CN112678837A - Anti-slippery precipitated silica, and preparation method and application thereof - Google Patents
Anti-slippery precipitated silica, and preparation method and application thereof Download PDFInfo
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- CN112678837A CN112678837A CN202011590509.8A CN202011590509A CN112678837A CN 112678837 A CN112678837 A CN 112678837A CN 202011590509 A CN202011590509 A CN 202011590509A CN 112678837 A CN112678837 A CN 112678837A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 83
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 64
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 239000010413 mother solution Substances 0.000 claims abstract description 20
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 238000007865 diluting Methods 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 105
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 24
- 239000004115 Sodium Silicate Substances 0.000 claims description 22
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 108090000765 processed proteins & peptides Proteins 0.000 claims 1
- 239000004636 vulcanized rubber Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 18
- 239000013078 crystal Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides anti-slippery precipitated silica, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing the water glass solution with sulfate to obtain a raw material mother solution; (2) diluting a water glass solution at constant temperature, and then adjusting the pH value to 7-8.5 to obtain a reaction base solution; (3) mixing a silane coupling agent mixed solution, a pH regulator, a raw material mother solution and a reaction bottom solution, and reacting after mixing to obtain a mixed reaction solution; (4) adjusting the pH value of the mixed reaction liquid obtained in the step (3) to 4-6 to obtain a precipitated silica suspension; (5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the step (1) and the step (2) are not in sequence; the tan delta value of the vulcanized rubber corresponding to the obtained anti-slippery precipitated silica at 0 ℃ is more than 0.23, and the anti-slippery precipitated silica has excellent anti-slippery performance.
Description
Technical Field
The invention belongs to the technical field of materials, relates to silicon dioxide and a preparation method and application thereof, and particularly relates to anti-slippery precipitated silicon dioxide and a preparation method and application thereof.
Background
Wet skid resistance is an important measure of tire driving safety, particularly in rainy and snowy days. For passenger vehicles, the wet skid resistance of tires is particularly important due to their high driving speed. In rainy days, when an automobile runs on a wet road surface, due to the existence of water, a layer of water film interval exists between the tire tread and the road surface, so that the wet gripping force of the tire is greatly reduced, and the running safety is influenced, therefore, the improvement of the wet skid resistance of the tire has important significance for guaranteeing the running safety of the automobile.
At present, various large tire manufacturing enterprises are investing a great deal of research and development force to develop anti-wet safety tires so as to achieve higher market share. Since the 1990 green tire concept was proposed, precipitated silica began to be applied to tire tread rubber instead of carbon black to improve the wet skid resistance of tires and reduce the rolling resistance of tires. Improvement in wet skid resistance of tires has still been achieved primarily by adding large amounts of precipitated silica to the tread rubber formulation. Therefore, the influence of the level of the wet skid resistance of the precipitated silica on the tire rubber is important.
In addition, the existence of silicon hydroxyl in the precipitated silica enables the silica to have strong polarity and easily form agglomeration, so that the dispersibility of the precipitated silica in rubber compounds is poor, and the application range of rubber is further influenced. The proper preparation method is selected for preparing the precipitated silica, so that the dispersibility of the precipitated silica and the compatibility of a rubber matrix are improved, and the application of the precipitated silica in the field of tires is facilitated.
CN 108946745A discloses a preparation method of modified precipitated silica and the modified precipitated silica prepared by the same, the preparation method of the modified precipitated silica comprises the steps of firstly adding a cationic surfactant into a water glass solution, heating to obtain a solution A, then adding sodium sulfate into the solution A for precipitation reaction, adjusting the pH value by using sulfuric acid in the reaction process, and aging after the reaction is finished to obtain the modified precipitated silica. According to the method, the cationic surfactant is added into the water glass solution, the cationic surfactant can carry positive charges after being dissolved in water, the negative charges on the surface of the precipitated silica can carry positive charges after being dissolved in water, and the negative charges on the surface of the precipitated silica can interact with the positive charges of the cationic surfactant, so that the coating modification effect is achieved, and the stability and the dispersibility of the precipitated silica are improved. However, the preparation method is not studied with respect to the wet skid resistance of the modified silica.
CN 104291345a discloses a precipitated silica with low silanol groups, a preparation method and a use thereof, wherein water glass and sulfuric acid are subjected to precipitation reaction, so as to obtain a suspension of the precipitated silica, and then the suspension is subjected to filter pressing and washing, slurrying processes and drying. Silanol group density of the resulting precipitated silica<4 per nm2(ii) a BET specific surface area of 100-2(ii)/g; CTAB of 95-205m2(ii)/g; the pH value is 5.5-7.5; the pore volume is 1.65-2.25cm3(ii)/g; the ultrasonic particle size D50 is 1-10 μm; the water content is 4-8%; the conductivity was 800-1200 μm/cm. The precipitated silica can be used as a reinforcing agent for tires, reduces the rolling resistance of tires, and improves the wear resistance. But also no study has been made to improve the wet skid resistance of tires.
CN 104291342a discloses a precipitated silica, a preparation method and a use thereof, wherein the preparation method comprises the steps of carrying out a precipitation reaction between water glass and concentrated sulfuric acid to obtain a suspension of the precipitated silica, and then carrying out filter pressing, washing, slurrying processes and drying the suspension. The obtained precipitated silica is spherical microbead silica and granular granulated silica. The BET specific surface area of the silica is 185-235m2(g) CTAB of 165-2Per g, pH 5.5-7.5, pore volume 1.65-2.25cm3The diameter of the most probable pore is 15-35nm, and the ultrasonic particle diameter D50 is 6-10 μm. The precipitated silica can be used as a reinforcing agent for tires, reduces the rolling resistance of tires, and improves the wear resistance. But likewise not for improving the tyreThe wet skid resistance of (2) was investigated.
Therefore, it is desirable to provide a precipitated silica capable of improving wet skid resistance of a tire.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the anti-slippery precipitated silica and the preparation method and application thereof, and the obtained anti-slippery precipitated silica has excellent anti-slippery performance, and the tan delta value of the vulcanized rubber corresponding to the anti-slippery precipitated silica at 0 ℃ is more than 0.23.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of anti-slippery precipitated silica, said process comprising the steps of:
(1) mixing the water glass solution with sulfate to obtain a raw material mother solution;
(2) diluting a water glass solution at constant temperature, and then adjusting the pH value to 7-8.5 to obtain a reaction base solution;
(3) mixing a silane coupling agent mixed solution, a pH regulator, a raw material mother solution and a reaction bottom solution, and reacting after mixing to obtain a mixed reaction solution;
(4) adjusting the pH value of the mixed reaction liquid obtained in the step (3) to 4-6 to obtain a precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed solution is a mixed solution of a silane coupling agent, ethanol and water.
According to the preparation method, the silicon dioxide seed crystal is firstly generated in the reaction base solution, then the silicon dioxide seed crystal is continuously grown on the basis of the seed crystal by mixing the silane coupling agent mixed solution, the pH regulator, the raw material mother solution and the reaction base solution, so that the molecular surface hydroxyl content of the obtained anti-slippery precipitated silicon dioxide is low, the secondary structure of the silicon dioxide grown from the seed crystal is looser, the silicon dioxide has a more developed three-dimensional network structure, the dispersion performance is better, and the anti-slippery performance of the obtained anti-slippery precipitated silicon dioxide is improved.
Preferably, the silane coupling agent is Si 747.
According to the invention, Si747 is firstly hydrolyzed in an alcohol water solution, and the hydrolyzed active silicon hydroxyl of the silane coupling agent is firstly self-condensed to form active oligosiloxane. And then hydrogen bonds are formed between active hydroxyl groups on the surface of the oligosiloxane and hydroxyl groups on the surface of the precipitated silica, so that the surface of the precipitated silica is covered by a silane coupling agent, further growth of precipitated silica molecules is prevented, and a larger agglomeration structure is prevented from being formed.
Preferably, the volume ratio of the silane coupling agent to the ethanol to the water in the silane coupling agent mixed solution is 1 (1-3) to 1; for example, the ratio may be 1:1:1, 1:1.5:1, 1:2:1, 1:2.5:1 or 1:3:1, but the present invention is not limited to the enumerated values, and other values not enumerated in the numerical range are also applicable.
When the amount of the silane coupling agent in the silane coupling agent mixed solution is too small, the concentration of the hydrolyzed active hydroxyl of the silane coupling agent is low, the bonding amount with the generated hydroxyl on the surface of the silicon dioxide is small, the dispersibility of the silicon dioxide is reduced due to the increase of the hydroxyl content, and the wet skid resistance of the silicon dioxide is reduced; if the dosage of the silane coupling agent in the silane coupling agent mixed solution is large, the concentration of active silicon hydroxyl after the silane coupling agent is hydrolyzed is large, and before the silane coupling agent is combined with the hydroxyl on the surface of silicon dioxide, self-condensation reaction is easy to generate, so that the waste of the silane coupling agent is caused, and the economy is low.
Preferably, the mass fraction of sodium silicate in the water glass solution in step (1) is 20-40 wt%, for example 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the sulfate in step (1) is anhydrous sodium sulfate.
Preferably, the concentration of sodium sulfate in the raw mother liquor obtained in step (1) is 3 to 8g/L, and may be, for example, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L or 8g/L, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the temperature for isothermal dilution in step (2) is 70-98 ℃, for example 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 98 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the mass fraction of sodium silicate in the water glass solution in step (2) is 20-40 wt%, for example 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the mass fraction of sodium silicate in the reaction base solution of step (2) is 5-15 wt%, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% or 15 wt%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the pH value is adjusted by using sulfuric acid with the concentration of 5-30 wt% in the step (2); the concentration of the sulfuric acid used for the adjustment in step (2) is 5 to 30% by weight, and may be, for example, 5%, 10%, 15%, 20%, 25% or 30% by weight, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the sulfuric acid is uniformly dropped during the pH value adjustment in the step (2), and the dropping time is 10-20min, for example, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min or 20min, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the mixing in step (3) is to drop the silane coupling agent mixed solution, the pH adjusting agent and the raw material mother solution into the reaction base solution simultaneously.
The invention adopts a method of dripping simultaneously, can lead the mixing to be carried out smoothly and can ensure the pH value and the temperature to be constant in the mixing process.
Preferably, the pH regulator is sulfuric acid with a concentration of 5-30 wt%; the concentration of the pH regulator is 5 to 30% by weight, and may be, for example, 5%, 10%, 15%, 20%, 25% or 30% by weight, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the amount of the pH adjuster added is such that the pH during the mixing in step (3) is maintained at 7-8.5, for example, 7, 7.2, 7.5, 7.8, 8, 8.1, 8.4 or 8.5, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the amount of the silane coupling agent mixture is 2 to 10 wt% of the raw material mother liquor, for example, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature of the mixing in step (3) is 70-98 ℃, for example 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 98 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the reaction temperature in step (3) is 70-98 ℃, for example 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 98 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable; the time is 30-60min, for example 30min, 35min, 40min, 45min, 50min, 55min or 60min, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the adjustment in the step (4) is performed by using sulfuric acid with a concentration of 5-30 wt%; the concentration of sulfuric acid is from 5 to 30% by weight, and may be, for example, 5%, 10%, 15%, 20%, 25% or 30% by weight, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Preferably, the post-treatment of step (5) comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out.
The solid-liquid separation, washing, slurrying and drying are all conventional means in the field, and can be reasonably set by a person skilled in the art according to needs, and the invention is not particularly limited. Specifically, the operations of solid-liquid separation, washing, slurrying and drying in the post-treatment include, but are not limited to, pressure filtration, washing, slurrying and drying disclosed in CN 104291342 a.
As a preferable technical solution of the preparation method of the first aspect, the preparation method comprises the steps of:
(1) mixing the water glass solution with anhydrous sodium sulfate to obtain a raw material mother liquor with the concentration of sodium sulfate of 3-8 g/L; the mass fraction of the sodium silicate in the water glass solution is 20-40 wt%;
(2) diluting 20-40 wt% water glass solution at constant temperature of 70-98 deg.C, and regulating pH to 7-8.5 with 5-30 wt% sulfuric acid to obtain 5-15 wt% sodium silicate reaction base solution; dropwise adding sulfuric acid at a constant speed in the process of adjusting the pH value, wherein the dropwise adding time is 10-20 min;
(3) simultaneously dripping the silane coupling agent mixed solution, 5-30 wt% sulfuric acid and the raw material mother solution into the reaction base solution for mixing at 70-98 ℃, and reacting at 70-98 ℃ for 30-60min after dripping to obtain a mixed reaction solution; the addition amount of the sulfuric acid is to maintain the pH value of 7-8.5 in the dropping process;
(4) regulating the pH value of the mixed reaction liquid obtained in the step (3) to 4-6 by using sulfuric acid with the concentration of 5-30 wt% to obtain a precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the post-treatment comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed liquid is a mixed liquid of a silane coupling agent Si747, ethanol and water, and the volume ratio of the silane coupling agent Si747 to the ethanol to the water is 1 (1-3) to 1.
In a second aspect, the present invention provides a wet skid resistant precipitated silica obtained by the method of the first aspect.
In a third aspect, the present invention provides the use of the anti-skid precipitated silica as described in the second aspect as a tire reinforcement
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method, the silicon dioxide seed crystal is firstly generated in the reaction base solution, then the silicon dioxide seed crystal is continuously grown on the basis of the seed crystal by mixing the silane coupling agent mixed solution, the pH regulator, the raw material mother solution and the reaction base solution, so that the molecular surface hydroxyl content of the obtained anti-slippery precipitated silicon dioxide is low, the secondary structure of the silicon dioxide grown from the seed crystal is looser, the silicon dioxide has a more developed three-dimensional network structure, the dispersion performance is better, and the anti-slippery performance of the obtained anti-slippery precipitated silicon dioxide is improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
This example provides a method for preparing anti-slippery precipitated silica, comprising the steps of:
(1) mixing the water glass solution with anhydrous sodium sulfate to obtain a raw material mother liquor with the concentration of the sodium sulfate of 5 g/L; the mass fraction of the sodium silicate in the water glass solution is 30 wt%;
(2) diluting a 30 wt% water glass solution at a constant temperature of 85 ℃, and then adjusting the pH value to 7.5 by using 20 wt% sulfuric acid to obtain a reaction base solution with the mass fraction of sodium silicate of 10 wt%; dropwise adding sulfuric acid at a constant speed in the process of adjusting the pH value, wherein the dropwise adding time is 15 min;
(3) simultaneously dripping the silane coupling agent mixed solution, the sulfuric acid with the concentration of 20 wt% and the raw material mother solution into the reaction base solution for mixing under the condition of maintaining the constant temperature of 85 ℃, and reacting at 85 ℃ for 45min after dripping is finished to obtain mixed reaction solution; the addition amount of the sulfuric acid is to maintain the pH value of 7.5 in the dropping process;
(4) adjusting the pH value of the mixed reaction liquid obtained in the step (3) to 5 by using sulfuric acid with the concentration of 20 wt% to obtain a precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the post-treatment comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed liquid is a mixed liquid of a silane coupling agent Si747, ethanol and water, and the volume ratio of the silane coupling agent Si747 to the ethanol to the water is 1:2: 1.
Example 2
This example provides a method for preparing anti-slippery precipitated silica, comprising the steps of:
(1) mixing the water glass solution with anhydrous sodium sulfate to obtain a raw material mother liquor with the concentration of sodium sulfate of 4 g/L; the mass fraction of the sodium silicate in the water glass solution is 25 wt%;
(2) diluting a 25 wt% water glass solution at a constant temperature of 80 ℃, and then adjusting the pH value to 7.5 by using 10 wt% sulfuric acid to obtain a reaction base solution with the mass fraction of sodium silicate of 8 wt%; dropwise adding sulfuric acid at a constant speed in the process of adjusting the pH value, wherein the dropwise adding time is 12 min;
(3) simultaneously dripping the silane coupling agent mixed solution, sulfuric acid with the concentration of 10 wt% and the raw material mother solution into the reaction base solution for mixing under the condition of maintaining the constant temperature of 80 ℃, and reacting at 80 ℃ for 50min after dripping is finished to obtain mixed reaction solution; the addition amount of the sulfuric acid is to maintain the pH value of 7.5 in the dropping process;
(4) regulating the pH value of the mixed reaction liquid obtained in the step (3) to be 4.5 by using sulfuric acid with the concentration of 10 wt% to obtain precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the post-treatment comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed liquid is a mixed liquid of a silane coupling agent Si747, ethanol and water, and the volume ratio of the silane coupling agent Si747 to the ethanol to the water is 1:2: 1.
Example 3
This example provides a method for preparing anti-slippery precipitated silica, comprising the steps of:
(1) mixing the water glass solution with anhydrous sodium sulfate to obtain a raw material mother liquor with the concentration of the sodium sulfate of 6 g/L; the mass fraction of the sodium silicate in the water glass solution is 35 wt%;
(2) diluting 35 wt% water glass solution at constant temperature of 90 ℃, and then adjusting the pH value to 8 by using 25 wt% sulfuric acid to obtain 12 wt% sodium silicate reaction base solution; dropwise adding sulfuric acid at a constant speed in the process of adjusting the pH value, wherein the dropwise adding time is 18 min;
(3) simultaneously dripping the silane coupling agent mixed solution, 25 wt% sulfuric acid and the raw material mother solution into the reaction base solution for mixing under the condition of maintaining the constant temperature of 80 ℃, and reacting at 90 ℃ for 40min after dripping is finished to obtain mixed reaction solution; the addition amount of the sulfuric acid is to maintain the pH value of 8 in the dropping process;
(4) regulating the pH value of the mixed reaction liquid obtained in the step (3) to 5.5 by using 25 wt% sulfuric acid to obtain a precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the post-treatment comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed liquid is a mixed liquid of a silane coupling agent Si747, ethanol and water, and the volume ratio of the silane coupling agent Si747 to the ethanol to the water is 1:2: 1.
Example 4
This example provides a method for preparing anti-slippery precipitated silica, comprising the steps of:
(1) mixing the water glass solution with anhydrous sodium sulfate to obtain a raw material mother liquor with the concentration of sodium sulfate of 3 g/L; the mass fraction of the sodium silicate in the water glass solution is 20 wt%;
(2) diluting a 20 wt% water glass solution at a constant temperature of 70 ℃, and then adjusting the pH value to 8.5 by using 5 wt% sulfuric acid to obtain a reaction base solution with the mass fraction of sodium silicate of 5 wt%; dropwise adding sulfuric acid at a constant speed in the process of adjusting the pH value, wherein the dropwise adding time is 10 min;
(3) simultaneously dripping the silane coupling agent mixed solution, 5 wt% sulfuric acid and the raw material mother solution into the reaction base solution for mixing under the condition of maintaining a constant temperature of 70 ℃, and reacting at 70 ℃ for 60min after dripping is finished to obtain a mixed reaction solution; the addition amount of the sulfuric acid is to maintain the pH value of 8.5 in the dropping process;
(4) adjusting the pH value of the mixed reaction liquid obtained in the step (3) to 6 by using sulfuric acid with the concentration of 5 wt% to obtain precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the post-treatment comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed liquid is a mixed liquid of a silane coupling agent Si747, ethanol and water, and the volume ratio of the silane coupling agent Si747 to the ethanol to the water is 1:1: 1.
Example 5
This example provides a method for preparing anti-slippery precipitated silica, comprising the steps of:
(1) mixing the water glass solution with anhydrous sodium sulfate to obtain a raw material mother liquor with the concentration of the sodium sulfate of 8 g/L; the mass fraction of the sodium silicate in the water glass solution is 40 wt%;
(2) diluting a 40 wt% water glass solution at a constant temperature of 98 ℃, and then adjusting the pH value to 7 by using 30 wt% sulfuric acid to obtain a reaction base solution with the mass fraction of sodium silicate of 15 wt%; dropwise adding sulfuric acid at a constant speed in the process of adjusting the pH value, wherein the dropwise adding time is 20 min;
(3) simultaneously dripping the silane coupling agent mixed solution, sulfuric acid with the concentration of 30 wt% and the raw material mother solution into the reaction bottom solution for mixing under the condition of maintaining the constant temperature of 98 ℃, and reacting at 98 ℃ for 30min after dripping is finished to obtain mixed reaction solution; the addition amount of the sulfuric acid is to maintain the pH value of 7 in the dropping process;
(4) adjusting the pH value of the mixed reaction liquid obtained in the step (3) to be 4 by using 30 wt% sulfuric acid to obtain a precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the post-treatment comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed liquid is a mixed liquid of a silane coupling agent Si747, ethanol and water, and the volume ratio of the silane coupling agent Si747 to the ethanol to the water is 1:3: 1.
Example 6
This example provides a method for preparing anti-slippery precipitated silica, which is the same as example 1, except that the silane coupling agent Si747, the volume ratio of ethanol to water is 0.5:2: 1.
Example 7
This example provides a method for preparing anti-slippery precipitated silica, which is the same as example 1 except that the silane coupling agent Si747, the volume ratio of ethanol to water is 1.5:2: 1.
Comparative example 1
This comparative example provides a method of preparing anti-slippery precipitated silica, comprising the steps of:
(1) taking a water glass solution with the sodium silicate concentration of 30 wt% as a raw material mother solution;
(2) diluting a 30 wt% water glass solution at a constant temperature of 85 ℃, and then adjusting the pH value to 7.5 by using 20 wt% sulfuric acid to obtain a reaction base solution with the mass fraction of sodium silicate of 10 wt%; dropwise adding sulfuric acid at a constant speed in the process of adjusting the pH value, wherein the dropwise adding time is 15 min;
(3) simultaneously dripping the silane coupling agent mixed solution, the sulfuric acid with the concentration of 20 wt% and the raw material mother solution into the reaction base solution for mixing under the condition of maintaining the constant temperature of 85 ℃, and reacting at 85 ℃ for 45min after dripping is finished to obtain mixed reaction solution; the addition amount of the sulfuric acid is to maintain the pH value of 7.5 in the dropping process;
(4) adjusting the pH value of the mixed reaction liquid obtained in the step (3) to 5 by using sulfuric acid with the concentration of 20 wt% to obtain a precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the post-treatment comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed liquid is a mixed liquid of a silane coupling agent Si747, ethanol and water, and the volume ratio of the silane coupling agent Si747 to the ethanol to the water is 1:2: 1.
Comparative example 2
The precipitated silica obtained in example 1 of CN 104291342 a.
Comparative example 3
The precipitated silica obtained in example 1 of CN 104291345 a.
The precipitated silicas provided in examples 1 to 7 and comparative examples 1 to 3 were prepared as vulcanizates in accordance with HG/T2404-2008 and tested for loss factor tan delta at 0 ℃ in accordance with GB/T13937-92.
The BET specific surface areas of the precipitated silicas provided in examples 1 to 7 and comparative examples 1 to 3 were determined in accordance with GB/T19587-2017; the CTAB specific surface areas of the precipitated silicas provided in examples 1 to 7 and comparative examples 1 to 3 were determined in accordance with GB/T23656-.
The test data of BET specific surface area, CTAB specific surface area, and loss factor tan δ at 0 ℃ are shown in table 1.
TABLE 1
The loss factor tan delta at 0 ℃ can be used to indicate the wet skid resistance, the greater the value of tan delta, the stronger the wet skid resistance. As can be seen from Table 1, the anti-slippery precipitated silica prepared according to the present invention has a loss factor tan delta of 0.23 or more at 0 ℃ and excellent anti-slippery properties.
In conclusion, according to the preparation method provided by the invention, the silica seed crystal is firstly generated in the reaction base solution, and then the mixed solution of the silane coupling agent, the pH regulator, the raw material mother solution and the reaction base solution are mixed to continue to grow on the basis of the seed crystal, so that the molecular surface hydroxyl content of the obtained anti-slippery precipitated silica is low, the secondary structure of the silica grown from the seed crystal is looser, the anti-slippery precipitated silica has a more developed three-dimensional network structure and better dispersion performance, the anti-slippery performance of the obtained anti-slippery precipitated silica is improved, and the loss factor tan delta of the anti-slippery precipitated silica at 0 ℃ is above 0.23.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing anti-slippery precipitated silica, comprising the steps of:
(1) mixing the water glass solution with sulfate to obtain a raw material mother solution;
(2) diluting a water glass solution at constant temperature, and then adjusting the pH value to 7-8.5 to obtain a reaction base solution;
(3) mixing a silane coupling agent mixed solution, a pH regulator, a raw material mother solution and a reaction bottom solution, and reacting after mixing to obtain a mixed reaction solution;
(4) adjusting the pH value of the mixed reaction liquid obtained in the step (3) to 4-6 to obtain a precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed solution is a mixed solution of a silane coupling agent, ethanol and water.
2. The production method according to claim 1, wherein the silane coupling agent is Si 747;
preferably, the volume ratio of the silane coupling agent to the ethanol to the water in the silane coupling agent mixed solution is 1 (1-3) to 1.
3. The preparation method according to claim 1 or 2, characterized in that the mass fraction of sodium silicate in the water glass solution in step (1) is 20-40 wt%;
preferably, the sulfate in step (1) is anhydrous sodium sulfate;
preferably, the concentration of sodium sulfate in the raw material mother liquor obtained in the step (1) is 3-8 g/L.
4. The method for preparing a peptide according to any one of claims 1 to 3, wherein the temperature for the isothermal dilution in the step (2) is 70 to 98 ℃;
preferably, the mass fraction of the sodium silicate in the water glass solution in the step (2) is 20-40 wt%;
preferably, the mass fraction of the sodium silicate in the reaction base solution in the step (2) is 5-15 wt%;
preferably, the pH value is adjusted by using sulfuric acid with the concentration of 5-30 wt% in the step (2);
preferably, the sulfuric acid is uniformly dripped in the process of adjusting the pH value in the step (2), and the dripping time is 10-20 min.
5. The preparation method according to any one of claims 1 to 4, wherein the mixing in step (3) is performed by adding the silane coupling agent mixture, the pH adjusting agent and the raw material mother liquor dropwise to the reaction base liquor simultaneously;
preferably, the pH regulator is sulfuric acid with a concentration of 5-30 wt%;
preferably, the pH regulator is added in an amount to maintain the pH value in the mixing process in the step (3) at 7-8.5;
preferably, the adding amount of the silane coupling agent mixed solution is 2-10 wt% of the raw material mother solution;
preferably, the temperature of the mixing in the step (3) is 70-98 ℃;
preferably, the reaction temperature of the step (3) is 70-98 ℃, and the time is 30-60 min.
6. The production method according to any one of claims 1 to 5, wherein the adjustment in the step (4) is performed using sulfuric acid having a concentration of 5 to 30 wt%.
7. The production method according to any one of claims 1 to 6, wherein the post-treatment of step (5) comprises solid-liquid separation, washing, slurrying and drying which are performed in this order.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) mixing the water glass solution with anhydrous sodium sulfate to obtain a raw material mother liquor with the concentration of sodium sulfate of 3-8 g/L; the mass fraction of the sodium silicate in the water glass solution is 20-40 wt%;
(2) diluting 20-40 wt% water glass solution at constant temperature of 70-98 deg.C, and regulating pH to 7-8.5 with 5-30 wt% sulfuric acid to obtain 5-15 wt% sodium silicate reaction base solution; dropwise adding sulfuric acid at a constant speed in the process of adjusting the pH value, wherein the dropwise adding time is 10-20 min;
(3) simultaneously dripping the silane coupling agent mixed solution, 5-30 wt% sulfuric acid and the raw material mother solution into the reaction base solution for mixing at 70-98 ℃, and reacting at 70-98 ℃ for 30-60min after dripping to obtain a mixed reaction solution; the addition amount of the sulfuric acid is to maintain the pH value of 7-8.5 in the dropping process;
(4) regulating the pH value of the mixed reaction liquid obtained in the step (3) to 4-6 by using sulfuric acid with the concentration of 5-30 wt% to obtain a precipitated silica suspension;
(5) post-treating the precipitated silica suspension obtained in the step (4) to obtain the anti-slippery precipitated silica; the post-treatment comprises solid-liquid separation, washing, slurrying and drying which are sequentially carried out;
the step (1) and the step (2) are not in sequence;
the silane coupling agent mixed liquid is a mixed liquid of a silane coupling agent Si747, ethanol and water, and the volume ratio of the silane coupling agent Si747 to the ethanol to the water is 1 (1-3) to 1.
9. A wet skid resistant precipitated silica obtainable by the process of any one of claims 1 to 8.
10. Use of the anti-slippery precipitated silica as defined in claim 9 as a tire reinforcement.
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