CN114957801A - Silicon dioxide for high-temperature aging resistant silicone rubber and preparation method thereof - Google Patents
Silicon dioxide for high-temperature aging resistant silicone rubber and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of new inorganic materials, and provides silicon dioxide for high-temperature-aging-resistant silicone rubber and a preparation method thereof, wherein the preparation method comprises the following steps: s1, diluting and dissolving solid sodium silicate; s2, preparing a sodium silicate solution; s3, preparing a sulfuric acid solution containing a zinc source; s4, heating the sodium silicate solution; dropwise adding a sulfuric acid solution containing a zinc source, and controlling the pH value of the reaction end point to be 8.0-10; s5, slowly raising the temperature, simultaneously dropwise adding a sodium silicate solution and a sulfuric acid solution containing a zinc source, controlling the pH to be 8.0-10.0, after the dropwise adding of the preset amount of the sodium silicate solution is finished, dropwise adding the sulfuric acid solution containing the zinc source, controlling the final pH to be 3.0-5.5, and after the reaction is finished, carrying out aging; s6, aging the slurry, press filtering and washing, spray drying and crushing to obtain the finished product silicon dioxide. The silicon dioxide provided by the invention has a good reinforcing effect on the silicon rubber, and the high-temperature aging resistance of the silicon rubber is improved.
Description
Technical Field
The invention belongs to the technical field of new inorganic materials, and particularly relates to silicon dioxide for high-temperature-aging-resistant silicone rubber and a preparation method thereof.
Background
The main component of the silicone rubber is methyl vinyl silicone raw rubber, the main chain structure of the raw rubber is a silicon-oxygen bond, the cracking energy of the silicon-oxygen bond is 193.5kcal/mol, while the main chain structure of the common organic polymer material is mostly carbon-carbon bond, and the cracking energy of the carbon-carbon bond is 145 kcal/mol. The high cracking energy of the silicon-oxygen bond determines that the chemical bond is not easy to break under the high temperature condition, so that the silicon rubber has better high temperature aging resistance than the common organic polymer material, and is an elastic material widely applied to high temperature places. However, with the development of high and new technologies, the requirement for the high temperature aging resistance of silicone rubber is continuously increased, and the existing commercial silicone rubber products can not meet the required performance gradually, so that the high temperature aging resistance of silicone rubber needs to be further improved.
The silicone rubber is an elastomer which is formed by taking a linear polyorganosiloxane polymer as a base and vulcanizing the linear polyorganosiloxane polymer in cooperation with a cross-linking agent, a reinforcing filler and other auxiliary agents, and the main structure of the elastomer is a linear siloxane aggregate, so that the mechanical properties such as stretching after vulcanization are poor. The methyl vinyl silicone rubber raw rubber which is the main component of the silicone rubber is straight-chain organosiloxane, the interaction between chains is weak, and the strength of the raw rubber is not high, so that the raw rubber needs to be reinforced by adding a filler such as reinforcing agent white carbon black and the like when the raw rubber is used in production and life.
At present, silicon rubber fillers are generally fumed silica and precipitated silica, and the addition of the fumed silica and the precipitated silica can greatly improve the strength of silicon rubber, but the silica prepared by different types of preparation methods has different particle sizes, aggregation states, surface properties and interaction with silicon rubber, so that the heat resistance of the silicon rubber prepared by the silica serving as the fillers is greatly influenced. Therefore, although the strength of the rubber compound can be greatly improved by adding the common white carbon black, the high-temperature aging resistance of the rubber compound is poor. Chinese patent CN110229432A discloses a method for preparing a sizing material with high temperature and thermal aging resistance, which adopts a reinforcing agent: the fast extrusion carbon black N550 and the medium particle thermal cracking carbon black MT N990 are reinforced, so that the technical effect of low compression permanent deformation of the sizing material can be effectively maintained for a long time under the high-temperature condition while the thermal aging resistance of the sizing material is not influenced.
Therefore, there is a need to develop a high temperature aging resistant silicon dioxide for silicone rubber, which, when used as a filler of silicone rubber, has a high temperature aging resistance exceeding that of conventional common silicone rubber on the basis of having good strength properties of conventional silicone rubber.
Disclosure of Invention
The invention aims to provide silicon dioxide for high-temperature-resistant and aging-resistant silicon rubber and a preparation method thereof, and zinc oxide-doped precipitated silicon dioxide is prepared by a coprecipitation method. The silicon dioxide provided by the invention has a good reinforcing effect on the silicon rubber, and the high-temperature aging resistance of the silicon rubber is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first purpose of the invention is to provide a preparation method of silicon dioxide for high-temperature aging resistant silicone rubber, which comprises the following steps:
s1, putting the solid sodium silicate into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 0.5-2mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 1-4mol/L from the concentrated sulfuric acid solution, adding polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring for a period of time to completely dissolve the polyethylene glycol PEG2000, and adding zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding process water into the reaction tank, and then adding the sodium silicate solution prepared in the step S2; heating to 60-75 ℃, starting stirring, dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3, and controlling the pH value of the reaction end point to be 8.0-10.0;
s5, opening the heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 8.0-10.0, and continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, so that the final pH value is controlled to be 3.0-5.5;
s6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the silicon dioxide for the high-temperature aging resistant silicon rubber.
Preferably, the modulus of the solid sodium silicate in the step S1 is 3.0-3.5.
Preferably, the addition amount of the polyethylene glycol PEG2000 in the step S3 is 0.05-0.3 wt%.
Preferably, the zinc sulfate is added in an amount of 0.5 to 6wt% in the step S3.
Preferably, the addition amount of the process water in the step S4 is 10-14m 3 The addition amount of the sodium silicate solution is 1-5m 3 。
Preferably, in the step S4, the stirring speed is 25-30Hz, and the dropping speed of the sulfuric acid solution containing the zinc source is 1-5m 3 /h。
Preferably, the dropping speed of the sulfuric acid solution containing the zinc source in the step S5 is 3-8m 3 H, the dropping speed of the sodium silicate solution is 12-16m 3 /h。
Preferably, the preset amount of the sodium silicate solution in the step S5 is 7-11m 3 。
Preferably, in the step S5, the heating device is turned on, the temperature of the reaction tank is slowly increased, and the temperature in the reaction tank is controlled to be 90-95 ℃ at the end of the reaction.
The second object of the present invention is to provide a silica for high temperature aging resistant silicone rubber prepared according to the above-described preparation method.
The invention concept of the invention is as follows:
(1) PEG2000 is used as a nonionic surfactant, although molecules have OH < - >, the OH < - > exists only at two ends of a polymer chain, and the PEG2000 is introduced to adsorb on the surface of silicon dioxide particles and perform condensation reaction with hydroxyl on the surface of the silicon dioxide, so that the content of the hydroxyl on the surface of the silicon dioxide is reduced. Meanwhile, the polymer adsorbed on the surface of the silicon dioxide can reduce the thermal rearrangement degradation problem of a silicon rubber chain due to the steric hindrance effect, and improve the high-temperature aging resistance of the silicon rubber.
(2) The zinc oxide is introduced by a coprecipitation method, and can be used for cooperatively absorbing acidic substances capable of catalyzing the degradation of the silicon rubber with the PEG-2000, so that the rearrangement degradation of the main chain of the silicon rubber is reduced, and the high-temperature aging resistance of the silicon rubber is improved.
(3) The reaction temperature has important influence on the structure and the performance of the white carbon black, the uniformity of particle size can be effectively improved by slowly increasing the temperature of the reaction tank in the second step, and the reaction temperature reaches 90-95 ℃ at the end point of the reaction, the mechanical property when the white carbon black is added into a silicon rubber system is improved, and meanwhile, the high-activity silicon hydroxyl content on the surface of the white carbon black can be effectively reduced by increasing the end point temperature, the breakage of silicon hydroxyl at high temperature is reduced, and the high-temperature aging resistance of the silicon rubber is improved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the silicon dioxide for the high-temperature aging resistant silicon rubber provided by the invention has moderate specific surface area, is used as a reinforcing agent in the preparation process of the silicon rubber, has good reinforcing effect on the silicon rubber, simultaneously weakens the adverse effect of the addition of the reinforcing agent on the heat resistance of the silicon rubber, and improves the high-temperature aging resistant performance of the silicon rubber.
(2) According to the invention, the zinc oxide-doped precipitated silica is prepared by a coprecipitation method, and in the process of preparing the silicone rubber by using the zinc oxide-doped precipitated silica as a reinforcing agent, the defect of the structure of the silica is increased by introducing zinc ions, the acting force between aggregates is reduced, so that the aggregates are more easily dispersed into small aggregates when being mixed with raw rubber, the powder dispersibility is improved, and the energy consumption and the production cost are reduced.
(3) In the process of preparing the silicon rubber, the zinc oxide-doped precipitated silica prepared by the coprecipitation method can be used as an accelerator by uniformly distributed zinc oxide, so that the vulcanization efficiency of rubber compound is improved, and the vulcanization time is shortened.
(4) In the process of preparing the silicon rubber, the zinc oxide-doped precipitated silica prepared by the coprecipitation method is introduced, so that the tensile strength, the tearing strength and the high-temperature aging resistance of the silicon rubber product can be obviously improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Example 1 silica for high temperature aging resistant Silicone rubber of the invention and preparation thereof
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.25wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 4.5wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m of solution into a reaction tank 3 After the process water, 3m of water is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 9.0;
s5, opening a heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.5, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 93 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the silicon dioxide for the high-temperature aging resistant silicon rubber.
Example 2 silica for high temperature aging resistant Silicone rubber of the invention and preparation thereof
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.0mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.15wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 0.5wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m into the reaction tank 3 After the process water of (1), 4m is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 25Hz for 4m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 9.0;
s5, opening the heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.0, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 5m 3 H, the dropping speed of the sodium silicate solution is 13m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 95 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the silicon dioxide for the high-temperature aging resistant silicon rubber.
Example 3 silica for high temperature aging resistant Silicone rubber of the invention and preparation thereof
S1, putting the solid sodium silicate with the modulus of 3.5 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.3wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 2.5wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 13m into the reaction tank 3 After the process water of (1), 4m is added 3 The sodium silicate solution prepared in the step S2; heating to 60 deg.C, stirring at 25Hz and a speed of 3m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 10.0;
s5, opening a heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 10.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.0, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 6m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 90 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the silicon dioxide for the high-temperature aging resistant silicon rubber.
Example 4 silica for high temperature aging resistant Silicone rubber of the invention and preparation thereof
S1, putting the solid sodium silicate with the modulus of 3.5 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.05wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 6wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m into the reaction tank 3 After the process water, 3m of water is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and 4m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 9.0;
s5, opening the heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.0, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 6m 3 H, the dropping speed of the sodium silicate solution is 13m 3 H; the preset amount of the sodium silicate solution is 10m 3 (ii) a The temperature of the reaction tank is 92 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the silicon dioxide for the high-temperature aging resistant silicon rubber.
Comparative example 1
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.03wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 4.5wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m into the reaction tank 3 After the process water, 3m of 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 9.0;
s5, opening a heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.5, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 93 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the finished product silicon dioxide.
The present comparative example is different from example 1 in that the polyethylene glycol PEG2000 is added in an amount of 0.03wt% in step S3, and the rest is the same as example 1.
Comparative example 2
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.4wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 4.5wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m into the reaction tank 3 After the process water of (1), addingInto 3m 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 9.0;
s5, opening a heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.5, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 93 ℃ after the reaction is finished
And S6, performing filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the finished product silicon dioxide.
The present comparative example is different from example 1 in that polyethylene glycol PEG2000 is added in an amount of 0.4wt% in step S3, and the other is the same as example 1.
Comparative example 3
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, and adding 4.5wt% of zinc sulfate into the dilute sulfuric acid solution to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m into the reaction tank 3 After the process water, 3m of water is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dripping the sulfuric acid solution containing the zinc source prepared in the step S3 at a dripping speed of per hour, and controlling the pH value of the reaction end point to be 9.0;
s5, turning on heatingThe device slowly increases the temperature of the reaction tank, continuously and simultaneously dropwise adds the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank, controls the pH value in the process to be 9.0, continuously dropwise adds the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controls the pH value at the end point to be 4.5, and carries out aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 93 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the finished product silicon dioxide.
The present comparative example is different from example 1 in that polyethylene glycol PEG2000 is not added in step S3, and the rest is the same as example 1.
Comparative example 4
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.25wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 0.3wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m into the reaction tank 3 After the process water, 3m of water is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 9.0;
s5, opening the heating device, slowly raising the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH in the process to be 9.0, after the dropwise adding of the preset amount of the sodium silicate solution is finished,continuously dropwise adding a sulfuric acid solution containing a zinc source to control the end point pH to be 4.5, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3; the temperature of the reaction tank is 93 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the finished product silicon dioxide.
The comparative example is different from example 1 in that zinc sulfate is added in an amount of 0.25wt% in step S3, and is otherwise the same as example 1.
Comparative example 5
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.25wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 6.5wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m into the reaction tank 3 After the process water, 3m of water is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 9.0;
s5, opening the heating device, slowly increasing the temperature of the reaction tank, continuously and simultaneously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.5, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the sodium silicateThe preset amount of the solution is 9m 3 (ii) a The temperature of the reaction tank is 93 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the finished product silicon dioxide.
The comparative example is different from example 1 in that zinc sulfate is added in an amount of 6.5wt% in step S3, and is otherwise the same as example 1.
Comparative example 6
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.03wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, and stirring to completely dissolve the polyethylene glycol PEG2000 to obtain a sulfuric acid solution for later use;
s4, adding 12m into the reaction tank 3 After the process water, 3m of water is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dripping the sulfuric acid solution prepared in the step S3 at a dripping speed of/h, and controlling the pH value of the reaction end point to be 9.0;
s5, opening the heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.5, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution is 5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 93 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the finished product silicon dioxide.
The comparative example is different from example 1 in that zinc sulfate is not added in step S3, and the rest is the same as example 1.
Comparative example 7
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.25wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 4.5wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m into the reaction tank 3 After the process water, 3m of water is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3 at the dropwise adding speed of/h, and controlling the pH of the reaction end point to be 9.0;
s5, opening a heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.5, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 85 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the finished product silicon dioxide.
The present comparative example is different from example 1 in that the pot temperature was slowly increased in step S5, and the pot temperature was 85 deg.c after the completion of the reaction, and the rest was the same as example 1.
Comparative example 8
S1, putting the solid sodium silicate with the modulus of 3.0 into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 1.5mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 3mol/L from the concentrated sulfuric acid solution, adding 0.25wt% of polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding 4.5wt% of zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding 12m of solution into a reaction tank 3 After the process water, 3m of water is added 3 The sodium silicate solution prepared in the step S2; heating to 70 deg.C, stirring at 28Hz and a speed of 3m 3 Dripping the sulfuric acid solution containing the zinc source prepared in the step S3 at a dripping speed of per hour, and controlling the pH value of the reaction end point to be 9.0;
s5, opening a heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 9.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the pH value at the end point to be 4.5, and aging after the reaction is finished; the dropping speed of the sulfuric acid solution containing the zinc source is 5m 3 H, the dropping speed of the sodium silicate solution is 14m 3 H; the preset amount of the sodium silicate solution is 9m 3 (ii) a The temperature of the reaction tank is 98 ℃ after the reaction is finished
S6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the finished product silicon dioxide.
The present comparative example is different from example 1 in that the pot temperature was slowly increased in step S5, and the pot temperature was 98 c after the completion of the reaction, and the rest was the same as example 1.
Experimental example A Performance test of silica for high temperature aging resistant Silicone rubber of the present invention
The silica prepared in examples 1 to 4 was tested for oil absorption value, specific surface area and apparent particle diameter (D50), and the results are shown in table 1.
The test method comprises the following steps:
determining the oil absorption value of the silica according to HG/T3072-2008;
measuring the BET specific surface area of the silicon dioxide according to GB/T19587-2017;
the particle size of the silica (D50) was determined according to GB/T32698-2016.
TABLE 1 Performance test results of silica products for high temperature aging resistant Silicone rubber of the present invention
As can be seen from Table 1, the specific surface area of the silica for high temperature aging resistant silicone rubber provided by the invention is 170-185m 2 The particle size of D50 is 10-14 μm, and the oil absorption value is 195-210mL/100 g. The silica for high-temperature aging resistant silicone rubber prepared in example 1 has the largest specific surface area and the highest oil absorption value, and is the best example of the present invention. The silicon dioxide for the high-temperature aging resistant silicon rubber prepared by the preparation method has the advantages of moderate specific surface area, high oil absorption value, small particle size and good comprehensive performance.
Experimental example II high temperature aging resistant Silicone rubber Performance test
1.1 test materials: silica for Silicone rubber prepared in examples 1-4 and comparative examples 1-8
1.2 test methods: the silicon dioxide for silicon rubber prepared by the embodiments 1 to 4 and the comparative examples 1 to 8 of the invention is prepared into silicon rubber, and the formula of the silicon rubber is as follows: 100 parts of raw rubber, 45 parts of the silica samples of examples 1 to 4 or comparative examples 1 to 8 and 3 parts of hydroxy silicone oil, wherein the silicon rubber is subjected to mixing by an internal mixer and vacuumizing, then 0.5% of bis-dipenta-vulcanizing agent is added for vulcanization, and a vulcanized rubber sheet is prepared for subsequent tests.
The test of the high-temperature aging property of the silicone rubber is carried out according to GB/T3512-2001 test of accelerated aging and heat resistance of vulcanized rubber or thermoplastic rubber by hot air, the performance of the silicone rubber prepared by the silica samples of examples 1-4 or comparative examples 1-8 of the invention is measured after aging at high temperature, and the performance is compared with the performance of the unaged testThen the obtained product is obtained. The degree of aging of the silicone rubber sample was determined by measuring the tensile strength, stress at definite elongation, elongation at break, hardness, and the like of the sample. And tested for rate of change of properties and change in hardness. The calculation formula of the performance change rate is as follows: p = (x) 1 -x 0 ）/x 0 X 100%, where P is the rate of change of property, x 1 As a measure of the properties of the sample after ageing, x 0 Is a performance measurement value before the sample is aged; the calculation formula of the hardness change is as follows: h = x 1 -x 0 Wherein H is a change in hardness, x 1 As a measure of the hardness of the sample after ageing, x 0 The hardness of the test piece before aging was measured.
The test was carried out using a hot air aging oven with a size of 800 × 580 × 1300 mm, a temperature of 225 ℃, an air flow rate of 0.5m/s, and a sample size of 130mm × 100mm, and after air blast aging for 72 hours, tensile strength, stress at definite elongation, elongation at break, and hardness were tested.
An electronic tensile testing machine is adopted to measure the tensile strength, purchased from Tulon, model/goods number QL-5E;
measuring the stress at definite elongation by using an electronic tensile testing machine, wherein the stress is purchased from Juilong, model/goods number QL-5E;
an electronic tensile testing machine is adopted to measure the elongation at break, and the elongation is purchased from Juilong, model/goods number QL-5E;
hardness was measured using a Shore LX-A durometer.
1.3 test results
TABLE 2 test results of mechanical properties at room temperature for unaged silicone rubber samples
TABLE 3 mechanical property test results of silicone rubber samples after high-temperature aging
TABLE 4225 ℃ mechanical property change result of silicone rubber after 72h of aging
As shown in tables 2-4, when the silicon dioxide for the high-temperature aging resistant silicone rubber is applied to the silicone rubber, the tensile strength change rate, the tear strength change rate and the elongation at break change rate are minimum after high-temperature aging, and the performance is kept to be optimal. The silica prepared in example 1 has the lowest change rate due to the synergistic effect of polyethylene glycol and zinc oxide, and is the best example of the invention. Therefore, the zinc oxide-doped silicon dioxide prepared by the preparation method can obviously improve the high-temperature aging resistance of the silicon rubber product.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the silicon dioxide for the high-temperature aging resistant silicone rubber is characterized by comprising the following steps:
s1, putting the solid sodium silicate into a closed container, adding process water, and reacting at high temperature and high pressure to obtain a sodium silicate solution;
s2, adding process water into the sodium silicate solution obtained in the step S1 for dilution and blending, and fully stirring to prepare the sodium silicate solution with the concentration of 0.5-2mol/L for later use;
s3, preparing a dilute sulfuric acid solution with the concentration of 1-4mol/L from the concentrated sulfuric acid solution, adding polyethylene glycol PEG2000 into the dilute sulfuric acid solution, stirring to completely dissolve the polyethylene glycol PEG2000, and adding zinc sulfate to obtain a sulfuric acid solution containing a zinc source for later use;
s4, adding process water into the reaction tank, and then adding the sodium silicate solution prepared in the step S2; heating to 60-75 ℃, starting stirring, dropwise adding the sulfuric acid solution containing the zinc source prepared in the step S3, and controlling the pH value of the reaction end point to be 8.0-10.0;
s5, opening a heating device, slowly increasing the temperature of the reaction tank, continuously dropwise adding the sodium silicate solution prepared in the step S2 and the sulfuric acid solution containing the zinc source prepared in the step S3 into the reaction tank at the same time, controlling the pH value in the process to be 8.0-10.0, continuously dropwise adding the sulfuric acid solution containing the zinc source after the dropwise adding of the preset amount of the sodium silicate solution is finished, controlling the final pH value to be 3.0-5.5, and aging after the reaction is finished;
s6, carrying out filter pressing washing, spray drying and crushing on the slurry aged in the step S5 to obtain the silicon dioxide for the high-temperature aging resistant silicon rubber.
2. The method of preparing the silica for high temperature aging-resistant silicone rubber according to claim 1, wherein the modulus of the solid sodium silicate in the step S1 is 3.0 to 3.5.
3. The method for preparing silica for high temperature aging resistant silicone rubber according to claim 1, wherein the amount of polyethylene glycol PEG2000 added in step S3 is 0.05 to 0.3 wt%.
4. The method for preparing silica for high temperature aging resistant silicone rubber according to claim 1, wherein the amount of zinc sulfate added in step S3 is 0.5 to 6 wt%.
5. The method for preparing silica for high temperature aging resistant silicone rubber according to claim 1, wherein the process water is added in an amount of 10 to 14m in step S4 3 The addition amount of the sodium silicate solution is 1-5m 3 。
6. The method for preparing silica for high temperature aging resistant silicone rubber according to claim 1, wherein the stirring speed in step S4 is 25 to 30Hz, and the dropping speed of the sulfuric acid solution containing the zinc source is 1 to 5m 3 /h。
7. According to claimThe preparation method of the silicon dioxide for the high-temperature aging resistant silicone rubber is characterized in that the dropping speed of the sulfuric acid solution containing the zinc source in the step S5 is 3-8m 3 H, the dropping speed of the sodium silicate solution is 12-16m 3 /h。
8. The method for preparing silica for high temperature aging resistant silicone rubber according to claim 1, wherein the predetermined amount of sodium silicate solution of step S5 is 7 to 11m 3 。
9. The method for preparing silica for high temperature aging resistant silicone rubber according to claim 1, wherein in step S5, the heating device is turned on, the temperature in the reaction tank is slowly increased and controlled to 90 to 95 ℃ at the end of the reaction.
10. Silica for high temperature aging resistant silicone rubber produced by the production method according to any one of claims 1 to 7.
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