S-triazinyl modified silicon oxide microspheres as well as preparation method and application thereof

Abstract

The invention relates to s-triazinyl modified silicon oxide microspheres and a preparation method and application thereof.The preparation method of the s-triazinyl modified silicon oxide microspheres comprises the following steps that a silane coupling agent with the tail end containing amino is subjected to a hydrolysis reaction, and silanol with the tail end containing amino is obtained; the preparation method comprises the following steps: carrying out condensation reaction on silanol containing amino at the tail end and 2, 4, 6-trihalo-1, 3, 5-triazine to obtain a reaction solution; and providing a dispersion liquid containing the silicon oxide microspheres, adding the reaction liquid and a silicate ester solution into the dispersion liquid, and carrying out a coating reaction to obtain the s-triazinyl modified silicon oxide microspheres after the reaction is finished. According to the preparation method of the s-triazinyl modified silicon oxide microspheres, s-triazinyl is introduced into amino-containing silanol in advance, then the silicon oxide microspheres are coated, and the reaction of a two-phase system is avoided, so that the reaction conditions are mild, and the preparation cost is controllable.

Description

Technical Field

[0001] The invention relates to the technical field of inorganic materials, in particular to s-triazine-modified silicon oxide microspheres and a preparation method and application thereof. Background Art

[0002] As aromatic smells are gradually admired, spices have been widely used in the fields of cosmetics, silk, leather, and wallpaper. However, spices are mainly volatile small molecule compounds with unstable and volatile components. Silica microspheres modified with s-triazine groups can solve the problems of unstable, volatile, and too fast release of spices. Therefore, they are widely used in the field of spice loading. Traditional s-triazine group-modified silica microspheres are obtained by substitution reaction of hollow mesoporous silica nanoparticles with amino groups on the surface with cyanuric chloride. However, the substitution reaction conditions are relatively harsh and require the use of organic solvents such as tetrahydrofuran and N,N-diisopropylethylamine, which makes the subsequent separation and washing process cumbersome and increases the preparation cost. Summary of the invention

[0003] Based on this, it is necessary to provide a triazine-modified silica microsphere and a preparation method and application thereof to address the above problems. The preparation method of the triazine-modified silica microsphere introduces the triazine group into the amino-containing silanol in advance, and then coats the silica microsphere, thereby avoiding the reaction of the two-phase system. Therefore, the reaction conditions are mild and the preparation cost is controllable.

[0004] The present invention discloses a method for preparing triazine-modified silica microspheres, comprising the following steps:

[0005] The silane coupling agent containing an amino group at the end is subjected to a hydrolysis reaction to obtain a silanol containing an amino group at the end;

[0006] Carrying out a condensation reaction between the silanol containing an amino group at the end and 2,4,6-trihalogenated-1,3,5-triazine to obtain a reaction solution;

[0007] A dispersion liquid containing silicon oxide microspheres is provided, and the reaction liquid and a silicate solution are added to the dispersion liquid to carry out a coating reaction, and after the reaction is completed, triazine-modified silicon oxide microspheres are obtained.

[0008] In one embodiment, the silane coupling agent having an amino group at the end includes at least one of aminopropyltrimethoxysilane or aminopropyltriethoxysilane.

[0009] In one embodiment, the step of hydrolyzing the silane coupling agent containing an amino group at the end satisfies at least one of the following conditions:

[0010] (1) The hydrolysis reaction is carried out under acidic conditions;

[0011] (2) The temperature of the hydrolysis reaction is 15°C-60°C;

[0012] (3) The hydrolysis reaction time is 1h-24h.

[0013] In one embodiment, the step of condensing the amino-terminated silanol with 2,4,6-trihalogenated-1,3,5-triazine satisfies at least one of the following conditions:

[0014] (1) The molar ratio of the silanol containing an amino group at the end to the 2,4,6-trihalogenated-1,3,5-triazine is 1:1-3:1;

[0015] (2) The 2,4,6-trihalogenated-1,3,5-triazine comprises at least one of cyanuric fluoride and cyanuric chloride.

[0016] (3) The temperature of the condensation reaction is 15°C-90°C;

[0017] (4) The condensation reaction time is 1h-3h;

[0018] (5) The condensation reaction is carried out under acidic conditions. After the condensation reaction is completed, the pH of the reaction solution of the condensation reaction is adjusted to 6.0-8.0.

[0019] In one embodiment, the dispersion liquid including silica microspheres includes silica microspheres, alkali, water, alcohol compounds and surfactants.

[0020] In one embodiment, the dispersion comprising silica microspheres satisfies at least one of the following conditions:

[0021] (1) The surfactant comprises at least one of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide or polyvinylpyrrolidone;

[0022] (2) The concentration of the surfactant in the dispersion is 0.1 g / L-50 g / L;

[0023] (3) The volume ratio of the alcohol compound to water is 0.5:1-5:1.

[0024] In one embodiment, the step of adding the reaction solution and the silicate solution to the dispersion to perform a coating reaction satisfies at least one of the following conditions:

[0025] (1) The silicate comprises at least one of ethyl orthosilicate or methyl orthosilicate;

[0026] (2) the molar ratio of the condensation product to the silicate in the reaction solution is 1:1-20:1;

[0027] (3) The mass ratio of the condensation product in the reaction solution to the silica microspheres in the dispersion solution is 1:1-1:10.

[0028] In one embodiment, the coating reaction temperature is 15°C-60°C, and the time is 5h-10h.

[0029] A s-triazine-modified silica microsphere is prepared by the above-mentioned preparation method of s-triazine-modified silica microsphere. The s-triazine-modified silica microsphere comprises a silica core and a silica shell layer, and the silica shell layer comprises s-triazine groups.

[0030] A use of the s-triazine-modified silica microspheres as described above for loading functional drugs in natural textiles or in preparing perfumes.

[0031] The preparation method of s-triazine group-modified silica microspheres provided by the present invention first introduces s-triazine group into silanol containing amino group at the end through condensation reaction, and then coats the silica microspheres by adding reaction liquid of condensation reaction and silicate solution simultaneously into dispersion liquid containing silica microspheres, so that s-triazine group is coated on the surface of silica microspheres. Since the s-triazine group is not directly grafted on the surface of silica microspheres, that is, the reaction of two-phase system is avoided, the condensation reaction and the coating reaction can be carried out under mild conditions. The preparation method of s-triazine group-modified silica microspheres provided by the present invention has mild reaction conditions and controllable preparation cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0033] Figure 1 This is a SEM image of the s-triazine-modified silica microspheres prepared in Example 1;

[0034] Figure 2 This is a SEM image of the s-triazine-modified silica microspheres prepared in Example 2;

[0035] Figure 3 This is the SEM image of the s-triazine-modified silica microspheres prepared in Example 3. DETAILED DESCRIPTION

[0036] For ease of understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific implementation methods or embodiments, and are not intended to limit the present invention. The optional scope of the term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of related listed items, and the combinations include any two related listed items, any more related listed items, or all related listed items.

[0038] In the present invention, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0039] The present invention provides a method for preparing triazine-modified silica microspheres, comprising the following steps:

[0040] S10, hydrolyzing a silane coupling agent having an amino group at the end to obtain a silanol having an amino group at the end;

[0041] S20, condensing the silanol containing an amino group at the end with 2,4,6-trihalogenated-1,3,5-triazine to obtain a reaction solution;

[0042] S30, providing a dispersion liquid including silica microspheres, adding a reaction liquid and a silicate solution to the dispersion liquid for coating reaction, and obtaining triazine-modified silica microspheres after the reaction is completed.

[0043] The preparation method of s-triazine group-modified silica microspheres provided by the present invention first introduces s-triazine group into silanol containing amino group at the end through condensation reaction, and then coats the silica microspheres by adding reaction liquid of condensation reaction and silicate solution simultaneously into dispersion liquid containing silica microspheres, so that s-triazine group is coated on the surface of silica microspheres. Since the s-triazine group is not directly grafted on the surface of silica microspheres, that is, the reaction of two-phase system is avoided, the condensation reaction and the coating reaction can be carried out under mild conditions. The preparation method of s-triazine group-modified silica microspheres provided by the present invention has mild reaction conditions and controllable preparation cost.

[0044] In step S10, the silane coupling agent containing an amino group at the end is hydrolyzed to obtain a silanol containing an amino group at the end, and the amino group in the silanol containing an amino group at the end can undergo a substitution reaction with 2,4,6-trihalogenated-1,3,5-triazine, and the hydroxyl group in the silanol containing an amino group at the end can be coated on the surface of the silica microsphere together with the silicate; in one embodiment, the silane coupling agent containing an amino group at the end includes at least one of aminopropyltrimethoxysilane or aminopropyltriethoxysilane.

[0045] In order to enable the obtained silanol containing an amino group at the end to react better with 2,4,6-trihalo-1,3,5-triazine subsequently, in one embodiment, the hydrolysis reaction is carried out under acidic conditions, preferably, the hydrolysis reaction is carried out under pH 2.0-4.0, including but not limited to pH 2.0, pH 2.25, pH 2.5, pH 2.75, pH 3.0, pH 3.25, pH 3.5, pH 3.75 or pH 4.0.

[0046] In one embodiment, the temperature of the hydrolysis reaction is 15°C-60°C, including but not limited to 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C.

[0047] In one embodiment, the hydrolysis reaction time is 1 h-24 h, including but not limited to 1 h, 3.5 h, 6 h, 9 h, 12 h, 15 h, 18 h, 21 h or 24 h.

[0048] In step S20, the 2,4,6-trihalogenated-1,3,5-triazine includes at least one of cyanuric fluoride, cyanuric chloride, cyanuric bromide or cyanuric iodine. Preferably, the 2,4,6-trihalogenated-1,3,5-triazine includes at least one of cyanuric fluoride or cyanuric chloride.

[0049] In one embodiment, the molar ratio of the silanol containing an amino group at the end to the 2,4,6-trihalo-1,3,5-triazine is 1:1-3:1, including but not limited to 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3:1.

[0050] In one embodiment, the temperature of the condensation reaction is 15°C-90°C, including but not limited to 15°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C or 90°C.

[0051] In one embodiment, the condensation reaction time is 1 h-3 h, including but not limited to 1 h, 1.5 h, 2 h, 2.5 h or 3 h.

[0052] In one embodiment, the condensation reaction is carried out under acidic conditions, preferably, the condensation reaction is carried out under pH conditions of 2.0-4.0, including but not limited to pH 2.0, pH 2.5, pH 3.0, pH 3.5 or pH 4.0; at the same time, after the condensation reaction is completed, the pH of the reaction solution of the condensation reaction is adjusted to 6.0-8.0, including but not limited to adjusting the pH of the reaction solution of the condensation reaction to 6.0, 6.5, 7.0, 7.5 or 8.0.

[0053] In step S30, the silica microspheres can be purchased or prepared by a sol-gel method. When the silica microspheres are prepared by a sol-gel method, the preparation method includes the following steps: mixing an alcohol compound, water, and a base, and then adding a silicate to react to obtain a transparent sol system; the transparent sol system is sequentially gelled, dried, and calcined to obtain silica microspheres.

[0054] In one embodiment, the reaction temperature is 15°C-60°C, including but not limited to 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C.

[0055] In one embodiment, the process is carried out at a pH of 10.5-12.5, including but not limited to pH 10.5, pH 11, pH 11.5, pH 12 or pH 12.5.

[0056] In one embodiment, the silicate includes at least one of ethyl orthosilicate or methyl orthosilicate, and the mass fraction of the silicate in the reaction solution is 5.0%-20.0%.

[0057] In one embodiment, the alcohol compound is selected from at least one of ethanol or methanol, and the volume ratio of the alcohol compound to water is 1:1-5:1.

[0058] In one embodiment, the dispersion liquid including silica microspheres includes silica microspheres, alkali, water, alcohol compounds and surfactants.

[0059] The role of the surfactant is to provide positive charge on the surface of the silica microspheres. In one embodiment, the surfactant includes at least one of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide or polyvinylpyrrolidone; preferably, the concentration of the surfactant in the dispersion is 0.1g / L-50g / L, including but not limited to 0.1g / L, 5g / L, 10g / L, 15g / L, 20g / L, 25g / L, 30g / L, 35g / L, 40g / L, 45g / L or 50g / L.

[0060] In one embodiment, the silicate includes at least one of ethyl orthosilicate or methyl orthosilicate; preferably, the molar ratio of the condensation product to the silicate in the reaction solution is 1:1-20:1, including but not limited to 1:1, 2.5:1, 5:1, 7.5:1, 10:1, 12.5:1, 15:1, 17.5:1 or 20:1.

[0061] In one embodiment, the mass ratio of the condensation product in the reaction solution to the silica microspheres in the dispersion solution is 1:1-1:10, including but not limited to 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0062] In one embodiment, the volume ratio of the alcohol compound to water is 0.5:1-5:1, including but not limited to 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1.

[0063] In one embodiment, the reaction is carried out under alkaline conditions, preferably, the reaction is carried out under pH conditions of 10.5-12.5, including but not limited to pH 10.5, pH 11, pH 11.5, pH 12, and pH 12.5.

[0064] In one embodiment, the reaction temperature is 15°C-60°C, including but not limited to 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C.

[0065] In one embodiment, the time is 5 h-10 h, including but not limited to 5 h, 6 h, 7 h, 8 h, 9 h or 10 h.

[0066] The present invention also provides a s-triazine-modified silica microsphere, which is prepared by the above-mentioned preparation method of s-triazine-modified silica microsphere; the s-triazine-modified silica microsphere comprises a silica core and a silica shell layer, and the silica shell layer comprises s-triazine groups.

[0067] The present invention also provides a use of the above-mentioned s-triazine-modified silicon oxide microspheres for loading functional drugs in natural textiles or in preparing perfumes.

[0068] Hereinafter, the s-triazine-modified silica microspheres and their preparation method and application will be further described through the following specific examples.

[0069] Example 1

[0070] 2.2 g of aminopropyltriethoxysilane was mixed with 25 ml of deionized water, and then the pH of the system was adjusted to about 2.0 using a 5% dilute hydrochloric acid solution, and hydrolyzed at room temperature for 12 hours to obtain silanol containing an amino group at the end.

[0071] Dissolve 0.92 g of cyanuric chloride in 5 ml of acetone; mix with silanol containing an amino group at the end, maintain the pH at around 2.0, react at room temperature for 3 hours, filter to remove the hydrolyzed cyanuric chloride, and obtain 40 ml of reaction solution.

[0072] 50 ml of ethanol, 40 ml of deionized water and 10 ml of 25% concentrated ammonia water were rapidly stirred at 60° C. for 10 min, and a mixed solution of 20 ml of ethyl orthosilicate and 80 ml of ethanol was added. After reacting for 10 h, the mixture was centrifuged, washed and dried in sequence to obtain silica microspheres.

[0073] 500 mg of silica microspheres were ultrasonically dispersed in 100 ml of water, and 0.6 g of hexadecyltrimethylammonium bromide, 150 ml of water, 150 ml of ethanol and 3 ml of 25% concentrated ammonia water were added under rapid stirring, and stirred for 30 min; 4 ml of the reaction solution and 1 ml of tetraethyl orthosilicate were added to the silica microsphere dispersion, and the reaction was carried out at room temperature of 25° C. for 10 h, and then aged for 24 h, and finally centrifuged, washed and dried in sequence to obtain s-triazine-modified silica microspheres. The SEM image of the s-triazine-modified silica microspheres prepared in Example 1 is shown in FIG. Figure 1 shown.

[0074] Example 2

[0075] 2.2 g of aminopropyltriethoxysilane was mixed with 25 ml of deionized water, and then the pH of the system was adjusted to about 2.0 using a 5% dilute hydrochloric acid solution, and hydrolyzed at room temperature for 12 hours to obtain silanol containing an amino group at the end.

[0076] Dissolve 0.92 g of cyanuric chloride in 5 ml of acetone; mix with silanol containing an amino group at the end, maintain the pH at around 2.0, react at room temperature for 3 hours, filter to remove the hydrolyzed cyanuric chloride, and obtain 40 ml of reaction solution.

[0077] 50 ml of ethanol, 40 ml of deionized water and 10 ml of 25% concentrated ammonia water were rapidly stirred at 60° C. for 10 min, and a mixed solution of 20 ml of ethyl orthosilicate and 80 ml of ethanol was added. After reacting for 10 h, the mixture was centrifuged, washed and dried in sequence to obtain silica microspheres.

[0078] 500 mg of silica microspheres were ultrasonically dispersed in 100 ml of water, and 0.6 g of hexadecyltrimethylammonium bromide, 150 ml of water, 150 ml of ethanol and 3 ml of 25% concentrated ammonia water were added under rapid stirring, and stirred for 30 min; 2 ml of the reaction solution and 1 ml of tetraethyl orthosilicate were added to the silica microsphere dispersion, and the reaction was carried out at room temperature of 25° C. for 10 h, and then aged for 24 h, and finally centrifuged, washed and dried in sequence to obtain s-triazine-modified silica microspheres. The SEM image of the s-triazine-modified silica microspheres prepared in Example 2 is shown in FIG. Figure 2 shown.

[0079] Example 3

[0080] 2.2 g of aminopropyltriethoxysilane was mixed with 25 ml of deionized water, and then the pH of the system was adjusted to about 2.0 using a 5% dilute hydrochloric acid solution, and hydrolyzed at room temperature for 12 hours to obtain silanol containing an amino group at the end.

[0081] Dissolve 0.92 g of cyanuric chloride in 5 ml of acetone; mix with silanol containing an amino group at the end, maintain the pH at around 2.0, react at room temperature for 3 hours, filter to remove the hydrolyzed cyanuric chloride, and obtain 40 ml of reaction solution.

[0082] 50 ml of ethanol, 40 ml of deionized water and 10 ml of 25% concentrated ammonia water were rapidly stirred at 60° C. for 10 min, and a mixed solution of 20 ml of ethyl orthosilicate and 80 ml of ethanol was added. After reacting for 10 h, the mixture was centrifuged, washed and dried in sequence to obtain silica microspheres.

[0083] 500 mg of silica microspheres were ultrasonically dispersed in 100 ml of water, and 0.6 g of hexadecyltrimethylammonium bromide, 150 ml of water, 150 ml of ethanol and 3 ml of 25% concentrated ammonia water were added under rapid stirring, and stirred for 30 min; 1 ml of the reaction solution and 1 ml of tetraethyl orthosilicate were added to the silica microsphere dispersion, and the reaction was carried out at room temperature of 25°C for 10 h, and then aged for 24 h, and finally centrifuged, washed and dried in sequence to obtain s-triazine-modified silica microspheres. The SEM image of the s-triazine-modified silica microspheres prepared in Example 3 is shown in FIG. Figure 3 shown.

[0084] Comparative Example 1

[0085] 50 ml of ethanol, 40 ml of deionized water and 10 ml of 25% concentrated ammonia water were rapidly stirred at 60° C. for 10 min, and a mixed solution of 20 ml of ethyl orthosilicate and 80 ml of ethanol was added. After reacting for 10 h, the mixture was centrifuged, washed and dried in sequence to obtain silica microspheres.

[0086] 500 mg of silica microspheres were ultrasonically dispersed in 100 ml of water, and 0.6 g of hexadecyltrimethylammonium bromide, 150 ml of water, 150 ml of ethanol and 3 ml of 25% concentrated ammonia water were added under rapid stirring, and stirred for 30 min; 1 ml of ethyl orthosilicate was added to the silica microsphere dispersion, reacted at room temperature of 25°C for 10 h, then aged for 24 h, and finally centrifuged, washed and dried in sequence to obtain silica microspheres.

[0087] Test Example 1

[0088] The triazine-modified silica microspheres prepared in Examples 1-3 and the silica microspheres prepared in Comparative Example 1 were placed in 100 ml of water, and then acid red 34 dye was added, and the temperature was raised to 90°C under rapid stirring, the pH was adjusted to 10.0, and the reaction was performed for 3 hours, and then the microspheres were filtered and recovered. The obtained microspheres were soaked in 100 ml of DMF for 3 times, ultrasonicated for 10 minutes, and finally filtered and dried, and the color of the filter cake was observed, and the color is shown in Table 1.

[0089] Table 1

[0090] Is it colored Example 1 have Example 2 have Example 3 have Comparative Example 1 none

[0091] As can be seen from Table 1, the filter cakes in Examples 1-3 are colored silica microspheres, indicating that the triazine-modified silica microspheres prepared in Examples 1-3 contain triazine groups, which react chemically with the amino groups in the acid red 34 dye, while there are no triazine groups or other groups that can react with the dye in Comparative Example 1, so the filter cake in Comparative Example 1 is colorless.

[0092] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0093] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing triazine-modified silica microspheres, characterized in that: The following steps are involved: The silane coupling agent containing an amino group at the end is subjected to a hydrolysis reaction to obtain a silanol containing an amino group at the end; Carrying out a condensation reaction between the silanol containing an amino group at the end and 2,4,6-trihalogenated-1,3,5-triazine to obtain a reaction solution; A dispersion liquid containing silicon oxide microspheres is provided, and the reaction liquid and a silicate solution are added to the dispersion liquid to carry out a coating reaction, and after the reaction is completed, triazine-modified silicon oxide microspheres are obtained.

2. The method for preparing triazine-modified silica microspheres according to claim 1, characterized in that: The silane coupling agent having an amino group at the end includes at least one of aminopropyltrimethoxysilane and aminopropyltriethoxysilane.

3. The method for preparing triazine-modified silica microspheres according to claim 1, characterized in that: The step of hydrolyzing the silane coupling agent containing an amino group at the end satisfies at least one of the following conditions: (1) The hydrolysis reaction is carried out under acidic conditions; (2) The temperature of the hydrolysis reaction is 15°C-60°C; (3) The hydrolysis reaction time is 1h-24h.

4. The method for preparing triazine-modified silica microspheres according to any one of claims 1 to 3, characterized in that: The step of condensing the silanol containing an amino group at the end with 2,4,6-trihalogenated-1,3,5-triazine satisfies at least one of the following conditions: (1) The molar ratio of the silanol containing an amino group at the end to the 2,4,6-trihalogenated-1,3,5-triazine is 1:1-3:1; (2) the 2,4,6-trihalogenated-1,3,5-triazine comprises at least one of cyanuric fluoride or cyanuric chloride; (3) The temperature of the condensation reaction is 15°C-90°C; (4) The condensation reaction time is 1h-3h; (5) The condensation reaction is carried out under acidic conditions. After the condensation reaction is completed, the pH of the reaction solution of the condensation reaction is adjusted to 6.0-8.

0.

5. The method for preparing triazine-modified silica microspheres according to any one of claims 1 to 3, characterized in that: The dispersion liquid containing silicon oxide microspheres contains silicon oxide microspheres, alkali, water, alcohol compounds and surfactants.

6. The method for preparing s-triazine-modified silica microspheres according to claim 5, characterized in that: The dispersion containing silicon oxide microspheres satisfies at least one of the following conditions: (1) The surfactant comprises at least one of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide or polyvinylpyrrolidone; (2) The concentration of the surfactant in the dispersion is 0.1 g / L-50 g / L; (3) The volume ratio of the alcohol compound to water is 0.5:1-5:

1.

7. The method for preparing triazine-modified silica microspheres according to any one of claims 1 to 3, characterized in that: The step of adding the reaction solution and the silicate solution to the dispersion to perform a coating reaction satisfies at least one of the following conditions: (1) The silicate comprises at least one of ethyl orthosilicate or methyl orthosilicate; (2) the molar ratio of the condensation product to the silicate in the reaction solution is 1:1-20:1; (3) The mass ratio of the condensation product in the reaction solution to the silica microspheres in the dispersion solution is 1:1-1:

10.

8. The method for preparing s-triazine-modified silica microspheres according to any one of claims 1 to 3, characterized in that: The coating reaction temperature is 15°C-60°C and the time is 5h-10h.

9. A triazine-modified silica microsphere, characterized in that: The s-triazine-modified silica microspheres are prepared by the preparation method of s-triazine-modified silica microspheres according to any one of claims 1 to 8, wherein the s-triazine-modified silica microspheres comprise a silica core and a silica shell layer, wherein the silica shell layer comprises s-triazine groups.

10. Use of the s-triazine-modified silica microspheres as claimed in claim 9 for loading functional drugs in natural textiles or in preparing perfumes.

Images