CN109370265B - Surface oleophylic modification method of nano-silica and oleophylic nano-silica prepared by method - Google Patents

Surface oleophylic modification method of nano-silica and oleophylic nano-silica prepared by method Download PDF

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CN109370265B
CN109370265B CN201811189218.0A CN201811189218A CN109370265B CN 109370265 B CN109370265 B CN 109370265B CN 201811189218 A CN201811189218 A CN 201811189218A CN 109370265 B CN109370265 B CN 109370265B
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silica
silicon dioxide
nano
amino
oleophylic
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CN109370265A (en
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聂俊
李三保
朱晓群
王群璎
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Anqing Beihuada Science And Technology Park Co ltd
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Anqing Beihuada Science And Technology Park Co ltd
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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
    • 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
    • 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
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention discloses a surface oleophylic modification method of nano-silica and oleophylic nano-silica prepared by the method, which takes the nano-silica as a reaction initiator, takes siloxane containing amino and siloxane containing epoxy as a surface modifier, adopts a sol-gel method, and prepares modified nano-silica under the catalysis of alkali; then adding acrylic acid long-chain ester, and linking a long carbon chain on the surface of the silicon dioxide through the Michael addition reaction of double bonds and amino; or long carbon chain amino is added later, the long carbon chain is introduced to the surface of the silicon dioxide through the ring opening reaction of the amino and the epoxy, the silicon dioxide is endowed with high stability and lipophilicity through the long carbon chain, the stable dispersion of the silicon dioxide is realized, and the agglomeration and precipitation of the silicon dioxide are prevented; in addition, the prepared modified silicon dioxide can bring different functions of oleophylicity, antifouling, low gloss, scratch resistance, high hardness and the like to the material.

Description

Surface oleophylic modification method of nano-silica and oleophylic nano-silica prepared by method
Technical Field
The invention belongs to the technical field of preparation of functionalized nano particles, and particularly relates to a surface oleophylic modification method of nano silicon dioxide and oleophylic nano silicon dioxide prepared by the method.
Background
Nano silicon dioxide (SiO)2) As a fine chemical product, the product has a plurality of applications in the aspects of material reinforcement, system thickening, thixotropy and extinction. The nano silicon dioxide used in the coating can also improve the performances of washing resistance, scratch resistance, weather resistance, stain resistance and the like.
For unmodified SiO2Nanoparticles, due to their large specific surface area, have a tendency to agglomerate and thus have a tendency to precipitate at the bottom, especially for low viscosity systems, thus affecting the application of silica. Therefore, silica is required to be chemically modified to improve the dispersion stability, and therefore, we propose that the silica is modified by aminoalkyl-containing trimethylsiloxane or epoxy-containing siloxane, and then the amino and epoxy are secondarily modified by the reactivity of the amino and epoxy, so that the surface of the silica is provided with long carbon chain functional groups with low surface energy, thereby improving the dispersion stability of the silica in an oily systemAnd (5) performing qualitative determination. Meanwhile, the silica particles capable of being distributed in a gradient way can also endow the coating with good hydrophobic, water-resistant and stain-resistant properties.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: for unmodified SiO2Nanoparticles, due to their large specific surface area, have a tendency to agglomerate and thus have a tendency to precipitate at the bottom, especially for low viscosity systems, thus affecting the application of silica.
The invention adopts the following technical scheme to solve the technical problems:
a surface oleophylic modification method of nano silicon dioxide comprises the following steps:
(1) adding silicon dioxide and a trimethyl siloxane modifier into a solvent, and carrying out a grafting reaction on trimethyl siloxane on the surface of the silicon dioxide under the catalysis of alkali to obtain modified silicon dioxide;
(2) and (2) reacting the modified silicon dioxide obtained in the step (1) with a corresponding functional reagent, carrying out secondary modification, and grafting a long carbon chain alkyl structure on the surface of the silicon dioxide particle.
Further, the trimethyl siloxane modifier is one or the mixture of trimethoxy silane containing amino and trimethoxy silane containing epoxy.
Further, the amino-containing trimethoxy silane is trimethoxy propyl amino silane, and the corresponding functional reagent is one or more of lauryl acrylate, cetyl acrylate and stearyl acrylate.
Furthermore, the trimethoxy silane containing epoxy groups is trimethoxy epoxy amino silane, and the corresponding functional reagent is one or more of dodecylamine, hexadecylamine and octadecylamine.
Further, the mass ratio of the silicon dioxide to the trimethylsiloxane modifier in the step (1) is 1: 1.0-1.5.
Further, the solvent is any one or a mixture of water, methanol, ethanol and isopropanol, and after the solvent is added, the silicon dioxide and trimethyl siloxane modifier accounts for 10-20 wt% of the mass fraction of the reaction system.
Further, the alkali comprises any one of ammonia water, sodium hydroxide, potassium hydroxide, ethanolamine, diethanolamine, triethanolamine and urea, preferably ammonia water and urea, and the addition amount of the alkali is 0.5-1.0 wt% of the mass fraction of the silicon dioxide.
Further, the reaction temperature of the amino-containing trimethoxy silane and the corresponding functional reagent in the step (2) is 0-90 ℃, and the reaction time is 0.5-14 h.
Further, the reaction temperature of the trimethoxy silane containing epoxy groups and the corresponding functional reagent in the step (2) is 0-50 ℃, and the reaction time is 2-14 h.
Furthermore, the invention also provides oleophylic modified nano silicon dioxide which is prepared by the surface oleophylic modification method of the nano silicon dioxide.
The invention has the following beneficial effects: the invention discloses a surface oleophylic modification method of nano-silica, which takes the nano-silica as a reaction initiator, takes siloxane containing amino and siloxane containing epoxy as a surface modifier, and adopts a sol-gel method to prepare the modified nano-silica under the catalysis of alkali; then adding acrylic acid long-chain ester, and linking a long carbon chain on the surface of the silicon dioxide through the Michael addition reaction of double bonds and amino; or long carbon chain amino is added later, the long carbon chain is introduced to the surface of the silicon dioxide through the ring opening reaction of the amino and the epoxy, the silicon dioxide is endowed with high stability and lipophilicity through the long carbon chain, the stable dispersion of the silicon dioxide is realized, and the agglomeration and precipitation of the silicon dioxide are prevented; in addition, the prepared modified silicon dioxide can bring different functions of oleophylicity, antifouling, low gloss, scratch resistance, high hardness and the like to the material.
Detailed Description
In order to facilitate the understanding of the technical solutions of the present invention for those skilled in the art, the technical solutions of the present invention are further described below by way of specific embodiments.
Example 1
100mL of ethanol, 0.3g of ammonia water, 4g of deionized water and 8g of unmodified nano silicon dioxide powder are added into a 250mL three-neck flask and uniformly mixed. Under mechanical stirring, 13.3g of trimethoxypropylaminosilane was placed in a constant pressure funnel and added dropwise to the above mixed solution over 1 hour. Heating to 35 ℃, stirring and reacting for 5 hours to obtain a modified nano-silica microsphere solution, dissolving 16g of octadecyl acrylate in 50g of ethanol, dropwise adding the mixture into the reactant within 1 hour, and stirring and reacting for 4 hours at 35 ℃ to obtain the nano-silica microsphere solution, so that the nano-silica stably dispersed in an oily system can be obtained.
Example 2
100mL of ethanol, 0.1g of ammonia water, 3g of deionized water and 10g of unmodified nano silicon dioxide powder are added into a 250mL three-neck flask and mixed uniformly. Under the mechanical stirring, 12.8g of trimethoxypropylaminosilane is placed in a constant pressure funnel and added into the mixed solution in a dropwise manner within half an hour. Heating to 35 ℃, stirring and reacting for 6 hours to obtain a modified nano-silica microsphere solution, then dissolving 19g of dodecyl acrylate in 50g of ethanol, dropwise adding the mixture into the reactant within two hours, stirring and reacting for 5 hours to obtain a nano-silica microsphere solution, and obtaining the nano-silica stably dispersed in an oily system.
Example 3
200mL of ethanol, 0.1g of sodium hydroxide, 15g of deionized water and 20g of unmodified nano silicon dioxide powder are added into a 250mL three-neck flask and mixed uniformly. Under the mechanical stirring, 17.3g of trimethoxypropylaminosilane was placed in a constant pressure funnel and added dropwise to the above mixed solution over a half hour. Heating to 45 ℃, stirring and reacting for 3 hours to obtain a modified nano-silica microsphere solution, dissolving 28g of hexadecyl acrylate in 100g of ethanol, dropwise adding the solution into the reactant within 1 hour, and stirring and reacting for 7 hours to obtain the nano-silica microsphere solution, thereby obtaining the nano-silica stably dispersed in an oily system.
Example 4
100mL of ethanol, 0.2g of ammonia water, 5g of deionized water and 10g of unmodified nano silicon dioxide powder are added into a 250mL three-neck flask and mixed uniformly. 14.8g of trimethoxypropylepoxysilane was added dropwise to the above mixed solution over 1 hour in a constant pressure funnel under mechanical stirring. Heating to 45 ℃, stirring and reacting for 3 hours to obtain a modified nano-silica microsphere solution, dissolving 11.5g of hexadecylamine in 20g of ethanol, dropwise adding the solution into the reactant within 2 hours, stirring and reacting for 4 hours to obtain a nano-silica microsphere solution, and obtaining the nano-silica stably dispersed in an oily system.
Example 5
100mL of ethanol, 0.1g of sodium hydroxide, 10g of deionized water and 11g of unmodified nano silicon dioxide powder are added into a 250mL three-neck flask and mixed uniformly. Under mechanical stirring, 28.8g of trimethoxypropylepoxysilane was added dropwise to the above mixed solution in a constant pressure funnel over a half hour. Heating to 55 ℃, stirring and reacting for 2 hours to obtain a modified nano-silica microsphere solution, dissolving 15.8g of dodecylamine in 30g of ethanol, dropwise adding the solution into the reactant within 2 hours, stirring and reacting for 6 hours to obtain a nano-silica microsphere solution, and obtaining the nano-silica stably dispersed in an oily system.
Example 6
200mL of ethanol, 0.2g of sodium hydroxide, 30g of deionized water and 25g of unmodified nano silicon dioxide powder are added into a 250mL three-neck flask and mixed uniformly. Under mechanical stirring, 22.3g of trimethoxypropylepoxysilane was added dropwise to the above mixed solution in a constant pressure funnel over a half hour. Heating to 45 ℃, stirring and reacting for 4 hours to obtain a modified nano-silica microsphere solution, dissolving 31g of dodecylamine in 50g of ethanol, dropwise adding the solution into the reactant within two hours, stirring and reacting for 5 hours to obtain the nano-silica microsphere solution, and obtaining the nano-silica stably dispersed in an oily system.

Claims (5)

1. A surface oleophylic modification method of nano silicon dioxide is characterized by comprising the following steps:
(1) adding silicon dioxide and a trimethyl siloxane modifier into a solvent, and carrying out a grafting reaction on trimethyl siloxane on the surface of the silicon dioxide under the catalysis of alkali to obtain modified silicon dioxide; the trimethyl siloxane modifier is one or the mixture of trimethoxy silane containing amino and trimethoxy silane containing epoxy;
(2) reacting the modified silicon dioxide obtained in the step (1) with a corresponding functional reagent, performing secondary modification, and grafting a long-carbon chain alkyl structure on the surface of a silicon dioxide particle, wherein the trimethoxy silane containing an epoxy group is trimethoxy epoxy amino silane, and the corresponding functional reagent is one or more of dodecylamine, hexadecylamine and octadecylamine; the amino-containing trimethoxy silane is trimethoxy propyl amino silane, and the corresponding functional reagent is one or more of lauryl acrylate, cetyl acrylate and stearyl acrylate; the reaction temperature of the amino-containing trimethoxy silane and the corresponding functional reagent in the step (2) is 0-90 ℃, and the reaction time is 0.5-14 h; the reaction temperature of the trimethoxy silane containing epoxy groups and the corresponding functional reagent in the step (2) is 0-50 ℃, and the reaction time is 2-14 h.
2. The method for the lipophilic modification of the surface of nano-silica as claimed in claim 1, wherein the mass ratio of the silica to the trimethylsiloxane modifier in the step (1) is 1: 1.0-1.5.
3. The method for lipophilic modification of the surface of nano-silica as claimed in claim 1, wherein the solvent is any one or a mixture of water, methanol, ethanol and isopropanol, and after the solvent is added, the mass fraction of the silica and the trimethylsiloxane modifier in the reaction system is 10-20 wt%.
4. The method for lipophilic modification of surface of nano-silica as claimed in claim 1, wherein the alkali comprises any one of ammonia, sodium hydroxide, potassium hydroxide, ethanolamine, diethanolamine, triethanolamine, and urea, and the addition amount is 0.5-1.0 wt% of the mass fraction of silica.
5. An oleophilic nanosilica made by the method of any one of claims 1-4.
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CN102775640A (en) * 2005-05-27 2012-11-14 西巴特殊化学品控股有限公司 Functionalized nanoparticles

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