CN116177555B - Vinyl functional modified acidic silica sol and preparation method thereof - Google Patents
Vinyl functional modified acidic silica sol and preparation method thereof Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses an acidic silica sol modified by vinyl function and a preparation method thereof, belonging to the technical field of silica sol preparation. According to the invention, the original silica sol product is firstly modified by polymer grafting, and then vinyl functionalization is carried out to obtain the highly stable acidic silica sol product. The two-step synergistic modified acidic silica sol product provided by the invention has the advantages that the dispersibility of the obtained acidic silica sol is better, the stability is greatly improved, the normal-temperature storage time is not less than two years, the commercial acidic silica sol product is taken as a basic raw material, the large-scale batch production is easy to realize, the practicability is higher, and the application prospect in the fields of precision casting, coating, chemical polishing, fireproof materials and the like is wide.
Description
Technical Field
The invention belongs to the technical field of silica sol preparation, and particularly relates to an acidic silica sol with a modified vinyl function and a preparation method thereof.
Background
Silica sols are colloidal solutions of colloidal particles of silica dispersed in water, also known as silicic acid sols, polysilicic acids, or silica hydrosols. The silica sol is widely applied to the fields of precision casting industry, refractory materials, textile industry, catalyst carrier preparation, electronic industry, paint and the like. Silica sol is colloid formed by nano-scale silicon dioxide in aqueous solution, while acidic silica sol is in a metastable state, and gel is caused by polymerization to form a large number of dimers and multimers in the placing process, particularly, the condensation reaction is caused by a large number of hydroxyl groups on the surface of the high-concentration acidic silica sol micelle, so that the gel speed is obviously accelerated, and the instability of the acidic silica sol becomes a main influencing factor for restricting the application of the acidic silica sol.
At present, many researches on acidic silica sol exist, for example, patent CN201711286942.0 discloses an aluminum modified acidic silica sol and a preparation method thereof, the acidic silica sol obtained by modifying the silica sol with aluminate improves the stability of the silica sol, however, the introduced aluminum ions limit the application of the acidic silica sol in various fields, for example, when the acidic silica sol is applied to the field of paint, the introduced aluminum ions obviously reduce the blackening resistance of the paint.
Chinese patent CN201610324627.1 discloses an acidic silica sol and a preparation method thereof, the preparation method comprises the steps of 1) diluting water glass with deionized water, and then passing through a strong acid cation exchange column and a strong base anion exchange column in sequence; 2) Then alkali liquor is used for adjusting the pH value of the solution to be more than 7.0, and active silicic acid solution is prepared; 3) Taking a certain volume of the active silicic acid solution in a reaction container, and heating for a certain time to obtain seed crystals; 4) Adopting a constant liquid level heating concentration method, and continuously dripping an active silicic acid solution into the seed crystal to prepare alkaline silica sol; 5) And (3) passing the alkaline silica sol through a strong acid cation exchange column to prepare the acidic silica sol. In the technical scheme, the alkaline silica sol is made into the acidic silica sol through a static strong acid type cation exchange column, and when the cation exchange column is used initially and is fast in failure, the pH and the property of the obtained acidic silica sol product are different to a certain extent, so that the quality of the same batch of products is different, the silica sol is nonuniform, and the stability is influenced. In addition, when the ion exchange column is regenerated, the ion exchange column also needs to be inflated manually, and a large amount of resources and labor are required to be consumed.
Patent TW234579B discloses a silica slurry containing methanol at a pH of 1-6 useful for polishing silicon substrates; patents JP6199515 and JP63123807 provide relatively stable acidic silica sols by adding a small amount of alumina to the silica sol and then subjecting the silica sol to an ion exchange treatment.
However, the preparation scheme of the acidic silica sol has the advantages that although stability is improved, the stability time is still short, the problems of complex preparation process, high cost, incapability of practical popularization and utilization and the like exist generally, and the application value is low.
Therefore, how to develop an acidic silica sol with simple preparation process, low cost and long stability time and a preparation method thereof is a technical problem to be solved at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a long-acting stable acidic silica sol, the stability period of which is more than two years, the storage stability of the acidic silica sol is greatly improved, and the application field is widened.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the acidic silica sol is prepared by grafting and modifying an original silica sol product through a polymer and then performing vinyl functionalization.
Preferably, the raw silica sol product is acidic silica sol, the average particle diameter is 8-20nm, the pH is 2-4, the solid content is 20-35%, and the zata potential is-9 to-11.
The original silica sol product can be purchased with commercial acidic silica sol, and also can be self-prepared silica sol meeting the requirements.
The conventional silica sol preparation methods, such as a direct acid adding method, a resin direct mixing method, an ion exchange method, a heating concentration method and a method combining ion exchange and concentration, can be used as the raw materials for preparing the high-stability acidic silica sol.
The preparation method of the vinyl functional modified acidic silica sol comprises the following preparation steps:
(1) The method for grafting and modifying the polymer comprises the following steps: adding water and maleic anhydride into a container, heating and dissolving at 85-90 ℃, simultaneously dripping acrylic acid and hydrogen peroxide solution after dissolving, and carrying out heat preservation reaction for 30-60min at 89-95 ℃ after finishing dripping to obtain copolymer solution, wherein the pH value is controlled to be less than 5; then mixing and stirring the copolymer solution and the acidic silica sol according to the mass ratio of 1:1 for 3-5h to finish the polymer grafting modified silica sol;
(2) Adding organic acid into polymer grafted modified silica sol, heating to 40-90 deg.c, adding vinyl silane,
and reacting for 2-8h to obtain the final product of the vinyl functional modified acidic silica sol.
Preferably, the molar ratio of water to maleic anhydride in step (1) is 20:1.
Preferably, the molar ratio of maleic anhydride to acrylic acid in step (1) is 1:3.
Preferably, the adding amount of the hydrogen peroxide solution in the step (1) is 30-40% of the total mass of water, maleic anhydride and acrylic acid, and the mass concentration of the hydrogen peroxide solution is 30%.
Preferably, the addition amount of the organic acid in the step (2) is 0.01-0.3% of the mass of the polymer grafted modified silica sol; the organic acid is citric acid and/or lactic acid.
Preferably, the mass ratio of the vinyl silane to the polymer graft modified silica sol is (0.1-5): (94.7-99.8).
Preferably, the vinyl silane is one or more of methyl vinyl dimethoxy silane, dimethyl vinyl ethoxy silane (vinyl single end socket), vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (dimethoxyethoxy) silane and vinyl triisopropoxy silane.
The final product of the invention is acidic silica sol, and the silica content is as follows: 22-38%, pH2-3.5, particle size 8-20nm, and zeta potential of-2 to-8.
Firstly, polymer grafting modification is carried out on orthogenic silica sol products, partial organic groups are utilized to replace partial hydroxyl groups on the surfaces of acidic silica sol, steric hindrance among particles is increased, aggregation is reduced, meanwhile, longer molecular chains are used for enlarging distance between colloidal particles, the silica sol is prevented from being gelled, and dispersion performance is improved; the organic acid is added later, a denser hydration layer formed on the surface of the silicon dioxide particles is combined with the vinyl silane, and the two steps are matched with each other, so that the surface of the silicon dioxide is coated by a large amount of organic groups, the metastable acidic silica sol solution becomes more stable, the phenomena of coagulation and gel are avoided when the silicon dioxide particles are stored for more than 2 years at normal temperature, and the stability is greatly improved.
Advantageous effects
The two-step synergistic modified acidic silica sol product has better dispersibility, greatly improved stability, and wide application prospect in the fields of precision casting, coating, chemical polishing, fireproof materials and the like, and can be easily realized in large-scale batch production by taking the commercial acidic silica sol product as a basic raw material, wherein the normal-temperature storage time is not less than two years
Drawings
FIG. 1 is a transmission electron microscopic image of the acidic silica sol obtained in example 4 and comparative example 3 of the present invention;
FIG. 2 is a graph showing the particle size distribution of the acidic silica sols obtained in example 4 and comparative example 3 of the present invention.
Detailed Description
The technical scheme of the present invention is further described below with reference to specific examples, but is not limited thereto.
Example 1
The acidic silica sol is prepared by grafting and modifying an original silica sol product through a polymer and then performing vinyl functionalization.
The raw silica sol product is acidic silica sol, the average particle diameter is 8-20nm, the pH value is 2-4, the solid content is 20-35%, the zata potential is-9 to-11.
The original silica sol product of the embodiment uses KHAS25 acidic series silica sol of the product of Kahn silicon Co., ltd. In Yi-type city, and meets the parameter requirements.
The preparation method of the vinyl functional modified acidic silica sol comprises the following preparation steps:
(1) The method for grafting and modifying the polymer comprises the following steps: adding water and maleic anhydride into a container, heating and dissolving at 85 ℃, simultaneously dripping acrylic acid and hydrogen peroxide solution after dissolving, and carrying out heat preservation reaction for 30min at 89 ℃ after finishing dripping to obtain copolymer solution, wherein the pH value is controlled to be less than 5; then mixing and stirring the copolymer solution and the acidic silica sol for 3 hours according to the mass ratio of 1:1 to finish the polymer grafting modified silica sol;
(2) Adding organic acid into the polymer grafted modified silica sol, heating to 40 ℃, adding vinyl silane, and reacting for 2 hours to obtain the final product, namely the acidic silica sol with modified vinyl function.
The molar ratio of water to maleic anhydride in step (1) was 20:1.
The molar ratio of maleic anhydride to acrylic acid in the step (1) is 1:3.
The adding amount of the hydrogen peroxide solution in the step (1) is 30% of the total mass of water, maleic anhydride and acrylic acid, and the mass concentration of the hydrogen peroxide solution is 30%.
The addition amount of the organic acid in the step (2) is 0.01% of the mass of the polymer grafted modified silica sol; the organic acid is citric acid.
The mass ratio of the vinyl silane to the polymer grafted modified silica sol is 0.1:94.7.
the vinyl silane is methyl vinyl dimethoxy silane.
Example 2
The acidic silica sol is prepared by grafting and modifying an original silica sol product through a polymer and then performing vinyl functionalization.
The raw silica sol product is acidic silica sol, the average particle diameter is 8-20nm, the pH value is 2-4, the solid content is 20-35%, the zata potential is-9 to-11.
The original silica sol product of the embodiment uses KHAS30 acid series silica sol of the silicon product of Kahn of Linyi, and meets the parameter requirements.
The preparation method of the vinyl functional modified acidic silica sol comprises the following preparation steps:
(1) The method for grafting and modifying the polymer comprises the following steps: adding water and maleic anhydride into a container, heating and dissolving at 90 ℃, simultaneously dripping acrylic acid and hydrogen peroxide solution after dissolving, and carrying out heat preservation reaction for 50min at 95 ℃ after finishing dripping to obtain copolymer solution, wherein the pH value is controlled to be less than 5; then mixing and stirring the copolymer solution and the acidic silica sol for 4 hours according to the mass ratio of 1:1 to finish the polymer grafting modified silica sol;
(2) Adding organic acid into the polymer grafted modified silica sol, heating to 60 ℃, adding vinyl silane, and reacting for 6 hours to obtain the final product, namely the acidic silica sol with modified vinyl function.
The molar ratio of water to maleic anhydride in step (1) was 20:1.
The molar ratio of maleic anhydride to acrylic acid in the step (1) is 1:3.
The adding amount of the hydrogen peroxide solution in the step (1) is 35% of the total mass of water, maleic anhydride and acrylic acid, and the mass concentration of the hydrogen peroxide solution is 30%.
The addition amount of the organic acid in the step (2) is 0.1% of the mass of the polymer grafted modified silica sol; the organic acid is lactic acid.
The mass ratio of the vinyl silane to the polymer grafted modified silica sol is 1:95.5.
the vinyl silane is dimethyl vinyl ethoxy silane (vinyl single seal head).
Example 3
The acidic silica sol is prepared by grafting and modifying an original silica sol product through a polymer and then performing vinyl functionalization.
The raw silica sol product is acidic silica sol, the average particle diameter is 8-20nm, the pH value is 2-4, the solid content is 20-35%, the zata potential is-9 to-11.
The original silica sol product of the embodiment uses KHAS25 acidic series silica sol of the product of Kahn silicon Co., ltd. In Yi-type city, and meets the parameter requirements.
The preparation method of the vinyl functional modified acidic silica sol comprises the following preparation steps:
(1) The method for grafting and modifying the polymer comprises the following steps: adding water and maleic anhydride into a container, heating and dissolving at 85 ℃, simultaneously dripping acrylic acid and hydrogen peroxide solution after dissolving, and carrying out heat preservation reaction for 50min at 95 ℃ after finishing dripping to obtain copolymer solution, wherein the pH value is controlled to be less than 5; then mixing and stirring the copolymer solution and the acidic silica sol for 5 hours according to the mass ratio of 1:1 to finish the polymer grafting modified silica sol;
(2) Adding organic acid into the polymer grafted modified silica sol, heating to 90 ℃, adding vinyl silane, and reacting for 5 hours to obtain the final product, namely the acidic silica sol with modified vinyl function.
The molar ratio of water to maleic anhydride in step (1) was 20:1.
The molar ratio of maleic anhydride to acrylic acid in the step (1) is 1:3.
The adding amount of the hydrogen peroxide solution in the step (1) is 40% of the total mass of water, maleic anhydride and acrylic acid, and the mass concentration of the hydrogen peroxide solution is 30%.
The addition amount of the organic acid in the step (2) is 0.2% of the mass of the polymer grafted modified silica sol; the organic acid is citric acid and/or lactic acid.
The mass ratio of the vinyl silane to the polymer grafted modified silica sol is 2:96.
the vinyl silane is vinyl triethoxy silane.
Example 4
The acidic silica sol is prepared by grafting and modifying an original silica sol product through a polymer and then performing vinyl functionalization.
The raw silica sol product is acidic silica sol, the average particle diameter is 8-20nm, the pH value is 2-4, the solid content is 20-30%, and the zeta potential is-9 to-11.
The original silica sol product of the embodiment uses KHAS35 acid series silica sol of the silicon product of Kahn of Linyi, and meets the parameter requirements.
The preparation method of the vinyl functional modified acidic silica sol comprises the following preparation steps:
(1) The method for grafting and modifying the polymer comprises the following steps: adding water and maleic anhydride into a container, heating and dissolving at 90 ℃, simultaneously dripping acrylic acid and hydrogen peroxide solution after dissolving, and carrying out heat preservation reaction at 95 ℃ for 60min after finishing dripping to obtain copolymer solution, wherein the pH value is controlled to be less than 5; then mixing and stirring the copolymer solution and the acidic silica sol for 5 hours according to the mass ratio of 1:1 to finish the polymer grafting modified silica sol;
(2) Adding organic acid into the polymer grafted modified silica sol, heating to 90 ℃, adding vinyl silane, and reacting for 8 hours to obtain the final product, namely the acidic silica sol with modified vinyl function.
The molar ratio of water to maleic anhydride in step (1) was 20:1.
The molar ratio of maleic anhydride to acrylic acid in the step (1) is 1:3.
The adding amount of the hydrogen peroxide solution in the step (1) is 40% of the total mass of water, maleic anhydride and acrylic acid, and the mass concentration of the hydrogen peroxide solution is 30%.
The addition amount of the organic acid in the step (2) is 0.3% of the mass of the polymer grafted modified silica sol; the organic acid is prepared by mixing citric acid and lactic acid according to a mass ratio of 1:1.
The mass ratio of the vinyl silane to the polymer grafted modified silica sol is 5:99.8.
the vinyl silane is vinyl trimethoxy silane.
Comparative example 1
An acidic silica sol with modified vinyl function is obtained by performing vinyl functionalization on an original silica sol product.
The raw silica sol product is acidic silica sol, the average particle diameter is 8-20nm, the pH value is 2-4, the solid content is 20-35%, the zata potential is-9 to-11.
The comparative silica sol product uses KHAS35 acid series silica sol of the silicon product Limited company of Kehn in Yi city, and meets the parameter requirements.
The preparation method of the vinyl functional modified acidic silica sol comprises the following preparation steps:
(1) Adding organic acid into the original silica sol, heating to 90 ℃, adding vinyl silane, and reacting for 8 hours to obtain the final product, namely the acidic silica sol with modified vinyl function.
The addition amount of the organic acid is 0.3% of the mass of the silica sol; the organic acid is prepared by mixing citric acid and lactic acid according to a mass ratio of 1:1.
The mass ratio of the vinyl silane to the original silica sol is 5:99.8.
the vinyl silane is vinyl trimethoxy silane.
This comparative example was prepared as in example 4, except that the first polymer modification of the acidic silica sol was not performed.
Comparative example 2
The acidic silica sol is obtained by modifying an original silica sol product through polymer grafting.
The raw silica sol product is acidic silica sol, the average particle diameter is 8-20nm, the pH value is 2-4, the solid content is 20-35%, the zata potential is-9 to-11.
The comparative example original silica sol product uses KHAS35 acid series silica sol of Kahn silicon product Limited in Yi city, which meets the parameter requirements.
The preparation method of the polymer functional modified acidic silica sol comprises the following preparation steps: adding water and maleic anhydride into a container, heating and dissolving at 90 ℃, simultaneously dripping acrylic acid and hydrogen peroxide solution after dissolving, and carrying out heat preservation reaction at 95 ℃ for 60min after finishing dripping to obtain copolymer solution, wherein the pH value is controlled to be less than 5; and then mixing and stirring the copolymer solution and the acidic silica sol for 5 hours according to the mass ratio of 1:1 to finish the polymer grafting modified silica sol, thereby obtaining the final product vinyl functional modified acidic silica sol.
The molar ratio of water to maleic anhydride in step (1) was 20:1.
The molar ratio of maleic anhydride to acrylic acid in the step (1) is 1:3.
The adding amount of the hydrogen peroxide solution in the step (1) is 40% of the total mass of water, maleic anhydride and acrylic acid, and the mass concentration of the hydrogen peroxide solution is 30%.
The comparative example was conducted in the same manner as in example 4 except that the vinyl functional modification was not conducted.
Comparative example 3
KHAS35 acidic silica sol of silicon products Limited of Corhn, yi, city.
Comparative example 4
KHAS25 acidic silica sol of Kahn silicon products Co., linyi, inc.
Comparative example 5
KHAS30 acid series silica sol of Kahn silicon products Co., linyi, city.
Performance testing
Test sample
The silica sols obtained in example 4, the silica sols obtained in comparative examples 1-2, the KHAS35 acidic series silica sols from Kagaku silicon products Co., ltd. In Yi-city (comparative example 3), the KHAS25 acidic series silica sols from Kagaku silicon products Co., ltd. In Yi-city (comparative example 4) and the KHAS30 acidic series silica sols from Kagaku silicon products Co., ltd. In Yi-city (comparative example 5)
Test method
Morphology: a transmission electron microscope;
pH: taking 50ml of silica sol sample at room temperature, placing the silica sol sample in a 100ml beaker, taking a glass electrode as a measuring electrode and a saturated calomel electrode as a reference electrode, and measuring the pH value by an acidometer;
viscosity: a rotary viscometer;
silica content: in the solid method, about 2g of sample is weighed and 0.0002g of sample is precisely weighed by using a porcelain crucible which is burned to constant weight at 800-850 ℃. Drying at 105-110 deg.c and burning at 800-850 deg.c to constant weight. Silicon dioxide (SiO) 2 ) The content (X) is calculated according to the following equation:
wherein m1 is the mass of the residue after firing, g; m is the mass of the sample and g;
particle size measurement: an alkali adsorption method;
morphology: the morphology of the silica sol product was observed by a transmission electron microscope TEM, JEM-2000EX type, manufactured by JEOL corporation, japan.
Test temperature: 25 ℃;
the performance test results are shown in table 1:
TABLE 1 Performance test results
As can be seen from the data in the table, the acidic silica sols obtained in examples 1 to 4 of the present invention had a tendency to increase in average particle size (as shown in particle size distribution chart 2) after two-step modification, and the larger the particle size, the better the stability. After the silica sol is stored for 2 years at normal temperature, the performance of the silica sol is not greatly changed, and compared with unmodified original acidic silica sol, the stability is obviously improved; the original acidic silica sol has the aging stability at the high temperature of 80 ℃ of not more than 15 days, and the aging stability of the modified acidic silica sol at the high temperature of 80 ℃ can reach more than 45 days. As can also be seen from the transmission electron microscope image 1, the silica sol particles obtained in the embodiment 4 of the present invention are significantly agglomerated after being stored for half a year at normal temperature, the viscosity is significantly increased, the gel tendency is increased, and the aging stability time at 80 ℃ is only 5 days, compared with the silica sol product of the comparative example 3, which is obtained in the comparative example 3. According to the invention, the polymer grafting modified acidic silica sol is utilized to replace part of hydroxyl groups on the surface of the acidic silica sol, so that the steric hindrance between particles is increased, the agglomeration is reduced, meanwhile, the longer molecular chain is used for enlarging the distance between colloidal particles, preventing the silica sol from generating gel, and greatly improving the dispersion performance of silica particles in solution, so that the stability of a sol system is enhanced.
It should be noted that the above-mentioned embodiments are merely some, but not all embodiments of the preferred mode of carrying out the invention. It is evident that all other embodiments obtained by a person skilled in the art without making any inventive effort, based on the above-described embodiments of the invention, shall fall within the scope of protection of the invention.
Claims (8)
1. The acidic silica sol is prepared by grafting and modifying an original silica sol product through a polymer, and then performing vinyl functionalization; the preparation of the acidic silica sol comprises the following steps:
(1) The method for grafting and modifying the polymer comprises the following steps: adding water and maleic anhydride into a container, heating and dissolving at 85-90 ℃, simultaneously dripping acrylic acid and hydrogen peroxide solution after dissolving, and carrying out heat preservation reaction for 30-60min at 89-95 ℃ after finishing dripping to obtain copolymer solution, wherein the pH value is controlled to be less than 5; then mixing and stirring the copolymer solution and the acidic silica sol according to the mass ratio of 1:1 for 3-5h to finish the polymer grafting modified silica sol;
(2) Adding organic acid into the polymer grafted modified silica sol, heating to 40-90 ℃, adding vinyl silane, and reacting for 2-8h to obtain the final product, namely the vinyl functional modified acidic silica sol.
2. The vinyl functional modified acidic silica sol according to claim 1, wherein the raw silica sol product is an acidic silica sol having an average particle size of 8-20nm, a ph of 2-4, a solid content of 20-35%, and a zata potential of-9 to-11.
3. The method for preparing a vinyl functional modified acidic silica sol according to claim 1, wherein the molar ratio of water to maleic anhydride in step (1) is 20:1.
4. The method for preparing an acidic silica sol modified by vinyl functionality according to claim 1, wherein the molar ratio of maleic anhydride to acrylic acid in the step (1) is 1:3.
5. The method for preparing the vinyl functional modified acidic silica sol according to claim 1, wherein the hydrogen peroxide solution in the step (1) is added in an amount of 30-40% of the total mass of water, maleic anhydride and acrylic acid, and the mass concentration of the hydrogen peroxide solution is 30%.
6. The method for preparing vinyl functional modified acidic silica sol according to claim 1, wherein the addition amount of the organic acid in the step (2) is 0.01-0.3% of the mass of the polymer grafted modified silica sol; the organic acid is citric acid and/or lactic acid.
7. The method for preparing a vinyl functional modified acidic silica sol according to claim 1, wherein the mass ratio of the vinyl silane to the polymer graft modified silica sol in the step (2) is (0.1-5): (94.7-99.8).
8. The method for preparing the vinyl functional modified acidic silica sol according to claim 1, wherein the vinyl silane is one or more of methyl vinyl dimethoxy silane, dimethyl vinyl ethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (dimethoxyethoxy) silane and vinyl triisopropoxy silane.
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| CN107253726A (en) * | 2017-05-18 | 2017-10-17 | 江苏天恒纳米科技股份有限公司 | A kind of preparation technology of polymer modification Ludox |
| CN108948727A (en) * | 2018-08-01 | 2018-12-07 | 扬中市橡胶塑料厂有限公司 | A kind of high temperature resistant polyurethane rubber and its pouring technology |
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