CN107955412B - Preparation method and application of modified nano silicon dioxide - Google Patents
Preparation method and application of modified nano silicon dioxide Download PDFInfo
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- CN107955412B CN107955412B CN201711154070.2A CN201711154070A CN107955412B CN 107955412 B CN107955412 B CN 107955412B CN 201711154070 A CN201711154070 A CN 201711154070A CN 107955412 B CN107955412 B CN 107955412B
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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
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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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Abstract
The invention discloses a preparation method of modified nano-silica, which comprises the steps of mixing nano-silica and an organic solvent in a container to form a mixed solution, carrying out reflux dehydration on the mixed solution, dropwise adding isocyanate into the mixed solution after moisture removal in the presence of protective gas, and reacting to obtain the modified nano-silica, wherein the feeding molar ratio of the nano-silica to the isocyanate is 1: 0.05 ~ 0.30.30, the isocyanate is one or a combination of more of polyisocyanates, and the prepared modified nano-silica is applied to electrical insulating materials and heat-resistant materials.
Description
Technical Field
The invention belongs to the technical field of nano materials and polymer composite materials, is suitable for electrical insulating materials and heat-resistant materials, and particularly relates to a preparation method and application of modified nano silicon dioxide.
Background
The nano silicon dioxide is one of the earliest produced nano materials and is also a nano powder material produced in large scale in the world at present. As an excellent structure and function material, the nano-silica has the advantages of small particle size, high surface activity, high temperature resistance, no toxicity, no pollution and the like, and is applied in many aspects, however, the effect of the existing nano-silica in the application process in all aspects is still not ideal, and the reason for the effect is that the easy agglomeration phenomenon of the nano-material inhibits the full exertion of the nano-superfine effect, especially the hydroxyl group with larger quantity on the surface of the nano-silica, so that the surface energy of the nano-silica is larger, and further the nano-silica always tends to agglomerate.
Therefore, some improvements are made in the prior art to the above phenomena, for example, the gefeng silk and the like are used for modifying the surface of the ultrafine silica by using an alcohol ester method to obtain the ultrafine nano silica with a hydrophobic surface, see university of Anhui science (Nature science edition), VoI.25, No.4, but the method needs to be carried out at a higher temperature (225 ℃) and a certain pressure (3MPa), and the hydrophobicity is only 30-40%. Bogusaw Buszewski et al, through the study of the properties and preparation method of silica gel aggregates, surface modification of silica with alcohol compounds, the degree of modification being detectable by elemental analysis, i.e. by calculating the density of coverage on the surface of the complex, the modified structure being determined by solid-state NMR and FT-IR optical instruments, the phase transition being revealed by thermal stability analysis, and the heterogeneous nature of the filler surface being verified by chromatographic tests, see Materials Chemistry and Physics, 2001,72:30-40, however, this method is as complicated and energy intensive as the aforementioned modification process, when surface modification of nanosilica is carried out with boron amine compounds (such as boron trifluoride monoethylamine), the best results are 3h at 500 ℃ which enables the immobilisation of most of the boron amine groups on the silica surface, the modification of boron amines enables nanosilica as a rubber reinforcing filler, the comprehensive performance of the method can be improved, but the method also needs a high-temperature surface treatment process at 500 ℃, and the energy consumption is higher.
At present, a chinese invention patent CN105968305A discloses a waterproof moisture-permeable polyurethane material and a preparation method thereof, (1) synthesis of polyol modified nano silica: adding commercially available silicon dioxide with the particle size of 7-200 nm and a certain amount of diisocyanate into dry toluene, ultrasonically dispersing the mixture under the protection of nitrogen, and then carrying out heat preservation reaction at 50-70 ℃ for 7-10 h; cooling to room temperature, carrying out suction filtration and washing to obtain diisocyanate modified nano silicon dioxide; mixing the prepared diisocyanate modified nano silicon dioxide particles with a certain amount of dihydric alcohol, and carrying out heat preservation reaction for 7-10 h at 50-70 ℃ under the protection of nitrogen; cooling to room temperature, carrying out suction filtration and washing to obtain a polyol modified nano silicon dioxide product; (2) synthesizing polyol modified nano silicon dioxide hybrid polyurethane: filling the metered polyester polyol or polyether polyol into a three-mouth bottle with a thermometer and a nitrogen protection device for vacuum dehydration; cooling to 50-70 ℃, adding a certain amount of diisocyanate and butanone, and reacting for 2-8 h to obtain a prepolymer; adding a certain amount of dihydric alcohol, 2-dimethylolpropionic acid and polyalcohol modified nano silicon dioxide into the prepolymer, and reacting at 50-90 ℃ to obtain reaction liquid; cooling the reaction liquid to 45 ℃, adding a certain amount of triethylamine, keeping the temperature and stirring; then adding the mixture into a certain amount of deionized water, and mechanically stirring to obtain nano silicon dioxide hybrid waterborne polyurethane emulsion; and preparing the prepared nano silicon dioxide hybrid waterborne polyurethane emulsion into a film. Although the isocyanate modified silica disclosed in the patent is improved in hydrophobicity, the addition of fatty alcohol causes long chain to wrap active groups, the reaction is incomplete, and more silicon hydroxyl groups still remain, so that the modified nano silica material prepared by the isocyanate modified silica is still difficult to meet practical requirements in the aspects of heat resistance, adhesive property, electrical strength, mechanical strength and the like in the application of electrical insulating materials and heat-resistant materials.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide an improved preparation method of modified nano-silica, and the prepared modified nano-silica can obtain more excellent electrical properties, adhesive properties, heat resistance, mechanical properties and the like in the application of electrical insulating materials and heat-resistant materials.
The invention also provides application of the modified nano silicon dioxide prepared by the method in electrical insulating materials and heat-resistant materials.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
a preparation method of modified nano-silica, which is used for electrical insulation materials and heat-resistant materials, comprises the following steps: mixing nano-silica and an organic solvent in a container to form a mixed solution, refluxing and dehydrating the mixed solution, dropwise adding isocyanate into the mixed solution after moisture is removed in the presence of a protective gas, and reacting to obtain the modified nano-silica; wherein the feeding molar ratio of the nano silicon dioxide to the isocyanate is 1: 0.05-0.30, and the isocyanate is one or a combination of more of polyisocyanates. Preferably, the feeding molar ratio of the nano silicon dioxide to the isocyanate is 1: 0.05-0.20.
The isocyanate and the nano-silica can be reacted completely by adopting a dripping mode, so that the phenomenon that the nano-silica is incompletely reacted when silicon hydroxyl is wrapped by the nano-silica and the effect of inhibiting the nano-superfine effect caused by incomplete modification is avoided.
According to a preferred aspect of the present invention, the number of silicon hydroxyl groups on the surface of the nano-silica is 2.5 to 5.5 per square nanometer. More preferably, the number of silicon hydroxyl groups on the surface of the nano silicon dioxide is 3.5-5.5 per square nanometer.
In some preferred embodiments of the present invention, the reflux dehydration is performed at 80 to 95 ℃ for 1 to 3 hours.
According to some preferred embodiments of the present invention, the isocyanate is controlled to be added dropwise over a half hour period.
In some embodiments of the present invention, preferably, the feeding mass ratio of the nano silica to the organic solvent is 1: 0.8-1.5. More preferably, the mass ratio of the nano silicon dioxide to the organic solvent is 1: 0.8-1.2.
According to some preferred embodiments of the invention, the reaction is carried out in the presence of a catalyst, said catalyst being dibutyltin laurate and/or stannous octoate.
Further preferably, the feeding mass ratio of the catalyst to the nano silicon dioxide is 0.0001-0.0003: 1.
In some embodiments of the invention, the polyisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 4', 4 "triphenylmethane triisocyanate or isophorone diisocyanate; the protective gas is nitrogen and/or argon; the organic solvent is anhydrous toluene and/or petroleum ether.
In some embodiments of the present invention, the preparation method further comprises a post-treatment step, and the post-treatment step is specifically implemented by: and carrying out centrifugal filtration on the mixture obtained after the reaction to obtain rough modified nano-silica, then washing the rough modified nano-silica by using a solvent, carrying out centrifugal filtration to obtain a filter material, and carrying out vacuum drying on the filter material to obtain the refined modified nano-silica.
The invention provides another technical scheme that: the modified nano silicon dioxide prepared by the method is applied to electrical insulating materials and heat-resistant materials. The electrical insulation material includes an insulation paint, an insulation varnish, etc. used in electricians, and the heat-resistant material includes a heat-resistant rubber, a heat-resistant paint, etc.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the isocyanate-based modified nano-silica prepared by the preparation method disclosed by the invention has the advantages that the number of silicon hydroxyl groups in the prepared isocyanate-based modified nano-silica is extremely small by controlling the reaction conditions in the preparation process, the inhibition of the nanometer superfine effect caused by the overlarge surface energy of the nano-silica is avoided, the modified nano-silica prepared by the preparation method disclosed by the invention is extremely suitable for electrical insulating materials and heat-resistant materials, has excellent compatibility with other resin components of the electrical insulating materials and the heat-resistant materials, can be uniformly dispersed, and can enable the electrical insulating materials and the heat-resistant materials to obtain excellent effects in bonding strength, heat resistance, mechanical strength and electrical strength.
Detailed Description
Based on the problems existing in the modification process of the modified nano-silica in the prior art, the invention innovatively uses a reflux dehydration method, not only overcomes the problems that the nano-state of the nano-silica is incomplete (due to the easy agglomeration phenomenon of the nano-silica, most of particles of the commercially available nano-silica are difficult to maintain in the nano-state) and the nano-silica is difficult to disperse in an organic phase, but also enables the surface silicon hydroxyl groups of the nano-silica to be fully exposed in the organic phase, controls the reaction ratio, and is further combined with the modification by selecting polyisocyanate, so that the nano-silica of the invention is completely modified, has little residual quantity of the silicon hydroxyl groups, and retains high-activity isocyanate groups (-C-N-O) after the modification, thereby ensuring the excellent compatibility with other resin components in subsequent electrical insulating materials and heat-resistant materials, can be uniformly dispersed.
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following examples, all starting materials are either commercially available or prepared by conventional methods in the art, unless otherwise specified.
The determination of the content of silicon hydroxyl groups is carried out using methods customary in the art, and the "Grignard reagent method" is used in the examples below, the principle of which is as follows: using a Grignard reagent (CH)3MgI) reacts with surface active hydrogen to release CH4The gas volume and pressure at the test temperature are measured, and the amount of gas generated can be calculated by using the gas state equation, so that the content of surface active hydrogen (surface hydroxyl) can be obtained.
Example 1 preparation of modified nanosilica
Mixing 200g of nano silicon dioxide, 50g of anhydrous toluene and 150g of petroleum ether in a container to form a mixed solution, carrying out reflux dehydration on the mixed solution for 1 hour at 95 ℃, adding 0.02g of dibutyltin laurate into the container, then carrying out gas replacement on the container by using nitrogen, after three times of replacement, dropwise adding 100g of isophorone diisocyanate into the mixed solution after moisture removal within 30min, reacting, carrying out centrifugal filtration on the mixture obtained after the reaction to obtain crude modified nano silicon dioxide, then cleaning the crude modified nano silicon dioxide by using anhydrous toluene, carrying out centrifugal filtration again to obtain a filter material, and carrying out vacuum drying on the filter material to obtain 256g of refined modified nano silicon dioxide.
The surface silicon hydroxyl content of the nano-silicon dioxide before the reaction is 4.15 per square nanometer, and the surface silicon hydroxyl content of the refined modified nano-silicon dioxide obtained after the reaction is 0.028 per square nanometer, so that the modification degree is 99.30 percent. (by "titration method of content of silicon hydroxyl group on surface of Nano silica (Grignard reagent method)")
Example 2 preparation of modified nanosilica
Mixing 200g of nano silicon dioxide, 100g of anhydrous toluene and 60g of petroleum ether in a container to form a mixed solution, carrying out reflux dehydration on the mixed solution for 2 hours at 90 ℃, adding 0.04g of dibutyltin laurate into the container, then carrying out gas replacement on the container by using nitrogen, after three times of replacement, dropwise adding 80g of isophorone diisocyanate into the mixed solution after moisture removal within 30min, reacting, carrying out centrifugal filtration on the mixture obtained after the reaction to obtain crude modified nano silicon dioxide, then cleaning the crude modified nano silicon dioxide by using anhydrous toluene, carrying out centrifugal filtration again to obtain a filter material, and carrying out vacuum drying on the filter material to obtain 255g of refined modified nano silicon dioxide.
The surface silicon hydroxyl content of the nano-silica before the reaction is 4.15 per square nanometer, and the surface silicon hydroxyl content of the refined modified nano-silica obtained after the reaction is 0.032 per square nanometer, so that the modification degree is 99.23 percent.
Example 3 preparation of modified nanosilica
Mixing 200g of nano-silica, 100g of anhydrous toluene and 100g of petroleum ether in a container to form a mixed solution, performing reflux dehydration on the mixed solution for 3 hours at 85 ℃, adding 0.01g of dibutyltin laurate and 0.04g of stannous octoate into the container, performing gas replacement on the container by using nitrogen, performing gas replacement for three times, dropwise adding 120g of diphenylmethane diisocyanate into the mixed solution after moisture removal within 30min, reacting, performing centrifugal filtration on the mixture obtained after the reaction to obtain crude modified nano-silica, cleaning the crude modified nano-silica by using anhydrous toluene, performing centrifugal filtration to obtain a crude modified nano-silica filter material, and performing vacuum drying on the filter material to obtain 263g of refined modified nano-silica.
The surface silicon hydroxyl content of the nano-silica before the reaction is 4.15 per square nanometer, and the surface silicon hydroxyl content of the refined modified nano-silica obtained after the reaction is 0.025 per square nanometer, so that the modification degree is 99.40%.
Comparative example 1
It is basically the same as example 1 except that the nanosilicon dioxide, the organic solvent and the free water carried by the isocyanate are dried using a general drying oven and then directly mixed in an anhydrous environment to perform the reaction. 235g of refined modified nano silicon dioxide is obtained.
The surface silicon hydroxyl content of the nano-silica before the reaction is 4.15 per square nanometer, and the surface silicon hydroxyl content of the refined modified nano-silica obtained after the reaction is 1.55 per square nanometer, so that the modification degree is only 62.6 percent.
Comparative example 2
The method is basically the same as that of example 1, and is different from the method that a common drying oven is used for drying nano silica, an organic solvent and free water carried by isocyanate, then the nano silica, the organic solvent and the free water are directly mixed in a water-free environment for reaction, and then a soft segment compound containing hydroxyl (in the example, fatty alcohol-poly adipic acid-1, 2-propylene glycol ester is used) is added for reaction.
The surface silicon hydroxyl group content of the nano-silica before the reaction is 4.15 per square nanometer, and the surface silicon hydroxyl group content of the refined modified nano-silica obtained after the reaction is 1.06 per square nanometer, the modification degree is only 74.5%.
Application example 1 preparation of insulating impregnating varnish
Weighing: 50 parts of E51 bisphenol A type epoxy resin; JEw0110 alicyclic epoxy resin 50 parts; 75 parts of JH-0621 modified methyl hexahydrophthalic anhydride; 25 parts of glycidyl methacrylate; 0.25 part of DCP initiator; 0.01 part of DMP-30 accelerator; 0.02 part of hydroquinone; 5 parts of modified nano-silica prepared in example 1.
The specific preparation process comprises the following steps: adding the modified nano-silica prepared in the embodiment 1 into a 500ml four-mouth reaction bottle according to the formula amount, adding E51 bisphenol A type epoxy resin, reacting for 2-4 hours at 80-95 ℃ under the protection of nitrogen to obtain a nano-silica modified epoxy resin compound, cooling to 60 ℃, sequentially adding JEw0110 alicyclic epoxy resin, JH-0621 modified methylhexahydrophthalic anhydride, glycidyl methacrylate, a DCP initiator, a DMP-30 accelerator and hydroquinone, stirring for 0.5 hour at 55 +/-5 ℃, and filtering with a 200-mesh sieve to obtain the nano-silica modified epoxy resin compound.
Application example 2 preparation of Heat-resistant rubber sheet
100 parts of raw rubber (NR15+ SBR 85); 80 parts of modified nano-silica prepared in example 1; 4 parts of zinc oxide; SA2 portions; 6 parts of solid coumarone resin; 10 parts of pine tar; 20 parts of light calcium carbonate; 1.5 parts of an anti-aging agent D; 2 parts of sulfur; 0.5 part of an accelerator M; and 1 part of an accelerator DM.
The specific preparation process comprises the following steps: following conventional methods in the art: preparing raw materials → plasticating raw rubber → adding various fillers and accessory ingredients for mixing → molding → vulcanizing → finishing.
Application example comparative example 1
It is substantially the same as in application example 1 except that the modified nano-silica prepared in comparative example 1 was used.
Application example comparative example 2
It is substantially the same as in application example 1 except that the modified nano-silica prepared in comparative example 2 was used.
Application example comparative example 3
It is substantially the same as in application example 2 except that the modified nano-silica prepared in comparative example 1 was used.
Performance testing
The following performance tests were performed on application examples 1-2 and comparative application examples 1-3, as shown in Table 1.
TABLE 1
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A preparation method of modified nano-silica is characterized by comprising the steps of mixing nano-silica and an organic solvent in a container to form a mixed solution, carrying out reflux dehydration on the mixed solution, dropwise adding isocyanate into the mixed solution after moisture removal in the presence of protective gas, and reacting to obtain the modified nano-silica, wherein the feeding molar ratio of the nano-silica to the isocyanate is 1: 0.05 ~ 0.30.30, the isocyanate is one or a combination of polyisocyanates, the reflux dehydration is carried out at 80 ~ 95 ℃ for 1 ~ 3 hours, the organic solvent is a combination of anhydrous toluene and petroleum ether, the number of silicon hydroxyl groups on the surface of the nano-silica is 2.5 ~ 5.5.5 per square nanometer, and the polyisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 4', or triisophorone.
2. The method for preparing modified nano-silica according to claim 1, wherein the isocyanate is controlled to be added dropwise within half an hour.
3. The method for preparing modified nano-silica according to claim 1, wherein the mass ratio of the nano-silica to the organic solvent is 1: 0.8 ~ 1.5.5.
4. The process for the preparation of modified nanosilica as claimed in claim 1, characterized in that the reaction is carried out in the presence of a catalyst, said catalyst being dibutyltin laurate and/or stannous octoate.
5. The method of claim 4, wherein the mass ratio of the catalyst to the nanosilica is 0.0001 ~ 0.0003.0003: 1.
6. The method for preparing modified nanosilica as claimed in claim 1, wherein the protective gas is nitrogen and/or argon.
7. The preparation method of the modified nano-silica as claimed in claim 1, wherein the preparation method further comprises a post-treatment step, and the post-treatment step is implemented in a specific way as follows: and carrying out centrifugal filtration on the mixture obtained after the reaction to obtain rough modified nano-silica, then washing the rough modified nano-silica by using a solvent, carrying out centrifugal filtration to obtain a filter material, and carrying out vacuum drying on the filter material to obtain the refined modified nano-silica.
8. Use of the modified nanosilica prepared according to any of claims 1 to 7 in electrical insulation materials, heat resistant materials.
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Denomination of invention: A preparation method of modified nano silica and its application Effective date of registration: 20220530 Granted publication date: 20200114 Pledgee: CITIC Bank Limited by Share Ltd. Suzhou branch Pledgor: SUZHOU TAIHU ELECTRIC ADVANCED MATERIAL Co.,Ltd. Registration number: Y2022320010170 |