CN104556072A - Method for preparing monodisperse nanosilicon dioxide employing in-situ modification - Google Patents
Method for preparing monodisperse nanosilicon dioxide employing in-situ modification Download PDFInfo
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- CN104556072A CN104556072A CN201510013472.5A CN201510013472A CN104556072A CN 104556072 A CN104556072 A CN 104556072A CN 201510013472 A CN201510013472 A CN 201510013472A CN 104556072 A CN104556072 A CN 104556072A
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Abstract
The invention discloses a method for preparing a monodisperse nanosilicon dioxide employing in-situ modification. Aiming at the defects of relatively poor dispersity and relatively many aggregates of the nanosilicon dioxide, complicated secondary disperse modification technology and energy consumption, on the basis of an original sol-gel technology, the nanosilicon dioxide which is excellent in appearance, uniform in particle size and monodispersed is prepared by in-situ modification with the technologies such as modifier amount, addition time, addition temperature and reaction condition. The preparation and modification method is advanced in process, and accurate in data; the product is white powder granules; and the diameters of the granules are 80-120nm, so that the method disclosed by the invention can be applied to a plurality of fields such as macromolecule reinforcing and toughening and industrial coatings.
Description
Technical field
The present invention relates to a kind of in-situ modified method preparing monodisperse nano silicon dioxide, belong to the technical field of the preparations and applicatio of inorganic nano material.
Background technology
Nano silicon has the distinctive quantum size effect of nano material, surface-interface effect and macro quanta tunnel effect etc., has good heat endurance, thickening property, reinforcing etc.Being widely used in the composite modifications such as rubber, engineering plastics, biomedicine, pottery, building materials, resin-based, is one of ultra tiny New Inorganic Materials of extremely important high-tech.
Although the application prospect of nano silicon is good, because the particle diameter of nano silicon is less, surface-active is higher, produce and very easily produce soft, hard aggregation in application process, cause application performance to reduce, cannot play a role, even reduce the processed and applied performance of material.For this defect, existing counte-rplan mainly utilize all kinds of coupling agent to carry out secondary surface modification treatment to the nano silicon prepared, then use.Though these schemes can improve the agglomeration of nano silicon to a certain extent, improve application performance, but be limited to the native mode of nano silicon raw material, partly can only eliminate the soft aggregate in silica material, but cannot improve original hard agglomeration, nano silicon can not be made to reach monodisperse status.
At present, the report that the technology of preparing of domestic nano silicon can reach monodisperse status is less, representational " a kind of chemical precipitation method production technology of monodisperse nano silicon dioxide " having Shen Jie, adopt chemical precipitation method, take ethyl orthosilicate as raw material, ammoniacal liquor is catalyst, has prepared monodisperse spherical nano silica dioxide granule.The feature of its method is that technology and equipment is comparatively simple, and product is mainly used in the aspect such as toughness reinforcing of high polymer, but does not mention and in preparation process, carry out modification, to improve the stability of product; The people such as Chen Jianjun, Wang Naiyan, Gao Linhui " method for preparing monodisperse nano silicon dioxide spherical particle hydrosol and uses thereof " adopts sol-gel process, and the catalyst reacted as teos hydrolysis with ammonia is that Nano-meter SiO_2 prepared by solvent with ethanol
2particle, the feature of method adopts heating and blowing process by the most of alcohol volatilization in suspension, obtains nano-silicon dioxide particle slurry, for modified water-soluble exterior coating, aqueous fire-proof coating and water-borne wood coating.The method cannot obtain the material of powdery, and preparation technology is comparatively complicated, is of limited application; The preparation method of a kind of high-dispersion nano silica of people's inventions such as Duan Xianjian, Wang Yuelin, Yang Benyi, adopt the technique of vapour deposition, the water utilizing halosilanes burning to generate and the heat of generation carry out pyrohydrolysis condensation reaction, product obtains nano silicon through aftertreatment technologys such as overbunching gas solid separation depicklings, although method is comparatively novel, but it is higher to consume energy, and complex process, is comparatively not suitable for industrial production.
Summary of the invention
The present invention solves the technical problem preparing hard agglomeration phenomenon and the complex process existed in nano silicon process at present, provides a kind of in-situ modified method preparing monodisperse nano silicon dioxide.
The present invention realizes by the following technical solutions: a kind of in-situ modified method preparing monodisperse nano silicon dioxide, the chemical substance material used is: ethyl orthosilicate, with mass fraction calculating concentration be 25% ammoniacal liquor, absolute ethyl alcohol, silane coupler KH570, deionized water, described chemical substance material usage all calculates with volume parts;
Preparation method is as follows:
(1) selected each chemical substance material
(2) in-situ modifiedly nano silicon is prepared
1. obtain solution
Measure 39 ~ 41 parts of absolute ethyl alcohols and 7.5 ~ 8.5 parts of deionized waters, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by; Measure the conical flask that 29 ~ 31 parts of ammoniacal liquor are placed in rubber stopper stand-by; Measure the ethyl orthosilicate of 4.3 ~ 4.7 parts and the absolute ethyl alcohol of 39 ~ 41 parts, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by;
2. form nano silicon and prepare system
The ethanol solution configured and ammonia spirit are placed in there-necked flask, and be then placed in magnetic agitation heating jacket, turn on agitator, unlatching is heated, and agitator speed is set as 150r/min, and warm temperature is set as 60 DEG C, condensing reflux reaction 8h; Between temperature raising period when temperature reaches 40 DEG C, with the speed of 0.5 part/min, teos solution is added in there-necked flask;
3. in-situ modified process
After condensing reflux reaction 8h, measure silane coupler KH570 and 29 ~ 31 part absolute ethyl alcohol of 1.4 ~ 1.6 parts, be placed in beaker and mix, mixed solution is added in there-necked flask with the speed of 1 part/min, the stir speed (S.S.) of agitator is brought up to 250r/min, reaction 15min;
4. ultrasonic water bath reaction
After 3. step is reacted and terminated, there-necked flask is placed in ultrasonic water bath pond and continues reaction, bath temperature is 50 DEG C, and supersonic frequency is 80KHz, and power is 80W, and the reaction time is 1h;
5. absolute ethanol washing, suction filtration
By step 4. reaction mixture be placed in beaker, add absolute ethyl alcohol 100 parts, agitator treating 3min, become cleaning solution;
Cleaning solution is placed in the Buchner funnel of bottle,suction, carries out suction filtration with microporous inorganic filter membrane, remaining product filter cake on filter membrane, waste liquid is evacuated in filter flask, then product cake and absolute ethyl alcohol are mixed and made into solution;
6. deionized water washing, suction filtration
The reaction mixture made by filter cake is placed in beaker, adds deionized water 200 parts of agitator treating 5min, becomes cleaning solution; Cleaning solution is placed in the Buchner funnel of bottle,suction, carries out suction filtration with the organic filter membrane of micropore, remaining product filter cake on filter membrane, waste liquid is evacuated in filter flask;
7. vacuum drying
Product cake is placed in quartz container, then quartz container is placed in vacuum drying chamber dry, baking temperature 80 DEG C, vacuum 0.1MPa, drying time 1h;
Nano silica powder particle is obtained after drying;
8. grind, sieve
Dried powder granule agate mortar, pestle are ground, then sieves with 400 eye mesh screens, grind, sieving repeats, obtain nano silicon product.
Described ethyl orthosilicate is Si (OC
2h
5)
4, silane coupler KH570 is CH
2=C (CH
3) COOC
3h
6si (OCH
3)
3.
The pattern of nano silicon of preparation, color and luster, composition, Chemical Physics performance are detected, analyze, characterized: with JSM-6700F type field emission scanning electron microscope, morphology analysis is carried out to nano silicon; With FTIR-1730 type infrared spectrometer, FTIR spectrum analysis is carried out to product.
Conclusion: the nano silicon that the application obtains is white powder particle, particle diameter 80-120nm, regular appearance, uniform particle sizes, good dispersion, Chemical Physics stable performance.
Nano silicon is stored in the glass container of amber transparent, and airtight lucifuge stores, and waterproof, sun-proof, anti-acid-alkali salt to corrode, storage temperature 25 DEG C, relative humidity≤10%.
Beneficial effect of the present invention: the present invention compared with prior art has obvious advance, be poor for nano silicon dispersiveness, aggregate is more, the drawback that twice dispersing modified technique is complicated, expend the energy, on the basis of original sol-gel technique, utilize modifier consumption, joining day, the technology such as temperature, reaction condition that adds is in-situ modified prepares that exterior appearance is excellent, uniform particle sizes, mono-dispersed nano silica.This preparation is advanced with method of modifying technique, informative data is accurate, and product is white powder graininess, particle diameter 80-120nm, can, in multiple fields application such as macromolecule activeness and quietness, industrial coatings, be the preparation method of very good nano silicon.
Further, step (1) will be carried out selected to the chemical substance material that preparation uses, and carries out quality purity, concentration control: ethyl orthosilicate purity is 99.9%, absolute ethyl alcohol purity 99.9%; Silane coupler KH570 purity 99.9%; Deionized water purity 99.9%.
Further, 5. middle washing, suction filtration repeat 5 times to step; Step 6. middle washing, suction filtration repeats 10 times.
Further, step 1. in preparation ethanol solution time, adopt glass bar stir 3min; During preparation teos solution, glass bar stirs 5min; Step 3. middle silane coupler KH570 and the rear glass bar that adopts of absolute ethyl alcohol mixing stirs 5min.Mixing time can ensure that solution mixes.
Nano silicon product is dispersed better to adopt the raw material of above-mentioned purity, washing suction filtration number of times and mixing time effectively to guarantee.
The present invention is on the basis of sol-gel process, a certain amount of silane coupler KH570 is added at reasonable time in the reaction system of synthesis of nano silica, carry out in-situ modified to nano silicon, improve dispersiveness and the pattern of nano silicon, eliminate hard agglomeration phenomenon preferably, extend the range of application of nano silicon.
Accompanying drawing explanation
Fig. 1 in-situ modifiedly prepares monodisperse nano silicon dioxide state diagram.
Fig. 2 in-situ modifiedly prepares the ultrasonic state diagram of monodisperse nano silicon dioxide.
Fig. 3 is nano silicon microscopic appearance figure.
Fig. 4 is the partial enlarged drawing of Fig. 3.
Fig. 5 is nano silicon FTIR spectrum figure.
1-magnetic agitation heating block set, 2-there-necked flask, 3-addition funnel, 4-adds hydraulic control valve, 5-condensation reflux device, 6-temperature inductor, 7-temperature inductor fixed mount, 8-is in-situ modified prepares monodisperse nano silicon dioxide mixed liquor, 9-addition funnel fixed mount, 10-condensation reflux device fixed mount, 11-magnetic agitation rotor, 12-first temperature control knob, 13-rotating speed control knob, 14-ultrasonic wave transmitter module, 15-numerical control ultrasonic cleaner water-bath seat, 16-purified liquid water, 17-power control knob, 18-second temperature control knob.
Detailed description of the invention
The in-situ modified method preparing monodisperse nano silicon dioxide of embodiment 1 one kinds, the chemical substance material of use is: ethyl orthosilicate, with mass fraction calculating concentration be 25% ammoniacal liquor, absolute ethyl alcohol, silane coupler KH570, deionized water;
Preparation method is as follows:
(1) selected each chemical substance material
(2) in-situ modifiedly nano silicon is prepared
1. obtain solution
Measure 39ml absolute ethyl alcohol and 8.0ml deionized water, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by; Measure the conical flask that 29ml ammoniacal liquor is placed in rubber stopper stand-by; Measure the ethyl orthosilicate of 4.5ml and the absolute ethyl alcohol of 40ml, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by;
2. form nano silicon and prepare system
The ethanol solution configured and ammonia spirit are placed in there-necked flask, and be then placed in magnetic agitation heating jacket, turn on agitator, unlatching is heated, and agitator speed is set as 150r/min, and warm temperature is set as 60 DEG C, condensing reflux reaction 8h; Between temperature raising period when temperature reaches 40 DEG C, with the speed of 0.5ml/min, teos solution is added in there-necked flask;
3. in-situ modified process
After condensing reflux reaction 8h, measure silane coupler KH570 and the 31ml absolute ethyl alcohol of 1.4ml, be placed in beaker and mix, mixed solution is added in there-necked flask with the speed of 1ml/min, the stir speed (S.S.) of agitator is brought up to 250r/min, reaction 15min.
The in-situ modified method preparing monodisperse nano silicon dioxide of embodiment 2 one kinds, the chemical substance material of use is: ethyl orthosilicate, with mass fraction calculating concentration be 25% ammoniacal liquor, absolute ethyl alcohol, silane coupler KH570, deionized water;
Preparation method is as follows:
(1) selected each chemical substance material
(2) in-situ modifiedly nano silicon is prepared
1. obtain solution
Measure 40ml absolute ethyl alcohol and 8.5ml deionized water, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by; Measure the conical flask that 30ml ammoniacal liquor is placed in rubber stopper stand-by; Measure the ethyl orthosilicate of 4.3ml and the absolute ethyl alcohol of 41ml, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by;
2. form nano silicon and prepare system
The ethanol solution configured and ammonia spirit are placed in there-necked flask, and be then placed in magnetic agitation heating jacket, turn on agitator, unlatching is heated, and agitator speed is set as 150r/min, and warm temperature is set as 60 DEG C, condensing reflux reaction 8h; Between temperature raising period when temperature reaches 40 DEG C, with the speed of 0.5ml/min, teos solution is added in there-necked flask;
3. in-situ modified process
After condensing reflux reaction 8h, measure silane coupler KH570 and 30ml part absolute ethyl alcohol of 1.5ml part, be placed in beaker and mix, mixed solution is added in there-necked flask with the speed of 1ml/min, the stir speed (S.S.) of agitator is brought up to 250r/min, reaction 15min.
The in-situ modified method preparing monodisperse nano silicon dioxide of embodiment 3 one kinds, the chemical substance material of use is: ethyl orthosilicate, with mass fraction calculating concentration be 25% ammoniacal liquor, absolute ethyl alcohol, silane coupler KH570, deionized water;
Preparation method is as follows:
(1) selected each chemical substance material
(2) in-situ modifiedly nano silicon is prepared
1. obtain solution
Measure 41ml absolute ethyl alcohol and 7.5ml deionized water, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by; Measure the conical flask that 31ml ammoniacal liquor is placed in rubber stopper stand-by; Measure the ethyl orthosilicate of 4.7ml and the absolute ethyl alcohol of 39ml, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by;
2. form nano silicon and prepare system
The ethanol solution configured and ammonia spirit are placed in there-necked flask, and be then placed in magnetic agitation heating jacket, turn on agitator, unlatching is heated, and agitator speed is set as 150r/min, and warm temperature is set as 60 DEG C, condensing reflux reaction 8h; Between temperature raising period when temperature reaches 40 DEG C, with the speed of 0.5ml/min, teos solution is added in there-necked flask;
3. in-situ modified process
After condensing reflux reaction 8h, measure silane coupler KH570 and the 29ml absolute ethyl alcohol of 1.6ml, be placed in beaker and mix, mixed solution is added in there-necked flask with the speed of 1ml/min, the stir speed (S.S.) of agitator is brought up to 250r/min, reaction 15min.
All the other steps of three embodiments are identical.
Below in conjunction with accompanying drawing, the present invention will be further described: shown in Fig. 1, prepares monodisperse nano silicon dioxide state diagram for in-situ modified, and each position wants correct, and proportioning according to quantity, operates according to the order of sequence.
The value of the chemical substance that preparation uses determines by the scope preset, with gram, milliliter for measurement unit.
There-necked flask 2 is placed on magnetic agitation heating jacket 1, and the heating-up temperature of magnetic agitation heating jacket 1 controls by the first temperature control knob 12; Addition funnel 3, condensation reflux device 5, temperature inductor 6 is set gradually from left to right on the top of there-necked flask 2; Addition funnel 3 bottom is provided with and adds hydraulic control valve 4, and is fixed by addition funnel fixed mount 9; Condensation reflux device 5 is fixed by condensation reflux device control cage 10; Temperature inductor 6 is fixed by inductor fixed mount 7; It is in-situ modified monodisperse nano silicon dioxide mixed liquor 8 of preparing in there-necked flask 2; Magnetic agitation rotor 11 is had bottom there-necked flask 2; Magnetic agitation rotor 11 rotating speed is controlled by rotating speed control knob 13.
Fig. 2 in-situ modifiedly prepares monodisperse nano silicon dioxide ultrasound bath figure, and each position wants correct, and proportioning according to quantity, operates according to the order of sequence.
There-necked flask 2 is placed on numerical control ultrasonic cleaner water-bath seat 15, purified liquid water 16 is added in sea water bath, the bath temperature of numerical control ultrasonic cleaner water-bath seat 15 controls by the second temperature control knob 18, and the power of ultrasonic wave transmitter module 14 controls by power control knob 17 and regulates; Addition funnel 3, condensation reflux device 5, temperature inductor 6 is set gradually from left to right on the top of there-necked flask 2; Addition funnel 3 bottom is provided with and adds hydraulic control valve 4, and is fixed by addition funnel fixed mount 9; Condensation reflux device 5 is fixed by condensation reflux device control cage 10; Temperature inductor 6 is fixed by inductor fixed mount 7; Monodisperse nano silicon dioxide mixed liquor 8 is prepared for in-situ modified in there-necked flask 2.
Fig. 3, Fig. 4 are the monodisperse nano silicon dioxide microscopic appearance figure of in-situ modified preparation, visible in figure: nano-silica surface pattern whole smooth is mellow and full, uniform particle sizes is full, particle diameter between 80-120nm, in monodisperse status, hard aggregation-free and soft-agglomerated phenomenon.
Fig. 5 is the monodisperse nano silicon dioxide FTIR spectrum figure of in-situ modified preparation, as we can clearly see from the figure the infrared signature absworption peak of nano silicon, 1096cm
-1the absworption peak of Qiang Erkuan is the antisymmetric stretching vibration peak of Si-O-Si, 802cm
-1and 470cm
-1for symmetrical stretching vibration peak and the flexural vibrations peak of Si-O key, 950cm
-1place is the flexural vibrations peak of Si-OH key; 3440cm
-1place's broad peak is the antisymmetric stretching vibration peak of constitution water-OH; Meanwhile, the characteristic absorption peak of modifier silane coupler KH570 can obviously be seen, 1629cm
-1place is the stretching vibration peak of C=C key, 1445cm
-1and 2895cm
-1place is methyl, the flexural vibrations of methylene and stretching vibration peak, analyze display silane coupler KH570 preferably and nano silicon combine, play the effect of dispersion.
Claims (4)
1. the in-situ modified method preparing monodisperse nano silicon dioxide, it is characterized in that, the chemical substance material used is: ethyl orthosilicate, with mass fraction calculating concentration be 25% ammoniacal liquor, absolute ethyl alcohol, silane coupler KH570, deionized water, described chemical substance material usage all calculates with volume parts;
Preparation method is as follows:
(1) selected each chemical substance material
(2) in-situ modifiedly nano silicon is prepared
1. obtain solution
Measure 39 ~ 41 parts of absolute ethyl alcohols and 7.5 ~ 8.5 parts of deionized waters, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by; Measure the conical flask that 29 ~ 31 parts of ammoniacal liquor are placed in rubber stopper stand-by; Measure the ethyl orthosilicate of 4.3 ~ 4.7 parts and the absolute ethyl alcohol of 39 ~ 41 parts, be placed in beaker and mix, make it mix with glass bar stirring rear stand-by;
2. form nano silicon and prepare system
The ethanol solution configured and ammonia spirit are placed in there-necked flask, and be then placed in magnetic agitation heating jacket, turn on agitator, unlatching is heated, and agitator speed is set as 150r/min, and warm temperature is set as 60 DEG C, condensing reflux reaction 8h; Between temperature raising period when temperature reaches 40 DEG C, with the speed of 0.5 part/min, teos solution is added in there-necked flask;
3. in-situ modified process
After condensing reflux reaction 8h, measure silane coupler KH570 and 29 ~ 31 part absolute ethyl alcohol of 1.4 ~ 1.6 parts, be placed in beaker and mix, mixed solution is added in there-necked flask with the speed of 1 part/min, the stir speed (S.S.) of agitator is brought up to 250r/min, reaction 15min;
4. ultrasonic water bath reaction
After 3. step is reacted and terminated, there-necked flask is placed in ultrasonic water bath pond and continues reaction, bath temperature is 50 DEG C, and supersonic frequency is 80KHz, and power is 80W, and the reaction time is 1h;
5. absolute ethanol washing, suction filtration
By step 4. reaction mixture be placed in beaker, add absolute ethyl alcohol 100 parts, agitator treating 3min, become cleaning solution;
Cleaning solution is placed in the Buchner funnel of bottle,suction, carries out suction filtration with microporous inorganic filter membrane, remaining product filter cake on filter membrane, waste liquid is evacuated in filter flask, then product cake and absolute ethyl alcohol are mixed and made into solution;
6. deionized water washing, suction filtration
The reaction mixture made by filter cake is placed in beaker, adds deionized water 200 parts of agitator treating 5min, becomes cleaning solution; Cleaning solution is placed in the Buchner funnel of bottle,suction, carries out suction filtration with the organic filter membrane of micropore, remaining product filter cake on filter membrane, waste liquid is evacuated in filter flask;
7. vacuum drying
Product cake is placed in quartz container, then quartz container is placed in vacuum drying chamber dry, baking temperature 80 DEG C, vacuum 0.1MPa, drying time 1h;
Nano silica powder particle is obtained after drying;
8. grind, sieve
Dried powder granule agate mortar, pestle are ground, then sieves with 400 eye mesh screens, grind, sieving repeats, obtain nano silicon product.
2. a kind of in-situ modified method preparing monodisperse nano silicon dioxide according to claim 1, it is characterized in that, step (1) will be carried out selected to the chemical substance material that preparation uses, and carry out quality purity, concentration control: ethyl orthosilicate purity is 99.9%, absolute ethyl alcohol purity 99.9%; Silane coupler KH570 purity 99.9%; Deionized water purity 99.9%.
3. a kind of in-situ modified method preparing monodisperse nano silicon dioxide according to claim 1 and 2, is characterized in that: step 5. middle washing, suction filtration repeats 5 times; Step 6. middle washing, suction filtration repeats 10 times.
4. a kind of in-situ modified method preparing monodisperse nano silicon dioxide according to claim 1 and 2, is characterized in that, step 1. in preparation ethanol solution time, adopt glass bar stir 3min; During preparation teos solution, glass bar stirs 5min; Step 3. middle silane coupler KH570 and the rear glass bar that adopts of absolute ethyl alcohol mixing stirs 5min.
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