WO2018133586A1 - Uniform silica microsphere, preparation method therefor, and application thereof - Google Patents

Uniform silica microsphere, preparation method therefor, and application thereof Download PDF

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WO2018133586A1
WO2018133586A1 PCT/CN2017/115818 CN2017115818W WO2018133586A1 WO 2018133586 A1 WO2018133586 A1 WO 2018133586A1 CN 2017115818 W CN2017115818 W CN 2017115818W WO 2018133586 A1 WO2018133586 A1 WO 2018133586A1
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organosilicon compound
teos
silica microspheres
uniform
rpm
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PCT/CN2017/115818
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French (fr)
Chinese (zh)
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马士禹
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华东师范大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Definitions

  • the invention relates to a uniform silica microsphere and a preparation method thereof, in particular to a green and batch silica microsphere and a preparation method thereof, and belongs to the technical field of chemical and inorganic materials.
  • Silica microspheres are non-toxic, odorless non-metallic materials with broad application prospects in paper, plastics, coatings, pigments, rubber, ceramics, adhesives, cosmetics, catalyst carriers and antibacterial materials.
  • the sol-gel method is one of the commonly used methods for preparing silica microspheres.
  • the method is based on an inorganic salt or a metal alkoxide as a precursor, which is gradually gelled by a hydrolysis polycondensation process, and then subjected to post-treatment (aging, drying) to obtain a desired material.
  • the sol-gel method has the advantages of mild reaction conditions, good controllability of microspheres, and high particle uniformity.
  • Non-Patent Document 1 J. Colloid Interface Sci., 26, 62-69 (1968) systematically studied the preparation speed of silica microspheres in the ester-alcohol-water-alkali system. With the influence of particle size and distribution, silica microspheres with a particle size of 0.05 to 2 ⁇ m were successfully prepared. However, the prepared spherical particles have poor uniformity and the stability of the system is not satisfactory.
  • uniform silica microspheres can be prepared on a certain scale by the sol-gel method. It is considered that the mechanism of preparing silica microspheres by the sol-gel method conforms to the viewpoint of Non-Patent Document 2 (J. Am. Chem. Soc., 72, 4847-4854 (1950)). Therefore, to prepare uniform silica microspheres, it is necessary to try to separate the nucleation phase from the growth phase.
  • the seed growth method is a commonly used method for separating uniform nucleation and growth phases to prepare uniform silica microspheres (CN101913612A, CN10149216A, CN102070152A, CN104003408A, US2006088470A1). However, the operation steps of the method are cumbersome, have many influencing factors, and the process is not easy to control.
  • the formation process of uniform silica microspheres is very sensitive to the change of conditions.
  • the mechanism of uniform particle formation has not yet been fully understood. How to control the particle size of silica microspheres more effectively is still a difficult problem.
  • the sol-gel method is used to prepare uniform silica microspheres, generally using alcohol as a solvent, which is high in preparation cost and easily causes environmental pollution.
  • the object of the present invention is to solve the deficiencies of the prior art sol-gel process for preparing silica microspheres.
  • the invention firstly prepares the reactant and the solvent into a uniform transparent organosilicon compound/alcohol-H 2 O mixed liquid, and on the basis of this, adding a base or an acid-base combined catalyst to initiate hydrolysis and polycondensation reaction to prepare silica micro ball.
  • the invention solves the problem of particle size control and batch preparation scale of the silica microspheres, reduces the production cost and reduces the environmental pollution.
  • a method for preparing uniform silica microspheres comprising the steps of:
  • silica sol a catalyst is added to the organosilicon compound/alcohol-H 2 O mixture of the step (2) to carry out a hydrolysis polycondensation reaction, and a clear transparent organosilicon compound/alcohol-H 2 O mixture is obtained.
  • a milky white silica sol Preparation of a milky white silica sol; (4) Preparation of uniform silica microspheres: The silica sol of the step (3) is subjected to centrifugation to obtain the silica microspheres.
  • the mixing of the organosilicon compound and the aqueous medium is carried out under stirring, and the stirring speed is 200 to 300 rpm.
  • the mixing temperature is 15 to 30 ° C, preferably room temperature (20 ° C), 30 ° C.
  • the mixing time is 1 hour or longer; preferably, 1 to 3 hours; further preferably, 2 hours.
  • the organosilicon compound includes a silicate (including but not limited to methyl silicate, ethyl silicate, propyl silicate, etc.), a silane coupling agent (including but not limited to ⁇ - Aminopropyltriethoxysilane (KH550), ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane (KH560), ⁇ -(methacryloyloxy)propyltrimethoxysilane ( KH570), ⁇ -mercaptopropyltriethoxysilane (KH580), ⁇ -mercaptopropyltrimethoxysilane (KH590), vinyltriethoxysilane (KH151), vinyltrimethoxysilane (KH171) One or more of the others; preferably, ethyl silicate (TEOS).
  • TEOS ethyl silicate
  • the aqueous medium comprises water and an aqueous solution; preferably, water, which may be, but not limited to, pure water or ultrapure water (18.2 m ⁇ ).
  • the aqueous solution refers to an inorganic salt solution of water including, but not limited to, NaCl, KNO 3 , Na 2 SO 4 , and the like.
  • the volume ratio of the organosilicon compound to the aqueous medium is 1:50 ⁇ V organosilicon compound : V H2O ⁇ 1:5, preferably 1:5, 1:10, 1: 50, 3:50.
  • the mixing method may be any method that can achieve a mixing effect, and may be, for example, stirring, ultrasonic, high-speed shearing, gear crushing, vortex pulverization, vortex pulverization, etc.; preferably, stirring, Ultrasonic, vortex pulverization; further preferably, stirring (rotation speed 200 rpm to 300 rpm) 2 h; or, ultrasonic 30 min (power 40 kHz); or, vortex pulverization for 5 min (pressure 2.5 atm).
  • the mixing temperature is 15 to 30 ° C, preferably room temperature (20 ° C).
  • the mixing time is from 1 to 3 hours, preferably 2 hours.
  • the small molecule alcohol has the formula ROH, wherein R is a C1-C4 alkyl group; preferably, the small molecule alcohol comprises methanol (CH 3 OH), ethanol (C 2 H 5 OH) ), n-propanol (CH 3 CH 2 CH 2 OH), isopropanol ((CH 3 ) 2 CHOH), sec-butanol (CH 3 CH 2 CH(OH)CH 3 ), tert-butanol (CH 3 ) One or more of 3 COH); further preferably, a mixed solution of ethanol, methanol and isopropanol, a mixed solution of methanol and t-butanol; further preferably, ethanol, in a volume ratio of 3:1 a mixed solution of methanol and isopropanol, a mixed solution of methanol and isopropanol in a volume ratio of 1:1, a mixed solution of methanol and isopropanol in a volume ratio of 1:
  • the small molecule alcohol may be, but not limited to, analytically pure.
  • the volume ratio of the small molecule alcohol to the organosilicon compound/H 2 O emulsion is from 1:2 to 8:5; preferably, from 3:5 to 7:5; further preferably For, 10:11, 40:33, 40:51, 7:6, 45:33, 32:33, 27:33, 28:53, 50:33 or 4:3.
  • the concentration of the organosilicon compound in the organosilicon compound/alcohol-H 2 O mixture is 0.05 to 0.5 M, preferably 0.05 to 0.42 M; further preferably 0.05 M, 0.12 M, 0.15 M, 0.16 M, 0.17 M, 0.19 M, 0.20 M, 0.21 M, 0.22 M, 0.36 M, 0.42 M.
  • the hydrolysis polycondensation reaction is carried out at 20 to 60 ° C, preferably 20 ° C to 40 ° C, 40 ° C to 60 ° C; further preferably, room temperature (20 ° C), 40 °C, 60 °C.
  • the hydrolysis polycondensation reaction is carried out for 1 to 5 hours; preferably, 2 to 5 hours, or preferably 1 hour, 2 hours, 3 hours, 4 hours, and 5 hours.
  • the hydrolysis polycondensation reaction is carried out under stirring, and the stirring speed is 200 to 300 rpm.
  • the catalyst comprises a strong base catalyst, a weak base catalyst or an acid-base combined catalyst; the strong base catalyst comprises NaOH, KOH.
  • the weak base catalyst includes ammonia water, Na 2 CO 3 , NaAc; further preferably, .
  • the acid-base combination catalyst is selected from the group consisting of hydrochloric acid-ammonia water (HCl-NH 3 .H 2 O), nitric acid-ammonia water (HNO 3 -NH 3 .H 2 O), and sulfuric acid-ammonia water (H 2 SO 4 -NH 3 .
  • H 2 O preferably, NaOH, ammonia water, hydrochloric acid-ammonia water (HCl-NH 3 .H 2 O); further preferably, 28% (mass fraction) of aqueous ammonia solution or concentrated hydrochloric acid -28% (mass fraction) )ammonia.
  • a catalyst is added to the organosilicon compound/alcohol-H 2 O mixture of the step (2) to initiate a hydrolysis polycondensation reaction.
  • concentration of the catalyst in the entire reaction system is 0.01 to 5.0 mol/L; preferably, 0.01 to 0.03 mol/L, 0.5 to 5.0 mol/L; further preferably 0.02 mol/L, 0.5 mol/L. , 2.0 mol / L, 3.0 mol / L or 5.0 mol / L.
  • the concentration of the strong base catalyst in the entire reaction system is from 0.01 to 0.03 mol/L; preferably, from 0.02 mol/L.
  • the concentration of the weak base catalyst in the entire reaction system is from 0.5 to 5.0 mol/L; preferably, 0.5 mol/L, 2.0 mol/L, 3.0 mol/L or 5.0 mol/ L. Further preferably, the concentration of the aqueous ammonia catalyst in the entire reaction system is 0.5 to 5.0 mol/L; further preferably, the concentration of the aqueous ammonia catalyst in the entire reaction system is 0.5 mol/L, 2.0 mol/L, 3.0 mol/L or 5.0 mol. /L.
  • the acid concentration in the acid-base combination catalyst in the entire reaction system is from 10 -3 to 10 -2 mol/L, preferably, from 1.5 ⁇ 10 -3 mol/L, 1.5 ⁇ 10 -2 mol/L; alkali concentration: 1.0 to 5.0 mol/L, preferably 0.5 mol/L, 2.0 mol/L, 3.0 mol/L, or 5.0 mol/L.
  • the hydrochloric acid concentration is 1.5 ⁇ 10 -3 mol / L, 1.5 ⁇ 10 -2 mol / L; the concentration of ammonia is 0.5 mol / L, 2.0 mol / L, 3.0 mol / L, or 5.0 mol / L.
  • the acid-base combination catalyst is added by adding an acid to the organosilicon compound/alcohol-H 2 O mixture prepared in the step (2), and then adding the alkali after 5 minutes. .
  • the organosilicon compound/alcohol-H 2 O mixture prepared in the step (2) is heated to the reaction temperature, and kept for 15 min to 25 min; Preferably, the incubation is for 15 min or 25 min.
  • the centrifugal separation condition is that the rotation speed may be 3000 rpm or more, 4000 rpm or more or 5000 rpm or more; preferably, 3000 to 15000 rpm, 4000 to 15000 rpm or 5000 to 15000 rpm; further preferably, 3000. 4000, 5000rmp, 6000rmp, 8000rmp, 9000rmp, 10000rmp, 12000rmp, 13000rmp, 15000rmp.
  • the temperature of the centrifugation is 20 to 30 ° C; preferably, it is room temperature (20 ° C).
  • the centrifugation time is 10 to 30 min; preferably, 10 min, 20 min, and 30 min.
  • the step of washing the prepared uniform silica microspheres with an organic solvent may be further included, and preferably, the uniform silica microspheres are washed 3 times with ethanol.
  • the preparation method has different conditions, and the prepared uniform silica microspheres are different, but the silica microspheres prepared by using the specific conditions of the invention have uniform size, and the particle size range of the prepared silica microspheres can be prepared.
  • the uniform silica microspheres are smooth, spherical, and solid (as shown in FIG. 7B for the SEM image of the silica microspheres obtained in Example 10).
  • the present invention also provides uniform silica microspheres prepared by the preparation method, wherein the uniform silica microspheres have a uniform particle size, and the silica microspheres have a particle size ranging from 57 to 467 nm (eg, Is 57 nm, 96 nm, 104 nm, 105 nm, 122 nm, 130 nm, 157 nm, 180 nm, 184 nm, 193 nm, 200 nm, 203 nm, 210 nm, 223 nm, 228 nm, 278 nm, 320 nm, 325 nm, 354 nm, 398 nm, 467 nm), the surface is smooth, spherical, Solid (see SEM image of the silica microspheres obtained in Example 10).
  • 57 to 467 nm eg, Is 57 nm, 96 nm, 104 nm, 105
  • the invention also proposes the use of the uniform silica microspheres in calibration standard particles, model catalysts, non-porous chromatography fillers, colloidal crystals, electrorheological fluids.
  • the preparation method of the uniform silica microsphere provided by the invention has the following advantages:
  • the reactant and the solvent are first formulated into a uniform transparent organosilicon compound/alcohol-H 2 O mixture, and on this basis, a base or an acid-base combination catalyst is added to initiate hydrolysis and polycondensation reaction to prepare a solution.
  • Uniform silica microspheres The organosilicon compound/H 2 O emulsion obtained in the step (1) of the present invention and the organosilicon compound/alcohol-H 2 O mixture obtained in the step (2) are a homogeneous system, by regulating the uniformity of the reaction system. The uniformity of the finally prepared silica microspheres was controlled.
  • the invention can effectively avoid the problems existing in the preparation technology of the existing silica microspheres, the control system uniformity and the uniformity of the particle uniformity, and the problem that the reaction scale is difficult to enlarge.
  • the invention mainly prepares uniform silica microspheres by using an aqueous medium as a solvent, which can effectively reduce production cost and reduce pollutant emissions.
  • the invention has the characteristics of simple method, mild conditions, uniform and controllable particle size and large reaction batch size.
  • the invention solves the problem of particle size control and batch preparation scale of the silica microspheres, reduces the production cost and reduces the environmental pollution.
  • Example 1 is a particle size distribution NTA (particle tracking analysis technique) of uniform silica microspheres prepared in Example 4; in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration ( ⁇ 10 6 /mL). ).
  • Example 2 is a NTA chart of particle size distribution of uniform silica microspheres prepared in Example 5; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration ( ⁇ 10 6 /mL).
  • Example 3 is a NTA chart of particle size distribution of uniform silica microspheres prepared in Example 6; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration ( ⁇ 10 6 /mL).
  • Example 4 is a NTA chart of particle size distribution of uniform silica microspheres prepared in Example 7; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration ( ⁇ 10 6 /mL).
  • Example 5 is a NTA chart of particle size distribution of uniform silica microspheres prepared in Example 8; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration ( ⁇ 10 6 /mL).
  • Figure 6 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 9; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
  • FIG. 7 is a particle size distribution NTA diagram of the uniform silica microspheres prepared in Example 10 (FIG. 7A); in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration ( ⁇ 10 6 /mL); Figure 7B is an SEM image of silica microspheres; Figure 7C silica assembled into a monolayer film with an ultraviolet-visible absorption spectrum.
  • Figure 8 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 11 (Fig. 8A); in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration ( ⁇ 10 6 /mL); Figure 8B silica assembled into a monolayer film with an ultraviolet-visible absorption spectrum.
  • Figure 9 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 12; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
  • Figure 10 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 13 (Fig. 10A); in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration ( ⁇ 10 6 /mL);
  • Figure 10B shows the silica assembled into a monolayer film with an ultraviolet-visible absorption spectrum.
  • Figure 11 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 14 (Fig. 11A); in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration ( ⁇ 10 6 /mL);
  • Figure 11B Silica assembled into a monolayer film with an ultraviolet-visible absorption spectrum.
  • Figure 12 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 15; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
  • Figure 13 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 17; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
  • Figure 14 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 18; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
  • methanol, ethanol, isopropanol, tert-butanol, methyl silicate, ethyl silicate, propyl silicate, ammonia, NaOH and HCl used in the following examples were all analytically pure, and the water was ultrapure water (18.2 m ⁇ ). ).
  • Example 1 adding a mass fraction of 28% aqueous ammonia solution to the above TEOS/(CH 3 ) 2 CHOH-H 2 O mixture, so that the concentration of ammonia in the entire reaction system reaches 0.5 mol/L, under stirring (200 rmp) After 3 hours of reaction, the reaction system changed from clear and transparent to milky white to obtain a silica sol.
  • the silica sol was centrifuged at a room temperature of 20 ° C (rotation speed: 5000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 223 nm.
  • Example 2 adding a mass fraction of 28% aqueous ammonia solution to the above TEOS/(CH 3 ) 2 CHOH-H 2 O mixture, so that the concentration of ammonia in the entire reaction system reaches 2.0 mol/L, under stirring (200 rpm) After the next reaction for 2 hours, the reaction system changed from clear and transparent to milky white to obtain a silica sol.
  • the silica sol was centrifuged at a room temperature of 20 ° C (rotation speed: 5000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 278 nm.
  • Example 3 adding a mass fraction of 28% aqueous ammonia solution to the above TEOS/(CH 3 ) 2 CHOH-H 2 O mixed solution, so that the concentration of ammonia in the entire reaction system reaches 5.0 mol/L, under stirring (200 rpm) After 1 h of reaction, the reaction system changed from clear and transparent to milky white to obtain a silica sol.
  • the silica sol was centrifuged at a room temperature of 20 ° C (rotation speed: 5000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 354 nm.
  • Example 4 adding a mass fraction of 28% aqueous ammonia solution to the above TEOS/C 2 H 5 OH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches 2.0 mol/L, under stirring (200 rpm) After reacting for 2 hours, the reaction system changed from clear and transparent to milky white to obtain a silica sol.
  • the silica sol was centrifuged at a temperature of 20 ° C at a temperature of 20 ° C (rotation speed 5000 rpm, time 10 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 320 nm (see Figure 1). .
  • Example 5 After the above TEOS/C 2 H 5 OH-H 2 O mixture was kept at a constant temperature of 40 ° C for 15 min, a mass fraction of 28% aqueous ammonia solution was added to make the concentration of ammonia in the entire reaction system reach 2.0 mol/L. After 1.5 h of reaction under stirring (200 rpm), the reaction system changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a temperature of 20 ° C (rotation speed 10000 rpm, time 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle diameter of 184 nm (see FIG. 2).
  • Example 6 After the above TEOS/C 2 H 5 OH-H 2 O mixture was kept at 60 ° C for 25 min, a mass fraction of 28% aqueous ammonia solution was added to make the concentration of ammonia in the whole reaction system reach 2.0 mol/L. After reacting for 1 hour under stirring (200 rpm), the reaction system changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 13000 rmp, time 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 105 nm (see Fig. 3).
  • Example 7 (1) 50 ml of water and 1 ml of TEOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) 40 mL of ethanol was added to the TEOS/H 2 O emulsion, and stirred at room temperature (20 ° C) for 2 hours at room temperature, and the system became clear and transparent from turbidity to obtain a clear and transparent TEOS/C 2 H 5 OH-H. 2 O mixed solution; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture was 0.05 M.
  • Example 8 (1) 25 ml of water and 5 ml of TEOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 35 ml of ethanol to the TEOS/H 2 O emulsion and stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours. The system is clear and transparent from turbidity to obtain clear and transparent TEOS/C 2 H 5 OH-H. 2 O mixed liquor; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture was 0.36 M.
  • silica sol was centrifuged at a temperature of 20 ° C (rotation speed 15000 rmp, 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 96 nm (see Fig. 6).
  • silica sol was centrifuged at a temperature of 20 ° C (rotation speed 8000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 157 nm (see Fig. 7A). SEM image of silica microspheres (see Figure 7B). As can be seen from Fig. 7B, the silica microspheres are smooth, solid spheres.
  • the 157 nm silica microspheres prepared above were dispersed in an aqueous solution of ethanol having a volume ratio of 1:1, dropped onto a quartz glass plate, and dried to form a silicon dioxide film.
  • the ultraviolet-visible absorption test was carried out, and the test results are shown in Fig. 7C.
  • the silica microspheres obtained by the present invention can be easily assembled to obtain a silicon dioxide film which is obviously absorbed at 350 nm, and can be further assembled into an optical device capable of absorbing light having a wavelength of about 350 nm.
  • silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 6000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle diameter of 200 nm (see Fig. 8A).
  • the 200 nm silica microspheres prepared above were dispersed in an aqueous solution of ethanol having a volume ratio of 1:1, dropped onto a quartz glass plate, and dried to form a silicon dioxide film.
  • the ultraviolet-visible absorption test was carried out, and the test results are shown in Fig. 8B.
  • the silica microspheres obtained by the present invention can be easily assembled to obtain a silicon dioxide film which is significantly absorbed at 490 nm, and can be further assembled into an optical device capable of absorbing light having a wavelength of about 490 nm.
  • silica sol was centrifuged at a temperature of 20 ° C (rotation speed 8000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 130 nm (see Fig. 9).
  • silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 6000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle diameter of 180 nm (see FIG. 10A).
  • the 180 nm silica microspheres prepared above were dispersed in an aqueous solution of ethanol having a volume ratio of 1:1, dropped onto a quartz glass plate, and dried to form a silicon dioxide film.
  • the ultraviolet-visible absorption test was carried out, and the test results are shown in Fig. 10B.
  • the silica microspheres obtained by the present invention can be easily assembled to obtain a silicon dioxide film which is obviously absorbed at 390 nm, and can be further assembled into an optical device capable of absorbing light having a wavelength of about 390 nm.
  • silica sol was centrifuged at a room temperature of 20 ° C (rotation speed: 5000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 228 nm (see FIG. 11A).
  • the 228 nm silica microspheres prepared above were dispersed in an aqueous solution of ethanol having a volume ratio of 1:1, dropped onto a quartz glass plate, and dried to form a silicon dioxide film.
  • the ultraviolet-visible absorption test was carried out, and the test results are shown in Fig. 11B.
  • the silica microspheres obtained by the present invention can be easily assembled to obtain a silicon dioxide film which is obviously absorbed at 500 nm, and can be further assembled into an optical device capable of absorbing light having a wavelength of about 500 nm.
  • Example 15 A concentrated HCl solution was added dropwise to the above TEOS/C 2 H 5 OH-H 2 O mixture to bring the concentration of HCl in the mixture to 1.5 ⁇ 10 -3 mol/L. After 5 minutes, a mass fraction of 28% aqueous ammonia solution was added to bring the concentration of ammonia in the entire reaction system to 2.0 mol/L. After reacting for 2 hours under stirring (200 rpm), the reaction system was changed from clear and transparent to milky white to obtain a silica sol.
  • the silica sol was centrifuged at a temperature of 20 ° C (rotation speed 9000 rpm, time 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 193 nm (see FIG. 12).
  • Example 16 A concentrated HCl solution was added dropwise to the above TEOS/C 2 H 5 OH-H 2 O mixture to bring the concentration of HCl in the mixture to 1.5 ⁇ 10 -2 mol/L. After 5 minutes, a mass fraction of 28% aqueous ammonia solution was added to bring the concentration of ammonia in the entire reaction system to 2.0 mol/L. After reacting for 2 hours under stirring (200 rpm), the reaction system was changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 5000 rpm, time 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle diameter of 210 nm.
  • silica microspheres having different particle diameters and uniform particle sizes can be prepared by adjusting the acid-base combined catalyst by the embodiment of the present invention.
  • silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 3000 rpm, time 20 min), and the silica sol was washed three times with ethanol to obtain silica microspheres having an average particle size of 398 nm. Figure 14).
  • TEOS/C 2 H 5 OH-H 2 O mixture can be prepared by using different homogenization methods according to the embodiment of the present invention.
  • the silica microspheres were prepared by using alcohol as a solvent, water as a reactant, and ammonia as a catalyst. Generally, the alcohol, water and the catalyst are first mixed to obtain an alcohol-water-ammonia aqueous solution, and then, under stirring, the silicate/alcohol solution is added dropwise to the alcohol-water-ammonia aqueous solution, and the silicate is hydrolyzed to obtain (Si). (OH) 4 ), Si(OH) 4 polycondensation-nucleation growth, to obtain silica microspheres. The silicate/alcohol solution is mixed with the alcohol-water-ammonia aqueous solution, and the silicate hydrolysis and polycondensation process is carried out simultaneously.
  • the controllability of the preparation of the silica microspheres is poor, and the reaction system is difficult to amplify.
  • the invention mainly uses an aqueous medium as a solvent, and firstly prepares a reactant organosilicon compound, a small molecule alcohol and a solvent into a uniform organosilicon compound/alcohol-H 2 O mixture, and modulates the organosilicon compound/alcohol-H 2 O mixture.
  • System uniformity which in turn controls the uniformity of the silica microspheres.
  • the invention can effectively avoid the problems existing in the preparation technology of the existing silica microspheres, the control system uniformity and the uniformity of the particle uniformity, and the problem that the reaction scale is difficult to enlarge.

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Abstract

Provided are a uniform silica microsphere, a preparation method therefor, and an application thereof. The method comprises the following steps: (1) mixing an organosilicon compound and an aqueous medium according to a certain ratio to obtain an organosilicon compound/H2O emulsion; (2) adding a small molecule alcohol or mixed small-molecule alcohol solution to the organosilicon compound/H2O emulsion of step (1), to obtain a transparent organosilicon compound/alcohol-H2O mixture; (3) adding a catalyst to the organosilicon compound/alcohol-H2O mixture of step (2) to conduct a hydrolytic polycondensation reaction, turning the transparent organosilicon compound/alcohol-H2O mixture into a milky-white silica sol; and (4) subjecting the silica sol of step (3) to centrifugal separation to obtain the uniform silica microspheres. The method uses an aqueous medium as a solvent, and features a simple and controllable process, mild conditions, a uniform and controllable particle size, and large batches of reaction, and can overcome various disadvantages in the prior art and has wide application prospects.

Description

一种均匀二氧化硅微球及其制备方法和应用Uniform silica microsphere and preparation method and application thereof 技术领域Technical field
本发明涉及一种均匀二氧化硅微球及其制备方法，具体涉及一种绿色、批量二氧化硅微球及其制备方法，属于化学及无机材料类技术领域。The invention relates to a uniform silica microsphere and a preparation method thereof, in particular to a green and batch silica microsphere and a preparation method thereof, and belongs to the technical field of chemical and inorganic materials.
背景技术Background technique
二氧化硅微球是一种无毒、无味的非金属材料，在造纸、塑料、涂料、颜料、橡胶、陶瓷、胶粘剂、化妆品、催化剂载体及抗菌材料等领域有着广泛的应用前景。Silica microspheres are non-toxic, odorless non-metallic materials with broad application prospects in paper, plastics, coatings, pigments, rubber, ceramics, adhesives, cosmetics, catalyst carriers and antibacterial materials.
二氧化硅微球的制备方法有很多，其中，溶胶-凝胶法是制备二氧化硅微球常用的方法之一。该方法是以无机盐或金属醇盐为前驱物，经水解缩聚过程逐渐凝胶化，然后经过后处理(陈化、干燥)得到所需的材料。溶胶-凝胶法具有反应条件温和，微球的粒度可控性较好、颗粒均匀度较高等优点。由于溶胶-凝胶法制备二氧化硅微球影响因素多(主要包括：反应物-水和NH 3的浓度、有机硅化合物的类型(TMOS、TEOS、TPOS等)；溶剂-醇的种类(甲醇、乙醇、丙醇、丁醇等)；催化剂的种类(酸或碱)，以及反应温度等，实际上，制备均匀的二氧化硅微球(特别是批量制备)并非易事。 There are many methods for preparing silica microspheres, and the sol-gel method is one of the commonly used methods for preparing silica microspheres. The method is based on an inorganic salt or a metal alkoxide as a precursor, which is gradually gelled by a hydrolysis polycondensation process, and then subjected to post-treatment (aging, drying) to obtain a desired material. The sol-gel method has the advantages of mild reaction conditions, good controllability of microspheres, and high particle uniformity. There are many factors affecting the preparation of silica microspheres by sol-gel method (mainly including: reactant-water and NH 3 concentration, type of organosilicon compound (TMOS, TEOS, TPOS, etc.); solvent-alcohol type (methanol) , ethanol, propanol, butanol, etc.; the type of catalyst (acid or base), and the reaction temperature, etc. In fact, it is not easy to prepare uniform silica microspheres (especially in batch preparation).
1968年，非专利文献1(J.Colloid Interface Sci.,26,62-69(1968))系统地研究了酯-醇-水-碱体系中，各组分浓度对二氧化硅微球制备速度、颗粒粒径及分布的影响，成功地制备出粒径在0.05～2μm的二氧化硅微球。但是，所制备的球形颗粒均匀性不好，体系稳定性也不理想。In 1968, Non-Patent Document 1 (J. Colloid Interface Sci., 26, 62-69 (1968)) systematically studied the preparation speed of silica microspheres in the ester-alcohol-water-alkali system. With the influence of particle size and distribution, silica microspheres with a particle size of 0.05 to 2 μm were successfully prepared. However, the prepared spherical particles have poor uniformity and the stability of the system is not satisfactory.
目前，利用溶胶-凝胶法，能在一定规模上制备出均匀的二氧化硅微球。一般认为，溶胶-凝胶法制备二氧化硅微球机理符合非专利文献2(J.Am.Chem.Soc.,72,4847-4854(1950))的观点。因此，要制备均匀的二氧化硅微球，必须设法使成核期和生长期分开。而种子生长法便是一种常用的将成核期和生长期分开来制备均匀的二氧化硅微球的方法(CN101913612A,CN10149216A,CN102070152A,CN104003408A,US2006088470A1)。但是，该方法操作步骤较繁琐、影响因素较多、过程不易控制。At present, uniform silica microspheres can be prepared on a certain scale by the sol-gel method. It is considered that the mechanism of preparing silica microspheres by the sol-gel method conforms to the viewpoint of Non-Patent Document 2 (J. Am. Chem. Soc., 72, 4847-4854 (1950)). Therefore, to prepare uniform silica microspheres, it is necessary to try to separate the nucleation phase from the growth phase. The seed growth method is a commonly used method for separating uniform nucleation and growth phases to prepare uniform silica microspheres (CN101913612A, CN10149216A, CN102070152A, CN104003408A, US2006088470A1). However, the operation steps of the method are cumbersome, have many influencing factors, and the process is not easy to control.
均匀的二氧化硅微球的形成过程对条件变化十分敏感，均匀颗粒形成机制至今尚未被完全认识，如何更有效地控制二氧化硅微球的粒径，达到批量制备规模仍是一个难题。此外，溶胶-凝胶法制备均匀二氧化硅微球，一般使用醇作溶剂，制备成本高，易造成环境污染。The formation process of uniform silica microspheres is very sensitive to the change of conditions. The mechanism of uniform particle formation has not yet been fully understood. How to control the particle size of silica microspheres more effectively is still a difficult problem. In addition, the sol-gel method is used to prepare uniform silica microspheres, generally using alcohol as a solvent, which is high in preparation cost and easily causes environmental pollution.
发明内容Summary of the invention
本发明的目的是解决现有溶胶-凝胶法制备二氧化硅微球技术的不足。本发明先将反应物和溶剂配制成均匀透明的有机硅化合物/醇-H 2O混合液，在此基础上，加入碱或酸-碱联合催 化剂，启动水解和缩聚反应，制备二氧化硅微球。本发明解决了二氧化硅微球的粒径控制和批量制备规模问题，降低了生产成本，减轻了环境污染。 The object of the present invention is to solve the deficiencies of the prior art sol-gel process for preparing silica microspheres. The invention firstly prepares the reactant and the solvent into a uniform transparent organosilicon compound/alcohol-H 2 O mixed liquid, and on the basis of this, adding a base or an acid-base combined catalyst to initiate hydrolysis and polycondensation reaction to prepare silica micro ball. The invention solves the problem of particle size control and batch preparation scale of the silica microspheres, reduces the production cost and reduces the environmental pollution.
为了实现以上目的，本发明采取的技术方案为：In order to achieve the above object, the technical solution adopted by the present invention is:
一种均匀二氧化硅微球的制备方法，包括以下步骤：A method for preparing uniform silica microspheres, comprising the steps of:
(1)有机硅化合物/H 2O乳状液的制备：将有机硅化合物与水介质按照一定比例混合，得到有机硅化合物/H 2O乳状液； (1) Preparation of organosilicon compound/H 2 O emulsion: the organosilicon compound and the aqueous medium are mixed in a certain ratio to obtain an organosilicon compound/H 2 O emulsion;
(2)有机硅化合物/醇-H 2O混合液的制备：将一定量的小分子醇或小分子醇的混合溶液与步骤(1)的有机硅化合物/H 2O乳状液进行混合，得到澄清透明的有机硅化合物/醇-H 2O混合液； (2) Preparation of a mixture of an organosilicon compound/alcohol-H 2 O: mixing a certain amount of a mixed solution of a small molecule alcohol or a small molecule alcohol with the organosilicon compound/H 2 O emulsion of the step (1), Clarifying a transparent organosilicon compound/alcohol-H 2 O mixture;
(3)二氧化硅溶胶的制备：向步骤(2)的有机硅化合物/醇-H 2O混合液中加入催化剂，进行水解缩聚反应，由澄清透明有机硅化合物/醇-H 2O混合液制备得到乳白色二氧化硅溶胶；(4)均匀二氧化硅微球的制备：对步骤(3)的二氧化硅溶胶进行离心分离，得到所述二氧化硅微球。 (3) Preparation of silica sol: a catalyst is added to the organosilicon compound/alcohol-H 2 O mixture of the step (2) to carry out a hydrolysis polycondensation reaction, and a clear transparent organosilicon compound/alcohol-H 2 O mixture is obtained. Preparation of a milky white silica sol; (4) Preparation of uniform silica microspheres: The silica sol of the step (3) is subjected to centrifugation to obtain the silica microspheres.
本发明步骤(1)中，所述有机硅化合物与水介质的混合在搅拌条件下进行，所述搅拌的转速为200～300rpm。In the step (1) of the present invention, the mixing of the organosilicon compound and the aqueous medium is carried out under stirring, and the stirring speed is 200 to 300 rpm.
本发明步骤(1)中，所述混合的温度为15～30℃，优选地为，室温(20℃)、30℃。In the step (1) of the present invention, the mixing temperature is 15 to 30 ° C, preferably room temperature (20 ° C), 30 ° C.
本发明步骤(1)中，所述混合的时间为1小时以上；优选地，为1～3小时；进一步优选地，为2小时。In the step (1) of the present invention, the mixing time is 1 hour or longer; preferably, 1 to 3 hours; further preferably, 2 hours.
本发明步骤(1)中，所述有机硅化合物包括硅酸酯(包括但不限于硅酸甲酯、硅酸乙酯、硅酸丙酯等)、硅烷偶联剂(包括但不限于γ-氨丙基三乙氧基硅烷(KH550)、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷(KH560)、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH570)、γ-巯丙基三乙氧基硅烷(KH580)、γ-巯丙基三甲氧基硅烷(KH590)、乙烯基三乙氧基硅烷(KH151)、乙烯基三甲氧基硅烷(KH171)等)中的一种或多种；优选地，为硅酸乙酯(TEOS)。In the step (1) of the present invention, the organosilicon compound includes a silicate (including but not limited to methyl silicate, ethyl silicate, propyl silicate, etc.), a silane coupling agent (including but not limited to γ- Aminopropyltriethoxysilane (KH550), γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560), γ-(methacryloyloxy)propyltrimethoxysilane ( KH570), γ-mercaptopropyltriethoxysilane (KH580), γ-mercaptopropyltrimethoxysilane (KH590), vinyltriethoxysilane (KH151), vinyltrimethoxysilane (KH171) One or more of the others; preferably, ethyl silicate (TEOS).
本发明步骤(1)中，所述水介质包括水和水溶液；优选地，为水，所述水可以但不限于是纯水、或超纯水(18.2mΩ)。所述水溶液是指水的无机盐溶液，包括但不限于NaCl、KNO 3、Na 2SO 4等)。 In the step (1) of the present invention, the aqueous medium comprises water and an aqueous solution; preferably, water, which may be, but not limited to, pure water or ultrapure water (18.2 mΩ). The aqueous solution refers to an inorganic salt solution of water including, but not limited to, NaCl, KNO 3 , Na 2 SO 4 , and the like.
本发明步骤(1)中，所述有机硅化合物与水介质的体积比：1:50≤V 有机硅化合物：V H2O≤1:5，优选地为，1:5、1:10、1:50、3:50。 In the step (1) of the present invention, the volume ratio of the organosilicon compound to the aqueous medium is 1:50 ≤ V organosilicon compound : V H2O ≤ 1:5, preferably 1:5, 1:10, 1: 50, 3:50.
本发明步骤(2)中，所述混合的方法可以是任何可实现混合效果的方法，例如可以是搅拌、超声、高速剪切、齿轮粉碎、涡流粉碎、旋涡粉碎等；优选地，为搅拌、超声、旋涡粉 碎；进一步优选地，为搅拌(转速200rmp～300rmp)2h；或，超声30min(功率40KHz)；或，旋涡粉碎5min(压力2.5atm)。In the step (2) of the present invention, the mixing method may be any method that can achieve a mixing effect, and may be, for example, stirring, ultrasonic, high-speed shearing, gear crushing, vortex pulverization, vortex pulverization, etc.; preferably, stirring, Ultrasonic, vortex pulverization; further preferably, stirring (rotation speed 200 rpm to 300 rpm) 2 h; or, ultrasonic 30 min (power 40 kHz); or, vortex pulverization for 5 min (pressure 2.5 atm).
本发明步骤(2)中，所述混合的温度为15～30℃，优选地为，室温(20℃)。In the step (2) of the present invention, the mixing temperature is 15 to 30 ° C, preferably room temperature (20 ° C).
本发明步骤(2)中，所述混合的时间为1～3小时，优选地为2小时。In the step (2) of the present invention, the mixing time is from 1 to 3 hours, preferably 2 hours.
本发明步骤(2)中，所述小分子醇分子式为ROH，其中R为C1-C4的烷基；优选地，所述小分子醇包括甲醇(CH 3OH)、乙醇(C 2H 5OH)、正丙醇(CH 3CH 2CH 2OH)、异丙醇((CH 3) 2CHOH)、仲丁醇(CH 3CH 2CH(OH)CH 3)、叔丁醇((CH 3) 3COH)中的一种或多种；进一步优选地，为乙醇，甲醇和异丙醇的混合溶液，甲醇和叔丁醇的混合溶液；进一步优选地，为乙醇，体积比为3:1的甲醇和异丙醇的混合溶液，体积比为1:1的甲醇和异丙醇的混合溶液，体积比为1:3的甲醇和异丙醇的混合溶液，体积比为3:1的甲醇和叔丁醇的混合溶液，体积比为1:1的甲醇和叔丁醇的混合溶液，或体积比为1:3的甲醇和叔丁醇的混合溶液。 In the step (2) of the present invention, the small molecule alcohol has the formula ROH, wherein R is a C1-C4 alkyl group; preferably, the small molecule alcohol comprises methanol (CH 3 OH), ethanol (C 2 H 5 OH) ), n-propanol (CH 3 CH 2 CH 2 OH), isopropanol ((CH 3 ) 2 CHOH), sec-butanol (CH 3 CH 2 CH(OH)CH 3 ), tert-butanol (CH 3 ) One or more of 3 COH); further preferably, a mixed solution of ethanol, methanol and isopropanol, a mixed solution of methanol and t-butanol; further preferably, ethanol, in a volume ratio of 3:1 a mixed solution of methanol and isopropanol, a mixed solution of methanol and isopropanol in a volume ratio of 1:1, a mixed solution of methanol and isopropanol in a volume ratio of 1:3, and a methanol ratio of 3:1 by volume. A mixed solution of t-butanol, a mixed solution of methanol and t-butanol in a volume ratio of 1:1, or a mixed solution of methanol and t-butanol in a volume ratio of 1:3.
本发明步骤(2)中，所述小分子醇可以但不限于是分析纯。In the step (2) of the present invention, the small molecule alcohol may be, but not limited to, analytically pure.
本发明步骤(2)中，所述小分子醇与有机硅化合物/H 2O乳状液的体积比为1:2～8:5；优选地，为3:5～7:5；进一步优选地为，10:11、40:33、40:51、7:6、45:33、32:33、27:33、28:53、50:33或4:3。 In the step (2) of the present invention, the volume ratio of the small molecule alcohol to the organosilicon compound/H 2 O emulsion is from 1:2 to 8:5; preferably, from 3:5 to 7:5; further preferably For, 10:11, 40:33, 40:51, 7:6, 45:33, 32:33, 27:33, 28:53, 50:33 or 4:3.
本发明步骤(2)中，所述有机硅化合物在有机硅化合物/醇-H 2O混合液中的浓度为0.05～0.5M，优选地为0.05～0.42M；进一步优选地，为0.05M、0.12M、0.15M、0.16M、0.17M、0.19M、0.20M、0.21M、0.22M、0.36M、0.42M。 In the step (2) of the present invention, the concentration of the organosilicon compound in the organosilicon compound/alcohol-H 2 O mixture is 0.05 to 0.5 M, preferably 0.05 to 0.42 M; further preferably 0.05 M, 0.12 M, 0.15 M, 0.16 M, 0.17 M, 0.19 M, 0.20 M, 0.21 M, 0.22 M, 0.36 M, 0.42 M.
本发明步骤(3)中，所述水解缩聚反应在20～60℃条件下进行，优选地，为20℃～40℃、40℃～60℃；进一步优选地，为室温(20℃)、40℃、60℃。In the step (3) of the present invention, the hydrolysis polycondensation reaction is carried out at 20 to 60 ° C, preferably 20 ° C to 40 ° C, 40 ° C to 60 ° C; further preferably, room temperature (20 ° C), 40 °C, 60 °C.
本发明步骤(3)中，所述水解缩聚反应的时间为1～5h；优选地，为2～5h，或优选地，为1h、2h、3h、4h、5h。In the step (3) of the present invention, the hydrolysis polycondensation reaction is carried out for 1 to 5 hours; preferably, 2 to 5 hours, or preferably 1 hour, 2 hours, 3 hours, 4 hours, and 5 hours.
本发明步骤(3)中，所述水解缩聚反应在搅拌条件下进行，所述搅拌的转速为200～300rpm。In the step (3) of the present invention, the hydrolysis polycondensation reaction is carried out under stirring, and the stirring speed is 200 to 300 rpm.
本发明步骤(3)中，所述催化剂包括强碱催化剂、弱碱催化剂或酸-碱联合催化剂；所述强碱催化剂包括NaOH、KOH。所述弱碱催化剂包括氨水、Na 2CO 3、NaAc；进一步优选地，为。所述酸-碱联合催化剂选自盐酸-氨水(HCl-NH 3﹒H 2O)、硝酸-氨水(HNO 3-NH 3﹒H 2O)、硫酸-氨水(H 2SO 4-NH 3﹒H 2O)；优选地，为NaOH、氨水、盐酸-氨水(HCl-NH 3﹒H 2O)；进一步优选地，为28％(质量分数)的氨水溶液或浓盐酸-28％(质量分数)氨水。 In the step (3) of the present invention, the catalyst comprises a strong base catalyst, a weak base catalyst or an acid-base combined catalyst; the strong base catalyst comprises NaOH, KOH. The weak base catalyst includes ammonia water, Na 2 CO 3 , NaAc; further preferably, . The acid-base combination catalyst is selected from the group consisting of hydrochloric acid-ammonia water (HCl-NH 3 .H 2 O), nitric acid-ammonia water (HNO 3 -NH 3 .H 2 O), and sulfuric acid-ammonia water (H 2 SO 4 -NH 3 . H 2 O); preferably, NaOH, ammonia water, hydrochloric acid-ammonia water (HCl-NH 3 .H 2 O); further preferably, 28% (mass fraction) of aqueous ammonia solution or concentrated hydrochloric acid -28% (mass fraction) )ammonia.
本发明步骤(3)中，向步骤(2)的有机硅化合物/醇-H 2O混合液中加入催化剂，启动水解缩聚反应。所述催化剂在整个反应体系中的浓度为0.01～5.0mol/L；优选地，为0.01～0.03 mol/L、0.5～5.0mol/L；进一步优选地，为0.02mol/L、0.5mol/L、2.0mol/L、3.0mol/L或5.0mol/L。 In the step (3) of the present invention, a catalyst is added to the organosilicon compound/alcohol-H 2 O mixture of the step (2) to initiate a hydrolysis polycondensation reaction. The concentration of the catalyst in the entire reaction system is 0.01 to 5.0 mol/L; preferably, 0.01 to 0.03 mol/L, 0.5 to 5.0 mol/L; further preferably 0.02 mol/L, 0.5 mol/L. , 2.0 mol / L, 3.0 mol / L or 5.0 mol / L.
优选地，当使用强碱作为催化剂时，整个反应体系中强碱催化剂的浓度为0.01～0.03mol/L；优选地为，0.02mol/L。Preferably, when a strong base is used as the catalyst, the concentration of the strong base catalyst in the entire reaction system is from 0.01 to 0.03 mol/L; preferably, from 0.02 mol/L.
优选地，当使用弱碱作为催化剂时，整个反应体系中弱碱催化剂的浓度为0.5～5.0mol/L；优选地为，0.5mol/L、2.0mol/L、3.0mol/L或5.0mol/L。进一步优选地，整个反应体系中氨水催化剂的浓度为0.5～5.0mol/L；进一步优选地，整个反应体系中氨水催化剂的浓度为0.5mol/L、2.0mol/L、3.0mol/L或5.0mol/L。Preferably, when a weak base is used as the catalyst, the concentration of the weak base catalyst in the entire reaction system is from 0.5 to 5.0 mol/L; preferably, 0.5 mol/L, 2.0 mol/L, 3.0 mol/L or 5.0 mol/ L. Further preferably, the concentration of the aqueous ammonia catalyst in the entire reaction system is 0.5 to 5.0 mol/L; further preferably, the concentration of the aqueous ammonia catalyst in the entire reaction system is 0.5 mol/L, 2.0 mol/L, 3.0 mol/L or 5.0 mol. /L.
优选地，当使用酸-碱作为催化剂时，整个反应体系中酸-碱联合催化剂中的酸浓度为10 -3～10 -2mol/L，优选地为，1.5×10 -3mol/L、1.5×10 -2mol/L；碱浓度1.0～5.0mol/L，优选地为，0.5mol/L、2.0mol/L、3.0mol/L、或5.0mol/L。进一步优选地，盐酸浓度为1.5×10 -3mol/L、1.5×10 -2mol/L；氨的浓度为0.5mol/L、2.0mol/L、3.0mol/L、或5.0mol/L。 Preferably, when an acid-base is used as the catalyst, the acid concentration in the acid-base combination catalyst in the entire reaction system is from 10 -3 to 10 -2 mol/L, preferably, from 1.5 × 10 -3 mol/L, 1.5×10 -2 mol/L; alkali concentration: 1.0 to 5.0 mol/L, preferably 0.5 mol/L, 2.0 mol/L, 3.0 mol/L, or 5.0 mol/L. Further preferably, the hydrochloric acid concentration is 1.5 × 10 -3 mol / L, 1.5 × 10 -2 mol / L; the concentration of ammonia is 0.5 mol / L, 2.0 mol / L, 3.0 mol / L, or 5.0 mol / L.
本发明步骤(3)中，优选地，酸-碱联合催化剂的加入方式为，在步骤(2)制备的有机硅化合物/醇-H 2O混合液的中先加酸，5min后再加碱。 In the step (3) of the present invention, preferably, the acid-base combination catalyst is added by adding an acid to the organosilicon compound/alcohol-H 2 O mixture prepared in the step (2), and then adding the alkali after 5 minutes. .
本发明步骤(3)中，优选地，在加入催化剂进行水解缩聚反应前，先将步骤(2)制备的有机硅化合物/醇-H 2O混合液加热至反应温度，并保温15min～25min；优选地，保温15min或25min。 In the step (3) of the present invention, preferably, before adding the catalyst to carry out the hydrolysis polycondensation reaction, the organosilicon compound/alcohol-H 2 O mixture prepared in the step (2) is heated to the reaction temperature, and kept for 15 min to 25 min; Preferably, the incubation is for 15 min or 25 min.
本发明步骤(4)中，所述离心分离的条件为：转速可以是3000rmp以上、4000rmp以上或5000rmp以上；优选地，为3000～15000rmp、4000～15000rmp或5000～15000rmp；进一步优选地，为3000、4000、5000rmp、6000rmp、8000rmp、9000rmp、10000rmp、12000rmp、13000rmp、15000rmp。In the step (4) of the present invention, the centrifugal separation condition is that the rotation speed may be 3000 rpm or more, 4000 rpm or more or 5000 rpm or more; preferably, 3000 to 15000 rpm, 4000 to 15000 rpm or 5000 to 15000 rpm; further preferably, 3000. 4000, 5000rmp, 6000rmp, 8000rmp, 9000rmp, 10000rmp, 12000rmp, 13000rmp, 15000rmp.
本发明步骤(4)中，所述离心分离的温度为20～30℃；优选地，为室温(20℃)。In the step (4) of the present invention, the temperature of the centrifugation is 20 to 30 ° C; preferably, it is room temperature (20 ° C).
本发明步骤(4)中，所述离心分离的时间为10～30min；优选地，为10min、20min、30min。In the step (4) of the present invention, the centrifugation time is 10 to 30 min; preferably, 10 min, 20 min, and 30 min.
本发明步骤(4)中，所述离心分离后还可以包括采用有机溶剂对制备的均匀二氧化硅微球进行洗涤的步骤，优选地，用乙醇对均匀二氧化硅微球洗涤3次。In the step (4) of the present invention, after the centrifugation, the step of washing the prepared uniform silica microspheres with an organic solvent may be further included, and preferably, the uniform silica microspheres are washed 3 times with ethanol.
本发明中，制备方法条件不同，制备得到的均匀二氧化硅微球不同，但采用本发明的特定条件制备得到的二氧化硅微球大小均一，可以制备的二氧化硅微球的粒径范围为57～467nm之间(如，可以是57nm、96nm、104nm、105nm、122nm、130nm、157nm、180nm、184nm、193nm、200nm、203nm、210nm、223nm、228nm、278nm、320nm、325nm、354nm、398nm、467nm)，所述均匀二氧化硅微球表面光滑、呈球形、实心(如实施例10得到的二氧化硅微球SEM图见图7B)。In the present invention, the preparation method has different conditions, and the prepared uniform silica microspheres are different, but the silica microspheres prepared by using the specific conditions of the invention have uniform size, and the particle size range of the prepared silica microspheres can be prepared. Between 57 and 467 nm (eg, 57 nm, 96 nm, 104 nm, 105 nm, 122 nm, 130 nm, 157 nm, 180 nm, 184 nm, 193 nm, 200 nm, 203 nm, 210 nm, 223 nm, 228 nm, 278 nm, 320 nm, 325 nm, 354 nm, 398 nm) 467 nm), the uniform silica microspheres are smooth, spherical, and solid (as shown in FIG. 7B for the SEM image of the silica microspheres obtained in Example 10).
本发明还提出了由所述制备方法制备得到的均匀二氧化硅微球，所述均匀二氧化硅微球粒径大小均一，二氧化硅微球的粒径范围为57～467nm(如，可以是57nm、96nm、104nm、105nm、122nm、130nm、157nm、180nm、184nm、193nm、200nm、203nm、210nm、223nm、228nm、278nm、320nm、325nm、354nm、398nm、467nm)，表面光滑、呈球形、实心(如实施例10得到的二氧化硅微球SEM图见图7B)。The present invention also provides uniform silica microspheres prepared by the preparation method, wherein the uniform silica microspheres have a uniform particle size, and the silica microspheres have a particle size ranging from 57 to 467 nm (eg, Is 57 nm, 96 nm, 104 nm, 105 nm, 122 nm, 130 nm, 157 nm, 180 nm, 184 nm, 193 nm, 200 nm, 203 nm, 210 nm, 223 nm, 228 nm, 278 nm, 320 nm, 325 nm, 354 nm, 398 nm, 467 nm), the surface is smooth, spherical, Solid (see SEM image of the silica microspheres obtained in Example 10).
本发明还提出了所述均匀二氧化硅微球在校正用标准粒子、模型催化剂、无孔色谱填料、胶体晶体、电流变液中的应用。The invention also proposes the use of the uniform silica microspheres in calibration standard particles, model catalysts, non-porous chromatography fillers, colloidal crystals, electrorheological fluids.
本发明提供的均匀二氧化硅微球的制备方法和现有技术相比，具有以下优点：Compared with the prior art, the preparation method of the uniform silica microsphere provided by the invention has the following advantages:
(1)本发明先将反应物和溶剂配制成均一透明的有机硅化合物/醇-H 2O混合液，在此基础上，加入碱或酸-碱联合催化剂，启动水解和缩聚反应，制备出均匀二氧化硅微球。本发明步骤(1)得到的有机硅化合物/H 2O乳状液和步骤(2)得到的有机硅化合物/醇-H 2O混合液为均一性的体系，通过调控反应体系的均一性，来控制最终制备的二氧化硅微球的均匀度。可有效避免现有二氧化硅微球制备技术中存在的，反应体系均一性和颗粒均匀度控制难，以及反应规模难放大的问题。 (1) In the present invention, the reactant and the solvent are first formulated into a uniform transparent organosilicon compound/alcohol-H 2 O mixture, and on this basis, a base or an acid-base combination catalyst is added to initiate hydrolysis and polycondensation reaction to prepare a solution. Uniform silica microspheres. The organosilicon compound/H 2 O emulsion obtained in the step (1) of the present invention and the organosilicon compound/alcohol-H 2 O mixture obtained in the step (2) are a homogeneous system, by regulating the uniformity of the reaction system. The uniformity of the finally prepared silica microspheres was controlled. The invention can effectively avoid the problems existing in the preparation technology of the existing silica microspheres, the control system uniformity and the uniformity of the particle uniformity, and the problem that the reaction scale is difficult to enlarge.
(2)本发明主要以水介质做溶剂制备均匀二氧化硅微球，可有效减低生产成本，减少污染物排放。(2) The invention mainly prepares uniform silica microspheres by using an aqueous medium as a solvent, which can effectively reduce production cost and reduce pollutant emissions.
(3)本发明具有方法简单、条件温和、颗粒大小均匀可控且反应批量大等特点。(3) The invention has the characteristics of simple method, mild conditions, uniform and controllable particle size and large reaction batch size.
本发明解决了二氧化硅微球的粒径控制和批量制备规模问题，降低了生产成本，减轻了环境污染。The invention solves the problem of particle size control and batch preparation scale of the silica microspheres, reduces the production cost and reduces the environmental pollution.
附图说明DRAWINGS
图1是实施例4制备的均匀二氧化硅微球的粒度分布NTA(颗粒跟踪分析技术)图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 1 is a particle size distribution NTA (particle tracking analysis technique) of uniform silica microspheres prepared in Example 4; in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration (×10 6 /mL). ).
图2是实施例5制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 2 is a NTA chart of particle size distribution of uniform silica microspheres prepared in Example 5; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (×10 6 /mL).
图3是实施例6制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 3 is a NTA chart of particle size distribution of uniform silica microspheres prepared in Example 6; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (×10 6 /mL).
图4是实施例7制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 4 is a NTA chart of particle size distribution of uniform silica microspheres prepared in Example 7; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (×10 6 /mL).
图5是实施例8制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 5 is a NTA chart of particle size distribution of uniform silica microspheres prepared in Example 8; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (×10 6 /mL).
图6是实施例9制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小 (nm)，纵坐标为颗粒浓度(×10 6个/mL)。 Figure 6 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 9; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
图7是实施例10制备的均匀二氧化硅微球的粒度分布NTA图(图7A)；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)；图7B二氧化硅微球的SEM图；图7C二氧化硅组装成单层膜，其紫外-可见吸收光谱图。 7 is a particle size distribution NTA diagram of the uniform silica microspheres prepared in Example 10 (FIG. 7A); in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration (×10 6 /mL); Figure 7B is an SEM image of silica microspheres; Figure 7C silica assembled into a monolayer film with an ultraviolet-visible absorption spectrum.
图8是实施例11制备的均匀二氧化硅微球的粒度分布NTA图(图8A)；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)；图8B二氧化硅组装成单层膜，其紫外-可见吸收光谱图。 Figure 8 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 11 (Fig. 8A); in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration (×10 6 /mL); Figure 8B silica assembled into a monolayer film with an ultraviolet-visible absorption spectrum.
图9是实施例12制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 Figure 9 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 12; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
图10是实施例13制备的均匀二氧化硅微球的粒度分布NTA图(图10A)；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)；图10B二氧化硅组装成单层膜，其紫外-可见吸收光谱图。 Figure 10 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 13 (Fig. 10A); in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration (×10 6 /mL); Figure 10B shows the silica assembled into a monolayer film with an ultraviolet-visible absorption spectrum.
图11是实施例14制备的均匀二氧化硅微球的粒度分布NTA图(图11A)；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)；图11B二氧化硅组装成单层膜，其紫外-可见吸收光谱图。 Figure 11 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 14 (Fig. 11A); in the figure, the abscissa is the particle size (nm), and the ordinate is the particle concentration (×10 6 /mL); Figure 11B Silica assembled into a monolayer film with an ultraviolet-visible absorption spectrum.
图12是实施例15制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 Figure 12 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 15; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
图13是实施例17制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 Figure 13 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 17; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
图14是实施例18制备的均匀二氧化硅微球的粒度分布NTA图；图中，横坐标为粒度大小(nm)，纵坐标为颗粒浓度(×10 6个/mL)。 Figure 14 is a graph showing the particle size distribution NTA of the uniform silica microspheres prepared in Example 18; in the figure, the abscissa is the particle size (nm) and the ordinate is the particle concentration (x 10 6 /mL).
具体实施方式detailed description
结合以下具体实施例和附图，对本发明作进一步地详细说明，本发明的保护内容不局限于以下实施例。在不背离发明构思的精神和范围下，本领域技术人员能够想到的变化和优点都被包括在本发明中，并且以所附的权利要求书为保护范围。实施本发明的过程、条件、试剂、实验方法等，除以下专门提及的内容之外，均为本领域的普遍知识和公知常识，本发明没有特别限制内容。The present invention will be further described in detail in conjunction with the following specific embodiments and drawings, which are not limited to the following embodiments. Variations and advantages that may be conceived by those skilled in the art are intended to be included within the scope of the invention and the scope of the appended claims. The processes, conditions, reagents, experimental methods, and the like of the present invention are generally known in the art and common knowledge in addition to the contents specifically mentioned below, and the present invention is not particularly limited.
以下实施例所用的甲醇、乙醇、异丙醇、叔丁醇，硅酸甲酯、硅酸乙酯、硅酸丙酯，氨水、NaOH、HCl皆为分析纯，水为超纯水(18.2mΩ)。The methanol, ethanol, isopropanol, tert-butanol, methyl silicate, ethyl silicate, propyl silicate, ammonia, NaOH and HCl used in the following examples were all analytically pure, and the water was ultrapure water (18.2 mΩ). ).
实施例1～3(试验条件及结果见表1)Examples 1 to 3 (test conditions and results are shown in Table 1)
在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入150mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。向TEOS/H 2O乳状液中加入30ml异丙醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/(CH 3) 2CHOH-H 2O混合液；其中，所述TEOS在TEOS/(CH 3) 2CHOH-H 2O混合液中的浓度为0.22M。 30 ml of water and 3 ml of TEOS were poured into a 150 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. 30 ml of isopropanol was added to the TEOS/H 2 O emulsion, and the mixture was stirred at room temperature (temperature: 300 rpm) for 2 hours at room temperature, and the system became clear and transparent from turbidity to obtain a clear and transparent TEOS/(CH 3 ) 2 CHOH-H. 2 O mixed solution; wherein the concentration of the TEOS in the TEOS/(CH 3 ) 2 CHOH-H 2 O mixture was 0.22 M.
实施例1:向上述TEOS/(CH 3) 2CHOH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到0.5mol/L，在搅拌(转速200rmp)条件下反应3h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。在室温20℃条件下对二氧化硅溶胶进行离心分离(转速5000rmp，20min)，乙醇洗涤3次，可得到平均粒径223nm大小均匀的二氧化硅微球。 Example 1: adding a mass fraction of 28% aqueous ammonia solution to the above TEOS/(CH 3 ) 2 CHOH-H 2 O mixture, so that the concentration of ammonia in the entire reaction system reaches 0.5 mol/L, under stirring (200 rmp) After 3 hours of reaction, the reaction system changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed: 5000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 223 nm.
实施例2:向上述TEOS/(CH 3) 2CHOH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。在室温20℃条件下对二氧化硅溶胶进行离心分离(转速5000rmp，20min)，乙醇洗涤3次，可得到平均粒径278nm大小均匀的二氧化硅微球。 Example 2: adding a mass fraction of 28% aqueous ammonia solution to the above TEOS/(CH 3 ) 2 CHOH-H 2 O mixture, so that the concentration of ammonia in the entire reaction system reaches 2.0 mol/L, under stirring (200 rpm) After the next reaction for 2 hours, the reaction system changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed: 5000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 278 nm.
实施例3:向上述TEOS/(CH 3) 2CHOH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到5.0mol/L，在搅拌(转速200rmp)条件下反应1h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。在室温20℃条件下对二氧化硅溶胶进行离心分离(转速5000rmp，20min)，乙醇洗涤3次，可得到平均粒径354nm大小均匀的二氧化硅微球。 Example 3: adding a mass fraction of 28% aqueous ammonia solution to the above TEOS/(CH 3 ) 2 CHOH-H 2 O mixed solution, so that the concentration of ammonia in the entire reaction system reaches 5.0 mol/L, under stirring (200 rpm) After 1 h of reaction, the reaction system changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed: 5000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 354 nm.
表1不同浓度催化剂对二氧化硅微球的影响Table 1 Effect of different concentrations of catalyst on silica microspheres
Figure PCTCN2017115818-appb-000001
Figure PCTCN2017115818-appb-000001
从表1所列实施例1～3得到的实验结果可知，采用本发明提出的实施方案，仅仅改变催化剂的浓度和反应时间，便可制备得到粒径不同、粒度均匀的二氧化硅微球，催化剂浓度越大，得到的均匀二氧化硅微球粒径越大。From the experimental results obtained in Examples 1 to 3 listed in Table 1, it is understood that, by using the embodiment of the present invention, only the concentration of the catalyst and the reaction time can be changed, and silica microspheres having different particle diameters and uniform particle sizes can be prepared. The larger the catalyst concentration, the larger the particle size of the obtained uniform silica microspheres.
实施例4～6(试验条件及结果见表2)Examples 4 to 6 (test conditions and results are shown in Table 2)
在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入250mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。向TEOS/H 2O乳状液中加入40ml乙醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的 TEOS/C 2H 5OH-H 2O混合液；其中，所述TEOS在TEOS/C 2H 5OH-H 2O混合液中的浓度为0.19M。 30 ml of water and 3 ml of TEOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. 40 mL of ethanol was added to the TEOS/H 2 O emulsion, and stirred at room temperature (20 ° C) for 2 hours at room temperature. The system became clear and transparent from turbidity to obtain a clear and transparent TEOS/C 2 H 5 OH-H 2 O mixture. a solution; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture is 0.19 M.
实施例4：向上述TEOS/C 2H 5OH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。在室温20℃条件下对二氧化硅溶胶进行离心分离(转速5000rmp，时间10min)二氧化硅溶胶，乙醇洗涤3次，可得到平均粒径320nm大小均匀的二氧化硅微球(见图1)。 Example 4: adding a mass fraction of 28% aqueous ammonia solution to the above TEOS/C 2 H 5 OH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches 2.0 mol/L, under stirring (200 rpm) After reacting for 2 hours, the reaction system changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a temperature of 20 ° C at a temperature of 20 ° C (rotation speed 5000 rpm, time 10 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 320 nm (see Figure 1). .
实施例5：将上述TEOS/C 2H 5OH-H 2O混合液置于40℃恒温15min后，加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应1.5h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。在室温20℃条件下对二氧化硅溶胶进行离心分离(转速10000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径184nm大小均匀的二氧化硅微球(见图2)。 Example 5: After the above TEOS/C 2 H 5 OH-H 2 O mixture was kept at a constant temperature of 40 ° C for 15 min, a mass fraction of 28% aqueous ammonia solution was added to make the concentration of ammonia in the entire reaction system reach 2.0 mol/L. After 1.5 h of reaction under stirring (200 rpm), the reaction system changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a temperature of 20 ° C (rotation speed 10000 rpm, time 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle diameter of 184 nm (see FIG. 2).
实施例6：将上述TEOS/C 2H 5OH-H 2O混合液置于60℃恒温25min后，加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应1h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。在室温20℃条件下对二氧化硅溶胶进行离心分离(转速13000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径105nm大小均匀的二氧化硅微球(见图3)。 Example 6: After the above TEOS/C 2 H 5 OH-H 2 O mixture was kept at 60 ° C for 25 min, a mass fraction of 28% aqueous ammonia solution was added to make the concentration of ammonia in the whole reaction system reach 2.0 mol/L. After reacting for 1 hour under stirring (200 rpm), the reaction system changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 13000 rmp, time 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 105 nm (see Fig. 3).
表2不同水解缩聚反应温度对二氧化硅微球的影响Table 2 Effect of different hydrolysis polycondensation temperature on silica microspheres
Figure PCTCN2017115818-appb-000002
Figure PCTCN2017115818-appb-000002
从表2所列实施例4～6得到的实验结果可知，采用本发明提出的实施方案，通过改变反应温度和反应时间，便可制备出粒径不同、粒度均匀的二氧化硅微球，反应温度越高，二氧化硅微球粒径越小。From the experimental results obtained in Examples 4 to 6 listed in Table 2, it is understood that by using the embodiment of the present invention, by changing the reaction temperature and the reaction time, silica microspheres having different particle diameters and uniform particle sizes can be prepared. The higher the temperature, the smaller the particle size of the silica microspheres.
实施例7～8(试验条件及结果见表3)Examples 7 to 8 (test conditions and results are shown in Table 3)
实施例7：(1)在室温20℃和搅拌条件下，将50ml水和1ml TEOS注入250mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入40ml乙醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/C 2H 5OH-H 2O混合液；其中，所述TEOS在TEOS/C 2H 5OH-H 2O混合液中 的浓度为0.05M。(3)向TEOS/C 2H 5OH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为微乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速15000rmp，时间30min)，乙醇洗涤3次，可得到平均粒径57nm大小均匀的二氧化硅微球(见图4)。 Example 7: (1) 50 ml of water and 1 ml of TEOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) 40 mL of ethanol was added to the TEOS/H 2 O emulsion, and stirred at room temperature (20 ° C) for 2 hours at room temperature, and the system became clear and transparent from turbidity to obtain a clear and transparent TEOS/C 2 H 5 OH-H. 2 O mixed solution; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture was 0.05 M. (3) Adding a 28% ammonia aqueous solution to the TEOS/C 2 H 5 OH-H 2 O mixture, so that the ammonia concentration in the whole reaction system reaches 2.0 mol/L, and the reaction is carried out for 2 hours under stirring (200 rpm). Thereafter, the reaction system was changed from clear and transparent to slightly milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 15000 rpm, time 30 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 57 nm (see Fig. 4).
实施例8：(1)在室温20℃和搅拌条件下，将25ml水和5ml TEOS注入250mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入35ml乙醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/C 2H 5OH-H 2O混合液；其中，所述TEOS在TEOS/C 2H 5OH-H 2O混合液中的浓度为0.36M。(3)向TEOS/C 2H 5OH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速4000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径467nm大小均匀的二氧化硅微球(见图5)。 Example 8: (1) 25 ml of water and 5 ml of TEOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 35 ml of ethanol to the TEOS/H 2 O emulsion and stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours. The system is clear and transparent from turbidity to obtain clear and transparent TEOS/C 2 H 5 OH-H. 2 O mixed liquor; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture was 0.36 M. (3) Adding a 28% ammonia aqueous solution to the TEOS/C 2 H 5 OH-H 2 O mixture, so that the ammonia concentration in the whole reaction system reaches 2.0 mol/L, and the reaction is carried out for 2 hours under stirring (200 rpm). Thereafter, the reaction system was changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 4000 rpm, time 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 467 nm (see FIG. 5).
表3不同浓度TEOS对二氧化硅微球的影响Table 3 Effect of different concentrations of TEOS on silica microspheres
Figure PCTCN2017115818-appb-000003
Figure PCTCN2017115818-appb-000003
从表3所列实施例4、7、8得到的实验结果可知，采用本发明提出的实施方案，通过改变有机硅化合物的浓度，便可制备出粒径不同、粒度均匀的二氧化硅微球，有机硅化合物的浓度越大，二氧化硅微球粒径越大。From the experimental results obtained in Examples 4, 7, and 8 listed in Table 3, it is understood that by using the embodiment of the present invention, by changing the concentration of the organosilicon compound, silica microspheres having different particle diameters and uniform particle sizes can be prepared. The greater the concentration of the organosilicon compound, the larger the particle size of the silica microspheres.
实施例9～11(试验条件及结果见表4)Examples 9 to 11 (test conditions and results are shown in Table 4)
实施例9：(1)在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入150mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入50ml醇混合溶液(甲醇:异丙醇＝3:1v/v)，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液；其中，所述TEOS在TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液中的浓度为0.16M。(3)向TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨 的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速15000rmp，20min)，乙醇洗涤3次，可得到平均粒径96nm大小均匀的二氧化硅微球(见图6)。 Example 9: (1) 30 ml of water and 3 ml of TEOS were poured into a 150 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 50 ml of an alcohol mixed solution (methanol: isopropanol = 3:1 v/v) to the TEOS/H 2 O emulsion, and stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours, and the system is clarified by turbidity. Transparent to give a clear and transparent mixture of TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O; wherein the TEOS is in a mixture of TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O The concentration is 0.16M. (3) Adding a mass fraction of 28% ammonia solution to the TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches 2.0 mol/L, stirring (200 rmp) After reacting for 2 h under the conditions, the reaction system changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a temperature of 20 ° C (rotation speed 15000 rmp, 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 96 nm (see Fig. 6).
实施例10：(1)在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入150mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入35ml醇混合溶液(甲醇:异丙醇＝1:1v/v)，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液；其中，所述TEOS在TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液中的浓度为0.20M。(3)向TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速8000rmp，20min)，乙醇洗涤3次，可得到平均粒径157nm大小均匀的二氧化硅微球(见图7A)。二氧化硅微球的SEM图(见图7B)。由图7B可以看出，二氧化硅微球为表面光滑、实心圆球。 Example 10: (1) 30 ml of water and 3 ml of TEOS were poured into a 150 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 35 ml of alcohol mixed solution (methanol: isopropanol = 1:1 v/v) to TEOS/H 2 O emulsion, stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours, and the system is clarified by turbidity. Transparent to give a clear and transparent mixture of TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O; wherein the TEOS is in a mixture of TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O The concentration is 0.20M. (3) Adding a mass fraction of 28% ammonia solution to the TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches 2.0 mol/L, stirring (200 rmp) After reacting for 2 h under the conditions, the reaction system changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a temperature of 20 ° C (rotation speed 8000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 157 nm (see Fig. 7A). SEM image of silica microspheres (see Figure 7B). As can be seen from Fig. 7B, the silica microspheres are smooth, solid spheres.
将上述制备的157nm二氧化硅微球分散于体积比1:1的乙醇水溶液中，滴涂到石英玻璃板上，干燥后，形成一层二氧化硅膜。进行紫外-可见光吸收测试，测试结果见图7C。本发明得到的二氧化硅微球，经过简单的组装，便可得到在350nm处有明显吸收的二氧化硅薄膜，可进一步组装成可吸收波长350nm左右光的光学器件。The 157 nm silica microspheres prepared above were dispersed in an aqueous solution of ethanol having a volume ratio of 1:1, dropped onto a quartz glass plate, and dried to form a silicon dioxide film. The ultraviolet-visible absorption test was carried out, and the test results are shown in Fig. 7C. The silica microspheres obtained by the present invention can be easily assembled to obtain a silicon dioxide film which is obviously absorbed at 350 nm, and can be further assembled into an optical device capable of absorbing light having a wavelength of about 350 nm.
实施例11：(1)在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入150mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入30ml醇混合溶液(甲醇:异丙醇＝1:3v/v)，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液；其中，所述TEOS在TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液中的浓度为0.42M。(3)向TEOS/CH 3OH-(CH 3) 2CHOH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速6000rmp，20min)，乙醇洗涤3次，可得到平均粒径200nm大小均匀的二氧化硅微球(见图8A)。 Example 11: (1) 30 ml of water and 3 ml of TEOS were poured into a 150 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 30 ml of an alcohol mixed solution (methanol: isopropanol = 1:3 v/v) to the TEOS/H 2 O emulsion, and stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours, and the system is clarified by turbidity. Transparent to give a clear and transparent mixture of TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O; wherein the TEOS is in a mixture of TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O The concentration is 0.42M. (3) Adding a mass fraction of 28% ammonia solution to the TEOS/CH 3 OH-(CH 3 ) 2 CHOH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches 2.0 mol/L, stirring (200 rmp) After reacting for 2 h under the conditions, the reaction system changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 6000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle diameter of 200 nm (see Fig. 8A).
将上述制备的200nm二氧化硅微球分散于体积比1:1的乙醇水溶液中，滴涂到石英玻璃板上，干燥后，形成一层二氧化硅膜。进行紫外-可见光吸收测试，测试结果见图8B。本发明得到的二氧化硅微球，经过简单的组装，便可得到在490nm处有明显吸收的二氧化硅薄膜， 可进一步组装成可吸收波长490nm左右光的光学器件。The 200 nm silica microspheres prepared above were dispersed in an aqueous solution of ethanol having a volume ratio of 1:1, dropped onto a quartz glass plate, and dried to form a silicon dioxide film. The ultraviolet-visible absorption test was carried out, and the test results are shown in Fig. 8B. The silica microspheres obtained by the present invention can be easily assembled to obtain a silicon dioxide film which is significantly absorbed at 490 nm, and can be further assembled into an optical device capable of absorbing light having a wavelength of about 490 nm.
表4不同比例甲醇-异丙醇混合对二氧化硅微球的影响Table 4 Effect of different ratios of methanol-isopropanol on silica microspheres
Figure PCTCN2017115818-appb-000004
Figure PCTCN2017115818-appb-000004
从表4所列实施例9～11得到的实验结果可知，采用本发明提出的实施方案，通过改变混合醇溶液中甲醇和异丙醇的体积比，便可制备出粒径不同、粒度均匀的二氧化硅微球，混合醇溶液中异丙醇的体积比越大，二氧化硅微球粒径越大。From the experimental results obtained in Examples 9 to 11 listed in Table 4, it can be seen that by using the embodiment of the present invention, by changing the volume ratio of methanol and isopropanol in the mixed alcohol solution, it is possible to prepare particles having different particle diameters and uniform particle sizes. For silica microspheres, the larger the volume ratio of isopropanol in the mixed alcohol solution, the larger the particle size of the silica microspheres.
实施例12～14(试验条件及结果见表5)Examples 12 to 14 (test conditions and results are shown in Table 5)
实施例12：(1)在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入150mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入45ml醇混合溶液(甲醇:叔丁醇＝3:1v/v)，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液；其中，所述TEOS在TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液中的浓度为0.17M。(3)向TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速8000rmp，20min)，乙醇洗涤3次，可得到平均粒径130nm大小均匀的二氧化硅微球(见图9)。 Example 12: (1) 30 ml of water and 3 ml of TEOS were poured into a 150 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 45 ml of an alcohol mixed solution (methanol: tert-butanol = 3:1 v/v) to the TEOS/H 2 O emulsion, and stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours, and the system is clarified by turbidity. Transparent to give a clear and transparent TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture; wherein the TEOS is in a TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture The concentration is 0.17M. (3) Adding a mass fraction of 28% ammonia solution to the TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches 2.0 mol/L, stirring (200 rmp) After reacting for 2 h under the conditions, the reaction system changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a temperature of 20 ° C (rotation speed 8000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 130 nm (see Fig. 9).
实施例13：(1)在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入150mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入32ml醇混合溶液(甲醇:叔丁醇＝1:1v/v)，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液；其中，所述TEOS在TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液中的浓度为0.21M。(3)向TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到一定值2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速6000rmp，20min)，乙醇洗涤3次，可得到平均粒径180nm大小均匀的二氧化硅微球(见 图10A)。 Example 13: (1) 30 ml of water and 3 ml of TEOS were poured into a 150 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 32 ml of an alcohol mixed solution (methanol: tert-butanol = 1:1 v/v) to the TEOS/H 2 O emulsion, and stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours, and the system is clarified by turbidity. Transparent to give a clear and transparent TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture; wherein the TEOS is in a TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture The concentration was 0.21M. (3) adding a mass fraction of 28% aqueous ammonia solution to the TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches a certain value of 2.0 mol/L, while stirring ( After reacting for 2 hours at a rotation speed of 200 rpm, the reaction system was changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 6000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle diameter of 180 nm (see FIG. 10A).
将上述制备的180nm二氧化硅微球分散于体积比1:1的乙醇水溶液中，滴涂到石英玻璃板上，干燥后，形成一层二氧化硅膜。进行紫外-可见光吸收测试，测试结果见图10B。本发明得到的二氧化硅微球，经过简单的组装，便可得到在390nm处有明显吸收的二氧化硅薄膜，可进一步组装成可吸收波长390nm左右光的光学器件。The 180 nm silica microspheres prepared above were dispersed in an aqueous solution of ethanol having a volume ratio of 1:1, dropped onto a quartz glass plate, and dried to form a silicon dioxide film. The ultraviolet-visible absorption test was carried out, and the test results are shown in Fig. 10B. The silica microspheres obtained by the present invention can be easily assembled to obtain a silicon dioxide film which is obviously absorbed at 390 nm, and can be further assembled into an optical device capable of absorbing light having a wavelength of about 390 nm.
实施例14：(1)在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入150mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入27ml醇混合溶液(甲醇:叔丁醇＝1:3v/v)，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液；其中，所述TEOS在TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液中的浓度为0.22M。(3)向TEOS/CH 3OH-(CH 3) 3COH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速5000rmp，20min)，乙醇洗涤3次，可得到平均粒径228nm大小均匀的二氧化硅微球(见图11A)。 Example 14: (1) 30 ml of water and 3 ml of TEOS were poured into a 150 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 27 ml of an alcohol mixed solution (methanol: tert-butanol = 1:3 v/v) to TEOS/H 2 O emulsion, stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours, and the system is clarified by turbidity. Transparent to give a clear and transparent TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture; wherein the TEOS is in a TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture The concentration is 0.22M. (3) Adding a mass fraction of 28% ammonia solution to the TEOS/CH 3 OH-(CH 3 ) 3 COH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches 2.0 mol/L, stirring (200 rmp) After reacting for 2 h under the conditions, the reaction system changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed: 5000 rpm, 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 228 nm (see FIG. 11A).
将上述制备的228nm二氧化硅微球分散于体积比1:1的乙醇水溶液中，滴涂到石英玻璃板上，干燥后，形成一层二氧化硅膜。进行紫外-可见光吸收测试，测试结果见图11B。本发明得到的二氧化硅微球，经过简单的组装，便可得到在500nm处有明显吸收的二氧化硅薄膜，可进一步组装成可吸收波长500nm左右光的光学器件。The 228 nm silica microspheres prepared above were dispersed in an aqueous solution of ethanol having a volume ratio of 1:1, dropped onto a quartz glass plate, and dried to form a silicon dioxide film. The ultraviolet-visible absorption test was carried out, and the test results are shown in Fig. 11B. The silica microspheres obtained by the present invention can be easily assembled to obtain a silicon dioxide film which is obviously absorbed at 500 nm, and can be further assembled into an optical device capable of absorbing light having a wavelength of about 500 nm.
表5不同比例甲醇-叔丁醇混合对二氧化硅微球的影响Table 5 Effect of different ratios of methanol-tert-butanol on silica microspheres
Figure PCTCN2017115818-appb-000005
Figure PCTCN2017115818-appb-000005
从表5所列实施例12～14得到的实验结果可知，采用本发明提出的实施方案，仅仅改变混合醇溶液中甲醇和叔丁醇的体积比，便可制备出粒径不同、粒度均匀的二氧化硅微球，混合醇溶液中叔丁醇的体积比越大，二氧化硅微球粒径越大。From the experimental results obtained in Examples 12 to 14 listed in Table 5, it can be understood that, by using the embodiment of the present invention, only by changing the volume ratio of methanol to tert-butanol in the mixed alcohol solution, uniform particle diameters and uniform particle sizes can be prepared. For silica microspheres, the larger the volume ratio of tert-butanol in the mixed alcohol solution, the larger the particle size of the silica microspheres.
实施例15～16(试验条件及结果见表6)Examples 15 to 16 (test conditions and results are shown in Table 6)
在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入250mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。向TEOS/H 2O乳状液中加入40ml乙醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清透明，得到澄清透明的TEOS/C 2H 5OH-H 2O混合液；其中，所述TEOS在TEOS/C 2H 5OH-H 2O混合液中的浓度为0.19M。 30 ml of water and 3 ml of TEOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (300 rmp) for 2 hours to obtain a TEOS/H 2 O emulsion. 40 mL of ethanol was added to the TEOS/H 2 O emulsion, and stirred at room temperature (20 ° C) for 2 hours at room temperature. The system became clear and transparent from turbidity to obtain a clear and transparent TEOS/C 2 H 5 OH-H 2 O mixture. a solution; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture is 0.19 M.
实施例15：向上述TEOS/C 2H 5OH-H 2O混合液中滴加浓HCl溶液，使混合液中HCl的浓度达到1.5×10 -3mol/L。5min后，加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L。在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。在室温20℃条件下对二氧化硅溶胶进行离心分离(转速9000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径193nm大小均匀的二氧化硅微球(见图12)。 Example 15: A concentrated HCl solution was added dropwise to the above TEOS/C 2 H 5 OH-H 2 O mixture to bring the concentration of HCl in the mixture to 1.5 × 10 -3 mol/L. After 5 minutes, a mass fraction of 28% aqueous ammonia solution was added to bring the concentration of ammonia in the entire reaction system to 2.0 mol/L. After reacting for 2 hours under stirring (200 rpm), the reaction system was changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a temperature of 20 ° C (rotation speed 9000 rpm, time 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle size of 193 nm (see FIG. 12).
实施例16：向上述TEOS/C 2H 5OH-H 2O混合液中滴加浓HCl溶液，使混合液中HCl的浓度达到1.5×10 -2mol/L。5min后，加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L。在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。在室温20℃条件下对二氧化硅溶胶进行离心分离(转速5000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径210nm大小均匀的二氧化硅微球。 Example 16: A concentrated HCl solution was added dropwise to the above TEOS/C 2 H 5 OH-H 2 O mixture to bring the concentration of HCl in the mixture to 1.5 × 10 -2 mol/L. After 5 minutes, a mass fraction of 28% aqueous ammonia solution was added to bring the concentration of ammonia in the entire reaction system to 2.0 mol/L. After reacting for 2 hours under stirring (200 rpm), the reaction system was changed from clear and transparent to milky white to obtain a silica sol. The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 5000 rpm, time 20 min), and washed three times with ethanol to obtain silica microspheres having an average particle diameter of 210 nm.
表6酸-碱联合催化剂对二氧化硅微球的影响Table 6 Effect of acid-base combined catalyst on silica microspheres
Figure PCTCN2017115818-appb-000006
Figure PCTCN2017115818-appb-000006
从表6所列实施例15、16得到的实验结果可知，采用本发明提出实施方案，通过调整酸-碱联合催化剂，可以制备出粒径不同、粒度均匀的二氧化硅微球。From the experimental results obtained in Examples 15 and 16 listed in Table 6, it is understood that the silica microspheres having different particle diameters and uniform particle sizes can be prepared by adjusting the acid-base combined catalyst by the embodiment of the present invention.
实施例17Example 17
(1)在室温20℃和搅拌条件下，将50ml水和3ml TMOS注入250mL锥形瓶中，搅拌(转速300rmp)2小时，得到TMOS/H 2O乳状液。(2)向TMOS/H 2O乳状液中加入28ml乙醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清，得到澄清透明的TMOS/C 2H 5OH-H 2O混合液；其中，所述TMOS在TMOS/C 2H 5OH-H 2O混合液中的浓度为0.15M。(3)向TMOS/C 2H 5OH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转 速13000rmp，时间30min)，乙醇洗涤3次，可得到平均粒径104nm大小均匀的二氧化硅微球(见图13)。 (1) 50 ml of water and 3 ml of TMOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TMOS/H 2 O emulsion. (2) Add 28 ml of ethanol to the TMOS/H 2 O emulsion, stir at room temperature (at 300 ° C) for 2 hours at room temperature, and the system is clarified by turbidity to obtain clear and transparent TMOS/C 2 H 5 OH-H 2 O mixed solution; wherein the concentration of the TMOS in the TMOS/C 2 H 5 OH-H 2 O mixture is 0.15 M. (3) Adding a mass fraction of 28% ammonia aqueous solution to the TMOS/C 2 H 5 OH-H 2 O mixture, so that the concentration of ammonia in the whole reaction system reaches 2.0 mol/L, and reacts for 2 hours under stirring (200 rpm). Thereafter, the reaction system was changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 13000 rmp, time 30 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 104 nm (see FIG. 13).
实施例18Example 18
(1)在温度30℃和搅拌条件下，将30ml水和3ml TPOS注入250mL锥形瓶中，搅拌(转速300rmp)2小时，得到TPOS/H 2O乳状液。(2)向TPOS/H 2O乳状液中加入50ml叔丁醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清，得到澄清透明的TMOS/(CH 3) 3COH-H 2O混合液；其中，所述TPOS在TMOS/(CH 3) 3COH-H 2O混合液中的浓度为0.12M。(3)向TMOS/(CH 3) 3COH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rmp)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速3000rmp，时间20min)二氧化硅溶胶，乙醇洗涤3次，可得到平均粒径398nm大小均匀的二氧化硅微球(见图14)。 (1) 30 ml of water and 3 ml of TPOS were poured into a 250 mL Erlenmeyer flask under stirring at a temperature of 30 ° C and stirred (rotation speed 300 rpm) for 2 hours to obtain a TPOS/H 2 O emulsion. (2) 50 ml of t-butanol was added to the TPOS/H 2 O emulsion, and stirred at room temperature of 20 ° C (rotation speed 300 rpm) for 2 hours, and the system was clarified by turbidity to obtain a clear and transparent TMOS/(CH 3 ) 3 COH. a mixture of H 2 O; wherein the concentration of the TPOS in the TMOS/(CH 3 ) 3 COH-H 2 O mixture is 0.12 M. (3) Adding a mass fraction of 28% ammonia aqueous solution to the TMOS/(CH 3 ) 3 COH-H 2 O mixture to make the concentration of ammonia in the whole reaction system reach 2.0 mol/L, and react under stirring (200 rpm) After 2 h, the reaction system changed from clear and transparent to milky white to give a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 3000 rpm, time 20 min), and the silica sol was washed three times with ethanol to obtain silica microspheres having an average particle size of 398 nm. Figure 14).
实施例19Example 19
(1)在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入250mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入40ml乙醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清，得到澄清透明的TEOS/C 2H 5OH-H 2O混合液；其中，所述TEOS在TEOS/C 2H 5OH-H 2O混合液中的浓度为0.19M。(3)向TEOS/C 2H 5OH-H 2O溶液中滴加1mol/LNaOH溶液，使整个反应体系中[OH -]的浓度达到2.0×10 -2mol/L，在搅拌(转速200rmp)条件下反应5h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速12000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径122nm大小均匀的二氧化硅微球。 (1) 30 ml of water and 3 ml of TEOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) 40 ml of ethanol was added to the TEOS/H 2 O emulsion, and stirred at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours, and the system was clarified by turbidity to obtain a clear and transparent TEOS/C 2 H 5 OH-H 2 O mixed solution; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture was 0.19 M. (3) Add 1 mol/L NaOH solution to TEOS/C 2 H 5 OH-H 2 O solution to make the concentration of [OH - ] in the whole reaction system reach 2.0×10 -2 mol/L, stirring (200 rmp) After reacting for 5 hours under the conditions, the reaction system changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 12000 rpm, time 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 122 nm.
实施例20～21(试验条件及结果见表7)Examples 20 to 21 (test conditions and results are shown in Table 7)
实施例20Example 20
(1)在室温20℃和搅拌条件下，将30ml水和3ml TEOS注入250mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入40ml乙醇，在室温20℃条件下，超声30min(功率40KHz)，体系由浑浊变澄清，得到澄清透明的TEOS/C 2H 5OH-H 2O混合液；其中，所述TEOS在TEOS/C 2H 5OH-H 2O混合液中的浓度为0.19M。(3)在搅拌条件下(转速200～300rpm)，向TEOS/C 2H 5OH-H 2O混合液中加入质量分数28％ 氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rpm)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速8000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径223nm大小均匀的二氧化硅微球。 (1) 30 ml of water and 3 ml of TEOS were poured into a 250 mL Erlenmeyer flask at room temperature 20 ° C under stirring, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 40 ml of ethanol to TEOS/H 2 O emulsion, and sonicate for 30 min (power 40 KHz) at room temperature 20 ° C. The system is clarified by turbidity to obtain clear and transparent TEOS/C 2 H 5 OH-H 2 O mixed solution; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture was 0.19 M. (3) Under stirring conditions (rotation speed 200-300 rpm), add 28% ammonia aqueous solution to the TEOS/C 2 H 5 OH-H 2 O mixture to make the ammonia concentration in the whole reaction system reach 2.0 mol/L. After reacting for 2 hours under stirring (rotation speed of 200 rpm), the reaction system was changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 8000 rpm, time 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 223 nm.
实施例21Example 21
(1)在室温20℃和搅拌条件下，将150ml水和15ml TEOS注入500mL锥形瓶中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入200ml乙醇，在室温20℃条件下旋涡粉碎5min(压力2.5atm)，体系由浑浊变澄清，得到澄清透明的TEOS/C 2H 5OH-H 2O混合液；其中，所述TEOS在TEOS/C 2H 5OH-H 2O混合液中的浓度为0.19M。(3)在搅拌条件下(转速200～300rpm)，向TEOS/C 2H 5OH-H 2O混合液中加入质量分数28％氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rpm)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速8000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径203nm大小均匀的二氧化硅微球。 (1) 150 ml of water and 15 ml of TEOS were poured into a 500 mL Erlenmeyer flask under stirring at room temperature at 20 ° C, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) 200 ml of ethanol was added to the TEOS/H 2 O emulsion, and vortexed at room temperature for 20 min (pressure: 2.5 atm), and the system was clarified by turbidity to obtain a clear and transparent TEOS/C 2 H 5 OH-H. 2 O mixed solution; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture was 0.19 M. (3) Under stirring conditions (rotation speed 200-300 rpm), a mass fraction of 28% ammonia aqueous solution is added to the TEOS/C 2 H 5 OH-H 2 O mixture to make the ammonia concentration in the whole reaction system reach 2.0 mol/L. After reacting for 2 hours under stirring (rotation speed of 200 rpm), the reaction system was changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 8000 rpm, time 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 203 nm.
表7混合条件对对二氧化硅微球的影响Table 7 Effect of mixing conditions on silica microspheres
Figure PCTCN2017115818-appb-000007
Figure PCTCN2017115818-appb-000007
从表7所列实施例4、20、21得到的实验结果可知，采用本发明提出的实施方案，针对TEOS/C 2H 5OH-H 2O混合液，可以采用不同的匀化方式制备出粒径不同、粒度均匀的二氧化硅微球。 From the experimental results obtained in Examples 4, 20, and 21 listed in Table 7, it is understood that the TEOS/C 2 H 5 OH-H 2 O mixture can be prepared by using different homogenization methods according to the embodiment of the present invention. Silica microspheres with different particle sizes and uniform particle size.
实施例22Example 22
(1)在室温20℃和搅拌条件下，将6000ml水和600ml TEOS注入25000mL容器中，搅拌(转速300rmp)2小时，得到TEOS/H 2O乳状液。(2)向TEOS/H 2O乳状液中加入8000ml乙醇，在室温20℃条件下搅拌(转速300rmp)2小时，体系由浑浊变澄清，得到澄清透明的TEOS/C 2H 5OH-H 2O混合液；其中，所述TEOS在TEOS/C 2H 5OH-H 2O混合液中的浓度为0.19M。(3)在搅拌条件下(转速200～300rpm)，向TEOS/C 2H 5OH-H 2O混合液中加入质量分数28％ 氨水溶液，使整个反应体系中氨的浓度达到2.0mol/L，在搅拌(转速200rpm)条件下反应2h后，反应体系由澄清透明变为乳白色，得到二氧化硅溶胶。(4)在室温20℃条件下对二氧化硅溶胶进行离心分离(转速8000rmp，时间20min)，乙醇洗涤3次，可得到平均粒径325nm大小均匀的二氧化硅微球。 (1) 6000 ml of water and 600 ml of TEOS were poured into a 25000 mL container under stirring at room temperature at 20 ° C, and stirred (rotation speed 300 rpm) for 2 hours to obtain a TEOS/H 2 O emulsion. (2) Add 8000 ml of ethanol to the TEOS/H 2 O emulsion, stir at room temperature 20 ° C (rotation speed 300 rpm) for 2 hours, and the system is clarified by turbidity to obtain clear and transparent TEOS/C 2 H 5 OH-H 2 O mixed solution; wherein the concentration of the TEOS in the TEOS/C 2 H 5 OH-H 2 O mixture was 0.19 M. (3) Under stirring conditions (rotation speed 200-300 rpm), add 28% ammonia aqueous solution to the TEOS/C 2 H 5 OH-H 2 O mixture to make the ammonia concentration in the whole reaction system reach 2.0 mol/L. After reacting for 2 hours under stirring (rotation speed of 200 rpm), the reaction system was changed from clear and transparent to milky white to obtain a silica sol. (4) The silica sol was centrifuged at a room temperature of 20 ° C (rotation speed 8000 rpm, time 20 min), and washed with ethanol three times to obtain silica microspheres having an average particle size of 325 nm.
经典的
Figure PCTCN2017115818-appb-000008
法制备二氧化硅微球，用醇作为溶剂，水作为反应物，氨水作催化剂。一般先将醇、水以及催化剂混合得到醇-水-氨水溶液，然后，在搅拌的条件下，将硅酸酯/醇溶液滴加至醇-水-氨水溶液中，硅酸酯水解得到(Si(OH) 4)，Si(OH) 4缩聚-成核生长，得到二氧化硅微球。硅酸酯/醇溶液与醇-水-氨水溶液混合过程，硅酸酯水解缩聚过程同时进行，二氧化硅微球制备的可控性差，反应体系也难以放大。本发明主要以水介质作溶剂，先将反应物有机硅化合物、小分子醇和溶剂配制成均一的有机硅化合物/醇-H 2O混合液，通过调控有机硅化合物/醇-H 2O混合液的体系均一性，进而控制二氧化硅微球的均匀度。可有效避免现有二氧化硅微球制备技术中存在的，反应体系均一性和颗粒均匀度控制难，以及反应规模难放大的问题。 classic
Figure PCTCN2017115818-appb-000008
The silica microspheres were prepared by using alcohol as a solvent, water as a reactant, and ammonia as a catalyst. Generally, the alcohol, water and the catalyst are first mixed to obtain an alcohol-water-ammonia aqueous solution, and then, under stirring, the silicate/alcohol solution is added dropwise to the alcohol-water-ammonia aqueous solution, and the silicate is hydrolyzed to obtain (Si). (OH) 4 ), Si(OH) 4 polycondensation-nucleation growth, to obtain silica microspheres. The silicate/alcohol solution is mixed with the alcohol-water-ammonia aqueous solution, and the silicate hydrolysis and polycondensation process is carried out simultaneously. The controllability of the preparation of the silica microspheres is poor, and the reaction system is difficult to amplify. The invention mainly uses an aqueous medium as a solvent, and firstly prepares a reactant organosilicon compound, a small molecule alcohol and a solvent into a uniform organosilicon compound/alcohol-H 2 O mixture, and modulates the organosilicon compound/alcohol-H 2 O mixture. System uniformity, which in turn controls the uniformity of the silica microspheres. The invention can effectively avoid the problems existing in the preparation technology of the existing silica microspheres, the control system uniformity and the uniformity of the particle uniformity, and the problem that the reaction scale is difficult to enlarge.

Claims (13)

  1. 一种均匀二氧化硅微球的制备方法，其特征在于包括以下步骤：A method for preparing uniform silica microspheres, comprising the steps of:
    (1)将有机硅化合物与水介质进行混合，得到有机硅化合物/H 2O乳状液； (1) mixing an organosilicon compound with an aqueous medium to obtain an organosilicon compound/H 2 O emulsion;
    (2)将小分子醇与步骤(1)的有机硅化合物/H 2O乳状液进行混合，得到澄清透明的有机硅化合物/醇-H 2O混合液； (2) mixing a small molecule alcohol with the organosilicon compound/H 2 O emulsion of the step (1) to obtain a clear transparent organosilicon compound/alcohol-H 2 O mixture;
    (3)向步骤(2)的有机硅化合物/醇-H 2O混合液中加入催化剂，进行水解缩聚反应，得到二氧化硅溶胶； (3) adding a catalyst to the organosilicon compound/alcohol-H 2 O mixture of the step (2) to carry out a hydrolysis polycondensation reaction to obtain a silica sol;
    (4)对步骤(3)的二氧化硅溶胶进行离心分离，得到所述的二氧化硅微球。(4) The silica sol of the step (3) is subjected to centrifugation to obtain the silica microspheres.
  2. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(1)中，所述有机硅化合物与水介质混合在搅拌条件下进行，所述搅拌的转速为200～300rpm，所述混合的温度为15～30℃，所述混合的时间为1小时以上。The method for preparing a uniform silica microsphere according to claim 1, wherein in the step (1), the organosilicon compound is mixed with an aqueous medium under stirring, and the stirring speed is 200 ～. At 300 rpm, the mixing temperature was 15 to 30 ° C, and the mixing time was 1 hour or more.
  3. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(1)中，所述有机硅化合物包括硅酸酯、硅烷偶联剂中的一种或多种。The method for producing a uniform silica microsphere according to claim 1, wherein in the step (1), the organosilicon compound comprises one or more of a silicate and a silane coupling agent.
  4. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(1)中，所述水介质包括水和水溶液；所述水溶液是指水的无机盐溶液。The method for preparing uniform silica microspheres according to claim 1, wherein in the step (1), the aqueous medium comprises water and an aqueous solution; and the aqueous solution refers to an inorganic salt solution of water.
  5. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(1)中，所述有机硅化合物与水介质的体积比为：1:50≤V 有机硅化合物：V H2O≤1:5。 The method for preparing a uniform silica microsphere according to claim 1, wherein in the step (1), the volume ratio of the organosilicon compound to the aqueous medium is 1:50 ≤ V organosilicon compound : V H2O ≤ 1:5.
  6. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(2)中，所述混合的温度为15～30℃，所述混合的时间为1～3小时。The method for producing uniform silica microspheres according to claim 1, wherein in the step (2), the mixing temperature is 15 to 30 ° C, and the mixing time is 1 to 3 hours.
  7. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(2)中，所述小分子醇的分子式为ROH，其中R为C1-C4的烷基。The method for preparing a uniform silica microsphere according to claim 1, wherein in the step (2), the small molecule alcohol has a molecular formula of ROH, wherein R is a C1-C4 alkyl group.
  8. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(2)中，所述小分子醇与有机硅化合物/H 2O乳状液的体积比为1:2～8:5。 The method for preparing a uniform silica microsphere according to claim 1, wherein in the step (2), the volume ratio of the small molecule alcohol to the organosilicon compound/H 2 O emulsion is 1:2. 8:5.
  9. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(3)中，所述水解缩聚反应的温度为20～60℃，所述水解缩聚反应的时间为1～5h；所述水解缩聚反应在搅拌条件下进行，所述搅拌的转速为200～300rpm。The method for preparing a uniform silica microsphere according to claim 1, wherein in the step (3), the temperature of the hydrolysis polycondensation reaction is 20 to 60 ° C, and the time of the hydrolysis polycondensation reaction is 1 to 5h; the hydrolysis polycondensation reaction is carried out under stirring, and the stirring speed is 200 to 300 rpm.
  10. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(3)中，所述催化剂包括强碱催化剂、弱碱催化剂或酸-碱联合催化剂。The method for preparing uniform silica microspheres according to claim 1, wherein in the step (3), the catalyst comprises a strong base catalyst, a weak base catalyst or an acid-base combined catalyst.
  11. 如权利要求1所述的均匀二氧化硅微球的制备方法，其特征在于，步骤(4)中，所述离心分离的转速为3000rmp以上；时间为10～30min。The method for preparing uniform silica microspheres according to claim 1, wherein in the step (4), the rotational speed of the centrifugal separation is 3000 rpm or more; and the time is 10 to 30 minutes.
  12. 一种均匀二氧化硅微球，其特征在于，根据如权利要求1～11之任一项所述的方法制备得到。A uniform silica microsphere prepared by the method according to any one of claims 1 to 11.
  13. 如权利要求12所述的均匀二氧化硅微球在校正用标准粒子、模型催化剂、无孔色谱填料、胶体晶体、电流变液中的应用。Use of the uniform silica microspheres according to claim 12 in calibration standard particles, model catalysts, non-porous chromatography fillers, colloidal crystals, electrorheological fluids.
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