CN116022799B - Silicon dioxide particles, preparation method thereof and silicon rubber prepared from silicon dioxide particles - Google Patents
Silicon dioxide particles, preparation method thereof and silicon rubber prepared from silicon dioxide particles Download PDFInfo
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- CN116022799B CN116022799B CN202211709350.6A CN202211709350A CN116022799B CN 116022799 B CN116022799 B CN 116022799B CN 202211709350 A CN202211709350 A CN 202211709350A CN 116022799 B CN116022799 B CN 116022799B
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Abstract
The invention discloses silicon dioxide particles, a preparation method thereof and silicon rubber prepared from the silicon dioxide particles. The preparation method of the silica particles comprises the following steps: 1) Adding water into sodium silicate to prepare sodium silicate solution; 2) Adding water into polyethylene glycol with low molecular weight, adding a part of sodium silicate solution, uniformly mixing, and adding sulfuric acid solution for reaction to obtain a silica primary product dispersion; 3) Dispersing high molecular weight polyethylene glycol in a silica initial product dispersion liquid, adding a sodium silicate solution and a sulfuric acid solution for reaction, and then aging, press-filtering, washing, spray-drying and crushing to obtain silica particles. The silica particles of the invention have moderate specific surface area, particle diameter and oil absorption value, are suitable for preparing the low permanent deformation silicone rubber, and have wide application prospect.
Description
Technical Field
The invention relates to the technical field of inorganic fillers, in particular to silica particles, a preparation method thereof and silicon rubber prepared from the silica particles.
Background
Silicone rubber refers to rubber in which the main chain is composed of silicon and oxygen atoms alternately, and the silicon atoms are usually linked with two organic groups. The silicone rubber has the advantages of good low temperature resistance, good high temperature aging resistance, good air permeability and the like, and the application range is wider and wider. At present, white carbon black is mainly added into silicone rubber as a reinforcing filler, so that the mechanical strength of the silicone rubber can be increased, but the permanent deformation of the silicone rubber (the percentage of the deformation size to the original size after a sample is parked for a certain time after the stress is eliminated) is also increased, and the finally obtained silicone rubber product has larger permanent deformation and cannot meet the use requirement of a specific occasion.
Therefore, it is of great importance to develop an inorganic filler suitable for the preparation of low permanent deformation silicone rubber.
Disclosure of Invention
The invention aims to provide silica particles, a preparation method thereof and silicone rubber prepared from the silica particles.
The technical scheme adopted by the invention is as follows:
a method for preparing silica particles comprising the steps of:
1) Adding water into sodium silicate to prepare sodium silicate solution;
2) Adding water into polyethylene glycol with the number average molecular weight of 400-2000, adding a part of sodium silicate solution, uniformly mixing, heating to 85-95 ℃, and continuously adding sulfuric acid solution until the pH value of the reaction solution is 9.0-10.0 to obtain a silica primary product dispersion liquid;
3) Dispersing polyethylene glycol with the number average molecular weight of 4000-10000 in a silica initial product dispersion liquid, continuously adding a sodium silicate solution and a sulfuric acid solution for reaction, keeping the pH value of the reaction liquid to be 9.0-10.0 and the temperature to be 85-95 ℃ until the sodium silicate solution is completely added in the reaction process, continuously adding the sulfuric acid solution until the pH value of the reaction liquid is 3.0-5.5, and then aging, press-filtering, washing, spray-drying and crushing to obtain the silica particles.
Preferably, the sodium silicate in step 1) has a modulus of 3.0 to 3.5.
Preferably, the concentration of the sodium silicate solution in the step 1) is 1.5mol/L to 2.5mol/L.
Preferably, the addition amount of the sodium silicate solution in the step 2) is 40% -50% of the total volume of the sodium silicate solution.
Preferably, the concentration of the sulfuric acid solution in the step 2) is 3mol/L to 6mol/L.
Preferably, the polyethylene glycol with the number average molecular weight of 4000-10000 in the step 3) is added in an amount of 0.1-0.5% of the mass of the silica primary product dispersion liquid.
Preferably, the feeding speed ratio of the sodium silicate solution to the sulfuric acid solution in the step 3) is 1:0.18-0.67.
Preferably, the concentration of the sulfuric acid solution in the step 3) is 3mol/L to 6mol/L.
Silica particles produced by the above-described production process.
A silicone rubber comprising the above silica particles.
The beneficial effects of the invention are as follows: the silica particles of the invention have moderate specific surface area, particle diameter and oil absorption value, are suitable for preparing the low permanent deformation silicone rubber, and have wide application prospect.
Specifically:
1) The silica particles of the invention have moderate specific surface area, particle diameter and oil absorption value, and can be used as reinforcing filler to be added into the silicon rubber, so that the low permanent deformation characteristic of the silicon rubber can be endowed on the basis of ensuring that the silicon rubber has good tensile strength and elongation, and the application requirement of the low permanent deformation silicon rubber can be met;
2) According to the invention, polyethylene glycol with different molecular weights is added at different stages of the reaction, and the synergistic effect of polyethylene glycol with high molecular weight and polyethylene glycol with low molecular weight is utilized to effectively control the nucleation, growth and aggregation of silicon dioxide (the network condensation effect of polyethylene glycol with low molecular weight is far smaller than the steric hindrance effect, so that the agglomeration among particles at the beginning of the reaction can be reduced, and more silicon dioxide nano particles for growth are generated; the network coagulation effect of the polyethylene glycol with high molecular weight plays a main role, and can be adsorbed on the surface of the silicon dioxide particles in a reaction system and wound to form a high molecular network structure, so that coagulation among colloid particles is promoted, the particle size of particles generated by the reaction is more uniform), and the polyethylene glycol can leave a regular pore channel structure on the silicon dioxide particles after being washed and removed, so that the silicon rubber and the silicon dioxide particles are dispersed into fine and uniform aggregate structures during mixing, the strain amplification effect is reduced, and the low permanent deformation silicon rubber is obtained;
3) According to the invention, the amount of polyethylene glycol added is precisely regulated, so that the number of hydrogen bonds between raw rubber and the surface of the silica particles can be effectively reduced when the prepared silica particles are used for mixing silicon rubber (the addition of polyethylene glycol can modify the surface of the silica particles, when the number of polyethylene glycol molecules on the surface of the generated silica particles is larger than the number of bound water, the surface of the silica particles shows lipophilicity, when the number of polyethylene glycol molecules on the surface of the silica particles is equal to the number of bound water, the surface of the silica particles is in an equilibrium state, when the number of polyethylene glycol on the surface of the silica particles is smaller than the number of bound water, the surface of the silica particles shows hydrophilicity), and the cross-linking generated by adding reinforcing filler is reduced, so that the proportion of covalent cross-linking generated by peroxide vulcanization in a cross-linking network can be increased.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
Example 1:
a method for preparing silica particles comprising the steps of:
1) Adding water into sodium silicate with modulus of 3.0 to prepare sodium silicate solution with concentration of 1.5mol/L, wherein the preset quantity of the sodium silicate solution is 10m 3 ；
2) Will be 12m 3 Adding water into a reaction tank, adding PEG-800 to obtain 2% dispersion, and adding 5m 3 Uniformly mixing the sodium silicate solution, heating to 85 ℃, starting stirring at a stirring speed of 1500r/min and then adding 5m 3 Continuously adding sulfuric acid solution with the concentration of 3mol/L at the rate of/h until the pH value of the reaction solution is 9.0, so as to obtain silica primary product dispersion liquid;
3) Adding PEG-10000 into a reaction tank, wherein the addition amount of PEG-10000 is 0.5% of the mass of the silica primary product dispersion, continuously stirring for 60min after PEG-10000 is completely dissolved, continuously adding sodium silicate solution and sulfuric acid solution with the concentration of 3mol/L for reaction, and the feeding speed of the sodium silicate solution is 12m 3 The feed rate of the sulfuric acid solution was 6m 3 And/h, maintaining the pH value of the reaction solution at 9.0 and the temperature at 85 ℃ until the addition of the sodium silicate solution is completed, and then adding the sodium silicate solution at 6m 3 And (3) continuously adding sulfuric acid solution with the concentration of 3mol/L at the feeding speed of/h until the pH value of the reaction solution is 3.0, aging for 1h, and performing filter pressing, water washing, spray drying and crushing to obtain the silicon dioxide particles.
Example 2:
a method for preparing silica particles comprising the steps of:
1) Adding water into sodium silicate with modulus of 3.5 to prepare sodium silicate solution with concentration of 2mol/L, wherein the preset quantity of the sodium silicate solution is 8m 3 ；
2) Will be 12m 3 Adding water into a reaction tank, adding PEG-400 and PEG-2000 to obtain 3.5% dispersion (the mass ratio of PEG-400 to PEG-2000 is 1:4), and adding 3.5m 3 Uniformly mixing the sodium silicate solution, heating to 90 ℃, starting stirring at a stirring speed of 1500r/min and then adding 1m 3 Continuously adding sulfuric acid solution with the concentration of 4.5mol/L at the rate of/h until the pH value of the reaction solution is 9.5, so as to obtain silica initial product dispersion liquid;
3) Adding PEG-4000 into a reaction tank, wherein the addition amount of the PEG-4000 is 0.1% of the mass of the dispersion liquid of the silica primary product, continuously stirring for 30min after the PEG-4000 is completely dissolved, continuously adding sodium silicate solution and sulfuric acid solution with the concentration of 4.5mol/L for reaction, and the feeding speed of the sodium silicate solution is 12m 3 The feed rate of the sulfuric acid solution was 8m 3 And/h, maintaining the pH value of the reaction solution at 9.5 and the temperature of 90 ℃ until the addition of the sodium silicate solution is completed, and then adding the sodium silicate solution at 8m 3 And (3) continuously adding sulfuric acid solution with the concentration of 4.5mol/L at the feeding speed of/h until the pH value of the reaction solution is 4.0, aging for 30min, and performing filter pressing, water washing, spray drying and crushing to obtain the silicon dioxide particles.
Example 3:
a method for preparing silica particles comprising the steps of:
1) Adding water into sodium silicate with modulus of 3.3 to prepare sodium silicate solution with concentration of 2.5mol/L, wherein the preset quantity of the sodium silicate solution is 7m 3 ；
2) Will be 12m 3 Adding water into a reaction tank, adding PEG-600 and PEG-1000 to obtain 3.5% dispersion (the mass ratio of PEG-600 to PEG-1000 is 3:5), and adding 3m 3 Uniformly mixing the sodium silicate solution, heating to 95 ℃, starting stirring at 1800r/min, and adding 3m 3 The sulfuric acid solution with the concentration of 6mol/L is continuously added at the rate of/h until the pH value of the reaction solution is 9Fifthly, obtaining a silicon dioxide initial product dispersion liquid;
3) Adding PEG-6000 into a reaction tank, wherein the addition amount of PEG-6000 is 0.3% of the mass of the silica primary product dispersion, continuously stirring for 45min after the PEG-6000 is completely dissolved, and continuously adding sodium silicate solution and sulfuric acid solution with the concentration of 6mol/L for reaction, wherein the feeding speed of the sodium silicate solution is 16m 3 The feed rate of the sulfuric acid solution was 6m 3 And/h, maintaining the pH value of the reaction solution at 9.5 and the temperature of 95 ℃ until the addition of the sodium silicate solution is completed, and then adding the sodium silicate solution at 6m 3 And (3) continuously adding a sulfuric acid solution with the concentration of 6mol/L at the feeding speed of/h until the pH value of the reaction solution is 4.0, aging for 45min, and performing filter pressing, water washing, spray drying and crushing to obtain the silicon dioxide particles.
Example 4:
a method for preparing silica particles comprising the steps of:
1) Adding water into sodium silicate with modulus of 3.0 to prepare sodium silicate solution with concentration of 2.5mol/L, wherein the preset quantity of the sodium silicate solution is 7m 3 ；
2) Will be 12m 3 Adding water into a reaction tank, adding PEG-1000 to obtain 5% dispersion, and adding 3m 3 Uniformly mixing the sodium silicate solution, heating to 85 ℃, starting stirring at 1800r/min, and adding 3m 3 Continuously adding sulfuric acid solution with the concentration of 6mol/L at the rate of/h until the pH value of the reaction solution is 10.0, so as to obtain silica primary product dispersion liquid;
3) Adding PEG-4000 and PEG-8000 into a reaction tank, wherein the total addition amount of the PEG-4000 and the PEG-8000 is 0.3% of the mass of the silica primary product dispersion liquid, the mass ratio of the PEG-4000 to the PEG-8000 is 1:1, continuously stirring for 30min after the PEG-4000 and the PEG-8000 are completely dissolved, continuously adding sodium silicate solution and sulfuric acid solution with the concentration of 6mol/L for reaction, and the feeding speed of the sodium silicate solution is 12m 3 The feed rate of the sulfuric acid solution was 3m 3 And/h, maintaining the pH value of the reaction solution at 10.0 and the temperature at 85 ℃ until the sodium silicate solution is completely added, and then adding 3m of the sodium silicate solution 3 Continuously adding sulfuric acid solution with the concentration of 6mol/L at the feeding speed of/h until the pH value of the reaction solution is 5.5, and thenAging for 30min, press filtering, washing, spray drying and crushing to obtain silica particles.
Comparative example 1:
a method for preparing silica particles was the same as in example 3 except that PEG-600 and PEG-1000 were not added in step 2).
Comparative example 2:
a method for preparing silica particles was the same as in example 3 except that PEG-6000 was not added in step 3).
Comparative example 3:
a method for preparing silica particles was the same as in example 3 except that PEG-600 and PEG-1000 were added in step 2) to prepare a dispersion having a mass fraction of 10%.
Comparative example 4:
a method for preparing silica particles was the same as in example 3 except that PEG-6000 was replaced with PEG-20000 in step 3).
Performance test:
1) The silica particles prepared in examples 1 to 4 had oil absorption value, specific surface area and particle diameter (D 50 ) The test results are shown in the following table:
table 1 results of oil absorption value, specific surface area and particle size tests of silica particles prepared in examples 1 to 4
| Test item | Oil absorption value (g/100 g) | Specific surface area (m) 2 /g) | Particle size (nm) |
| Example 1 | 220 | 185 | 20 |
| Example 2 | 180 | 151 | 22 |
| Example 3 | 195 | 175 | 18 |
| Example 4 | 210 | 195 | 14 |
Note that:
oil absorption value: the test was performed with reference to "determination of absorption value of precipitated hydrated silica dibutyl phthalate (DBP) by HG/T3072-2008 rubber compounding agent";
specific surface area: the specific surface area of the solid substance is measured by referring to the GB/T19587-2017 gas adsorption BET method;
particle size: the test was conducted with reference to "GB/T32698-2016 laser diffraction method for measuring particle size distribution of precipitated hydrated silica as a rubber compounding agent".
As can be seen from table 1: the silica particles prepared in examples 1 to 4 had an oil absorption value of 180g/100g to 220g/100g and a specific surface area of 151m 2 /g～195m 2 The particle size of the silica particles is 14 nm-22 nm, which shows that the silica particles prepared by the invention have high oil absorption value, moderate specific surface area, moderate particle size and good comprehensive performance, wherein the silica particles prepared by the example 3 have excellent performances in all aspects,is the best embodiment.
2) The silica particles prepared in examples 1 to 4 and comparative examples 1 to 4 were made into silicone rubbers (the formulation of silicone rubbers is as follows: 100 parts by mass of raw rubber, 45 parts by mass of silicon dioxide particles and 3 parts by mass of hydroxyl silicone oil), mixing the silicon rubber by an internal mixer, vacuumizing, adding 0.5% of a bis-dipentaerythritol vulcanizing agent for vulcanization, and testing a vulcanized film to obtain the following mechanical property test results:
TABLE 2 mechanical test results of vulcanized rubber sheets
Note that:
shore hardness/a: reference is made to "GB/T531.1-2008 first part of the method for testing indentation hardness of vulcanized rubber or thermoplastic rubber: shore durometer "test;
tensile strength, elongation at break, permanent set at break: testing is performed with reference to "measurement of tensile stress strain properties of GB/T528-2009 vulcanized rubber or thermoplastic rubber";
compression set: determination of compression set for reference "GB/T7759.1-2015 vulcanized rubber or thermoplastic rubber part 1: the test was performed at room temperature and high temperature, type B samples, 200℃for 24h.
As can be seen from table 2: the silica particles of the invention are applied to silicone rubber, have excellent dispersibility, and the prepared silicone rubber has lower permanent deformation under break and compression set on the basis that the tensile strength and the breaking elongation of the silicone rubber reach excellent levels, wherein the silica particles prepared in the embodiment 3 have the minimum permanent deformation under break and compression set due to different effects of polyethylene glycol molecules with different molecular weights in different reaction stages. Therefore, the silica particles prepared by the method can obviously reduce the permanent deformation of the silicone rubber product under the condition of ensuring that the silicone rubber product has better tensile strength and tensile elongation, so that the prepared product has stable quality, is not easy to deform and has excellent processability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (3)
1. A method for preparing silica particles, comprising the steps of:
1) Adding water into sodium silicate to prepare sodium silicate solution;
2) Adding water into polyethylene glycol with the number average molecular weight of 400-2000, adding a part of sodium silicate solution, uniformly mixing, heating to 85-95 ℃, and continuously adding sulfuric acid solution until the pH value of the reaction solution is 9.0-10.0 to obtain a silica primary product dispersion liquid;
3) Dispersing polyethylene glycol with the number average molecular weight of 4000-10000 in a silica initial product dispersion liquid, continuously adding a sodium silicate solution and a sulfuric acid solution for reaction, keeping the pH value of the reaction liquid to be 9.0-10.0 and the temperature to be 85-95 ℃ until the sodium silicate solution is completely added in the reaction process, continuously adding the sulfuric acid solution until the pH value of the reaction liquid is 3.0-5.5, and then aging, press-filtering, washing, spray-drying and crushing to obtain silica particles;
the modulus of the sodium silicate in the step 1) is 3.0-3.5;
the concentration of the sodium silicate solution in the step 1) is 1.5mol/L to 2.5mol/L;
the adding amount of the sodium silicate solution in the step 2) is 40% -50% of the total volume of the sodium silicate solution;
the concentration of the sulfuric acid solution in the step 2) is 3 mol/L-6 mol/L;
the addition amount of the polyethylene glycol with the number average molecular weight of 4000-10000 in the step 3) is 0.1-0.5% of the mass of the silica primary product dispersion liquid.
2. The method for producing silica particles according to claim 1, wherein: and 3) the feeding speed ratio of the sodium silicate solution to the sulfuric acid solution is 1:0.18-0.67.
3. The method for producing silica particles according to claim 1, wherein: the concentration of the sulfuric acid solution in the step 3) is 3 mol/L-6 mol/L.
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| CN117159743A (en) * | 2023-08-07 | 2023-12-05 | 金三江(肇庆)硅材料股份有限公司 | Lubricating and drug-carrying difunctional silicon dioxide microsphere as well as preparation method and application thereof |
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| FR2678259B1 (en) * | 1991-06-26 | 1993-11-05 | Rhone Poulenc Chimie | NOVEL PRECIPITATED SILICA IN THE FORM OF GRANULES OR POWDERS, METHODS OF SYNTHESIS AND USE FOR REINFORCING ELASTOMERS. |
| CN102020284B (en) * | 2011-01-12 | 2014-01-08 | 厦门大学 | Preparation method of silica |
| CN102320615B (en) * | 2011-09-11 | 2015-11-18 | 中国科学院过程工程研究所 | A kind of take SILICA FUME as the method that precipitated silica is prepared in raw material carbonization |
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| CN114957801B (en) * | 2022-06-06 | 2023-03-14 | 金三江(肇庆)硅材料股份有限公司 | Silicon dioxide for high-temperature-aging-resistant silicone rubber and preparation method thereof |
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