CN105255220A - Nano SiO2 surface modification method - Google Patents
Nano SiO2 surface modification method Download PDFInfo
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- CN105255220A CN105255220A CN201510680600.1A CN201510680600A CN105255220A CN 105255220 A CN105255220 A CN 105255220A CN 201510680600 A CN201510680600 A CN 201510680600A CN 105255220 A CN105255220 A CN 105255220A
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Abstract
The invention discloses a nano SiO2 surface modification method. The method comprises steps as follows: nano SiO2 is placed on watch glass and dried for 2-6 hours in a baking oven with the temperature of 100-130 DEG C; the dried nano SiO2 is added to a flask, an organic solvent is added, uniformly shaken and ultrasonically dispersed for 20-50 min, the nano SiO2 is uniformly dispersed; triallyl isocyanurate and dibutyltin dilaurate are added, inert gas is introduced for protection, the mixture is stirred and reacts for 0.5-5h at the temperature ranging from 50 DEG C to 90 DEG C, heating is stopped, and a reaction liquid is cooled to the room temperature; a reaction system is centrifugally separated, precipitates are washed with acetone, suction filtration is performed, the precipitates are dried for 8h at the temperature of 80 DEG C, and the dispersed nano SiO2 product is obtained. By means of the method, the number of hydrophilic hydroxyl (-OH) on the surface of nano silica is reduced, the lipophilicity and the hydrophobicity of nano silica are improved, the modified nano silica can be uniformly dispersed in an organic phase, and the hydrophobicity is high.
Description
Technical field
The present invention relates to a kind of Nano-meter SiO_2
2process for modifying surface, specifically, relate to a kind of Nano-meter SiO_2
2surface modifying method.
Background technology
SiO2 is a kind of tasteless, nontoxic, free of contamination nonmetal functional materials.Nano level SiO
2due to the size that it is special, have the advantages that particle diameter is little, specific surface area is large, surface effects, small-size effect, quantum tunneling effect, macro quanta tunnel effect and special photo electric etc. can be presented, be often used as the filler etc. of effective insulating materials, support of the catalyst, gas filtering material and high-grade paint, have a wide range of applications in fields such as rubber, plastics, coating, paint makeup, medicine and papermaking, cause in Materials science research field and pay close attention to widely, become one of focus of Materials science research.
Because nano particle specific surface area is large, atom is advanced activation state, be in thermodynamics unstable state, be easy to reunite together, form larger-size coacervate, therefore how to prepare the nanoparticle of dispersion, even particle size distribution, and to make itself and polymkeric substance compatible be better a focal issue of Application Areas, up to now, although there is a lot of surface modification of silica technique, all there is respective drawback.As: although silane coupler modified method is simple, expensive due to silane coupling agent, unsuitable scale operation; Carry out the method for modification of graft with polymkeric substance, owing to there is homopolymerization, percentage of grafting is lower, produces certain impact to the mechanical property of material; The shortcoming of esterification reaction method is that ester group is easily hydrolyzed, and its thermostability is poor.
Summary of the invention
Instant invention overcomes shortcoming of the prior art, provide a kind of Nano-meter SiO_2
2surface modifying method, its modification cost is low, and mechanical property is good, thermally-stabilised good, is easy to scale operation.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of Nano-meter SiO_2
2surface modifying method, it is characterized in that, comprise the steps:
(1) by Nano-meter SiO_2
2be placed on watch-glass, dry 2-6 hour in the baking oven at 100-130 DEG C;
(2) by dried Nano-meter SiO_2
2add in flask, then add organic solvent, shake up and ultrasonic wave dispersion 20-50min, make Nano-meter SiO_2
2be uniformly dispersed;
(3) add triallyl isocyanate and dibutyl tin laurate again, pass into protection of inert gas, stir, at 50-90 DEG C, react 0.5-5h, stop heating, reaction solution is cooled to room temperature;
(4) centrifugation reaction system, throw out washing with acetone, suction filtration, dries 8h at 80 DEG C, obtains scattered Nano-meter SiO_2
2product.
Organic solvent described in step (2) is the one in anhydrous benzene,toluene,xylene.
Rare gas element described in step (3) is nitrogen.
Described Nano-meter SiO_2
2before the reaction should first through microwave dispersion treatment.
The weight proportion of described nanosized SiO_2 and triallyl isocyanate is 1:0.5-3.
Compared with prior art, the invention has the beneficial effects as follows:
A kind of Nano-meter SiO_2 of the present invention
2surface modifying method, by modified-reaction, decrease hydrophilic hydroxyl (-OH) number on nano-silica surface, improve lipophilicity and the hydrophobicity of nano silicon to a certain extent.By Fourier infrared spectrum, the surface chemical structure of modified nano silicon and deployment conditions are in the solution characterized, result shows: modified nano silicon can be good at dispersed in organic phase, and its hydrophobicity is strong, reaches the object of expection.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, together with embodiments of the present invention for explaining the present invention, is not construed as limiting the invention, in the accompanying drawings:
Fig. 1 is Nano-meter SiO_2
2three-dimensional netted molecular structure.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
SiO
2there is the hydroxyl of undersaturated residual bond and different key and state in surface, as shown in Figure 1.
Due to SiO
2there is hydroxyl in surface, wetting ability is strong, and adjacent hydroxyl groups is each other with hydrogen bonded, and the hydrogen atom positive polarity of isolated hydroxyl is strong, and easy and electronegative atom adsorbs, with hydroxy-containing compounds generation dehydration condensation.The existence of surface hydroxyl makes surface have chemisorption activity, and form adsorption by hydrogen bond when meeting water molecules, and particle diameter is little, specific surface energy is large, easily reunites, causing its poor compatibility when coordinating with polymeric matrix, easily reuniting.Therefore, Nano-meter SiO_2 is solved
2the key issue of disperseing in macromolecule matrix is the process of its surface hydroxyl (-OH).
The present invention utilizes isocyanate groups (-NCO) to react with the hydroxyl (-OH) of nano-silica surface, carries out modification, modified SiO to nano-silica surface
2surface, both can by Nano-meter SiO_2 with acrylate group
2particle separates, and prevents it from reuniting, and obtains stable modified Nano; Meanwhile, this system further can also carry out polyreaction, preparation SiO
2nano composite material.Although domestic also useful isocyanate-modified Nano-meter SiO_2
2report, take generally tolylene diisocyanate as modified material, first utilize one of them isocyanate groups (-NCO) with Nano-meter SiO_2
2hydroxyl (-OH) carry out graft reaction, then utilize another-NCO connection on the group of various needs, this method needs two-step reaction, and technological process is comparatively loaded down with trivial details, and grafting efficiency is comparatively large by technogenic influence, have impact on its application.Compared with prior art, what the present invention adopted is triallyl isocyanate, compared with general graftomer modification method, the most outstanding advantage is not need preprocessing process, one step just can directly connect the acrylate group with chain-extension polymerization ability, technique is simple, and graft modification is respond well.
Embodiment 1
By Nano-meter SiO_2
2be placed on clean watch-glass, drying 3 hours in the baking oven at 130 DEG C, by dried Nano-meter SiO_2
2(median size of single particle is 50nm, is mainly distributed between 40-70nm, has reunion between particle) adds in there-necked flask, then adds dry toluene, shakes up and ultrasonic wave dispersion 30min, makes Nano-meter SiO_2
2dispersed in toluene.Then in system, triallyl isocyanate and the dibutyl tin laurate as catalyzer is added; pass into nitrogen protection; stir, at 50 DEG C, react 4h, stop heating; reaction solution is cooled to room temperature; then centrifugally operated is carried out to reaction solution, throw out washing with acetone, suction filtration; dry 8h at 80 DEG C, obtain scattered Nano-meter SiO_2
2product, its median size is 65nm (being mainly distributed between 50-80nm).
Embodiment 2
By Nano-meter SiO_2
2be placed on clean watch-glass, drying 3 hours in the baking oven at 130 DEG C, by dried Nano-meter SiO_2
2(median size of single particle is 50nm, is mainly distributed between 40-70nm, has reunion between particle) adds in there-necked flask, then adds anhydrous dimethyl benzene, shakes up and ultrasonic wave dispersion 30min, makes Nano-meter SiO_2
2dispersed in dimethylbenzene.Then in system, triallyl isocyanate and dibutyl tin laurate is added; pass into nitrogen protection; stir, at 65 DEG C, react 2h, stop heating; reaction solution is cooled to room temperature; then centrifugally operated is carried out to reaction solution, throw out washing with acetone, suction filtration; dry 8h at 80 DEG C, obtain scattered Nano-meter SiO_2
2product, its median size is 70nm (being mainly distributed between 50-80nm).
Embodiment 3
By Nano-meter SiO_2
2be placed on clean watch-glass, drying 2 hours in the baking oven at 140 DEG C, by dried Nano-meter SiO_2
2(median size of single particle is 50nm, mainly be distributed between 40-70nm, the median size of reunion single particle is had to be 60nm between particle, mainly be distributed between 50-80nm, reunion is had between particle) add in there-necked flask, add benzene again, shake up and ultrasonic wave dispersion 30min, make Nano-meter SiO_2
2dispersed in benzene.Then in system, triallyl isocyanate and dibutyl tin laurate is added; pass into nitrogen protection; stir, at 80 DEG C, react 1h, stop heating; reaction solution is cooled to room temperature; then centrifugally operated is carried out to reaction solution, throw out washing with acetone, suction filtration; dry 8h at 80 DEG C, obtain scattered Nano-meter SiO_2
2product, its median size is 60nm (being mainly distributed between 50-80nm).
Last it is noted that these are only the preferred embodiments of the present invention; be not limited to the present invention; although with reference to embodiment to invention has been detailed description; for a person skilled in the art; it still can be modified to the technical scheme described in foregoing embodiments; or equivalent replacement is carried out to wherein portion of techniques feature; but it is within the spirit and principles in the present invention all; any amendment of doing, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. a Nano-meter SiO_2
2surface modifying method, it is characterized in that, comprise the steps:
(1) by Nano-meter SiO_2
2be placed on watch-glass, dry 2-6 hour in the baking oven at 100-130 DEG C;
(2) by dried Nano-meter SiO_2
2add in flask, then add organic solvent, shake up and ultrasonic wave dispersion 20-50min, make Nano-meter SiO_2
2be uniformly dispersed;
(3) add triallyl isocyanate and dibutyl tin laurate again, pass into protection of inert gas, stir, at 50-90 DEG C, react 0.5-5h, stop heating, reaction solution is cooled to room temperature;
(4) centrifugation reaction system, throw out washing with acetone, suction filtration, dries 8h at 80 DEG C, obtains scattered Nano-meter SiO_2
2product.
2. a kind of Nano-meter SiO_2 according to claim 1
2surface modifying method, it is characterized in that, the organic solvent described in step (2) is the one in anhydrous benzene,toluene,xylene.
3. a kind of Nano-meter SiO_2 according to claim 1
2surface modifying method, it is characterized in that, the rare gas element described in step (3) is nitrogen.
4. a kind of Nano-meter SiO_2 according to claim 1
2surface modifying method, it is characterized in that, described Nano-meter SiO_2
2before the reaction should first through microwave dispersion treatment.
5. the surface modifying method of a kind of nanosized SiO_2 according to claim 1, is characterized in that, the weight proportion of described nanosized SiO_2 and triallyl isocyanate is 1:0.5-3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085277A (en) * | 2016-07-26 | 2016-11-09 | 安徽敬业纳米科技有限公司 | A kind of preparation method of silicone sealant hydrophilic nano-silicon dioxide |
| CN110591289A (en) * | 2019-09-18 | 2019-12-20 | 浙江工业大学之江学院 | Preparation of material special for 3D printing support |
| CN115974534A (en) * | 2023-02-07 | 2023-04-18 | 江西省萍乡市华东出口电瓷有限公司 | Suspension porcelain insulator with aluminum oxide cylindrical head structure |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085277A (en) * | 2016-07-26 | 2016-11-09 | 安徽敬业纳米科技有限公司 | A kind of preparation method of silicone sealant hydrophilic nano-silicon dioxide |
| CN110591289A (en) * | 2019-09-18 | 2019-12-20 | 浙江工业大学之江学院 | Preparation of material special for 3D printing support |
| CN110591289B (en) * | 2019-09-18 | 2021-11-19 | 浙江工业大学之江学院 | Preparation method of material special for 3D printing support |
| CN115974534A (en) * | 2023-02-07 | 2023-04-18 | 江西省萍乡市华东出口电瓷有限公司 | Suspension porcelain insulator with aluminum oxide cylindrical head structure |
| CN115974534B (en) * | 2023-02-07 | 2023-09-08 | 江西省萍乡市华东出口电瓷有限公司 | Suspension porcelain insulator with alumina cylindrical head structure |
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