CN1830777A - Manufacturing method of silica sol and obtained silica sol - Google Patents
Manufacturing method of silica sol and obtained silica sol Download PDFInfo
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- CN1830777A CN1830777A CN 200510024230 CN200510024230A CN1830777A CN 1830777 A CN1830777 A CN 1830777A CN 200510024230 CN200510024230 CN 200510024230 CN 200510024230 A CN200510024230 A CN 200510024230A CN 1830777 A CN1830777 A CN 1830777A
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Abstract
A process for preparing high-granularity Si sol includes such steps as heating the SiO2 dispersed water, stirring while adding alkaline catalyst and metallic Si powder, hydrolytic reaction at pH=7-14 to obtain active silicic acid micro-particles, and quickly adsorbing the micro-particles by SiO2 seed particles to become target sol. Its advantages are high speed and controllable and uniform granularity.
Description
Technical field
The manufacture method that the present invention relates to a kind of silicon sol reaches by its silicon sol that makes.
Background technology
At present, the method for the big particle diameter silicon sol of industrial manufacturing generally has following several.A kind of is the method that adopts high temperature and high pressure method and drip the active silicic acid raw material on heating evaporation limit, top, seed liquor basis in ion exchange method technology.As United States Patent (USP): US3012972 (1962), US4356107 (1982) adopts the small particle size silicon sol of handling alkalescence under the High Temperature High Pressure, exactly in the hope of obtaining the silicon sol of big particle diameter; Patent US3947376 (1976), US4304575 (1981) and Chinese patent CN1155514A (1997) have adopted silicon-dioxide with the certain granules size as seed liquor basically, adopt heating evaporation limit, limit to drip the silicon sol that the atomic method of active silicic acid obtains big particle diameter then.But there is weak point in these processing methodes: the granular size of the silicon sol of high temperature and high pressure method preparation is very limited, size of particles is inhomogeneous, as prepare the silicon dioxide gel of median size at about 20nm, just need 10～15 atmospheric pressure and nearly 160～180 ℃ water temperature; And to production unit performance requriements height, energy consumption is big, and the later stage also will be carried out a large amount of enrichment steps; Adopt seed liquor to drip the atomic method of active silicic acid and avoided High Temperature High Pressure, low to the equipment performance requirement, and can prepare the bigger silicon sol of particle.But still have weak points such as long reaction time, macrobead homogeneity can't be guaranteed, and, be generally less than 5% because the active silicic acid micropartical concentration that drips is very low, the silicon sol that obtain higher concentration also need evaporate a large amount of water, the energy consumption height.Patent CN1506306A (2003) discloses the method that a kind of new employing seed liquor prepares big particle diameter silicon sol.This patented method shortens the time of dropwise reaction by improving the atomic median size of active silicic acid, thereby just can obtain the silicon sol of larger particles in the relatively short time.But the prepared silicon-dioxide of the method that this patent provides is porous matter form, and spherical characteristic is also not obvious.And, the preparation temperature of the best that this patented method provides is at 70～120 ℃, under this temperature, moisture can't be evaporated in a large number, the silica concentration of seed liquor and the active silicic acid raw material that added all less than 5% situation under, the thickness of silica gel that finally obtains is on the low side, generally can not surpass 10%, the silicon sol for preparing 30% even 50% high density of market widespread demand, also to carry out a large amount of enrichment steps, no matter be that evaporation concentration or ultra-filtration membrane concentrate, all can increase the cycle and the cost of investment of production.
Another method of making big particle diameter is the silica flour hydrolysis method.In disclosed patent US2614994 of nineteen fifty-two, just adopted that the hydrolysis silica flour prepares silicon sol under the organic bases effect, but the particle of gained silicon sol is on the low side, generally at 8～15nm; Same year disclosed another piece patent US2614995 prepares the silicon sol of big particle diameter by the concentration hydrolysis silica flour that improves ammoniacal liquor.Obtained the silica dioxide granule of particle diameter about 30nm in the ammoniacal liquor mass percentage concentration under up to 28% condition.At application number is in the patent of invention of CN86100503, and disclosing a kind of mass concentration that adopts is 1% the dilute alkaline soln and the method for silica flour prepared in reaction silicon sol, and the silica sol granule that this method obtains is at 15～20nm; In another piece patent CN86104144A, the contriver adopts the method for direct and rare water glass of silica flour or the reaction of rare potassium silicate, has directly obtained the silicon sol of particle diameter in 20～30nm scope.But these adopt silica flour is that main raw material prepares in the method for silicon sol, and the particle of prepared silicon sol is all on the low side, all is difficult to satisfy the requirement of the more high-grade silicon sol of preparation, polishes special-purpose silicon sol etc. as semi-conductor chip.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective, a kind of silicon sol is provided, the new manufacture method of particularly big particle diameter silicon sol.
The present invention realizes that the technical scheme of above-mentioned purpose is: a kind of manufacture method of silicon sol, its with the silica aqueous dispersion of required regulation granular size as seed liquor, under heated and stirred, in seed liquor, add basic catalyst and metallic silicon power, be to react under the condition of 7～14 scopes at pH, the active silicic acid micropartical that goes out by the silica flour hydrolysis is attached to making seed particles increase on the silicon-dioxide seed particles, thereby makes the silicon sol of big particle diameter.
Wherein, as the particle diameter of the silica dioxide granule of seed particles in the seed liquor, can wait suitably according to the silica dioxide granule particle diameter of the final desired silicon sol that obtains and select.The present invention generally selects for use the particle diameter of measuring by scanning electronic microscope (SEM) to be no more than 1 μ m, the preferably silica dioxide granule in 5～500nm scope.Wherein, when its particle diameter be that 1 μ m is when above, because the particle of seed particles is too big, the activity of seed particles surface hydroxyl is lower, the active silicic acid micropartical is not easy to be easy to generate new seed particles attached to the seed particles surface, and the final silicon-dioxide homogeneity of acquisition is affected; And,, in silicon-dioxide (more than 20nm) the very long reaction times of needs that prepare larger particles, be unfavorable for shortening preparation cycle because seed particles is too small when particle diameter during less than 5nm.
And the mass percentage concentration of the silicon-dioxide seed particles in the above-mentioned seed liquor is in 0.5～30% scope, and 2～10% to be preferable selection, 3.5～10% is better.Wherein, the concentration of silicon-dioxide seed particles is too low, particularly be lower than at 0.1% o'clock, because the quantity of the seed particles in the unit volume is comparatively rare, active silicic acid micropartical and seed particles bump and then chance that condensation reaction takes place reduces greatly, therefore will influences the rate of growth of seed particles and the final homogeneity of silica dioxide granule; And the concentration of seed particles is too high, then in reaction process, the silica concentration of system will reach higher numerical value very soon, it is big that the viscosity of system will become earlier, the rate of growth of seed particles and the stability of silicon sol will be influenced, the silica flour quality that can add simultaneously will reduce, thereby limit the further growth of seed particles.
In manufacture method of the present invention, heating is preferably carried out 60～100 ℃ of scopes.Wherein, temperature is too low, as less than 60 ℃, and sluggish then; Temperature is too high, and when surpassing 100 ℃, must pressurize to obtain temperature more than 100 ℃, therefore will increase the performance of equipment, preparation process is also dangerous, causes reaction too fierce because temperature is too high simultaneously, process is difficult to control, and the homogeneity of final silicon-dioxide also is difficult to be protected.
Basic catalyst of the present invention is all mineral alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, or/and thanomin, diethanolamine, trolamine, one or several mixing in the organic basess such as ethamine and quadrol.
The method that the adding of basic catalyst can be adopted disposable adding before adding silica flour also can adopt the limit to add the method that the silica flour limit adds catalyzer.It is to add behind 2～20% the aqueous solution that catalyzer preferably is diluted with water to mass content earlier again.
And the silica flour that is adopted is the silica flour in 30～800 order scopes, and wherein with 100～400 orders, particularly the silica flour in 200～400 order scopes is best.Silicon powder particle is too thick, and sluggish will cause the overlong time of reacting; Particle is too thin, and speed of response is too fast, and is difficult with control.
The addition of silica flour can according to silica flour under certain condition yield and seed particles and required final silicon sol product in the median size size of silica dioxide granule estimate acquisition.Under certain conditions, the yield of silica flour can calculate by following formula:
Wherein, w
xAfter the reaction end, SiO in the gained silicon sol product
2Mass content; w
0Be SiO in the former seed liquor
2Mass content; w
SiQuality for the silica flour that adds; 28.08 and 60.08 be respectively Si and SiO
2Relative atomic mass.
The mass ratio of described basic catalyst and silica flour is generally 1: 5～200, and preferred proportion is 1: 10～100, and particularly 1: 27～100.Wherein, base catalysis dosage is too low, and particularly less than 1: 200 o'clock, reaction time was long, and silica flour is difficult to react completely, and the utilization ratio of silica flour is on the low side; Measure too high, particularly aforementioned proportion was greater than 1: 5 o'clock, then because the system alkali content is too high, the stability of silicon sol will be affected and the instability that becomes, cause the pH of final silicon sol product higher simultaneously, according to the demand in market, also to carry out the reduction of pH and handle, will increase the working load of aftertreatment.
Generally under alkaline condition, be preferably at pH is under 8～14 conditions to the reaction system of the inventive method.Because of pH is too low,, then cannot or hardly react as less than 7.
The present invention is the same with other chemical reaction, after adding whole NaOH and silica flour, and insulation reaction for some time, allowing silica flour react completely, thereby improve the utilization ratio of silica flour, its time length can be decided according to the silica flour response situation of reality.
Another object of the present invention provides the silicon sol that the manufacture method by the invention described above makes, the well big particle diameter silicon sol of homogeneity particularly, the ratio of the long and short axle of silica dioxide granule wherein is approximately equal to 1, and outward appearance is the full particle of approximate circle ball shape.
Utilize the manufacture method of big particle diameter silicon sol of the present invention can make silica flour active silicic acid micropartical that hydrolysis under the basic catalyst effect produces fast, equably attached to seed particles on, seed particles was increased rapidly in the relatively short time, thereby can under very economic situation, obtain big particle diameter silicon sol quickly and easily, and can obtain the well big particle diameter silicon dioxide gel of homogeneity.The method of the big particle diameter silicon sol of manufacturing of the present invention is compared with prior preparation method, has following advantage: the particulate rate of growth is fast, and the silica dioxide granule diameter per hour can increase about 2～6nm; Needn't adopt High Temperature High Pressure, the gentle control easily of reaction conditions requires low to equipment performance; Reaction finishes the concentration height of the resulting silicon sol in back, generally in 30～60% scopes, needn't carry out concentrating for a long time, and production technique is simple, and cost is low; Prepared silica dioxide granule size is even, dispersed, good stability.
Embodiment
Further specify the present invention by the following examples, but the present invention is not limited to these embodiment.The seed particles dispersion liquid that following examples adopted can the method by any manufacturing silicon dioxide gel obtain, as mentioned before the method for preparing silicon sol that provides for CN1155514A of application number; Also can buy silicon sol product, as the SNOWTEX of Japanese NISSAN, according to the silicon sol of the brands such as NAYCOL of blocking chemical company with certain silica dioxide granule size.The silica flour that adopts for conventional commercially available; Basic catalyst is common commercially available analytical pure or chemical pure.
The size of the silicon-dioxide that following examples are involved all adopts scanning electronic microscope (SEM) to measure SiO in the silicon sol
2Mass content adopt gravimetric determination, the viscosity of silicon sol adopts the rotary viscosimeter instrument to measure, the silica flour utilization ratio adopts the described formula of preamble to calculate and obtains.
Embodiment 1
In 2000 milliliters four-hole boiling flask of reflux is housed, be 30% (quality) with solid content (silica dioxide granule), particle diameter is that the silicon dioxide gel 200g of 40～50nm is diluted to SiO with 1000 ml waters
2Mass concentration is about 5%, begins to carry out stirring heating, and other takes by weighing 6g NaOH solid and is made into the solution of about 10% concentration with the less water dissolving.When temperature rose to 85 ℃, the beginning limit added NaOH solution limit and adds commercially available 200～300 purpose silica flours.The speed that NaOH adds is to keep system pH in 9.0～10.0 scopes; The speed that silica flour adds is no more than 90 ℃ to keep temperature of reaction, adds 220g (catalyzer: silica flour silica flour=1: 37) altogether.After adding whole NaOH and silica flour, insulation reaction 5 hours continues to stir to be cooled to below 60 ℃ to filter then.Resulting silicon dioxide gel index is as follows:
SiO
2Mass content: 35.0% SiO
2Particle diameter: 90～100nm
Viscosity (20 ℃): 3.5mp
aS silica flour utilization ratio: 89%
Embodiment 2
Adopt the condition identical with embodiment 1, difference is: the employing solid content is 20%, and particle diameter is that the silicon dioxide gel 300g of 5～8nm is diluted to SiO with 10000 ml waters
2Mass content is about 0.6%; NaOH is made into water dissolution adds again after concentration is about 2%.The silicon dioxide gel index that obtains at last is as follows:
SiO
2Mass content: 3.0% SiO
2Particle diameter: 5～20nm
Viscosity (20 ℃): 1.4mp
aS silica flour utilization ratio: 80%
Embodiment 3
Adopt the condition identical with embodiment 1, difference is: the employing particle diameter is that the silicon dioxide gel of 10～15nm is as seed liquor; NaOH is made into water dissolution adds again after concentration is about 20%.The silicon dioxide gel index that obtains at last is as follows:
SiO
2Mass content: 35.0% SiO
2Particle diameter: 20～30nm
Viscosity (20 ℃): 10.5mp
aS silica flour utilization ratio: 89%
Embodiment 4
Adopt the condition identical with embodiment 1, difference is: the employing particle diameter is that the silicon dioxide gel of 90～100nm is as seed liquor.The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 35.0% SiO
2Particle diameter: 180～210nm
Viscosity (20 ℃): 2.6mp
aS silica flour utilization ratio: 89%
According to the method for the foregoing description 4, department uses the prepared big particle diameter silicon sol of the present invention as seed liquor with circulation rice, prepares the silicon dioxide gel of larger particle.
Embodiment 5
Adopt the condition identical with embodiment 1, difference is: the silica flour quality of interpolation is increased to 300g (catalyzer: silica flour=1: 50).The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 44.0% SiO
2Particle diameter: 100～120nm
Viscosity (20 ℃): 4.0mp
aS silica flour utilization ratio: 88%
Embodiment 6
Adopt the condition identical with embodiment 1, difference is: the four-hole boiling flask that the reactor employing is 3000 milliliters; Seed liquor is diluted to 3.5% concentration with 1500 ml waters; The silica flour quality of adding is a 600g (catalyzer: silica flour=1: 100).The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 46.5% SiO
2Particle diameter: 100～140nm
Viscosity (20 ℃): 15.5mp
aS silica flour utilization ratio: 70%
Embodiment 7
Adopt the condition identical with embodiment 6, difference is: the consumption of seed liquor is reduced to 100g, and is diluted to 2% solid content with 1400 ml waters; The silica flour quality of adding is a 1080g (catalyzer: silica flour=1: 180).The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 51.5% SiO
2Particle diameter: 90～145nm
Viscosity (20 ℃): 25.5mp
aS silica flour utilization ratio: 45%
Embodiment 8
Adopt the condition identical with embodiment 1, difference is: seed liquor is diluted to SiO with 400 ml waters
2Mass concentration is about 10%, because that system concentration rises is very fast, viscosity increases, and the silica flour quality that can add reduces, the final silica flour quality that adds be 160g (catalyzer: silica flour=1: 27), the index of the silicon dioxide gel that obtains is as follows:
SiO
2Mass content: 52.0% SiO
2Particle diameter: 80～90nm
Viscosity (20 ℃): 14.5mp
aS silica flour utilization ratio: 92%
Embodiment 9
Adopt the condition identical with embodiment 1, difference is: 30%SiO
2The seed liquor of mass content is directly used without the water dilution; Adopt 8.5g KOH to replace NaOH as catalyzer.Under this condition, the silica flour quality that can add reduces, the final silica flour quality that adds be 30g (catalyzer: silica flour=1: 6), the index of the silicon dioxide gel that obtains is as follows:
SiO
2Mass content: 55.0% SiO
2Particle diameter: 50～60nm
Viscosity (20 ℃): 25.0mp
aS silica flour utilization ratio: 94%
Embodiment 10
Adopt the condition identical with embodiment 1, difference is: using 400～600 purpose silica flours instead is raw material; Use the 15g thanomin instead and substitute NaOH as basic catalyst; The speed of adding catalyzer is that maintenance system pH is in 7～8 scopes; The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 26.0% SiO
2Particle diameter: 35～80nm
Viscosity (20 ℃): 6.5mp
aS silica flour utilization ratio: 60%
Embodiment 11
Adopt the condition identical with embodiment 1, difference is: the temperature of reacting is controlled at 95～100 ℃ of scopes, and the index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 37.0% SiO
2Particle diameter: 40～90nm
Viscosity (20 ℃): 6.4mp
aS silica flour utilization ratio: 92%
Embodiment 12
Adopt the condition identical with embodiment 1, difference is: employing 20g quadrol is as basic catalyst; The speed of adding catalyzer is that maintenance system pH is in 10～11 scopes; The temperature of reaction is controlled at 80～85 ℃ scope.The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 36.0% SiO
2Particle diameter: 70～100nm
Viscosity (20 ℃): 3.0mp
aS powder utilization ratio: 90%
Embodiment 13
Adopt the condition identical with embodiment 1, difference is: employing 400～600 purpose silica flours are raw material; Adopt 3g NaOH and 8g quadrol as compound basic catalyst; Adding catalyst velocity is that maintenance system pH is in 12～13 scopes; Temperature of reaction is controlled at 60～70 ℃ of scopes.The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 36.5% SiO
2Particle diameter: 45～110nm
Viscosity (20 ℃): 5.5mp
aS silica flour utilization ratio: 92%
Embodiment 14
Adopt the condition identical with embodiment 1, difference is: using 30～60 purpose silica flours instead is raw material; After adding all raw materials, insulation reaction 20 hours.The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 23.0% SiO
2Particle diameter: 70～85nm
Viscosity (20 ℃): 2.0mp
aS silica flour utilization ratio: 50%
Embodiment 15
Adopt the condition identical with embodiment 1, difference is: using 100～200 purpose silica flours instead is raw material, add all raw materials after, insulation reaction 15 hours.The index of the silicon dioxide gel that obtains at last is as follows:
SiO
2Mass content: 29.2% SiO
2Particle diameter: 70～90nm
Viscosity (20 ℃): 3.0mp
aS silica flour utilization ratio: 70%
Embodiment 16
In 2000 milliliters four-hole boiling flask of reflux is housed, be 30% with solid content, particle diameter is that the silicon dioxide gel 200g of 40～50nm is diluted to SiO with 1000 ml waters
2Mass concentration is about 5%, begins to carry out stirring heating, and other takes by weighing 6g NaOH solid and dissolves the solution that is made into about 10% concentration with less water, disposable then all joining in the reaction flask, and the system pH of making is about 13.5.When temperature rises to 80 ℃, begin to add common commercially available 200～300 purpose silica flours.The speed that silica flour adds is no more than 85 ℃ to keep temperature of reaction, adds 220g (catalyzer: silica flour silica flour=1: 37) altogether.After adding silica flour, insulation reaction 4～6 hours continues to stir to be cooled to below 60 ℃ to filter then.Resulting silicon dioxide gel index is as follows:
SiO
2Mass content: 36.0% SiO
2Particle diameter: 55～80nm
Viscosity (20 ℃): 5.5mp
aS silica flour utilization ratio: 90%.
Claims (10)
1, a kind of manufacture method of silicon sol, it is characterized in that under heated and stirred, in as the silica aqueous dispersion of seed liquor, add basic catalyst and metallic silicon power, making it is to react under the condition of 7～14 scopes at pH, the active silicic acid micropartical that goes out by the silica flour hydrolysis is attached to making seed particles increase on the silicon-dioxide seed particles, thereby makes the silicon sol of big particle diameter.
2, manufacture method as claimed in claim 1 is characterized in that the silicon-dioxide in the described seed liquor is the silica dioxide granule of particle diameter in 5～500nm scope of measuring by scanning electronic microscope.
3, manufacture method as claimed in claim 1, the mass percentage concentration that it is characterized in that the silicon-dioxide seed particles in the described seed liquor is in 0.5～30% scope.
4, manufacture method as claimed in claim 1 is characterized in that described Heating temperature is 60～100 ℃.
5, manufacture method as claimed in claim 1 is characterized in that described basic catalyst is that mineral alkali is or/and one or several mixing in the organic bases.
6, manufacture method as claimed in claim 5 is characterized in that described mineral alkali is a sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide; Described organic bases is thanomin, diethanolamine, trolamine, ethamine and quadrol.
7, manufacture method as claimed in claim 1, the particle diameter that it is characterized in that described metallic silicon power is 30～800 orders.
8, manufacture method as claimed in claim 1, the mass ratio that it is characterized in that described basic catalyst and silica flour is 1: 5～200.
9, as the described manufacture method of the arbitrary claim of claim 1～8, the mass percentage concentration that it is characterized in that the silicon-dioxide in the described seed liquor is 2～10%; The particle diameter of described metallic silicon power is 100～400 orders; The mass ratio of this basic catalyst and silica flour is 1: 10～100; The pH of described reaction is 8～14.
10, the silicon sol that makes of the manufacture method of silicon sol as claimed in claim 1.
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