CN109370265A - The surface oleophylic method of modifying and the lipophilic nanometric silica as made from the method for a kind of nano silica - Google Patents
The surface oleophylic method of modifying and the lipophilic nanometric silica as made from the method for a kind of nano silica Download PDFInfo
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- CN109370265A CN109370265A CN201811189218.0A CN201811189218A CN109370265A CN 109370265 A CN109370265 A CN 109370265A CN 201811189218 A CN201811189218 A CN 201811189218A CN 109370265 A CN109370265 A CN 109370265A
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- silica
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- oleophylic
- nano silica
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3063—Treatment with low-molecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
Abstract
The invention discloses a kind of surface oleophylic method of modifying of nano silica and the lipophilic nanometric silicas as made from the method, using nano silica as start material, it is surface modifier with amino-containing siloxanes, the siloxanes containing epoxy group, using sol-gel method, under the catalysis of alkali, modified manometer silicon dioxide is prepared；Acrylate long-chain ester is then added, by the Michael addition reaction of double bond and amido, in the surface covalent linkage Long carbon chain of silica；Or Long carbon chain is introduced into silica surface by amino and epoxy ring opening reaction by rear addition Long carbon chain amido, is assigned silica high stability and lipophilicity by Long carbon chain, is realized the stable dispersion of silica, prevent the reunion and precipitating of silica；In addition modified silica made of can carry out the different function such as oleophylic, antifouling, low gloss, damage resistant, high rigidity to material strips.
Description
Technical field
The invention belongs to functionalized nano particle preparation technical fields, and in particular to a kind of surface parent of nano silica
Oily method of modifying and the lipophilic nanometric silica as made from the method.
Background technique
Nano silica (SiO2) be used as a kind of fine chemical product, it materials reinforcing, system thickening, thixotropy,
There are many applications in terms of delustring.Nano silica is for also can be improved washability, damage resistant, weatherability, stain resistant in coating
The performances such as property.
To unmodified SiO2Nanoparticle has the tendency reunited due to its large specific surface area, thus can have precipitating
Trend in bottom, especially to low viscosity system, to influence the application of silica.Therefore, general silica all needs
It carries out chemical modification and improves its dispersion stabilization, thus it is proposed that using the trimethicone containing aminoalkyl or containing
The siloxanes of epoxy group modifies silica, the reactivity of amido and epoxy is recycled, further to amido and ring
Oxygen progress is twice-modified, so that silica surface is had the Long carbon chain functional group of low-surface-energy, silica can be improved in oil
Dispersion stabilization in property system.Meanwhile it is this can the silicon dioxide granule of gradient distribution can also assign coating good hydrophobic, resistance to
Water, anti-pollution characteristic.
Summary of the invention
Technical problem to be solved by the present invention lies in: to unmodified SiO2Nanoparticle, due to its large specific surface area,
Tendency with reunion, thus can have the trend for being deposited in bottom, especially to low viscosity system, to influence silica
Application.
The present invention solves above-mentioned technical problem using following technical scheme:
A kind of surface oleophylic method of modifying of nano silica, comprising the following steps:
(1) it by silica and trimethicone modifying agent, is added in solvent, trimethyl silicane oxygen is made under base catalysis
Alkane obtains improved silica in silica surface graft reaction；
(2) improved silica obtained by step (1) is reacted with corresponding functionalized reagent, progress is twice-modified, two
Silicon oxide particle surface grafting Long carbon chain alkyl structure.
Further, the trimethicone modifying agent is amino-containing trimethoxy silane, the front three containing epoxy group
In oxysilane any one or both mixing.
Further, the amino-containing trimethoxy silane is trimethoxy propyl amino silane, corresponding function
Change reagent is one or more of dodecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate.
Further, the trimethoxy silane containing epoxy group is trimethoxy epoxy group amino silane, corresponding
Functionalized reagent is one or more of lauryl amine, cetylamine, octadecylamine.
Further, the mass ratio of silica and trimethicone modifying agent is 1: (1.0- in the step (1)
1.5)。
Further, the solvent be water, methanol, ethyl alcohol, in isopropanol any one or mixtures thereof, solvent is added
Afterwards, it is 10-20wt% that silica and trimethicone modifying agent, which account for reaction system mass fraction,.
Further, the alkali includes ammonium hydroxide, sodium hydroxide, potassium hydroxide, ethanol amine, diethanol amine, triethanolamine, urine
Any one in element, preferably ammonium hydroxide, urea, additional amount are the 0.5-1.0wt% of silica quality score.
Further, in the step (2) the amino-containing its corresponding functionalized reagent of trimethoxy silane reaction temperature
Degree is 0-90 DEG C, reaction time 0.5-14h.
Further, in the step (2) its corresponding functionalized reagent of trimethoxy silane containing epoxy group reaction
Temperature is 0-50 DEG C, reaction time 2-14h.
Further, the nano silica modified the present invention also provides a kind of oleophylic, by a kind of nanometer titanium dioxide
The surface oleophylic method of modifying of silicon is made.
The technology of the present invention the utility model has the advantages that the invention discloses a kind of surface oleophylic method of modifying of nano silica, with
Nano silica is start material, is surface modifier with amino-containing siloxanes, the siloxanes containing epoxy group, use is molten
Glue-gel method prepares modified manometer silicon dioxide under the catalysis of alkali；Acrylate long-chain ester is then added, passes through double bond and amine
The Michael addition reaction of base, in the surface covalent linkage Long carbon chain of silica；Or rear addition Long carbon chain amido, pass through ammonia
Long carbon chain is introduced into silica surface by base and epoxy ring opening reaction, by Long carbon chain assign silica high stability and
Lipophilicity realizes the stable dispersion of silica, prevents the reunion and precipitating of silica；In addition modified titanium dioxide made of
Silicon can carry out the different function such as oleophylic, antifouling, low gloss, damage resistant, high rigidity to material strips.
Specific embodiment
For convenient for those skilled in the art understand that technical solution of the present invention, below by specific embodiment to skill of the present invention
Art scheme is described further.
Embodiment 1
100mL ethyl alcohol, the ammonium hydroxide of 0.3g, the deionized water of 4g, the unmodified nanometer two of 8g are added into 250mL three-necked flask
Silicon oxide powder is uniformly mixed.Under mechanical stirring, trimethoxy propyl amino containing silane 13.3g is taken to be placed in constant pressure funnel, to be added dropwise
Mode be add to the above mixed solution in 1 hour.35 DEG C are warming up to, is stirred to react 5 hours and obtains modified nano-silica
SiClx microspheres solution then takes octadecyl acrylate 16g to be dissolved in 50g ethyl alcohol, is added drop-wise in above-mentioned reactant in 1 hour,
It 35 DEG C, is stirred to react 4 hours and obtains nano silica microsphere solution, the nanometer two of the stable dispersion in oleaginous system can be obtained
Silica.
Embodiment 2
100mL ethyl alcohol, the ammonium hydroxide of 0.1g, the deionized water of 3g, the unmodified nanometer of 10g are added into 250mL three-necked flask
SiO 2 powder is uniformly mixed.Under mechanical stirring, trimethoxy propyl amino containing silane 12.8g is taken to be placed in constant pressure funnel, with drop
The mode added is add to the above mixed solution within half an hour.35 DEG C are warming up to, is stirred to react 6 hours and obtains modified Nano two
Silicon oxide microsphere solution then takes dodecyl acrylate 19g to be dissolved in 50g ethyl alcohol, and above-mentioned reactant is added drop-wise in two hours
In, it 35 DEG C, is stirred to react 5 hours and obtains nano silica microsphere solution, receiving in oleaginous system stable dispersion can be obtained
Rice silica.
Embodiment 3
Into 250mL three-necked flask, addition 200mL ethyl alcohol, the sodium hydroxide of 0.1g, the deionized water of 15g, 20g are unmodified
Nano grade silica particles are uniformly mixed.Under mechanical stirring, trimethoxy propyl amino containing silane 17.3g is taken to be placed in constant pressure funnel,
It is add to the above mixed solution within half an hour in a manner of dropwise addition.45 DEG C are warming up to, is stirred to react and obtains within 3 hours modified receive
Rice silicon dioxide microsphere solution, then takes Process Conditions of Cetane Acrylate 28g to be dissolved in 100g ethyl alcohol, is added drop-wise in 1 hour above-mentioned anti-
It answers in object, 35 DEG C, is stirred to react 7 hours and obtains nano silica microsphere solution, the stable dispersion in oleaginous system can be obtained
Nano silica.
Embodiment 4
100mL ethyl alcohol, the ammonium hydroxide of 0.2g, the deionized water of 5g, the unmodified nanometer of 10g are added into 250mL three-necked flask
SiO 2 powder is uniformly mixed.Under mechanical stirring, trimethoxy propyl epoxy silane 14.8g is taken to be placed in constant pressure funnel, with
The mode of dropwise addition is add to the above mixed solution in 1 hour.45 DEG C are warming up to, is stirred to react 3 hours and obtains modified Nano
Silicon dioxide microsphere solution then takes cetylamine 11.5g to be dissolved in 20g ethyl alcohol, is added drop-wise in above-mentioned reactant in 2 hours,
It 55 DEG C, is stirred to react 4 hours and obtains nano silica microsphere solution, the nanometer two of the stable dispersion in oleaginous system can be obtained
Silica.
Embodiment 5
Into 250mL three-necked flask, addition 100mL ethyl alcohol, the sodium hydroxide of 0.1g, the deionized water of 10g, 11g are unmodified
Nano grade silica particles are uniformly mixed.Under mechanical stirring, trimethoxy propyl epoxy silane 28.8g is taken to be placed in constant pressure leakage
Bucket, is add to the above mixed solution within half an hour in a manner of dropwise addition.55 DEG C are warming up to, is stirred to react 2 hours and is changed
Property nano silica microsphere solution, then takes lauryl amine 15.8g to be dissolved in 30g ethyl alcohol, above-mentioned reaction is added drop-wise in 2 hours
In object, 35 DEG C, it is stirred to react 6 hours and obtains nano silica microsphere solution, the stable dispersion in oleaginous system can be obtained
Nano silica.
Embodiment 6
Into 250mL three-necked flask, addition 200mL ethyl alcohol, the sodium hydroxide of 0.2g, the deionized water of 30g, 25g are unmodified
Nano grade silica particles are uniformly mixed.Under mechanical stirring, trimethoxy propyl epoxy silane 22.3g is taken to be placed in constant pressure leakage
Bucket, is add to the above mixed solution within half an hour in a manner of dropwise addition.45 DEG C are warming up to, is stirred to react 4 hours and is changed
Property nano silica microsphere solution, then takes lauryl amine 31g to be dissolved in 50g ethyl alcohol, above-mentioned reaction is added drop-wise in two hours
In object, 45 DEG C, it is stirred to react 5 hours and obtains nano silica microsphere solution, the stable dispersion in oleaginous system can be obtained
Nano silica.
Claims (10)
1. a kind of surface oleophylic method of modifying of nano silica, which comprises the following steps:
(1) it by silica and trimethicone modifying agent, is added in solvent, so that trimethicone is existed under base catalysis
Silica surface graft reaction, obtains improved silica；
(2) improved silica obtained by step (1) is reacted with corresponding functionalized reagent, progress is twice-modified, in titanium dioxide
Silicon particle surface grafting Long carbon chain alkyl structure.
2. a kind of surface oleophylic method of modifying of nano silica according to claim 1, which is characterized in that described
Trimethicone modifying agent be amino-containing trimethoxy silane, in the trimethoxy silane containing epoxy group any one or
The mixing of the two.
3. a kind of surface oleophylic method of modifying of nano silica according to claim 2, which is characterized in that described
Amino-containing trimethoxy silane be trimethoxy propyl amino silane, corresponding functionalized reagent be dodecyl acrylate,
One or more of Process Conditions of Cetane Acrylate, octadecyl acrylate.
4. a kind of surface oleophylic method of modifying of nano silica according to claim 2, which is characterized in that described
Trimethoxy silane containing epoxy group is trimethoxy epoxy group amino silane, and corresponding functionalized reagent is lauryl amine, ten
One or more of hexamine, octadecylamine.
5. a kind of surface oleophylic method of modifying of nano silica according to claim 1, which is characterized in that the step
Suddenly the mass ratio of silica and trimethicone modifying agent is 1 in (1): (1.0-1.5).
6. a kind of surface oleophylic method of modifying of nano silica according to claim 1, which is characterized in that described
Solvent be water, methanol, ethyl alcohol, isopropanol any one or mixtures thereof, be added solvent after, silica and trimethicone
It is 10-20wt% that modifying agent, which accounts for reaction system mass fraction,.
7. a kind of surface oleophylic method of modifying of nano silica according to claim 1, which is characterized in that described
Alkali includes ammonium hydroxide, sodium hydroxide, potassium hydroxide, ethanol amine, diethanol amine, triethanolamine, any one in urea, is added
Amount is the 0.5-1.0wt% of silica quality score.
8. a kind of surface oleophylic method of modifying of nano silica according to claim 1, which is characterized in that the step
Suddenly the reaction temperature of the amino-containing its corresponding functionalized reagent of trimethoxy silane is 0-90 DEG C in (2), and the reaction time is
0.5-14h。
9. a kind of surface oleophylic method of modifying of nano silica according to claim 1, which is characterized in that the step
Suddenly the reaction temperature of its corresponding functionalized reagent of trimethoxy silane in (2) containing epoxy group is 0-50 DEG C, the reaction time
For 2-14h.
10. a kind of lipophilic nanometric silica made of claim 1-9 described in any item methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811189218.0A CN109370265B (en) | 2018-10-12 | 2018-10-12 | Surface oleophylic modification method of nano-silica and oleophylic nano-silica prepared by method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811189218.0A CN109370265B (en) | 2018-10-12 | 2018-10-12 | Surface oleophylic modification method of nano-silica and oleophylic nano-silica prepared by method |
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| CN109370265A true CN109370265A (en) | 2019-02-22 |
| CN109370265B CN109370265B (en) | 2021-04-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662203A (en) * | 2020-11-27 | 2021-04-16 | 中国科学院深圳先进技术研究院 | Modified silicon dioxide filler, preparation method thereof and resin composition |
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| CN102027074A (en) * | 2008-04-18 | 2011-04-20 | 纳米树脂股份公司 | Surface modified silicon dioxide particles |
| CN102775640A (en) * | 2005-05-27 | 2012-11-14 | 西巴特殊化学品控股有限公司 | Functionalized nanoparticles |
| CN103849165A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院化学研究所 | Functionalized nanometer silica with ultraviolet ray absorption function group grafted on surface, and preparation method thereof |
| CN104761692A (en) * | 2015-01-15 | 2015-07-08 | 西南石油大学 | Modification method for introducing carbon-carbon double bond to surface of nanometer silicon dioxide |
-
2018
- 2018-10-12 CN CN201811189218.0A patent/CN109370265B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775640A (en) * | 2005-05-27 | 2012-11-14 | 西巴特殊化学品控股有限公司 | Functionalized nanoparticles |
| CN102027074A (en) * | 2008-04-18 | 2011-04-20 | 纳米树脂股份公司 | Surface modified silicon dioxide particles |
| CN103849165A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院化学研究所 | Functionalized nanometer silica with ultraviolet ray absorption function group grafted on surface, and preparation method thereof |
| CN104761692A (en) * | 2015-01-15 | 2015-07-08 | 西南石油大学 | Modification method for introducing carbon-carbon double bond to surface of nanometer silicon dioxide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662203A (en) * | 2020-11-27 | 2021-04-16 | 中国科学院深圳先进技术研究院 | Modified silicon dioxide filler, preparation method thereof and resin composition |
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