method comprises the following steps:
(1) preparation of solid silica nanospheres: 74mL of ethanol, 10mL of water and 3.15mL of ammonia water are mixed and stirred for 5min,rapidly adding 6mL of ethyl orthosilicate, stirring vigorously at 25 deg.C for 2h, filtering, washing the product with water and ethanol three times, and vacuum drying for 12h to obtain solid silicon dioxide nanospheres (sSiO)2) (ii) a Solid silicon dioxide nanosphere (sSiO) prepared by transmission electron microscope2) The characterization is carried out, and the result is shown in figure 1;
(2) preparing double-layer silicon dioxide nano particles with amino groups modified on the surfaces: 300mg of sSiO2Dissolving in 50mL of water, performing ultrasonic treatment for 20min to uniformly disperse the mixture, adding the mixture into a solution containing 400mg of hexadecyl trimethyl ammonium bromide, 75mL of water, 75mL of ethanol and 1.375mL of ammonia water, vigorously stirring for 1h, rapidly adding 125 mu L N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and 600 mu L of ethyl orthosilicate, continuously stirring for 6h at 25 ℃, separating solid from liquid of a product after the reaction is finished, and performing vacuum drying for 12h to obtain double-layer silicon dioxide nanoparticles (sSiO) with surface modified amino groups2@mSiO2) (ii) a The prepared sSiO is subjected to transmission electron microscopy2@mSiO2The characterization was carried out, and the results are shown in fig. 2;
(3) the preparation of the hollow mesoporous silica nanoparticle with the surface modified with amino comprises the following steps: 60mg of sSiO are weighed2@mSiO2Adding into 10mL of 0.3M sodium carbonate aqueous solution, carrying out ultrasonic treatment for 15min, etching at 70 ℃ for 12h, centrifuging, washing the product with ethanol and water three times, and carrying out vacuum drying overnight. Removing residual surfactant by an extraction method: adding 1g of a product collected in the first reaction into 100mL of ethanol solution, adding 1mL of hydrochloric acid, refluxing for 12h at 75 ℃, extracting for three times, centrifuging, washing for three times by using ethanol and ultrapure water respectively, and drying for 12h in vacuum to obtain the hollow mesoporous silica nanoparticles with amino-modified surfaces;
(4) preparation of s-triazinyl modified hollow mesoporous silica: mixing 100mg of the hollow mesoporous silica nanoparticles with the surface modified amino group obtained in the step (3), 500mg of cyanuric chloride and 10mL of tetrahydrofuran, adding 500 mu L N of N-diisopropylethylamine, stirring at 0 ℃ for reaction for 24 hours, then carrying out centrifugal separation, thoroughly washing the product with dichloromethane, acetone, methanol and dichloromethane in sequence, and carrying out vacuum drying to obtain the hollow mesoporous silica nanoparticles with the surface modified amino group; the prepared triazine-modified hollow mesoporous silica nanoparticles are characterized by a transmission electron microscope, and the result is shown in figure 3, wherein the particle size of the obtained product is about 200 nm;
(5) preparation of s-triazinyl modified hollow mesoporous silica nano perfume: and (3) mixing the 100mg of the hollow mesoporous silica nano particles modified by the triazine group obtained in the step (4) with 10mL of 90% linalool solution, stirring, soaking for 24 hours, centrifuging, separating and drying in vacuum to obtain the hollow mesoporous silica nano perfume modified by the triazine group.
Example 2
The embodiment provides an s-triazinyl modified hollow mesoporous silica nano perfume, and the preparation method comprises the following steps:
(1) preparation of solid silica nanospheres: mixing 60mL of ethanol, 10mL of water and 3.15mL of ammonia water, stirring for 5min, rapidly adding 5mL of ethyl orthosilicate, stirring vigorously at 30 ℃ for 1h, filtering, washing the product with water and ethanol three times, and drying in vacuum for 12h to obtain solid silicon dioxide nanospheres (sSiO)2) (ii) a Solid silicon dioxide nanosphere (sSiO) prepared by transmission electron microscope2) The characterization was performed, and the results are shown in fig. 4;
(2) preparing double-layer silicon dioxide nano particles with amino groups modified on the surfaces: 300mg of sSiO2Dissolving in 50mL of water, performing ultrasonic treatment for 20min to uniformly disperse the mixture, adding the mixture into a solution containing 400mg of hexadecyl trimethyl ammonium bromide, 75mL of water, 75mL of ethanol and 1.375mL of ammonia water, violently stirring for 0.5h, quickly adding 125 mu L N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane and 600 mu L of ethyl orthosilicate, continuously stirring for 9h at the temperature of 20 ℃, performing solid-liquid separation on a product after the reaction is finished, and performing vacuum drying for 12h to obtain double-layer silicon dioxide nanoparticles (sSiO) with surface modified amino groups2@mSiO2) (ii) a The prepared sSiO is subjected to transmission electron microscopy2@mSiO2The characterization was performed, and the results are shown in fig. 5;
(3) the preparation of the hollow mesoporous silica nanoparticle with the surface modified with amino comprises the following steps: 60mg of sSiO are weighed2@mSiO2Adding into 10mL 0.3M sodium carbonate aqueous solution, ultrasonic treating for 15min, etching at 72 deg.C for 8h, centrifuging, washing the product with ethanol and water three times, vacuum drying overnight. Removing residual surfactant by an extraction method: adding 2g of a product collected in the first reaction into 100mL of ethanol solution, adding 5mL of hydrochloric acid, refluxing for 24h at 75 ℃, extracting for three times, centrifuging, washing for three times by using ethanol and ultrapure water respectively, and drying for 12h in vacuum to obtain the hollow mesoporous silica nanoparticles with amino-modified surfaces;
(4) preparation of s-triazinyl modified hollow mesoporous silica: mixing 100mg of the hollow mesoporous silica nanoparticles with the amino-modified surface obtained in the step (3), 300mg of cyanuric chloride and 5mL of tetrahydrofuran, adding 500 mu L N of N-diisopropylethylamine, stirring at-5 ℃ for reaction for 24h, then carrying out centrifugal separation, thoroughly washing the product with dichloromethane, acetone, methanol and dichloromethane in sequence, and carrying out vacuum drying to obtain the hollow mesoporous silica nanoparticles with the triazinyl-modified surface; the prepared triazine-modified hollow mesoporous silica nanoparticles are characterized by a transmission electron microscope, and the result is shown in FIG. 6;
(5) preparation of s-triazinyl modified hollow mesoporous silica nano perfume: and (3) mixing the 200mg of the triazine-modified hollow mesoporous silica nano particles obtained in the step (4) with 20mL of 90% linalool solution, stirring, soaking for 24 hours, performing centrifugal separation, and performing vacuum drying to obtain the s-triazine-modified hollow mesoporous silica nano perfume.
Example 3
The embodiment provides an s-triazinyl modified hollow mesoporous silica nano perfume, and the preparation method comprises the following steps:
(1) preparation of solid silica nanospheres: mixing 80mL of ethanol, 10mL of water and 3.15mL of ammonia water, stirring for 5min, rapidly adding 7mL of ethyl orthosilicate, stirring vigorously at 35 ℃ for 0.5h, filtering, washing the product with water and ethanol three times, and drying in vacuum for 12h to obtain solid silicon dioxide nanospheres (sSiO)2) (ii) a Solid silicon dioxide nanosphere (sSiO) prepared by transmission electron microscope2) The characterization was performed, and the results are shown in fig. 7;
(2) preparing double-layer silicon dioxide nano particles with amino groups modified on the surfaces: 300mg of sSiO2Dissolving in 50mL water, dispersing uniformly by ultrasonic treatment for 20min, adding into a solution containing 400mgCetyl trimethyl ammonium bromide, 75mL water, 75mL ethanol and 1.375mL ammonia water, vigorously stirring for 0.5h, rapidly adding 125 mu L N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane and 600 mu L ethyl orthosilicate, continuously stirring for 7h at 30 ℃, separating solid and liquid of the product after the reaction is finished, and vacuum drying for 12h to obtain the double-layer silicon dioxide nano particle (sSiO) with surface modified amino2@mSiO2) (ii) a The prepared sSiO is subjected to transmission electron microscopy2@mSiO2The characterization was performed, and the results are shown in fig. 8;
(3) the preparation of the hollow mesoporous silica nanoparticle with the surface modified with amino comprises the following steps: 60mg of sSiO are weighed2@mSiO2Adding into 10mL of 0.3M sodium carbonate aqueous solution, carrying out ultrasonic treatment for 15min, etching at 65 ℃ for 12h, centrifuging, washing the product with ethanol and water three times, and carrying out vacuum drying overnight. Removing residual surfactant by an extraction method: adding 2g of a product collected in the first reaction into 100mL of ethanol solution, adding 5mL of hydrochloric acid, refluxing for 24h at 75 ℃, extracting for three times, centrifuging, washing for three times by using ethanol and ultrapure water respectively, and drying for 12h in vacuum to obtain the surface-modified amino hollow mesoporous silica nanoparticles;
(4) preparation of s-triazinyl modified hollow mesoporous silica: mixing 100mg of the hollow mesoporous silica nanoparticles with the amino-modified surface obtained in the step (3), 200mg of cyanuric chloride and 3mL of tetrahydrofuran, adding 500 mu L N of N-diisopropylethylamine, stirring at-10 ℃ for reaction for 24h, then carrying out centrifugal separation, thoroughly washing the product with dichloromethane, acetone, methanol and dichloromethane in sequence, and carrying out vacuum drying to obtain the hollow mesoporous silica nanoparticles with the triazinyl-modified surface; the prepared triazine-modified hollow mesoporous silica nanoparticles are characterized by a transmission electron microscope, and the result is shown in fig. 9;
(5) preparation of s-triazinyl modified hollow mesoporous silica nano perfume: and (5) mixing the 200mg of triazine-modified hollow mesoporous silica nano particles obtained in the step (4) with 20mL of 90% linalool solution, stirring, soaking for 24 hours, performing centrifugal separation, and performing vacuum drying to obtain the s-triazine-modified hollow mesoporous silica nano perfume.
Application example 1
A sample of leather (25 cm)2) The solution was immersed in the s-triazinyl-modified hollow mesoporous silica nano-perfume solution prepared in example 1 and stirred at 25 ℃ for 12 hours, wherein the stirring speed was 1200 rpm. And the concentration of linalool is 1 mg/mL. The leather was then placed in an oven and dried at 40 ℃ for 1 h. The results of observing the adsorption effect of the perfume by a transmission electron microscope using leather soaked with the perfume solution as a blank control group and the hollow mesoporous silica nano perfume solution soaked in the unmodified s-triazine group as a control group (the preparation is different from that of example 1 only in that step (4) is omitted), are shown in fig. 10-12 (fig. 10 is a blank control group, fig. 11 is a control group, and fig. 12 is an example 1 group), and it can be seen that: compared with leather adsorption of blank leather and nano particles without surface modification, the leather adsorption effect of the s-triazine-based nano perfume modified on the surface is very obvious, and the hollow mesoporous silica nano perfume modified on the s-triazine-based nano perfume prepared in the example 1 is proved to be capable of being covalently combined with a chemical group on the surface of a leather base material due to the existence of the s-triazine group as a surface active group, so that the fragrance attaching efficiency of the nano perfume is greatly improved, the nano perfume is not easy to fall off, and the long-term use is facilitated.
Application example 2
A sample of leather (25 cm)2) The solution was immersed in the s-triazinyl-modified hollow mesoporous silica nano-perfume solution prepared in example 2 and stirred at 25 ℃ for 12 hours, wherein the stirring speed was 1200 rpm. And the concentration of linalool is 1 mg/mL. The leather was then placed in an oven and dried at 40 ℃ for 1 h. Using leather soaked with perfume solution as a blank control group, using hollow mesoporous silica nano perfume solution soaked in unmodified s-triazine group as a control group (the preparation difference from example 2 is only that step (4) is omitted), observing the adsorption effect of perfume by using a transmission electron microscope, and as a result, as shown in fig. 13-15 (fig. 13 is a blank control group, fig. 14 is a control group, and fig. 15 is an example 2 group), it can be seen that: compared with leather adsorption of blank leather and leather adsorption of nano particles with unmodified surfaces, the leather adsorption effect of the s-triazine-based nano perfume modified on the surfaces is very obvious, and the result shows that the hollow mesoporous silica nano perfume modified on the s-triazine groups prepared in example 2 can be obtained due to the existence of the s-triazine groups as surface active groupsCovalently combined with chemical groups on the surface of the leather substrate, greatly improves the fragrance attaching efficiency of the nano perfume, is not easy to fall off, and is beneficial to long-term use.
Application example 3
A sample of leather (25 cm)2) The solution was immersed in the s-triazinyl-modified hollow mesoporous silica nano-perfume solution prepared in example 2 and stirred at 25 ℃ for 12 hours, wherein the stirring speed was 1200 rpm. And the concentration of linalool is 1 mg/mL. The leather was then placed in an oven and dried at 40 ℃ for 1 h. Taking leather soaked with the perfume solution as a blank control group, taking a hollow mesoporous silica nano perfume solution soaked in an unmodified s-triazine group on the surface as a control group (the preparation difference from the example 3 is only that the step (4) is omitted), observing the adsorption effect of the perfume by using a transmission electron microscope, and then: compared with leather adsorption of blank leather and nano particles without surface modification, the leather adsorption effect of the s-triazine-based nano perfume modified on the surface is very obvious, and the hollow mesoporous silica nano perfume modified on the s-triazine-based nano perfume prepared in the example 3 is proved to be capable of being covalently combined with a chemical group on the surface of a leather base material due to the existence of the s-triazine group as a surface active group, so that the fragrance attaching efficiency of the nano perfume is greatly improved, the nano perfume is not easy to fall off, and the long-term use is facilitated.
And (3) putting the leather sample dried by the attached incense into a beaker filled with water, continuously stirring, taking out one leather sample every two days (2 days, 4 days and 6 days), drying, and performing SEM characterization. The hollow mesoporous silica nano perfume solution with unmodified s-triazine group soaked in the solution is taken as a control group. The results are shown in fig. 16-18 (fig. 16 is a 2-day characterization result, fig. 17 is a 4-day characterization result, and fig. 18 is a 6-day characterization result), and the results show that the s-triazine-based modified hollow mesoporous silica provided by the invention significantly improves the adhesion fastness of the nano perfume on leather.
The applicant states that the present invention is illustrated by the above examples to show an s-triazinyl modified hollow mesoporous silica, and a preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention is implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. A preparation method of s-triazinyl modified hollow mesoporous silica is characterized by comprising the following steps:
(1) preparing solid silicon dioxide nanospheres by a stober method;
(2) modifying a layer of mesoporous silica shell on the surface of the solid silica nanosphere obtained in the step (1) by using a sol-gel method by taking a silane coupling agent with terminal amino as the silane coupling agent to obtain double-layer silica nanoparticles with surface modified amino;
(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) and (4) carrying out mixing reaction on cyanuric chloride and the hollow mesoporous silica nanoparticles with the surface modified amino groups obtained in the step (3) to obtain the s-triazinyl modified hollow mesoporous silica.
2. The preparation method of s-triazinyl-modified mesoporous hollow silica according to claim 1, wherein the specific method in step (1) comprises: mixing silicate ester, ethanol, water and alkali for reaction to obtain solid silicon dioxide nanospheres;
preferably, the silicate comprises ethyl orthosilicate;
preferably, the volume ratio of silicate to water is (0.5-0.7): 1;
preferably, the volume ratio of the ethanol to the water is (6-8) to 1;
preferably, the base comprises aqueous ammonia;
preferably, the temperature of the mixing reaction is 15-35 ℃ and the time is 0.5-2 h.
3. The preparation method of s-triazinyl-modified mesoporous hollow silica according to claim 1 or 2, wherein the specific method in step (2) comprises: mixing solid silica nanospheres, a surfactant, alkali, water and ethanol, and then adding silicate ester 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) to 1 mg/mL;
preferably, the volume ratio of the base to the water is (0.01-0.04): 1;
preferably, the volume ratio of the base to the ethanol is (0.01-0.05): 1;
preferably, the mixing temperature is 15-35 ℃ and the mixing time is 0.5-1 h;
preferably, the silicate and the silane coupling agent having a terminal amino group are added with stirring, and the volume ratio of the total volume to the water is (0.005-0.01): 1;
preferably, the reaction temperature is 15-35 ℃ and the reaction time is 6-10 h.
4. The method for preparing s-triazinyl-modified mesoporous hollow silica according to any one of claims 1 to 3, wherein the specific method in step (3) comprises: mixing and reacting the double-layer silica nanoparticles with the surface modified with amino groups with an alkaline solution to obtain hollow mesoporous silica nanoparticles with the surface modified with amino groups;
preferably, the alkali solution comprises an aqueous sodium carbonate solution;
preferably, the reaction temperature is 60-72 ℃ and the reaction time is 8-12 h.
5. The method for preparing s-triazinyl-modified mesoporous hollow silica according to claim 4, wherein the surfactant remaining on the surface of the product is removed after the reaction in step (3) is finished, and the removal method is an extraction method;
preferably, the extraction method comprises: mixing the product with a solvent and an acid for reaction, carrying out solid-liquid separation, and drying to obtain the product;
preferably, the solvent comprises ethanol;
preferably, the acid comprises hydrochloric acid, the concentration of which is 0.8-4%;
preferably, the mass-to-volume ratio of the product to the solvent is (10-20):1 mg/mL;
preferably, the volume ratio of the acid to the solvent is (0.01-0.05): 1;
preferably, the reaction is carried out under reflux conditions for a reaction time of 12 to 48 h.
6. The preparation method of s-triazinyl-modified mesoporous hollow silica according to any one of claims 1 to 5, wherein the mass ratio of the cyanuric chloride to the surface-modified amino group hollow mesoporous silica nanoparticles in step (4) is (2-5): 1;
preferably, the reaction of step (4) is carried out in a solvent comprising tetrahydrofuran;
preferably, the mass-volume ratio of the hollow mesoporous silica nanoparticles with the surface modified amino groups to the solvent is (10-50):1 mg/mL;
preferably, the reaction of step (4) is carried out under catalysis of a catalyst comprising N, N-diisopropylethylamine;
preferably, the reaction temperature in the step (4) is-10-0 ℃ and the reaction time is 12-24 h.
7. The preparation method of the s-triazinyl-modified mesoporous hollow silica according to any one of claims 1 to 6, comprising the following steps:
(1) mixing silicate ester, ethanol, water and alkali at 15-35 deg.C, and reacting for 0.5-2h to obtain solid silicon dioxide nanospheres; the volume ratio of the silicate ester to the water is (0.5-0.7) to 1; the volume ratio of the ethanol to the water is (6-8) to 1;
(2) mixing solid silica nanospheres, a surfactant, alkali, water and ethanol at 15-35 ℃ for 0.5-1h, then adding silicate ester and a silane coupling agent with terminal amino under stirring, and reacting at 15-35 ℃ for 6-10h to obtain surface-modified amino double-layer silica nanoparticles; the mass-volume ratio of the surfactant to the water is (3-6) to 1 mg/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) to 1; the volume ratio of the total volume of the silicate and the silane coupling agent with the terminal amino group to the water is (0.005-0.01): 1;
(3) mixing and reacting the double-layer silica nanoparticles with the surface modified amino groups with an alkali solution at 60-72 ℃ for 8-12h to obtain hollow mesoporous silica nanoparticles with the surface modified amino groups; then mixing the mixed solution with a solvent and an acid, reacting for 12-48h under the reflux condition, carrying out solid-liquid separation, and drying to obtain the product; the mass-volume ratio of the hollow mesoporous silica nanoparticles with the surface modified amino groups to the solvent is (10-20):1 mg/mL; the volume ratio of the acid to the solvent is (0.01-0.05): 1;
(4) carrying out mixed reaction on cyanuric chloride and the hollow mesoporous silica nanoparticles with the surface modified with amino groups obtained in the step (3) for 12-24h at the temperature of-10-0 ℃ under the catalysis of a catalyst in a solvent to obtain the s-triazine modified hollow mesoporous silica; the mass ratio of the cyanuric chloride to the hollow mesoporous silica nanoparticles with the surface modified amino groups is (2-5) to 1; the mass-volume ratio of the hollow mesoporous silica nanoparticles with the surface modified amino groups to the solvent is (10-50):1 mg/mL.
8. The s-triazinyl-modified mesoporous hollow silica prepared by the method according to any one of claims 1 to 7.
9. An s-triazinyl-modified mesoporous hollow silica nano-perfume, characterized in that the s-triazinyl-modified mesoporous hollow silica nano-perfume comprises the s-triazinyl-modified mesoporous hollow silica according to claim 8 and a perfume coated therein.
10. The method for preparing the s-triazinyl-modified mesoporous hollow silica nanoforescent according to claim 9, comprising: mixing the s-triazinyl modified mesoporous hollow silica with a perfume solution, and performing solid-liquid separation and drying after soaking to obtain the s-triazinyl modified mesoporous hollow silica nano perfume;
preferably, the mass concentration of the perfume solution is 80-99%;
preferably, the soaking time is not less than 24 h.
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