CN1974385A - Prepn process of monodispersive silica sol - Google Patents
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Abstract
The present invention discloses one kind of nanometer monodispersive silica sol prepared with metal silicon powder and through reaction with water under the catalysis of certain amount of alkali catalyst at temperature of 50-95 deg.c. During the preparation, alkali solution adding speed is so controlled that the newly produced silicon sol precursor concentration is in the new nucleus forming concentration. Compared with available silica sol preparing process, the present invention has the advantages of homogeneous size distribution of nanometer silica sol, capacity of designing the sol size, simple preparation process, low cost and easy precise control.
Description
Technical field
The present invention relates to non-metallic element and compound thereof, specifically a kind of preparation method of monodispersity nano silicon dioxide sol.
Background technology
Nano silicon dioxide sol is the amorphous silica aggregated particles colloidal solution that homodisperse forms in solvent.Owing to have good characteristics such as bigger specific surface area, high absorption property, chemical stability, be widely used in the industries such as chemical industry, material, weaving/papermaking, electronics as a kind of broad-spectrum inorganic macromolecule material.In recent years, silicon dioxide gel also is applied to field of medicaments, as toothpaste, dental casting and drug delivery system.
At present, the preparation method of silicon sol has silica flour dissolution method, ion exchange method, electrolytic electro-dialysis method, peptisation, dispersion method and silicon ester hydrolysis method etc.But the silicon sol preparation method of industrial application is mainly ion exchange method and silica flour and diluted alkaline reaction method (being one step of elemental silicon dissolution method).
The existing many reports of existing preparation method about the monodispersive silica nano particle.As US Patent3,538,015 and US Patent 3,440,170 by with a kind of acidic silicasol with in the specific alkaline silica sol that joins 10～30nm at a high speed, keep the pH value simultaneously greater than 7, obtain weight average particle diameter and assemble the spherical colloidal silica of homogeneous in the nothing of 45-100nm.US Patent 3,789,009 and US Patent 4,410,405 have reported the silicon dioxide gel that adopts the ion exchange method preparation to have monodispersity, but these two patents do not propose the particle grain size distribution control method.CN1594079A adopt silicic acid but not water glass of the prior art be raw material by controlling conditions such as feed way, reaction pH value and temperature, make the narrower silicon sol of a series of size distribution.Above-mentioned preparation method all needs to prepare final silicon sol product through processes such as the preparation of ion exchange reaction, crystal seed, particle growth reaction, enrichment step, purification steps.Each step all has direct influence to the product quality of final silicon sol, and physico-chemical property indexs such as micelle size, homogeneity, foreign matter content and the stability thereof of silicon sol product are determined by the control of each condition of preparation process.It is low that this causes spent ion exchange resin to transform the silicon sol solution concentration of gained, thereby the used quantity of steam of concentrated solution is big, and the throughput of evaporation equipment is low; Ion exchange column needs periodical operation, and exchange, regeneration, washing hocket, and complicated operation except that having consumed a large amount of hydrochloric acid, also need consume a large amount of washing water in the production process.Therefore, this production method process complexity, big, high, the deficiency in economic performance of cost of consumption.
Have the monodispersity silica sol with above-mentioned ion exchange method preparation and compare, one step of elemental silicon dissolution method is by high purity elemental silica flour and dilute alkaline soln reaction, and obtaining the silicon sol micelle can be finer and close, more even, and foreign ion is few.Simultaneously, silicon one step dissolving rule has characteristics such as technology is simple, easy handling, forms the better selection into manufacture order dispersed silicon colloidal sol.In CN86100503, the contriver makes widely known the silicon sol manufacture method that has just proposed a kind of non-freezing type, good stability.This article adopts 100-300 order silica flour, and without oxidation and activation, direct and diluted alkaline reacts under 65-100 ℃ of temperature, is preferably in 72-83 ℃, by filtering or the centrifugal silicon sol finished product that obtains.At present, domestic most of enterprise that produces silicon sol with the silica flour method is the explained hereafter that adopts this patent introduction basically.But the resulting silicon sol particle diameter of this method is 15-20nm, and the viscosity of colloidal sol is bigger.Owing to lack the precision Control Technology of particle diameter, domestic each manufacturing enterprise can only produce 8-20, a few silicon sol such as 11 1 15.Problems such as the silicon-dioxide particle diameter is less than normal, lack of homogeneity are that restriction domestic enterprise produces principal element multi-functional, high quality silicon colloidal sol product always.Patent CN1830778A is no more than 5% of alkaline aqueous solution total amount by the silica flour amount of controlling each adding, and the timed interval is lower than under the condition of 60min, has synthesized the large grain size nanometer grade silicon dioxide colloid of particle diameter in 20～160 nanometers.Patent CN1830777A (2006) is by adding basic catalyst and metallic silicon power in as the silica aqueous dispersion of seed liquor, making it is to react under the condition of 7～14 scopes at pH, can directly obtain the silicon sol of big particle diameter.Can obtain the silicon sol of particle diameter by this patent, but this patent does not propose to control the method for particle size distribution, make it to reach controllable particle size distribution greater than 5 nanometers.Simultaneously, in experimenting, we find out that, and by add the method for silica flour in batches, very difficult preparation has the silica sol particle of higher monodispersity, particularly is difficult to prepare the particle deviation less than 5% small particle size silicon sol.And owing between thinner silica flour particle certain viscosity is arranged, the method that adopts silica flour and alkali lye to add simultaneously is difficult to the accurately adding speed of control silica flour, causes final silica sol granule deviation bigger easily.
Colloidal particle forms by nucleation in the supersaturation system and two processes of growth.In most of the cases, nucleation and being grown in the particle forming process is carried out simultaneously, and this just causes the particle size distribution broad that forms.In order to obtain monodispersed particle, must separate nucleation period and vegetative period clearly.The contriver finds accurately to control the speed of response of silica flour, thereby improve the saturation ratio of the active silicic acid in nucleation period as far as possible in the add-on of initial reaction stage by strict control alkali lye by a large amount of experiments, will make the silicon sol kind particle distribution of formation more even.Further in kind of particle, add silica flour,, can make the nano silicon dioxide sol of stability height, monodispersity and good sphericity by the add-on of control alkaline solution.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of technology of accurate control silicon sol size distribution is provided, make the nano silicon dioxide sol product that stability is high, particle diameter is controlled, have monodispersity in this way.
The inventor finds accurately to control the speed of response of silica flour, thereby improve the saturation ratio of the active silicic acid in nucleation period as far as possible in the add-on of initial reaction stage by strict control alkali lye by a large amount of experiments, will make the silicon sol kind particle distribution of formation more even.Further in kind of particle, add silica flour, make the silicic acid that goes out by the silica flour hydrolysis attached to kind of particle is increased.In order to prepare the good silicon dioxide gel of monodispersity, the silicic acid concentration that must control in the solution is lower than the concentration that forms new silicon dioxide gel kind particle, therefore needs the add-on of strict control alkaline solution.Like this, no new small-particle generates in the process of growth, can make the nano silicon dioxide sol of stability height, monodispersity and good sphericity.
The present invention is by the following technical solutions:
A kind of nano silicon dioxide sol with monodispersity, it is made with water reaction under the katalysis of a certain amount of alkali by metallic silicon power, and temperature of reaction is that the adding speed of control alkali lye makes the particle further growth in the solution under 50～90 ℃ the condition.In reaction process, reconcile the adding speed of dilute alkaline soln according to the speed of growth of the particle surface-area of sol particles (or in the solution), make no new karyomorphism one-tenth in the dilute alkaline soln adition process.Step is as follows:
1) a certain amount of deionized water is heated to 50～95 ℃, under intensive stirs, adds silica flour and dilute alkaline soln, behind the reaction certain hour, obtain containing the mixing solutions of silicon dioxide gel kind particle.Wherein, silica flour and dilute alkaline soln can add simultaneously, also can add step by step.To plant particle preferably in order obtaining distributing, to need the add-on of strict control silica flour and alkali.If the weight ratio of silica flour and alkali is low excessively, particularly the pH value of mixed solution is lower than at 9 o'clock, and the speed of response of silica flour is slower, and the saturation ratio of the active silicic acid in the solution is lower, the less and wider distribution of kind number of particles of formation; And if ratio is excessive, then react too fast, secondary nucleation takes place easily, cause formation than macroparticle.The silica flour that adds among the present invention and the weight ratio of alkali are 5～50: 1, and wherein with 10～30: 1 is optimum proportion.In order to obtain monodispersity silica sol preferably, need the particle diameter deviation of kind of particle to reach below 15% usually.In order to prepare polymolecularity, need the particle diameter of kind of particle usually less than 25% of the product cut size that finally obtains less than 2% silicon dioxide gel.
2) in the above-mentioned solution that contains kind of particle, add a certain amount of silica flour, obtain mixing suspension.Then, under violent stirring, a certain amount of dilute alkaline aqueous solution is joined in the above-mentioned suspension with certain speed, the reaction of diluted alkaline and silica flour, the silicate hydrate of generation is adsorbed on and polymerization takes place on the silicon sol kind particle surface makes kind of a particle further growth.In the adition process of alkali lye, need the adding speed of control alkali lye, make the concentration of monomer silicate hydrate in the solution be lower than the concentration that generates new nuclear.In order to improve speed of response, in reaction process, can also progressively accelerate the adding speed of alkali lye according to the speed of growth (being the specific surface area of silica sol particle) of particle.Because along with the raising of pH value, speed of response is accelerated, and the monomeric concentration of solution mesosilicic acid also improves rapidly.Therefore the adding speed of dilute alkaline aqueous solution is lower than 10% of silica flour add-on with the add-on of basic catalyst per hour and is advisable.In reaction process, along with the growth of particle diameter, the specific surface area of colloidal particle increases sharply in the solution, and the amount of adsorption activity silicic acid also increases.In order to reduce the reaction times of entire reaction, can accelerate the adding speed of dilute alkaline soln gradually along with the growth of particle diameter.
3) repeating step 2), different according to the add-on of silica flour and alkali lye, can obtain the narrower silica sol particle of a series of size distribution.After reaction is finished, get silica flour, can obtain having the silicon sol product of monodispersity through filtration or the centrifugal unreacted of removing.
Regulate the adding speed of dilute alkaline aqueous solution continuously, obtain the monodisperse nano silicon dioxide of size distribution homogeneous, the gained silicon sol obtains the silicon sol finished product through separation with after concentrating.
The preparation method of monodispersive silica sol comprises following more specifically step:
(1) under intensive stirs, joins simultaneously in the deionized water, after reacting by heating, make and contain silicon dioxide gel kind particle solution with silica flour with as the dilute alkaline soln of catalyzer;
(2) in above-mentioned silicon dioxide gel kind particle solution, add silica flour, obtain mixing suspension; Then, under violent stirring, in this suspension, add dilute alkaline soln lentamente, make the atomic concentration of silicic acid of generation be lower than the concentration that forms new colloidal sol kind particle;
(3) repeating step (2), different according to the add-on of silica flour and dilute alkaline soln, can obtain the narrower silica sol particle of a series of size distribution; After reaction is finished, through filtering or centrifugal unreacted silica flour, the silicon sol product that can obtain having monodispersity removed.
The particle diameter of described silica flour is 50～600 orders, wherein with 100～400 order the bests.
Described Heating temperature is 50～95 ℃.
In the described step (1), the weight ratio of silica flour and basic catalyst is 5～50: 1, and wherein with 20～40: 1 is optimum proportion; In the described step (2), the weight ratio of silica flour and basic catalyst is 5～50: 1, and wherein with 10～30: 1 is optimum proportion.
Described dilute alkaline aqueous solution as catalyzer can be sodium hydroxide, water glass, lithium hydroxide, potassium hydroxide, the mixed solution of one or more in ammoniacal liquor, the organic amine.
The kind particle diameter that described step (1) makes requires less than 25% of the finished product particle diameter, and deviation is less than 15%.
The adding speed of the middle dilute alkaline aqueous solution of described step (2) per hour is that the add-on of basic catalyst is lower than 10% of silica flour add-on.
Single dispersed silicon colloidal sol product cut size of gained is at 5～500nm, and the particle diameter deviation is less than 5%.
Isolation technique used among the present invention is prior art, can adopt centrifugation or vacuum filtration process.Can synthesize solid content at the silica sol product below 35% by present method, can concentrate etc. by evaporation concentration or ultra-filtration membrane and further be concentrated to 52%.
Adopt aforesaid method not only to provide and have the method for monodispersive silica sol by the preparation of elemental silicon single stage method, but also can the compound particle particle diameter greater than a series of silicon sol products of 5 nanometers with different-grain diameter, solved by the less shortcoming of elemental silicon dissolution method synthetic silica sol particle particle diameter.Because very thin silica flour has certain viscosity, be difficult to accurately control adding constant airspeed, therefore, the present invention is first with the disposable adding of silica flour in the solution that contains kind of particle, and then slowly add alkali lye, and coming controls reaction speed by the add-on of control alkali lye, operation controllability is good.The present invention compares with single method of silica sol of disperseing for preparing that present both at home and abroad enterprise adopts, and has that operating procedure is simple, a good reproducibility, low, the better advantage of quality product of cost.
Description of drawings
Fig. 1 is the size distribution figure of 18nm sample for particle diameter;
Fig. 2 is the size distribution figure of 80nm sample for particle diameter;
Fig. 3 is the transmission electron microscope picture of 26nm sample for particle diameter;
Fig. 4 is surveyed the particulate statistical graph by the transmission electron microscope of 26nm sample shown in Figure 3.
Embodiment
The present invention is described in further detail below in conjunction with example, and the cited case does not limit protection scope of the present invention:
Embodiment 1:
(1) gets 2000 gram distilled water, join in the reactor that reflux exchanger is housed, add 250 gram commercially available silica flours of 200 orders and 5 gram sodium hydroxide, start agitator and be warming up to 75 ℃;
(2) taking by weighing 10 gram sodium hydroxide joins in the 1000 gram distilled water;
(3) above-mentioned steps (2) gained alkali lye is joined in the mixed solution of step (1) gained lentamente, control initial adding speed for per hour 250 restraining solution.Improve alkali lye subsequently gradually and add speed, added in about 3 hours.Continue reaction 2～3 hours subsequently.Treat to filter or centrifugation when solution is cooled to 50 ℃, obtain nano silicon dioxide sol.
Recording particle diameter with dynamic light scattering laser particle size and potentiometric analyzer is 18 nanometers, sees Fig. 1, and wherein X-coordinate is a particle diameter, and ordinate zou is the shared percentage ratio of variable grain.SiO
2Content is 14.5% (weight percentage), viscosity 4.2CPS.Polydispersity is 0.03.
Embodiment 2:
(1) gets embodiment 1 gained silicon sol solution 300 grams, join in the 1700 gram distilled water.Start agitator, and be heated to 80 ℃;
(2) add the commercially available 300 order silica flours of 100 grams, stir;
(3) take by weighing 15 gram sodium hydroxide and join in the 1000 gram distilled water, add 10 gram ammoniacal liquor again, mix;
(4) step (3) gained alkali lye is slowly joined in step (2) the gained mixed solution, added in about 4 hours, continue reaction 1 hour;
(5) continue in step (4) gained mixed solution, to add 225 gram silica flours, stir;
(6) take by weighing 20 gram NaOH, join in the 1500 gram distilled water, mix; This alkali lye is slowly joined in step (5) the gained mixed solution, added in about 8 hours.Continue reaction 2～3 hours.Filter or centrifugation when solution is cooled to 50 ℃, obtain nano silicon dioxide sol.
Recording particle diameter with dynamic light scattering laser particle size and potentiometric analyzer is 80 nanometers, sees Fig. 2, and wherein X-coordinate is a particle diameter, and ordinate zou is the shared percentage ratio of variable grain.SiO
2Content is 15% (weight percentage), viscosity 3.8CPS.Polydispersity is 0.013.
Embodiment 3:
(1) gets 2000 gram distilled water, join in the reactor that reflux exchanger is housed, add 150 gram commercially available silica flours of 200 orders and 5 gram sodium hydroxide, start agitator and be warming up to 75 ℃;
(2) take by weighing 10 gram sodium hydroxide and join in the 1000 gram distilled water, add 10 gram ammoniacal liquor again, mix;
(3) above-mentioned steps (2) gained alkali lye is joined in the mixed solution of step (1) gained lentamente, control initial adding speed for per hour 150 restraining solution.Improve alkali lye subsequently gradually and add speed, added in about 6 hours.Continue reaction 1 hour subsequently;
(4) in above-mentioned solution, add 500 gram silica flours, and continue to stir;
(5) take by weighing 45 gram NaOH, join in the 2500 gram water, mix;
(6) shown in step (3), add alkali lye, added in about 8 hours.Continue reaction 2～3 hours.Filter or centrifugation when solution is cooled to 50 ℃, obtain nano silicon dioxide sol.
Recording particle diameter with transmission electron microscope is 26 nanometers, sees Fig. 3 and Fig. 4.Among Fig. 4, X-coordinate is a particle diameter, and ordinate zou is the shared percentage ratio of different-grain diameter particle.SiO
2Content is 27% (weight percentage), viscosity 4.5CPS.
Claims (10)
1, a kind of preparation method of monodispersive silica sol is characterized in that comprising the steps:
(1) under intensive stirs, joins simultaneously in the deionized water, after reacting by heating, make and contain silicon dioxide gel kind particle solution with silica flour with as the dilute alkaline soln of catalyzer;
(2) in above-mentioned silicon dioxide gel kind particle solution, add silica flour, obtain mixing suspension; Then, under violent stirring, in this suspension, add dilute alkaline soln lentamente, make the atomic concentration of silicic acid of generation be lower than the concentration that forms new colloidal sol kind particle;
(3) repeating step (2), different according to the add-on of silica flour and dilute alkaline soln, can obtain the narrower silica sol particle of a series of size distribution; After reaction is finished, through filtering or centrifugal unreacted silica flour, the silicon sol product that can obtain having monodispersity removed.
2, the preparation method of monodispersive silica sol according to claim 1 is characterized in that: the particle diameter of described silica flour is 50～600 orders.
3, the preparation method of monodispersive silica sol according to claim 2 is characterized in that: the particle diameter of described silica flour is 100～400 orders.
4, the preparation method of monodispersive silica sol according to claim 1 is characterized in that: described Heating temperature is 50～95 ℃.
5, the preparation method of monodispersive silica sol according to claim 1 is characterized in that: in the described step (1), the weight ratio of silica flour and basic catalyst is 5～50: 1; In the described step (2), the weight ratio of silica flour and basic catalyst is 5～50: 1.
6, the preparation method of monodispersive silica sol according to claim 5 is characterized in that: in the described step (1), the weight ratio of silica flour and basic catalyst is 20～40: 1; In the described step (2), the weight ratio of silica flour and basic catalyst is 10～30: 1.
7, the preparation method of monodispersive silica sol according to claim 1, it is characterized in that: described dilute alkaline aqueous solution as catalyzer can be sodium hydroxide, water glass, lithium hydroxide, potassium hydroxide, the mixed solution of one or more in ammoniacal liquor, the organic amine.
8, the preparation method of monodispersive silica sol according to claim 1 is characterized in that: the kind particle diameter that described step (1) makes is less than 25% of the finished product particle diameter, and deviation is less than 15%.
9, the preparation method of monodispersive silica sol according to claim 1 is characterized in that: the adding speed of the middle dilute alkaline aqueous solution of described step (2) per hour is that the add-on of basic catalyst is lower than 10% of silica flour add-on.
10, the preparation method of monodispersive silica sol according to claim 1 is characterized in that, single dispersed silicon colloidal sol product cut size of gained is at 5～500nm, and the particle diameter deviation is less than 5%.
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