CN113135573B - Zirconium-modified cationic silica sol and preparation method thereof - Google Patents
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Abstract
The invention provides zirconium modified cationic silica sol and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving a zirconium salt in water to obtain a zirconium salt aqueous solution; mixing aqueous solution of zirconium salt with alkaline silica solReacting to obtain zirconium modified cationic silica sol; siO in the obtained silica sol 2 The mass fraction of (A) is 6-37%, na 2 The mass fraction of O is 0.12-0.5%, the viscosity is 1-7mPa.s, the pH value is 1-4, the conductivity value is 5-60ms/cm, and the Zeta potential value is 15-60mV. The silica sol obtained by the invention has high stability, can be used in combination with a cation system, has simple preparation process route, is easy to realize large-scale production, meets the requirements of green chemical production, and is a safe and efficient novel silica sol production process.
Description
Technical Field
The invention relates to zirconium modified cationic silica sol and a preparation method thereof, belonging to the technical field of fine inorganic polymer chemical industry.
Background
The silica sol is a colloidal solution formed by uniformly dispersing amorphous silica aggregated particles in water, and is a green environment-friendly inorganic nano material. Silica sols can be classified into alkaline silica sols and acidic silica sols according to the pH range, and in industrial production, the most common preparation method of alkaline silica sols mainly comprises: the ion exchange method and the simple substance silicon hydrolysis method can obtain high-stability alkaline silica sol; treating the alkaline silica sol with cation exchange resin to remove Na in the system + Exchange into H + Acidic silica sol can be obtained. However, the acidic silica sol obtained by the cationic resin treatment has poor stability due to the change of the two electron layers, and cannot convert the electrical property of the surface charge of the basic silica sol, which is generally used in the case of SiO silica sol 2 The surface of the particle has negative charge, when the particle is mixed with a cation system, the gel or precipitation can occur, and the particle can hardly be mixed with cation emulsion, cation water-based resin and other cation systems for use, thereby greatly limiting the application of the acidic silica sol in many fields. Therefore, it is of great significance to develop a preparation method of the acidic silica sol with high stability and positively charged surface.
Hydroxyl on the surface of the silicon dioxide particles in the silica sol has reactivity, and modifiers with different structures can be selected to modify the surface of the silicon dioxide particles, so that the surface state of the silicon dioxide particles is changed, and the application range of the silicon dioxide particles is expanded. In recent years, there are also many patent documents on a method for improving the stability of an acidic silica sol. For example: chinese patent document CN110482559A provides an aluminum modified acidic silica sol and a preparation method thereof, the preparation method comprising: mixing and reacting an aluminum-containing silicic acid solution with an alkaline base solution to obtain an aluminum-modified alkaline silica sol, and reacting the aluminum-modified alkaline silica sol with a cation exchange resin to obtain the aluminum-modified acidic silica sol. However, although the stable acidic silica sol can be obtained by the above method, the colloidal particles of the acidic silica sol are still negatively charged, and the application of the acidic silica sol to the complex formulation with a cationic system is still limited. Chinese patent document CN112041267A provides a method for producing a charge-reversal aqueous silica sol, which comprises the following steps: (a) Providing a slurry of acidic cation exchange solids in an aqueous liquid; (b) Providing a starting aqueous silica sol having a basic pH and comprising one or more monovalent cations; (c) Contacting the slurry of (a) with the aqueous silica sol of (b); (d) Separating the acidic cation exchange solid from the mixture of (c) to leave a decationized aqueous silica sol having an acidic pH and a reduced content of monovalent cations as compared to the starting aqueous silica sol; (e) The decationized aqueous silica sol is contacted with one or more compounds comprising one or more modifying elements that may formally assume a +3 or +4 oxidation state to produce a charge-reversed aqueous silica sol whose silica particles comprise one or more modifying elements on their surface. The above patent uses an ion exchange method to perform a cation exchange treatment on an alkaline sol to remove a part of metal ions in a lower valence state in the silica sol, and then preferably selects Al 2 (OH) 5 Cl and Mg (CH) 3 COO) 2 (H 2 O) two modifiers are used for modifying the silica sol from which part of the low-valence metal ions are removed, on one hand, the process is relatively complicated, the use of more cation exchange resin can increase the discharge amount and the treatment amount of wastewater in the production process, and on the other hand, the silicon obtained by the treatment method of the patentThe specific gravity and solid content of the sol are generally low, while the solid content of the silica sol affects the stability of the final silica sol, and the general rule is that the lower the solid content of the silica sol is, the better the stability of the silica sol is relatively.
Therefore, it is of great significance to find a method capable of efficiently preparing cationic silica sol and ensuring that the obtained cationic silica sol has high solid content and stability.
Disclosure of Invention
Aiming at the defects of the prior art, particularly the defect that the conventional silica sol has negative charge and is mixed with other positive charge systems to cause precipitation or gelation, the invention provides a zirconium modified cationic silica sol and a preparation method thereof. The preparation method of the zirconium modified cationic silica sol is simple, is easy to popularize and realize large-scale production, and the modified silica sol has positive charges and good stability.
The technical scheme of the invention is as follows:
a preparation method of zirconium modified cationic silica sol comprises the following steps:
(1) Dissolving a zirconium salt in water to obtain a zirconium salt aqueous solution;
(2) And mixing the zirconium salt aqueous solution and the alkaline silica sol for reaction to obtain the zirconium modified cationic silica sol.
Preferably according to the present invention, the zirconium salt in step (1) comprises an inorganic zirconium salt and an organic zirconium salt; more preferably, the zirconium salt is ZrOCl 2 ·8H 2 O、Zr(NO 3 ) 4 ·5H 2 O or Zr (CH) 3 COO) 4 (ii) a More preferably, the zirconium salt is ZrOCl 2 ·8H 2 O。
According to the invention, the mass fraction of the zirconium salt in the aqueous solution of a zirconium salt described in step (1) is preferably 5 to 20%.
According to the invention, the SiO in the alkaline silica sol described in step (2) 2 The mass fraction of the sodium-containing composite material is 10-40 percent and Na 2 The mass fraction of O is 0.2-0.6%, the pH value is 8-11 2 The particle size of (A) is 5-120nm; the alkaline silica sol isThe water glass is prepared by a water glass ion exchange method or a simple substance silicon hydrolysis method, and the preparation method is the prior art.
According to the present invention, the mass ratio of the aqueous solution of a zirconium salt to the alkaline silica sol in step (2) is preferably 1.5 to 12, more preferably 1.
According to the present invention, the mixing manner in the step (2) is preferably to add the alkaline silica sol to the aqueous solution of the zirconium salt.
According to a preferred embodiment of the invention, the reaction temperature in step (2) is 70 to 90 ℃.
According to the invention, the reaction time in step (2) is preferably 0.5 to 1 hour.
The invention also provides zirconium modified cationic silica sol prepared by the method, and SiO in the obtained silica sol 2 The mass fraction of (A) is 6-37%, na 2 The mass fraction of O is 0.12-0.5%, the viscosity is 1-7mPa.s, the pH value is 1-4, the conductivity value is 5-60ms/cm, and the Zeta potential value is 15-60mV.
The principle of the invention is as follows:
the zirconium modified silica sol is obtained by modifying the surface of silica particles by taking zirconium salt as a modifier, is acidic, has positive charges on the surface, and is an acidic cationic silica sol. The invention utilizes the condensation reaction between (-OH) on the hydrolysate of zirconium salt and the activity (-OH) on the surface of the nano silicon dioxide to modify the surface of the nano silicon dioxide, wherein the zirconium salt is ZrOCl 2 ·8H 2 For example, the reaction principle is as follows: when ZrOCl 2 ·8H 2 Dissolving O in water to form Zr (OH) sol with HCl as stabilizer 4 Sol, zr (OH) 4 The novel silicon sol is in a metastable state, when alkaline silica sol is added, the pH value of the system is changed, two bonding modes exist in the system, one mode is that a ≡ Zr-OH bond and a ≡ Zr-OH bond are mutually bonded, the other mode is that the ≡ Zr-OH bond and an HO-Si-O-Si-O-bond on the surface of the silica sol are condensed to form a ≡ Zr-O-Si-O-Si-O-bond, and the newly formed ≡ Zr-O-Si-O-bond endows the silica sol with the change of the original electrical property to form the cationic silica sol.
The invention has the following beneficial effects:
1. according to the silica sol obtained by the invention, as the surface structure of the colloidal particles is changed, tetravalent zirconium ions are carried on the surfaces of the colloidal particles, and the positive repulsive force among the colloidal particles is stronger, so that the silica sol has the characteristic of high stability; the surface of the sol particles is positively charged, so the sol particles can be compounded with cationic systems such as cationic emulsion, cationic water-based resin and the like for use, and are used for improving the performances such as thermal stability, abrasion resistance, rigidity, mechanical property and the like of the coating; meanwhile, the surface modification enables the zirconium sol to have surface properties similar to those of the zirconium sol, but the cost is far lower than that of the zirconium sol, and the zirconium sol can be replaced to a certain extent to be used in the fields of high-temperature resistant coatings, fireproof coatings, ceramic coatings, flame retardant materials and the like.
2. The preparation process of the silica sol has simple route, easy realization of large-scale production, safe construction process and no waste, meets the requirements of green chemical production, and is a safe and efficient novel silica sol production process. The cationic silica sol has the characteristic of high stability and has wide market prospect.
Drawings
FIG. 1 is a Zeta potential diagram of the basic silica sol before modification in example 1.
FIG. 2 is a Zeta potential diagram of the modified cationic silica sol of example 1.
FIG. 3 is a Zeta potential diagram of the basic silica sol before modification in example 2.
FIG. 4 is a Zeta potential diagram of the modified cationic silica sol of example 2.
FIG. 5 is a Zeta potential diagram of the basic silica sol before modification in example 3.
FIG. 6 is a Zeta potential diagram of the modified cationic silica sol of example 3.
FIG. 7 is a Zeta potential diagram of the basic silica sol before modification in example 4.
FIG. 8 is a Zeta potential diagram of the modified cationic silica sol of example 4.
FIG. 9 is a Zeta potential diagram of a modified cationic silica sol of example 5.
FIG. 10 is a Zeta potential diagram of the acidic silica sol in comparative example 1.
Detailed Description
The embodiments of the present invention are described below with reference to specific examples, and those skilled in the art can further explain the present invention by referring to the disclosure of the present specification. The invention may be carried into practice or applied in different embodiments, and various modifications may be made without departing from the spirit of the invention in principle. The specific process equipment and apparatus not taught by the present invention is conventional in the art.
The alkaline silica sol used in the examples is prepared by an elemental silicon hydrolysis method, a stabilizer adopted in the preparation process is NaOH, and the preparation process can refer to patent CN101585541A.
Example 1
A preparation method of zirconium modified cationic silica sol comprises the following steps:
(1) ZrOCl 2 ·8H 2 Dissolving O in water to obtain ZrOCl with the mass fraction of 20% 2 ·8H 2 And (4) O aqueous solution.
(2) Alkaline silica sol (pH =9.17,sio 2 Particle diameter of 10nm, siO 2 Is 40% by mass of Na 2 The mass fraction of O is 0.3 percent) is added with ZrOCl at one time 2 ·8H 2 Stirring and mixing in O water solution, wherein ZrOCl 2 ·8H 2 The mass ratio of the O aqueous solution to the alkaline silica sol is 1; then heating to 70 ℃ and reacting for 1h to obtain the zirconium modified cationic silica sol.
The modified silica sol obtained in this example was examined for its index (see table 1 attached), pH =1.02, sio 2 Particle size of 10nm, siO 2 Is 28%. The Zeta potential diagrams of the silica sol before and after modification are respectively shown in figures 1 and 2, the Zeta potential value of the alkaline silica sol before modification is-34.41 mV, the Zeta potential value of the silica sol after modification is 44.03mV, and the results prove that the surface charge state of the nano particles is changed from negative charge to positive charge, and the Zeta potential value is higher, which indicates thatHas better stability, is placed at 60 ℃, and further proves that the thermal stability is better by observing that the stable period exceeds 3 months.
Example 2
A preparation method of zirconium modified cationic silica sol comprises the following steps:
(1) ZrOCl 2 ·8H 2 Dissolving O in water to obtain ZrOCl with the mass fraction of 20% 2 ·8H 2 And (4) O aqueous solution.
(2) An alkaline silica sol (pH =9.50 2 The grain diameter is 24nm, siO 2 Is 40% by mass of Na 2 The mass fraction of O is 0.22 percent) is added with ZrOCl at one time 2 ·8H 2 Stirring and mixing in O aqueous solution, wherein ZrOCl 2 ·8H 2 The mass ratio of the O aqueous solution to the alkaline silica sol is 1; then heating to 70 ℃ and reacting for 1h to obtain the zirconium modified cationic silica sol.
The silica sol modified in this example was examined for pH =2.05, sio (see table 1 for details) 2 Has a particle diameter of 24nm, siO 2 Is 35 percent. Zeta potential diagrams of the silica sol before and after modification are respectively shown in figures 3 and 4, the Zeta potential value of the silica sol before modification is-30.13 mV, the Zeta potential value of the silica sol after modification is 22.24mV, the fact that the surface charge state of the nano particles is changed from negative charge to positive charge is proved, the Zeta potential value is high, the nano particles have good stability, the nano particles are placed at the temperature of 60 ℃, the stability period is observed for more than 3 months, and the thermal stability is further proved to be good.
Example 3
A preparation method of zirconium modified cationic silica sol comprises the following steps:
(1) Reacting ZrOCl 2 ·8H 2 Dissolving O in water to obtain ZrOCl with the mass fraction of 20% 2 ·8H 2 And (4) O aqueous solution.
(2) An alkaline silica sol (pH =10.71 2 Has a particle diameter of 106nm and SiO 2 Is 40% by mass of Na 2 0.25 percent of O) is added into ZrOCl at one time 2 ·8H 2 Stirring and mixing in O aqueous solution, wherein ZrOCl 2 ·8H 2 The mass ratio of the O aqueous solution to the alkaline silica sol is 1; then heating to 70 ℃ and reacting for 1h to obtain the zirconium modified cationic silica sol.
The silica sol modified in this example was examined for pH =2.45, sio (see table 1 below for details) 2 With a particle diameter of 106nm, siO 2 Is 36 percent. Zeta potential diagrams of the silica sol before and after modification are respectively shown in figures 5 and 6, the Zeta potential value of the silica sol before modification is-26.83 mV, the Zeta potential value of the silica sol after modification is 25.08mV, the fact that the surface charge state of the nano particles is changed from negative charge to positive charge is proved, the Zeta potential value is higher, the nano particles have better stability, the nano particles are placed at the temperature of 60 ℃, the stability period is observed for more than 3 months, and the thermal stability is further proved to be better.
Example 4
A preparation method of zirconium modified cationic silica sol comprises the following steps:
(1) ZrOCl 2 ·8H 2 Dissolving O in water to obtain ZrOCl with the mass fraction of 20% 2 ·8H 2 And (4) O aqueous solution.
(2) Alkaline silica sol (pH =10.19,sio 2 Has a particle diameter of 39nm and is SiO 2 Is 40% by mass of Na 2 0.27 percent of O) is added into ZrOCl at one time 2 ·8H 2 Stirring and mixing in O water solution, wherein ZrOCl 2 ·8H 2 The mass ratio of the O aqueous solution to the alkaline silica sol is 1; then heating to 70 ℃ and reacting for 1h to obtain the zirconium modified cationic silica sol.
The silica sol modified in this example was examined for pH =2.02, sio (see table 1 below for details) 2 Has a particle diameter of 39nm and is SiO 2 Is 33% by mass. Zeta potential diagrams of the silica sol before and after modification are respectively shown in figures 7 and 8, the Zeta potential value of the silica sol before modification is-31.70 mV, the Zeta potential value of the silica sol after modification is 21.22mV, the fact that the surface charge state of the nano particles is changed from negative charge to positive charge is proved, the Zeta potential value is high, the nano particles have good stability, the nano particles are placed at the temperature of 60 ℃, the stability period is observed for more than 3 months, and the thermal stability is further proved to be good.
Example 5
A preparation method of zirconium modified cation silica sol comprises the following steps:
(1) Zr (NO) 3 ) 4 ·5H 2 Dissolving O in water to obtain Zr (NO) with the mass fraction of 20% 3 ) 4 ·5H 2 And (4) O aqueous solution.
(2) Alkaline silica sol (pH =10.19,sio 2 Has a particle diameter of 39nm and is SiO 2 Is 40% by mass of Na 2 0.27% of O, zr (NO) 3 ) 4 ·5H 2 Stirring and mixing in O water solution, wherein Zr (NO) 3 ) 4 ·5H 2 The mass ratio of the O aqueous solution to the alkaline silica sol is 1; then heating to 70 ℃ and reacting for 1h to obtain the zirconium modified cationic silica sol.
The modified silica sol of this example was examined for pH =1.91, pH (see table 1, below) 2 Has a particle diameter of 39nm and is SiO 2 Is 33% by mass. Zeta potential diagrams of the silica sol before and after modification are respectively shown in figures 7 and 9, the Zeta potential value of the silica sol before modification is-31.70 mV, the Zeta potential value of the silica sol after modification is 30.32mV, the fact that the surface charge state of the nano particles is changed from negative charge to positive charge is proved, the Zeta potential value is high, the nano particles have good stability, the nano particles are placed at the temperature of 60 ℃, the stability period is observed for more than 3 months, and the thermal stability is further proved to be good.
TABLE 1 results of index detection of silica sols prepared in examples 1 to 5
Note: the Zeta potential values and the conductivity test were all tested at 25 ℃.
Comparative example 1
A method for preparing acidic silica sol comprises the following steps:
(1) 750g of the same basic silica sol as in example 1 (pH =9.17 2 Particle diameter of 10nm, siO 2 Has a mass fraction of40%) and water were added to dilute to a total weight of 1000g.
(2) Pouring the silica sol into an ion exchange column filled with cation exchange resin, and performing ion exchange to finally obtain SiO 2 An acidic silica sol having a mass fraction of 30%, a pH of 2.80, a viscosity of 2.0 mPaS, an electric conductivity of 0.76ms/cm, a Zeta value of the acidic silica sol obtained after particle exchange of-0.65 mV, and a potential diagram thereof as shown in FIG. 10.
(3) The thermal stability of the acidic silica sol was observed by placing the acidic silica sol at 60 ℃ and it was found that the acidic silica sol was stable only for 1 day at 60 ℃ and had poor stability, and after 1 day, the acidic silica sol lost stability and formed a gel.
The absolute value of the Zeta potential value can reflect the relative stability of the colloid, the smaller the absolute value is, the poorer the stability of the colloid is, but the cation type silica sol can not be obtained by the ion exchange method, and the Zeta potential value of the obtained acid silica sol is smaller absolutely, and the stability is poorer.
Comparative example 2
A zirconium-modified cationic silica sol was prepared as described in example 1, except that: zrOCl 2 ·8H 2 Mass ratio of the aqueous O solution to the alkaline silica sol 1.
According to the experimental procedures, the silica sol is gelled during the reaction, and thus it is proved that stable cationic silica sol cannot be obtained at the ratio.
Comparative example 3
A zirconium-modified cationic silica sol was prepared as described in example 1, except that ZrOCl was used 2 ·8H 2 The aqueous O solution was added to the silica sol.
ZrOCl was used in this comparative example 2 ·8H 2 The addition of the aqueous O solution to the silica sol eventually leads to gel formation during the mixing with stirring, further illustrating the need for modification according to the mode of addition of the invention.
The above-mentioned embodiments are provided for illustration of the present invention on the one hand and for providing reference solutions to those skilled in the art on the other hand, and should not be construed as limitations of the present invention. It is obvious to those skilled in the art that different cationic silica sols can be obtained by adjusting the kinds and ratios of the zirconium salt and silica sol without departing from the spirit and principle of the present invention, and all such modifications are intended to be included in the scope of the present invention.
Claims (4)
1. A preparation method of zirconium modified cationic silica sol comprises the following steps:
(1) Dissolving zirconium salt in water to obtain a zirconium salt aqueous solution; the mass fraction of the zirconium salt in the zirconium salt aqueous solution is 20 percent; the zirconium salt is ZrOCl 2 ·8H 2 O、Zr(NO 3 ) 4 ·5H 2 O or Zr (CH) 3 COO) 4 ；
(2) Mixing a zirconium salt aqueous solution and alkaline silica sol for reaction to obtain zirconium modified cationic silica sol; siO in the alkaline silica sol 2 Is 40% by mass of Na 2 The mass fraction of O is 0.2-0.6%, the pH value is 8-11 2 The particle size of (A) is 5-120nm; the mass ratio of the zirconium salt aqueous solution to the alkaline silica sol is 1.5-12; the mixing mode is that the alkaline silica sol is added into the aqueous solution of zirconium salt; the reaction temperature is 70-90 ℃; the reaction time is 0.5-1h.
2. The method of claim 1, wherein the zirconium salt is ZrOCl 2 ·8H 2 O。
3. The method according to claim 1, wherein the mass ratio of the aqueous solution of a zirconium salt to the basic silica sol is 1.
4. A zirconium-modified cationic silica sol prepared by the process of any one of claims 1 to 3.
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