CN115612301A - Hydrophilic organic/inorganic composite spherical silicon resin and preparation method and application thereof - Google Patents
Hydrophilic organic/inorganic composite spherical silicon resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a hydrophilic organic/inorganic composite spherical silicon resin and a preparation method and application thereof. The composite spherical silicon resin is obtained by hydrolysis polycondensation reaction of an organic silicon monomer and silica sol; the composite spherical silicon resin is polymethyl silsesquioxane with hydroxyl groups on the main chain, the particle size of the composite spherical silicon resin is 1-500 mu m, and the contact angle is smaller than 90 degrees. The composite spherical silicon resin provided by the embodiment of the invention has hydrophilic property and can be obtained through one-step reaction, and the preparation method provided by the embodiment of the invention has the advantages of high production efficiency and low cost.
Description
Technical Field
The invention relates to the technical field of organic silicon resin, in particular to hydrophilic organic/inorganic composite spherical silicon resin and a preparation method and application thereof.
Background
The organic silicon resin is a product obtained by hydrolysis and polycondensation of siloxane monomers, and the organic silicon material has the characteristics of no toxicity, no odor, good lubricity and relative environmental protection, and is widely applied to the fields of fabric finishing agents, personal care products, cosmetics and other daily chemicals due to the unique structure and safety performance.
Compared with inorganic silicon powder, the spherical organic silicon resin has the advantages of narrow particle size distribution, low hardness, good lubricity and softer skin feel. Silicone resins used in the cosmetic field are required to have good hydrophilicity.
At present, the method for preparing the hydrophilic spherical organic silicon resin comprises the following steps: the hydrophobic spherical silicone resin is obtained by taking di-or trialkoxysilane as a monomer and then carrying out one-step or multi-step sol-gel method, emulsion polymerization method or hydrolysis-condensation method, and finally carrying out further processing or surface treatment to obtain the hydrophilic spherical silicone resin. That is, the preparation method in the prior art can not directly obtain hydrophilic spherical silicone resin, and the production process is complicated.
There are also some studies in the prior art on the preparation method of spherical silicone resin.
For example: japanese patent JPH0488023A PRODUCTION OF SPHERICAL FINE SILICONE PARTICLE discloses a method for synthesizing 0.1-20 um SPHERICAL organic silicon resin in water by taking methyltrimethoxysilane as a precursor; the Preparation of functional polysesquioxane and polysisquioxane-Metal nanoparticie Composite Sphere (Macromolecular Rapid Communications 27.15 (2010): 1247-1253) published by Kim Y B, kim Y A, yoon K S.: monodisperse spherical organic silicon resin with the grain diameter of 1.5 mu m is prepared by adopting vinyl trimethoxy silane and mercaptopropyl trimethoxy silane respectively. The spherical organic silicon resin prepared by the two methods has better comprehensive performance, but the obtained spherical organic silicon resin has no hydrophilicity.
The following steps are repeated: chinese patent CN105480983A discloses a preparation method of hydrophilic porous silica microspheres, which comprises pre-reacting 3-aminopropyltriethoxysilane (KH 550) and gamma-glycidoxypropyltrimethoxysilane (KH 560) under the protection of nitrogen, then compounding with hexamethylene diisocyanate trimer to form an organic complex, and calcining at high temperature to remove organic components, thereby obtaining hydrophilic inorganic porous silica microspheres, but the preparation process is complicated and the production cost is high.
For another example: dow Corning EP-9801 water dispersible cosmetic silicone elastomer powder is easy to disperse in water, and polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymerization is adopted to coat silica and butanediol, so that although a surfactant is abandoned, the preparation process is complex, and the stability of the product needs to be improved.
Disclosure of Invention
Therefore, the invention aims to solve the technical problem that the hydrophilic spherical silicone resin cannot be directly prepared in the prior art and the production process is complex.
In order to solve the technical problems, the invention provides hydrophilic organic/inorganic composite spherical silicon resin and a preparation method and application thereof.
The first purpose of the invention is to provide a hydrophilic organic/inorganic composite spherical silicon resin, which is obtained by hydrolysis and polycondensation reaction of an organic silicon monomer and silica sol; the composite spherical silicon resin is polymethylsilsesquioxane with a hydroxyl group on a main chain, the particle size of the composite spherical silicon resin is 1-500 mu m, and the contact angle is smaller than 90 degrees.
In one embodiment of the invention, the organic silicon monomer is gamma-glycidoxypropyltrimethoxysilane and/or gamma-glycidoxypropyltriethoxysilane.
The second object of the present invention is to provide a method for preparing the hydrophilic organic/inorganic composite spherical silicone resin, comprising the steps of:
s1, dissolving alkaline silica sol in water, stirring to obtain a glue solution, and adding an organic silicon monomer to obtain a mixed solution;
s2, stirring the mixed solution obtained in the step S1 until a milky suspension is formed, and standing to obtain a white precipitate;
and S3, washing the white precipitate obtained in the step S2 with water until the pH value of the filtrate is neutral, and drying to obtain the composite spherical silicone resin.
In one embodiment of the present invention, in the step S1, the mass ratio of the alkaline silica sol to water is 1 to 10:50.
in one embodiment of the present invention, the alkaline silica sol is one or more of a sodium type silica sol, a potassium type silica sol and an ammonium type silica sol.
In an embodiment of the invention, in the step S1, the content of the organosilicon monomer in the mixed solution is 5wt% to 20wt%.
In one embodiment of the invention, in the step S2, the stirring time is 1h to 4h, and the standing time is 1h to 12h.
In one embodiment of the present invention, in the step S3, the drying temperature is 80 ℃ to 120 ℃, and the drying time is 6h to 24h.
The third purpose of the invention is to provide the application of the hydrophilic organic/inorganic composite spherical silicone resin in cosmetics.
In one embodiment of the invention, the cosmetic is a foundation, a water-in-oil cream, an oil-in-water cream, an emulsion, a gel or a toner.
The fourth purpose of the invention is to provide the application of the hydrophilic organic/inorganic composite spherical silicon resin in the anti-aging agent.
In one embodiment of the present invention, the anti-aging agent is applied to the fields of rubber, plastics, paint, food, medicine, textile, and the like.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the preparation method can obtain the hydrophilic composite spherical silicone resin through one-step reaction, and has the advantages of low production cost and high efficiency. Specifically, the gamma-glycidoxypropyltrimethoxysilane and the gamma-glycidoxypropyltriethoxysilane are used as the organic silicon monomers, the organic silicon monomers are very easy to hydrolyze in water to form silanol, silicon-oxygen bond in the organic silicon monomers can be hydrolyzed to form silanol and form macromolecules in a crosslinking manner under the catalysis of alkali, meanwhile, hydroxyl of the silanol and hydroxyl on a nano silicon dioxide cluster can attack epoxy groups, so that the epoxy groups carry out ring opening reaction, after a proton of the hydroxyl is captured, the epoxy groups can form a hydroxyl and an ether bond, and finally, the composite spherical silicon resin with hydrophilic performance can be obtained through one-step reaction, so that the production efficiency is improved, and the production cost is reduced.
The composite spherical silicone resin with smooth surface, uniform size distribution, particle size of 1-500 microns and contact angle of less than 90 degrees can be obtained by the preparation method of the invention, and the composite spherical silicone resin has hydrophilic property and can be directly added into a water phase of a cosmetic formula, such as foundation solution, water-in-oil type cream, oil-in-water type cream, emulsion, gel, toner and the like, so that the composite spherical silicone resin can absorb oil of skin, enhance the oil control effect and improve smooth skin feel when being applied to cosmetics.
The composite spherical silicon resin has smooth surface and uniform size distribution, has the grain diameter of 1-500 mu m and the contact angle of less than 90 degrees, can be used as an anti-aging agent and is applied to the fields of rubber, plastics, paint, food, medicine, textile and the like.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a scanning electron micrograph of a composite spherical silicone resin according to example 1 of the present invention;
FIG. 2 is a particle size distribution diagram of a composite spherical silicone resin according to example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the composite spherical silicone resin of example 4 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formula is shown in the following table 1:
TABLE 1
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution of the S1;
s3, when the solution of the S2 turns to be milk white, continuing to stir at the same speed for 2 hours, and standing for 8 hours to form a white precipitate;
and S4, washing the white precipitate of the S3 with deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12h to obtain the white hydrophilic organic/inorganic composite spherical silicone resin.
The hydrophilic composite spherical silicone resin is obtained by adopting a Phenom XL electron scanning microscope, and as shown in figure 1, the spherical surface of the composite spherical silicone resin is smooth and the size distribution is uniform. The particle Size distribution diagram of the organic/inorganic composite spherical silicone resin was obtained by a setter Size 2000 laser particle sizer, as shown in fig. 2, the particle Size distribution of the composite spherical silicone resin of this example was narrow, the particle sizes were concentrated between 2 μm and 3 μm, and the average particle Size of the composite spherical silicone resin measured by the setter Size 2000 laser particle sizer is shown in table 14.
The contact angle of the composite spherical silicone resin measured by the contact angle measuring instrument SDC-200S is 15 degrees, as shown in Table 14, further indicating that the spherical silicone resin has hydrophilic property.
Comparative example 1 (comparison with example 1, differing in the chemical composition of the Silicone monomer)
This comparative example provides a preparation of spherical silicone resin similar to the preparation of example 1, as follows:
1. the raw material formula is shown in the following table 2:
TABLE 2
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol in deionized water for later use;
s2, stirring the solution obtained in the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution obtained in the step S1;
s3, when the solution in the step S2 is milk white, continuing to stir at the same speed for 2 hours to form a white sticky object attached to the stirring slurry;
and S4, drying the white sticky substance in an oven at 120 ℃ for 12h to obtain a white hydrophobic agglomeration.
The contact angle of the hydrophobic agglomerates obtained in this comparative example was measured using a contact angle measuring apparatus SDC-200S, and the results are shown in Table 14.
Example 2
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formulation is shown in table 3 below:
TABLE 3
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution in the step S1;
s3, when the solution in the step S2 is milk white, continuing to stir at the same speed for 2 hours, and standing for 8 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 by deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12 hours to obtain white hydrophilic organic/inorganic composite spherical silicone resin.
Example 3
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formulation is shown in table 4 below:
TABLE 4
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol in deionized water for later use;
s2, stirring the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution in the step S1;
s3, when the solution in the step S2 turns to be milky white, continuing stirring at the same speed for 2 hours, and standing
8h, a white precipitate formed;
s4, washing the white precipitate obtained in the step S3 by deionized water until the pH value of the filtrate is neutral, and placing the filtrate in a container
And drying in an oven at 120 ℃ for 12h to obtain the white hydrophilic organic/inorganic composite spherical silicone resin.
Example 4
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formulation is shown in table 5 below:
TABLE 5
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the step S1 at the speed of 100r/min, and simultaneously gradually adding an organic silicon monomer into the solution in the step S1;
s3, when the solution in the step S2 is milk white, continuing to stir at the same speed for 4 hours, and standing for 8 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 by deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12 hours to obtain white hydrophilic organic/inorganic composite spherical silicone resin.
As shown in fig. 3, it can be seen from fig. 3 that the particle size of the composite spherical silicone resin of this example is larger than that of example 1, that is, the composite spherical silicone resin with large particle size can be obtained by reducing the stirring speed and increasing the stirring time in the reaction process during hydrolytic polycondensation.
Example 5
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formulation is shown in table 6 below:
TABLE 6
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution in the step S1;
s3, when the solution in the step S2 turns to be milk white, continuing stirring at the same speed for 2 hours, and standing for 8 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 with deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12h to obtain the white hydrophilic organic/inorganic composite spherical silicone resin.
Example 6
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formulation is shown in table 7 below:
TABLE 7
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the solution obtained in the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution obtained in the step S1;
s3, when the solution in the step S2 turns to be milk white, continuing stirring at the same speed for 2 hours, and standing for 8 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 by deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12 hours to obtain white hydrophilic organic/inorganic composite spherical silicone resin.
Example 7
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formulation is shown in table 8 below:
TABLE 8
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution of the step S1;
s3, when the solution in the step S2 turns to be milk white, continuing stirring at the same speed for 4 hours, and standing for 12 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 with deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12h to obtain the white hydrophilic organic/inorganic composite spherical silicone resin.
Example 8
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formulation is shown in table 9 below:
TABLE 9
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution in the step S1;
s3, when the solution in the step S2 is milk white, continuing to stir at the same speed for 1 hour, and standing for 6 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 with deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12h to obtain the white hydrophilic organic/inorganic composite spherical silicone resin.
Example 9
The embodiment provides a preparation method of composite spherical silicone resin, which comprises the following specific steps:
1. the raw material formulation is shown in table 10 below:
watch 10
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the solution obtained in the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution obtained in the step S1;
s3, when the solution in the step S2 is milk white, continuing to stir at the same speed for 1 hour, and standing for 6 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 with deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12h to obtain the white hydrophilic organic/inorganic composite spherical silicone resin.
Example 10
The embodiment provides a preparation method of composite spherical silicone resin, which specifically comprises the following steps:
1. the raw material formulation is shown in table 11 below:
TABLE 11
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol in deionized water for later use;
s2, stirring the step S1 at the speed of 800r/min, and simultaneously gradually adding an organic silicon monomer into the solution in the step S1;
s3, when the solution in the step S2 turns to be milk white, continuing stirring at the same speed for 2 hours, and standing for 8 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 with deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12h to obtain the white hydrophilic organic/inorganic composite spherical silicone resin.
Example 11
The embodiment provides a preparation method of composite spherical silicone resin, which specifically comprises the following steps:
1. the raw material formulation is shown in table 12 below:
TABLE 12
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol into deionized water for later use;
s2, stirring the step S1 at the speed of 500r/min, and simultaneously gradually adding an organic silicon monomer into the solution in the step S1;
s3, when the solution in the step S2 is milk white, continuing to stir at the same speed for 2 hours, and standing for 8 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 by deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12 hours to obtain white hydrophilic organic/inorganic composite spherical silicone resin.
Example 12
The embodiment provides a preparation method of composite spherical silicone resin, which specifically comprises the following steps:
1. the raw material formulation is shown in table 13 below:
watch 13
2. According to the mass ratio, the process flow is as follows:
s1, dissolving alkaline silica sol in deionized water for later use;
s2, stirring the solution obtained in the step S1 at the speed of 1000r/min, and simultaneously gradually adding an organic silicon monomer into the solution obtained in the step S1;
s3, when the solution in the step S2 turns to be milk white, continuing stirring at the same speed for 2 hours, and standing for 8 hours to form a white precipitate;
and S4, washing the white precipitate obtained in the step S3 with deionized water until the pH value of the filtrate is neutral, and drying in an oven at 120 ℃ for 12h to obtain the white hydrophilic organic/inorganic composite spherical silicone resin.
Test example
The organic/inorganic composite spherical silicone resins obtained in examples 1 to 12 and comparative example were subjected to particle size and contact angle tests; wherein, the contact angle is measured by using a SDC-200S contact angle measuring instrument, and the experimental result is shown in Table 14. The average particle diameter and the contact angle of the composite spherical silicone resin were measured as shown in table 14.
TABLE 14 average particle diameter and contact angle of composite spherical silicone resins of examples 1 to 12 and spherical silicone resin of comparative example 1
As can be seen from Table 14, compared with comparative example 1, in examples 1-12 of the present invention, the composite spherical silicone resin with a contact angle of less than 90 ° can be directly obtained by using gamma-glycidoxypropyltrimethoxysilane and/or gamma-glycidoxypropyltriethoxysilane as silicone monomers and then subjecting the silicone monomers to hydrolytic polycondensation with silica sol, and the spherical surface of the composite spherical silicone resin obtained by the preparation method is smooth and has uniform size distribution and a particle size of 1 μm to 500 μm.
In the hydrolysis-polycondensation reaction, the stirring time of example 4 was longer than that of example 1, compared to examples 1 and 4, and further, as shown in fig. 1 and 3, and table 14, the particle size of the composite spherical silicone resin of example 4 was much larger than that of the composite spherical silicone resin of example 1. That is, the composite spherical silicone resin having a large particle size can be obtained by decreasing the stirring speed and increasing the stirring time during the reaction in the hydrolytic polycondensation.
In comparison with examples 1, 10 and 11, in the course of the hydrolytic polycondensation reaction, the stirring speed was changed to example 1 > example 10 > example 11, and as shown in table 14, the particle size of the composite spherical silicone resin of example 1 < the particle size of the composite spherical silicone resin of example 10 < the particle size of the composite spherical silicone resin of example 11. That is, the composite spherical silicone resin having a specific particle diameter can be obtained by controlling the stirring speed during the hydrolytic polycondensation reaction, and the particle diameter of the composite spherical silicone resin gradually decreases as the stirring speed increases.
The composite spherical silicone resin has hydrophilic performance, can be directly added into a water phase of a cosmetic formula, such as foundation liquid, water-in-oil type cream, oil-in-water type cream, emulsion, gel, toner and the like, and can absorb oil of skin, enhance the oil control effect and improve the smooth skin feel when being applied to cosmetics.
The composite spherical silicon resin has smooth surface and uniform size distribution, the particle size is 1-500 mu m, the contact angle is less than 90 degrees, and the composite spherical silicon resin can also be used as an anti-aging agent and applied to the fields of rubber, plastics, coatings, foods, medicines, textiles and the like.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The hydrophilic organic/inorganic composite spherical silicon resin is characterized in that the composite spherical silicon resin is obtained by hydrolysis polycondensation reaction of an organic silicon monomer and silica sol; the composite spherical silicon resin is polymethylsilsesquioxane with a hydroxyl group on a main chain, the particle size of the composite spherical silicon resin is 1-500 mu m, and the contact angle is smaller than 90 degrees.
2. The hydrophilic organic/inorganic composite spherical silicone resin as claimed in claim 1, wherein the silicone monomer is γ -glycidoxypropyltrimethoxysilane and/or γ -glycidoxypropyltriethoxysilane.
3. The method for preparing hydrophilic organic/inorganic composite spherical silicone resin according to claim 1 or 2, comprising the steps of:
s1, dissolving alkaline silica sol in water, stirring to obtain a glue solution, and adding an organic silicon monomer to obtain a mixed solution;
s2, stirring the mixed solution obtained in the step S1 until a milky suspension is formed, and standing to obtain a white precipitate;
and S3, washing the white precipitate obtained in the step S2 with water until the pH value of the filtrate is neutral, and drying to obtain the composite spherical silicon resin.
4. The method according to claim 3, wherein in the step S1, the content of the silica sol in the alkaline silica sol is 10 to 40wt%, and the average particle diameter of the silica sol is 3 to 20nm.
5. The production method according to claim 3, wherein in the step S1, the mass ratio of the alkaline silica sol to water is 1 to 10:50.
the alkaline silica sol is one or more of sodium silica sol, potassium silica sol and ammonium silica sol.
6. The method according to claim 3, wherein in the step S1, the content of the silicone monomer in the mixed solution is 5 to 20wt%.
7. The method according to claim 3, wherein the stirring time is 1 to 4 hours and the standing time is 1 to 12 hours in step S2.
8. The preparation method according to claim 3, wherein in the step S3, the drying temperature is 80 ℃ to 120 ℃ and the drying time is 6h to 24h.
9. Use of the hydrophilic organic/inorganic composite spherical silicone resin according to claim 1 or 2 in cosmetics.
10. Use of the hydrophilic organic/inorganic composite spherical silicone resin according to claim 1 or 2 as an anti-aging agent.
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| WO2010062436A1 (en) * | 2008-10-31 | 2010-06-03 | University Of Florida Research Foundation, Inc. | Transparent inorganic-organic hybrid materials via aqueous sol-gel processing |
| CN105480983A (en) * | 2015-12-16 | 2016-04-13 | 江南大学 | Preparation method of hydrophilic porous silicon dioxide microspheres |
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| CN112724718A (en) * | 2020-12-29 | 2021-04-30 | 济南百士多高分子化工技术有限公司 | Preparation method of inorganic mineral material modified inorganic silicone resin |
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| WO2010062436A1 (en) * | 2008-10-31 | 2010-06-03 | University Of Florida Research Foundation, Inc. | Transparent inorganic-organic hybrid materials via aqueous sol-gel processing |
| CN105480983A (en) * | 2015-12-16 | 2016-04-13 | 江南大学 | Preparation method of hydrophilic porous silicon dioxide microspheres |
| CN112680000A (en) * | 2020-12-29 | 2021-04-20 | 济南百士多高分子化工技术有限公司 | Preparation method of organic silicon monomer modified nano inorganic silicon resin |
| CN112724718A (en) * | 2020-12-29 | 2021-04-30 | 济南百士多高分子化工技术有限公司 | Preparation method of inorganic mineral material modified inorganic silicone resin |
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