Colored silicon oxide microspheres and preparation method thereof

Abstract

The invention relates to a colored silicon oxide microsphere and a preparation method thereof, and the preparation method of the colored silicon oxide microsphere comprises the following steps: mixing a coupling component or a diazo component with 2, 4, 6-trihalo-1, 3, 5-triazine, and carrying out a first condensation reaction to obtain a first condensation reactant; mixing silanol containing amino at the tail end with the first condensation reactant, and carrying out a second condensation reaction to obtain a second condensation reactant; providing a dispersion liquid containing silicon oxide microspheres, and adding a second condensation reactant and a silicate ester solution into the dispersion liquid for reaction to obtain silicon oxide microspheres with coupling components on the surfaces or silicon oxide microspheres with diazo components on the surfaces; and carrying out diazotization coupling reaction on the silicon oxide microspheres with the coupling components on the surfaces and diazo components or carrying out diazotization coupling reaction on the silicon oxide microspheres with the diazo components on the surfaces and the coupling components to obtain the colored silicon oxide microspheres. According to the preparation method of the colored silicon oxide microspheres, the fading phenomenon can be avoided.

Description

Technical Field

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

[0002] In the medical field, indirect agglutination tests are often used for rapid diagnosis. Indirect agglutination tests use colored microspheres as inert carriers, and then modify the microspheres with antibodies before clinical testing. Traditional colored microspheres are colored polystyrene microspheres, but polystyrene has poor hydrophilicity, poor protein binding ability, and poor agglutination ability, which seriously affect the development of indirect agglutination tests. For this reason, colored silica microspheres are used to replace colored polystyrene microspheres. However, in the current preparation process of colored silica microspheres, dye molecules are bonded to the surface of silica microspheres in the form of non-covalent bonds such as intermolecular forces or ionic bonds, which makes the dye easy to fall off in the presence of water or organic solvents, resulting in discoloration. Summary of the invention

[0003] Based on this, it is necessary to provide a colored silica microsphere and a preparation method thereof to address the above problems. The preparation method of the colored silica microsphere bonds the coupling component and the diazo component of the dye molecule to the surface of the silica microsphere through covalent bonds, which can avoid discoloration.

[0004] The invention discloses a method for preparing colored silicon oxide microspheres, comprising the following steps:

[0005] Mixing the coupling component or the diazo component with 2,4,6-trihalogenated-1,3,5-triazine to carry out a first condensation reaction to obtain a first condensation reactant;

[0006] 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;

[0007] Mixing the silanol containing an amino group at the end with the first condensation reactant to carry out a second condensation reaction to obtain a second condensation reactant;

[0008] Providing a dispersion liquid including silicon oxide microspheres, adding the second condensation reactant and a silicate solution to the dispersion liquid for reaction, and obtaining silicon oxide microspheres having coupling components on the surface or silicon oxide microspheres having diazo components on the surface after the reaction is completed;

[0009] When the obtained silica microspheres have coupling components on the surface, the silica microspheres with coupling components on the surface are subjected to diazo coupling reaction with diazo components to obtain colored silica microspheres. When the obtained silica microspheres have diazo components on the surface, the silica microspheres with diazo components on the surface are subjected to diazo coupling reaction with coupling components to obtain colored silica microspheres.

[0010] In one embodiment, the step of mixing the coupling component or the diazo component with the 2,4,6-trihalogeno-1,3,5-triazine for a first condensation reaction satisfies at least one of the following conditions:

[0011] (1) the coupling component comprises at least one of H acid, J acid, γ acid or K acid, and in this case, the step of mixing the coupling component or the diazo component with 2,4,6-trihalogeno-1,3,5-triazine for a first condensation reaction comprises: adjusting the pH of the aqueous solution comprising the coupling component to neutral with a base, and then mixing with 2,4,6-trihalogeno-1,3,5-triazine for a first condensation reaction;

[0012] (2) the diazo component comprises at least one of p-acetamidoaniline or p-nitroaniline;

[0013] (3) The 2,4,6-trihalogenated-1,3,5-triazine comprises at least one of cyanuric chloride or cyanuric fluoride;

[0014] (4) the molar ratio of the diazo component to 2,4,6-trihalogenated-1,3,5-triazine is 1:1.01-1:1.10;

[0015] (5) The molar ratio of the coupling component to 2,4,6-trihalogenated-1,3,5-triazine is 1:1.01-1:1.10;

[0016] (6) The temperature of the first condensation reaction is -5°C to 0°C;

[0017] (7) The time of the first condensation reaction is 1h-24h.

[0018] 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:

[0019] (1) The silane coupling agent containing an amino group at the end includes at least one of aminopropyltrimethoxysilane or aminopropyltriethoxysilane;

[0020] (2) the hydrolysis reaction is carried out under acidic conditions;

[0021] (3) The temperature of the hydrolysis reaction is 15°C-60°C;

[0022] (4) The hydrolysis reaction time is 1h-24h.

[0023] In one embodiment, the step of mixing the silanol containing an amino group at the end with the first condensation reactant to perform a second condensation reaction satisfies at least one of the following conditions:

[0024] (1) the molar ratio of the silanol containing an amino group at the end to the first condensation reactant is 1:1-1.10:1;

[0025] (2) The temperature of the second condensation reaction is 10°C-40°C;

[0026] (3) The time of the second condensation reaction is 1h-24h.

[0027] In one embodiment, the dispersion liquid including silica microspheres includes silica microspheres, alkali, water, alcohol compounds and surfactants.

[0028] In one embodiment, the dispersion comprising silica microspheres satisfies at least one of the following conditions:

[0029] (1) The surfactant comprises at least one of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide or polyvinylpyrrolidone;

[0030] (2) The concentration of the surfactant in the dispersion is 0.1 g / L-50 g / L;

[0031] (3) The volume ratio of the alcohol compound to water is 0.5:1-5:1.

[0032] In one embodiment, the step of adding the second condensation reactant and the silicate solution to the dispersion to react satisfies at least one of the following conditions:

[0033] (1) The silicate comprises at least one of ethyl orthosilicate or methyl orthosilicate;

[0034] (2) the molar ratio of the silicate to the second condensation reactant is 1:1-20:1;

[0035] (3) The reaction is carried out under alkaline conditions;

[0036] (4) The reaction temperature is 15°C-60°C.

[0037] In one embodiment, the step of subjecting the silicon oxide microspheres having the coupling component on the surface to a diazo coupling reaction with a diazo component comprises: subjecting the diazo component to a diazo reaction, and then subjecting the diazo component to a coupling reaction with the silicon oxide microspheres having the coupling component on the surface;

[0038] The step of subjecting the silicon oxide microspheres having diazo components on the surface to diazo coupling reaction with a coupling component comprises: subjecting the silicon oxide microspheres having diazo components on the surface to diazo reaction, and then subjecting the silicon oxide microspheres to coupling reaction with the coupling component.

[0039] In one embodiment, the diazotization coupling reaction satisfies at least one of the following conditions:

[0040] (1) The diazotization reaction is carried out at a temperature of 0°C to 5°C under acidic conditions;

[0041] (2) The coupling reaction is carried out at a temperature of 0°C to 40°C under alkaline conditions;

[0042] (3) When the obtained silicon oxide microspheres have coupling components on the surface, the molar ratio of the diazo component to the coupling component is 0.2:1-5:1;

[0043] (4) When the obtained silicon oxide microspheres have a diazo component on the surface, the molar ratio of the coupling component to the diazo component is 0.2:1-5:1.

[0044] A colored silicon oxide microsphere is prepared by the above-mentioned method for preparing the colored silicon oxide microsphere.

[0045] The method for preparing colored silica microspheres provided by the present invention comprises the following steps: firstly, using 2,4,6-trihalogenated-1,3,5-triazine as a bridge group, bonding a coupling component or a diazo component in a dye molecule to a silanol containing an amino group at the end, to obtain a second condensation reactant; secondly, simultaneously adding the second condensation reactant and a silicate solution into a dispersion liquid containing silica microspheres, coating the silica microspheres, thereby bonding the coupling component or the diazo component to the surface of the silica microspheres; and thirdly, connecting the coupling component and the diazo component through a diazo coupling reaction, thereby bonding the coupling component and the diazo component of the dye molecule to the surface of the silica microspheres through covalent bonds, thereby preventing the dye molecule from falling off in the presence of water or an organic solvent and causing discoloration. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] 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.

[0047] Figure 1 This is a SEM image of the orange silica microspheres prepared in Example 1;

[0048] Figure 2 This is the SEM image of the red silica microspheres prepared in Example 2. DETAILED DESCRIPTION

[0049] In order to facilitate the 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.

[0050] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the technical field of the terminology of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific implementation methods or embodiments and are not intended to limit the present invention.

[0051] The present invention provides a method for preparing colored silicon oxide microspheres, comprising the following steps:

[0052] S10, mixing the coupling component or the diazo component with 2,4,6-trihalogenated-1,3,5-triazine to carry out a first condensation reaction to obtain a first condensation reactant;

[0053] S20, hydrolyzing a silane coupling agent having an amino group at the end to obtain a silanol having an amino group at the end;

[0054] S30, mixing the silanol containing an amino group at the end with the first condensation reactant, and performing a second condensation reaction to obtain a second condensation reactant;

[0055] S40, providing a dispersion liquid including silica microspheres, adding a second condensation reactant and a silicate solution to the dispersion liquid for reaction, and obtaining silica microspheres having a coupling component on the surface or silica microspheres having a diazo component on the surface after the reaction is completed;

[0056] S50, when the obtained silica microspheres have coupling components on the surface, the silica microspheres have coupling components on the surface and the diazo components are subjected to diazo coupling reaction to obtain colored silica microspheres; when the obtained silica microspheres have diazo components on the surface, the silica microspheres have diazo components on the surface and the coupling components are subjected to diazo coupling reaction to obtain colored silica microspheres.

[0057] The method for preparing colored silica microspheres provided by the present invention comprises the following steps: firstly, using 2,4,6-trihalogenated-1,3,5-triazine as a bridge group, bonding a coupling component or a diazo component in a dye molecule to a silanol containing an amino group at the end, to obtain a second condensation reactant; secondly, simultaneously adding the second condensation reactant and a silicate solution into a dispersion liquid containing silica microspheres, coating the silica microspheres, thereby bonding the coupling component or the diazo component to the surface of the silica microspheres; and thirdly, connecting the coupling component and the diazo component through a diazo coupling reaction, thereby bonding the coupling component and the diazo component of the dye molecule to the surface of the silica microspheres through covalent bonds, thereby preventing the dye from falling off in the presence of water or an organic solvent and causing discoloration.

[0058] In step S10, the coupling component or the diazo component in the dye molecule is first condensed with 2,4,6-trihalogenated-1,3,5-triazine.

[0059] When the coupling component is first condensed with 2,4,6-trihalogen-1,3,5-triazine, in one embodiment, the coupling component includes at least one of H acid, J acid, γ acid or K acid. At this time, in order to promote the condensation reaction to proceed better, the step of mixing the coupling component or the diazo component with 2,4,6-trihalogen-1,3,5-triazine for the first condensation reaction includes: adjusting the pH of the aqueous solution including the coupling component to neutral with a base, Then, the coupling component is mixed with 2,4,6-trihalogeno-1,3,5-triazine to carry out a first condensation reaction; the molar ratio of the coupling component to 2,4,6-trihalogeno-1,3,5-triazine is 1:1.01-1:1.10, including but not limited to 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.10.

[0060] When the diazo component is first condensed with 2,4,6-trihalogeno-1,3,5-triazine, in one embodiment, the diazo component includes at least one of p-acetamidoaniline or p-nitroaniline, and the molar ratio of the diazo component to 2,4,6-trihalogeno-1,3,5-triazine is 1:1.01-1:1.10, including but not limited to 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.10.

[0061] In one embodiment, the 2,4,6-trihalo-1,3,5-triazine includes at least one of cyanuric chloride or cyanuric fluoride.

[0062] The temperature of the first condensation reaction affects the reactivity of 2,4,6-trihalogeno-1,3,5-triazine. In order to ensure that only one halogen atom is substituted in the molecular structure of 2,4,6-trihalogeno-1,3,5-triazine, in one embodiment, the temperature of the first condensation reaction is -5°C-0°C, including but not limited to -5°C, -4°C, -3°C, -2°C, -1°C or 0°C.

[0063] In one embodiment, the first condensation reaction time is 1 h-24 h, including but not limited to 1 h, 5 h, 10 h, 15 h, 20 h or 24 h.

[0064] In step S20, 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.

[0065] In one embodiment, the hydrolysis reaction is carried out under acidic conditions. Preferably, the hydrolysis reaction is carried out under the condition of pH = 2.0-4.0, including but not limited to the condition of pH = 2.0, 2.5, 3.0, 3.5 or 4.0.

[0066] 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.

[0067] In one embodiment, the hydrolysis reaction time is 1 h-24 h, including but not limited to 1 h, 5 h, 10 h, 15 h, 20 h or 24 h.

[0068] In step S30, the molar ratio of the silanol containing an amino group at the end to the first condensation reactant is preferably 1:1-1:1.10, including but not limited to 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09 or 1:1.10.

[0069] In one embodiment, the temperature of the second condensation reaction is 10°C-40°C, including but not limited to 10°C, 15°C, 20°C, 25°C, 30°C, 35°C or 40°C.

[0070] In one embodiment, the second condensation reaction time is 1 h-24 h, including but not limited to 1 h, 5 h, 10 h, 15 h, 20 h or 24 h.

[0071] In step S40, the second condensation reactant and the silica ester are co-coated on the silica microspheres. 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 an alkali, and then adding a silicate to react to obtain a transparent sol system, and sequentially gelling, drying, and calcining the transparent sol system to obtain silica microspheres; preferably, the reaction temperature is 15°C-60°C, and the reaction is carried out at a pH of 10.5-12.5. The silicate includes at least one of ethyl orthosilicate or methyl orthosilicate, and its mass fraction in the reaction solution is 5.0%-20.0%. The alcohol compound is selected from at least one of methanol or ethanol, and the volume ratio of the alcohol compound to water is 1:1-5:1.

[0072] In one embodiment, the dispersion liquid including silica microspheres includes silica microspheres, alkali, water, alcohol compounds and surfactants.

[0073] The role of the surfactant is to provide charge, thereby facilitating the coating 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.

[0074] In one embodiment, the silicate comprises at least one of ethyl orthosilicate or methyl orthosilicate; preferably, the molar ratio of the silicate to the second condensation reactant is 1:1-20:1, including but not limited to 1:1, 5:1, 10:1, 15:1 or 20:1.

[0075] 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.

[0076] In one embodiment, the reaction is carried out under alkaline conditions, preferably, the reaction is carried out under the condition of pH=10.5-12.5.

[0077] 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.

[0078] In step S50, another component of the dye molecule is covalently bonded to the surface of the silica microsphere through a diazo coupling reaction, whereby the coupling component and the diazo component together form a dye molecule to produce color.

[0079] When step S40 obtains silica microspheres with coupling components on the surface, the step of subjecting the silica microspheres with coupling components on the surface to diazotization coupling reaction with diazo components comprises: subjecting the diazo components to diazotization reaction, and then subjecting the diazo components to coupling reaction with the silica microspheres with coupling components on the surface; preferably, the diazo components include but are not limited to at least one of acetamidoaniline or p-nitroaniline, and the molar ratio of the diazo components to the coupling components is 0.2:1-5:1, including but not limited to 0.2:1, 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.

[0080] When step S40 obtains silicon oxide microspheres with diazo components on the surface, the step of subjecting the silicon oxide microspheres with diazo components on the surface to diazo coupling reaction with a coupling component comprises: subjecting the silicon oxide microspheres with diazo components on the surface to diazo reaction, and then subjecting the silicon oxide microspheres to coupling reaction with the coupling component; preferably, the coupling component includes but is not limited to at least one of H acid, J acid, γ acid or K acid, and the molar ratio of the coupling component to the diazo component is 0.2:1-5:1, including but not limited to 0.2:1, 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.

[0081] In one embodiment, the diazotization reaction is carried out at a temperature of 0°C to 5°C under acidic conditions.

[0082] In one embodiment, the coupling reaction is carried out at a temperature of 0°C-40°C under alkaline conditions, preferably at pH=8.0-9.0.

[0083] The present invention also provides a colored silicon oxide microsphere, which is prepared by the above-mentioned method for preparing the colored silicon oxide microsphere.

[0084] In the colored silica microspheres prepared by the above-mentioned preparation method provided by the present invention, the coupling component and the diazo component of the dye molecule are bonded to the surface of the silica microspheres by covalent bonds, so the dye molecule is not easy to fall off in the presence of water or organic solvents, thereby avoiding the color fading phenomenon.

[0085] Hereinafter, the colored silica microspheres and the preparation method thereof will be further described through the following specific examples.

[0086] Example 1

[0087] Dissolve 0.01 mol of J acid in 20 ml of deionized water, and adjust the pH to about 7.0 with sodium carbonate; weigh 0.0101 mol of cyanuric chloride and dissolve it in 5 ml of acetone, then mix the two, control the temperature at 0-5°C and pH 3.0-4.0 in an ice bath, and react for 2 hours; filter to remove insoluble impurities to obtain the first condensation reactant.

[0088] 0.01 mol of aminopropyltriethoxysilane was mixed with 10 ml of deionized water, and then the pH of the system was adjusted to about 2.0 using a 5 wt % dilute hydrochloric acid solution, and hydrolyzed at room temperature for 12 hours to obtain silanol containing an amino group at the end.

[0089] The silanol containing an amino group at the end is mixed with the first condensation reactant, the pH is maintained between 3.0 and 4.0, and the mixture is reacted at room temperature for 3 hours to obtain a second condensation reactant.

[0090] 150 ml of ethanol, 40 ml of deionized water and 5 ml of 25 wt% concentrated ammonia water were rapidly stirred at 60°C for 10 min, 5 ml of tetraethyl orthosilicate was quickly added, the reaction was continued for 10 h, and then the silica microspheres were obtained by centrifugation, washing and drying. 500 mg of silica microspheres were ultrasonically dispersed in 100 ml of water, 0.6 g of hexadecyltrimethylammonium bromide, 150 ml of water, 150 ml of ethanol and 3 ml of 25 wt% concentrated ammonia water were added under rapid stirring, and the mixture was stirred for 30 min to obtain a dispersion containing silica microspheres. 4 ml of the second condensation reactant and 1 ml of tetraethyl orthosilicate were quickly added to the dispersion containing silica microspheres, the reaction was continued at room temperature for 10 h, and then aged for 24 h to obtain a dispersion containing silica microspheres with J acid modified on the surface.

[0091] 0.003 mol of p-nitroaniline was dissolved in 10 ml of deionized water, 1 ml of concentrated hydrochloric acid was added, and the mixture was heated to 80°C, and then rapidly cooled to 0-5°C, and then 0.0033 mol of sodium nitrite was added to obtain p-nitroaniline diazonium salt; then the pH of the dispersion liquid including the silica microspheres with J acid modified on the surface was adjusted to 8.0, and then the p-nitroaniline diazonium salt was slowly added dropwise at 0-5°C and pH 8.0-9.0. After reacting for 1 hour, the excess diazonium salt was removed by washing with water to obtain orange silica microspheres. The SEM image of the orange silica microspheres is shown in the following figure. Figure 1 shown.

[0092] Example 2

[0093] Dissolve 0.01 mol H acid in 20 ml deionized water, and adjust the pH to about 7.0 with sodium carbonate; weigh 0.0101 mol cyanuric chloride and dissolve it in 5 ml acetone, then mix the two, control the temperature at 0-5°C and pH 3.0-4.0 in an ice bath, and react for 2 hours; filter to remove insoluble impurities to obtain the first condensation reactant.

[0094] 0.01 mol of aminopropyltriethoxysilane was mixed with 10 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.

[0095] The silanol containing an amino group at the end is mixed with the first condensation reactant, the pH is maintained between 3.0 and 4.0, and the mixture is reacted at room temperature for 3 hours to obtain a second condensation reactant.

[0096] 150 ml of ethanol, 40 ml of deionized water and 5 ml of 25 wt% concentrated ammonia water were rapidly stirred at 60°C for 10 min, 5 ml of tetraethyl orthosilicate was quickly added, the reaction was continued for 10 h, and then the silica microspheres were obtained by centrifugation, washing and drying. 500 mg of silica microspheres were ultrasonically dispersed in 100 ml of water, 0.6 g of hexadecyltrimethylammonium bromide, 150 ml of water, 150 ml of ethanol and 3 ml of 25 wt% concentrated ammonia water were added under rapid stirring, and the mixture was stirred for 30 min to obtain a dispersion containing silica microspheres. 4 ml of the second condensation reactant and 1 ml of tetraethyl orthosilicate were rapidly added to the dispersion containing silica microspheres, the reaction was continued at room temperature for 10 h, and then aged for 24 h to obtain a dispersion containing silica microspheres with H acid modified surfaces.

[0097] 0.003 mol of p-nitroaniline was dissolved in 10 ml of deionized water, 1 ml of concentrated hydrochloric acid was added, and the mixture was heated to 80°C, and then rapidly cooled to 0-5°C, and then 0.0033 mol of sodium nitrite was added to obtain p-nitroaniline diazonium salt; the pH of the dispersion liquid including the silicon oxide microspheres with surface H acid modification was then adjusted to 8.0, and then p-nitroaniline diazonium salt was slowly added dropwise at 0-5°C and pH 8.0-9.0. After reacting for 1 hour, the excess diazonium salt was removed by washing with water to obtain red silicon oxide microspheres. The SEM image of the red silicon oxide microspheres is shown in FIG. Figure 2 shown.

[0098] Comparative Example 1

[0099] Take 1g of silica microspheres and add them to 100ml of diethylenetriaminopropyltrimethoxysilane (2wt%) acetic acid solution (1wt%) and stir at room temperature. After reacting for 1h, add 10ml of CI Direct Yellow 49 solution (1wt%) to the reaction solution and continue stirring and reacting for 1h. After washing twice with pure water, yellow silica microspheres are obtained.

[0100] Test Example 1

[0101] The colored silica microspheres prepared in Examples 1-2 and Comparative Example 1 were tested to see whether they were discolored in the presence of an organic solvent. The specific test method is shown below, and the test results are shown in Table 1.

[0102] Test method: Take a small amount of the products prepared in Examples 1-2 and Comparative Example 1, respectively, place them in a DMF solution, ultrasonicate for 10 minutes, and observe whether the DMF has color. If the DMF has color, it proves that the colored silica microspheres are decolorized. If the DMF has no color, it proves that the colored silica microspheres are not decolorized.

[0103] Table 1

[0104]

[0105]

[0106] 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.

[0107] 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 colored silica microspheres, characterized in that: The following steps are involved: Mixing the coupling component or the diazo component with 2,4,6-trihalogenated-1,3,5-triazine to carry out a first condensation reaction to obtain a first condensation reactant; 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; Mixing the silanol containing an amino group at the end with the first condensation reactant to carry out a second condensation reaction to obtain a second condensation reactant; Providing a dispersion liquid including silicon oxide microspheres, adding the second condensation reactant and a silicate solution to the dispersion liquid for reaction, and obtaining silicon oxide microspheres having coupling components on the surface or silicon oxide microspheres having diazo components on the surface after the reaction is completed; When the obtained silica microspheres have coupling components on the surface, the silica microspheres with coupling components on the surface are subjected to diazo coupling reaction with diazo components to obtain colored silica microspheres. When the obtained silica microspheres have diazo components on the surface, the silica microspheres with diazo components on the surface are subjected to diazo coupling reaction with coupling components to obtain colored silica microspheres.

2. The method for preparing colored silica microspheres according to claim 1, characterized in that: The step of mixing the coupling component or the diazo component with 2,4,6-trihalogeno-1,3,5-triazine for a first condensation reaction satisfies at least one of the following conditions: (1) the coupling component comprises at least one of H acid, J acid, γ acid or K acid, and in this case, the step of mixing the coupling component or the diazo component with 2,4,6-trihalogeno-1,3,5-triazine for a first condensation reaction comprises: adjusting the pH of the aqueous solution comprising the coupling component to neutral with a base, and then mixing with 2,4,6-trihalogeno-1,3,5-triazine for a first condensation reaction; (2) the diazo component comprises at least one of p-acetamidoaniline or p-nitroaniline; (3) The 2,4,6-trihalogenated-1,3,5-triazine comprises at least one of cyanuric chloride or cyanuric fluoride; (4) the molar ratio of the diazo component to 2,4,6-trihalogenated-1,3,5-triazine is 1:1.01-1:1.10; (5) The molar ratio of the coupling component to 2,4,6-trihalogenated-1,3,5-triazine is 1:1.01-1:1.10; (6) The temperature of the first condensation reaction is -5°C to 0°C; (7) The time of the first condensation reaction is 1h-24h.

3. The method for preparing colored 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 silane coupling agent containing an amino group at the end includes at least one of aminopropyltrimethoxysilane or aminopropyltriethoxysilane; (2) the hydrolysis reaction is carried out under acidic conditions; (3) The temperature of the hydrolysis reaction is 15°C-60°C; (4) The hydrolysis reaction time is 1h-24h.

4. The method for preparing colored silica microspheres according to any one of claims 1 to 3, characterized in that: The step of mixing the silanol containing an amino group at the end with the first condensation reactant to perform a second condensation reaction satisfies at least one of the following conditions: (1) the molar ratio of the silanol containing an amino group at the end to the first condensation reactant is 1:1-1.10:1; (2) The temperature of the second condensation reaction is 10°C-40°C; (3) The time of the second condensation reaction is 1h-24h.

5. The method for preparing colored 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 colored 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 colored silica microspheres according to any one of claims 1 to 3, characterized in that: The step of adding the second condensation reactant and the silicate solution to the dispersion to react 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 silicate to the second condensation reactant is 1:1-20:1; (3) The reaction is carried out under alkaline conditions; (4) The reaction temperature is 15°C-60°C.

8. The method for preparing colored silica microspheres according to any one of claims 1 to 3, characterized in that: The step of subjecting the silicon oxide microspheres having the coupling component on the surface to a diazo coupling reaction with a diazo component comprises: subjecting the diazo component to a diazo reaction, and then subjecting the diazo component to a coupling reaction with the silicon oxide microspheres having the coupling component on the surface; The step of subjecting the silicon oxide microspheres having diazo components on the surface to diazo coupling reaction with a coupling component comprises: subjecting the silicon oxide microspheres having diazo components on the surface to diazo reaction, and then subjecting the silicon oxide microspheres to coupling reaction with the coupling component.

9. The method for preparing colored silica microspheres according to claim 8, characterized in that: The diazotization coupling reaction satisfies at least one of the following conditions: (1) The diazotization reaction is carried out at a temperature of 0°C to 5°C under acidic conditions; (2) The coupling reaction is carried out at a temperature of 0°C to 40°C under alkaline conditions; (3) When the obtained silicon oxide microspheres have coupling components on the surface, the molar ratio of the diazo component to the coupling component is 0.2:1-5:1; (4) When the obtained silicon oxide microspheres have a diazo component on the surface, the molar ratio of the coupling component to the diazo component is 0.2:1-5:

1.

10. A colored silica microsphere, characterized in that: The colored silicon oxide microspheres are prepared by the preparation method of any one of claims 1 to 9.

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