CN115386140B - Nanometer flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder and preparation method and application thereof - Google Patents
Nanometer flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of rubber reinforcement, in particular to nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder, and a preparation method and application thereof. The preparation method provided by the invention adopts the needle-shaped wollastonite and the flaky kaolin powder to be mixed, and the effective specific surface area of the needle-shaped wollastonite contacted with the rubber matrix can be increased due to the different morphology and properties of the needle-shaped wollastonite and the flaky kaolin powder, so that the mechanical property of butadiene rubber is improved. And when the needle-shaped/sheet-shaped structural powder is compounded and filled, the powder can be reinforced simultaneously along the X axis and the Y-Z plane direction during the mixing and molding of the sizing material, and the reinforcing effect is more excellent when the powder is added into butadiene rubber. Further, the hydroxy silicone oil has good compatibility with rubber molecules, so that the mechanical property and the wear resistance of the rubber product are improved. And the triethanolamine, the diisopropanolamine and the hydroxyl silicone oil are added for compound modification, and the modified powder is added into a rubber system, so that the anti-corrosion performance is excellent, and the service life of a rubber product can be prolonged.
Description
Technical Field
The invention relates to the technical field of rubber reinforcement, in particular to nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder, and a preparation method and application thereof.
Background
With the continuous development of the rubber industry, the demand for minerals as fillers is increasing. The development of novel mineral reinforcing agents plays an important role in reducing the production cost of rubber products. While research on inorganic mineral fillers today has gradually transitioned from single mineral reinforcement to composite mineral reinforcement, even multiple mineral hybrid reinforcement.
The physical properties of vulcanized rubber can be greatly improved by adding mineral mixtures with different forms, such as wollastonite, sericite and the like, into rubber. The surface modification and mixing of two or more inorganic mineral fillers can complicate the mechanism of the filler system and improve the surface activity of the powder and the compatibility of the powder with the rubber matrix. Inorganic mineral fillers with different structures, forms, chemical components and properties are organically combined, so that complementary advantages can be achieved when rubber is filled, the performance of the inorganic mineral powder filling rubber is optimized, the optimization degree is limited, and further improvement is needed.
Disclosure of Invention
The invention aims to provide nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder, and a preparation method and application thereof. The nano platy kaolin-wollastonite-hydroxyl silicone oil ternary composite powder prepared by the preparation method can greatly improve the mechanical property and heat resistance of vulcanized rubber, and can further reduce the cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder, which comprises the following steps:
after intercalation is carried out on the kaolin by adopting urea solution, the kaolin is first mixed with an organic dispersing agent to obtain nano flaky kaolin;
secondly mixing the nano flaky kaolin and water to obtain nano flaky kaolin slurry;
activating the nano flaky kaolin slurry by concentrated sulfuric acid, and then, performing third mixing with a cationic surfactant to perform first modification to obtain modified nano flaky kaolin;
mixing and grinding the pre-dispersed slurry of the modified nano flaky kaolin, the inorganic silicon source and the needle-shaped wollastonite to obtain a binary compound of the modified nano flaky kaolin-wollastonite;
and fourthly, mixing a composite modifier of triethanolamine and diisopropanolamine with the binary composite of the modified nano flaky kaolin-wollastonite, performing second modification, and adding hydroxyl silicone oil for aging to obtain the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder.
Preferably, the mass concentration of the urea solution is 75-85%;
the mass ratio of the kaolin to the urea solution is 1 (2-3);
the intercalation is carried out under the condition of grinding, the temperature of the grinding is 60-70 ℃, the rotating speed is 800-1000 rpm, and the time is 7.5-8.5 h.
Preferably, the organic dispersant is a cellulose derivative;
the mass ratio of the organic dispersant to the kaolin is (2-9) 100.
Preferably, the solid content of the nano flaky kaolin slurry is 15-30%;
the mass ratio of the nano flaky kaolin slurry to the concentrated sulfuric acid is 100 (5-7);
the activation temperature is 85-95 ℃ and the activation time is 3-4 h.
Preferably, the cationic surfactant comprises cetyltrimethylammonium bromide and/or octadecyl dimethylbenzyl ammonium chloride;
the mass ratio of the nano flaky kaolin slurry to the cationic surfactant is 100: (2-3);
the temperature of the first modification is 60-70 ℃ and the time is 20-30 min;
the specific surface area of the modified nano flaky kaolin is 120-130 m 2 /g。
Preferably, the solid content of the pre-dispersed slurry of the needle wollastonite is 45-60%;
the pre-dispersed slurry of the needle-shaped wollastonite comprises needle-shaped wollastonite, a pre-dispersing agent and water;
the pre-dispersion agent comprises sodium polyacrylate and/or phosphate; the mass ratio of the pre-dispersing agent to the needle-shaped wollastonite is (0.3-0.8): 100.
preferably, the mass ratio of the modified nano flaky kaolin to the needle-shaped wollastonite is (15-25): 100;
the ratio of the mass of the inorganic silicon source to the total mass of the modified nano flaky kaolin and the needle-like wollastonite is (0.8-1.3): 100;
the inorganic silicon source is sodium silicate.
Preferably, the mass ratio of the triethanolamine to the diisopropanolamine in the triethanolamine and diisopropanolamine composite modifier is (0.6-0.9): (0.3 to 0.7);
the mass ratio of the triethanolamine to the binary composite of the modified nano flaky kaolin-wollastonite is (0.6-0.9): 100;
the mass ratio of the diisopropanolamine to the binary composite of the modified nano flaky kaolin-wollastonite is (0.3-0.7): 100;
the mass ratio of the hydroxyl silicone oil to the binary composite of the modified nano flaky kaolin-wollastonite is (0.8-1.5): 100.
the invention also provides the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder prepared by the preparation method.
The invention also provides application of the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder in the field of rubber reinforcement.
The invention provides a preparation method of nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder, which comprises the following steps: after intercalation is carried out on the kaolin by adopting urea solution, the kaolin is first mixed with an organic dispersing agent to obtain nano flaky kaolin; secondly mixing the nano flaky kaolin and water to obtain nano flaky kaolin slurry; activating the nano flaky kaolin slurry by using concentrated sulfuric acid, and then, third mixing with a cationic surfactant, and performing first modification to obtain modified nano flaky kaolin; mixing and grinding the pre-dispersed slurry of the modified nano flaky kaolin, the inorganic silicon source and the needle-shaped wollastonite to obtain a binary compound of the modified nano flaky kaolin-wollastonite; and fourthly, mixing a composite modifier of triethanolamine and diisopropanolamine with the binary composite of the modified nano flaky kaolin-wollastonite, performing second modification, and adding hydroxyl silicone oil for aging to obtain the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) The invention adopts the needle-shaped wollastonite to be mixed with the platy kaolin, and because the two have different forms and different properties, the aggregate powder can be broken mutually, so that the maximum stacking volume (the ratio of the real volume of the filler to the occupied expression volume of the filler) reaches the extremum, thereby improving the effective specific surface area of the powder contacted with the rubber matrix and improving the mechanical property of the rubber when the powder is applied to the rubber;
2) According to the invention, needle-shaped wollastonite is mixed with platy kaolin, and needle-shaped/platy structural powder is simultaneously reinforced along the X-axis and Y-Z plane directions during mixing and molding of sizing materials during compound filling, so that the reinforcing effect is more excellent;
3) The invention adopts concentrated sulfuric acid and cationic surfactant to activate and modify the nano flaky kaolin in sequence, which can greatly increase the attachment points of needle wollastonite on the flaky kaolin, thereby enabling the maximum stacking volume to reach an extreme value;
4) The hydroxyl silicone oil is adopted to further modify the binary compound of the modified nano flaky kaolin-wollastonite, so that the finally prepared compound can have good compatibility with rubber molecules, and the mechanical property and the wear resistance of rubber products are further improved;
5) According to the invention, the modified powder is added into a rubber system through the synergistic modification of the composite modifier added with triethanolamine and diisopropanolamine and the hydroxyl silicone oil, so that the anti-corrosion performance is excellent, and the service life of a rubber product can be prolonged.
Detailed Description
The invention provides a preparation method of nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder, which comprises the following steps:
after intercalation is carried out on the kaolin by adopting urea solution, the kaolin is first mixed with an organic dispersing agent to obtain nano flaky kaolin;
secondly mixing the nano flaky kaolin and water to obtain nano flaky kaolin slurry;
activating the nano flaky kaolin slurry by using concentrated sulfuric acid, and then, third mixing with a cationic surfactant, and performing first modification to obtain modified nano flaky kaolin;
mixing and grinding the pre-dispersed slurry of the modified nano flaky kaolin, the inorganic silicon source and the needle-shaped wollastonite to obtain a binary compound of the modified nano flaky kaolin-wollastonite;
and fourthly, mixing a composite modifier of triethanolamine and diisopropanolamine with the binary composite of the modified nano flaky kaolin-wollastonite, performing second modification, and adding hydroxyl silicone oil for aging to obtain the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The invention adopts urea solution to intercalate the kaolin, and then the intercalated kaolin is first mixed with organic dispersant to obtain nano flaky kaolin.
In the present invention, the particle size of the kaolin is preferably 1.5 to 2.5. Mu.m.
In the invention, the kaolin is preferably prepared by a preparation process, and the preparation process of the kaolin preferably comprises the steps of coarsely crushing raw kaolin ores by a jaw crusher, then feeding the crushed raw kaolin ores into a ring roller mill, drying and grinding the crushed raw kaolin to about 400-500 meshes, and sieving the crushed raw kaolin by a 450-mesh sieve.
In the present invention, the urea solution preferably has a mass concentration of 75 to 85%, more preferably 78 to 82%. In the present invention, the mass ratio of the kaolin to the urea solution is preferably 1 (2 to 3), more preferably 1 (2.3 to 2.6).
In the present invention, the intercalation is preferably carried out under milling conditions, preferably assisted by ultrasound during the milling process; the temperature of the grinding is preferably 60-70 ℃, more preferably 60 ℃, and the rotating speed is preferably 800-1000 rpm, more preferably 800-900 rpm; the time is preferably 7.5 to 8.5 hours, more preferably 7.5 hours. The frequency of the ultrasound is preferably 60kHz. In the present invention, the grinding is preferably performed in a mill. In the present invention, under the above intercalation condition, the intercalation rate of the intercalation can reach 90%.
In the present invention, the organic dispersant is preferably a cellulose derivative; the cellulose derivative is preferably methylcellulose and/or hydroxypropyl methylcellulose; when the cellulose derivative is methyl cellulose and hydroxypropyl cellulose, the ratio of the methyl cellulose to the hydroxypropyl cellulose is not particularly limited, and the cellulose derivative and the hydroxypropyl cellulose are mixed according to any ratio.
In the present invention, the mass ratio of the organic dispersant to the kaolin is preferably (2 to 9): 100, more preferably (3 to 8): 100, most preferably (4 to 7): 100.
in the present invention, the first mixing is preferably performed under stirring, and the stirring process is not particularly limited, and may be performed by a process well known to those skilled in the art.
After the first mixing is completed, the invention also preferably comprises sequentially drying and grinding; the temperature of the drying is preferably 90 ℃ and the time is preferably 4 hours; the drying is preferably carried out in a drying oven. In the present invention, the grinding is preferably carried out in a mill, the rotation speed of the mill is preferably 1000rpm, the time is preferably 1h, and the feeding amount is preferably 0.8L/min.
After the nano flaky kaolin is obtained, the nano flaky kaolin and water are mixed for the second time to obtain nano flaky kaolin slurry.
The process of the second mixing is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the solid content of the nano flaky kaolin slurry is preferably 15 to 30%, more preferably 18 to 28%, and most preferably 20 to 23%.
After the nano flaky kaolin slurry is obtained, the invention adopts concentrated sulfuric acid to activate the nano flaky kaolin slurry, and then the nano flaky kaolin slurry is mixed with a cationic surfactant for the first modification, thus obtaining the modified nano flaky kaolin.
The concentration of the concentrated sulfuric acid is not particularly limited in the present invention, and may be any concentration known to those skilled in the art.
In the invention, the mass ratio of the nano flaky kaolin slurry to the concentrated sulfuric acid is preferably 100: (5 to 7), more preferably 100: (5.5 to 6.5), most preferably 100: (5.8-6.2).
In the present invention, the temperature of the activation is preferably 85 to 95 ℃, more preferably 95 ℃, and the time is preferably 3 to 4 hours, more preferably 3 hours. In the present invention, the activation process is preferably to add the concentrated sulfuric acid to the nano flaky kaolin slurry and then to place the mixture in a drying oven for activation.
In the present invention, the cationic surfactant preferably includes cetyltrimethylammonium bromide and/or octadecyl dimethylbenzyl ammonium chloride; when the cationic surfactant comprises cetyltrimethylammonium bromide and octadecyl dimethylbenzyl ammonium chloride, the mixture ratio of the cetyltrimethylammonium bromide and the octadecyl dimethylbenzyl ammonium chloride is not particularly limited, and the mixture ratio is mixed according to any mixture ratio.
In the invention, the mass ratio of the nano flaky kaolin slurry to the cationic surfactant is preferably 100: (2-3), more preferably 100: (2.2 to 2.8), most preferably 100: (2.3-2.5).
In the present invention, the third mixing is preferably to add the cationic surfactant to the product system obtained after the activation.
In the present invention, the first modification is preferably performed under stirring, and the stirring process is not particularly limited, and may be performed by a process well known to those skilled in the art. In the present invention, the temperature of the first modification is preferably 60 to 70 ℃, more preferably 60 ℃, and the time is preferably 20 to 30min, more preferably 20min.
After the first modification is finished, the invention also preferably comprises azeotropic distillation treatment, drying and depolymerization and break-up which are sequentially carried out; the process of the azeotropic distillation treatment is not particularly limited, and may be performed by a process known to those skilled in the art. The drying temperature is preferably 120 ℃ and the drying time is preferably 30min; the process of depolymerizing and scattering is not particularly limited, and the specific surface area of the obtained modified nano flaky kaolin is 120-130 m by adopting the process well known to the skilled in the art 2 The ratio/g is in the range.
After the modified nano flaky kaolin is obtained, the modified nano flaky kaolin, an inorganic silicon source and needle-shaped wollastonite pre-dispersed slurry are mixed and ground to obtain a binary compound of the modified nano flaky kaolin and the needle-shaped wollastonite.
In the present invention, the inorganic silicon source is preferably sodium silicate. In the present invention, the ratio of the mass of the inorganic silicon source to the total mass of the modified nano flaky kaolin and needle wollastonite is preferably (0.8 to 1.3): 100, more preferably (0.9 to 1.2): 100, most preferably (1.0 to 1.1): 100.
in the present invention, the solid content of the pre-dispersed slurry of the needle wollastonite is preferably 45 to 60%, more preferably 48 to 56%, most preferably 50 to 53%; the pre-dispersed slurry of the needle-shaped wollastonite preferably comprises needle-shaped wollastonite, a pre-dispersing agent and water; the pre-dispersion preferably comprises sodium polyacrylate and/or phosphate; when the pre-dispersion agent comprises sodium polyacrylate and phosphate, the proportion of the sodium polyacrylate and the phosphate is not limited in any particular way, and the sodium polyacrylate and the phosphate are mixed according to any proportion. In the invention, the mass ratio of the pre-dispersing agent to the needle-shaped wollastonite is preferably (0.3-0.8): 100, more preferably (0.4 to 0.7): 100, most preferably (0.5 to 0.6): 100. in the present invention, the needle-like wollastonite pre-dispersion slurry is preferably prepared by a process which preferably comprises mixing needle-like wollastonite, a pre-dispersion agent and water. In the present invention, the needle-like wollastonite preferably has a size of 300 to 400 mesh, more preferably 320 to 380 mesh, and most preferably 330 to 350 mesh. In the invention, the needle-shaped wollastonite is preferably prepared by a preparation process, wherein the preparation process of the needle-shaped wollastonite preferably comprises the steps of coarsely crushing wollastonite raw ore by a jaw crusher, then, feeding the coarse wollastonite raw ore into a ring roller mill, drying and grinding the coarse wollastonite raw ore to about 400-500 meshes, and sieving the coarse wollastonite raw ore by a 450-mesh sieve. The mixing is not particularly limited in this invention, and may be carried out by a process well known to those skilled in the art.
In the invention, the mass ratio of the modified nano flaky kaolin to the needle-like wollastonite is preferably (15-25): 100, more preferably (18 to 22): 100.
in the invention, the process of mixing and grinding is preferably that the pre-dispersed slurry of the needle-shaped wollastonite is firstly ground to 15-25 mu m, and then the modified nano flaky kaolin and the inorganic silicon source are added for continuous grinding. In the present invention, the rotation speed of the continuous grinding is preferably 800 to 1000rpm, more preferably 850 to 950rpm, and most preferably 880 to 920rpm; the feed rate is preferably 1 to 2t/h, more preferably 1.2 to 1.8t/h, most preferably 1.4 to 1.6t/h.
After the mixed grinding is finished, the invention also preferably comprises sieving and drying which are sequentially carried out; in the present invention, the sieving is preferably a 450 mesh sieve. In the present invention, the drying is preferably performed in a constant temperature microwave cyclone device; the temperature of the microwave drying is preferably 105-109 ℃, more preferably 106-108 ℃; the blowing speed is preferably 25 to 35m/s, more preferably 28 to 32m/s; the time is preferably 70 minutes.
After the binary compound of the modified nano flaky kaolin-wollastonite is obtained, the composite modifier of triethanolamine and diisopropanolamine is fourth mixed with the binary compound of the modified nano flaky kaolin-wollastonite, hydroxyl silicone oil is added for aging after the second modification, and the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder is obtained.
In the invention, the mass ratio of the triethanolamine to the diisopropanolamine in the triethanolamine and diisopropanolamine composite modifier is preferably (0.6-0.9): (0.3 to 0.7), more preferably (0.7 to 0.8): (0.4-0.6).
In the invention, the mass ratio of the triethanolamine to the binary composite of the modified nano flaky kaolin-wollastonite is preferably (0.6 to 0.9): 100, more preferably (0.7 to 0.8): 100; the mass ratio of the diisopropanolamine to the binary composite of the modified nano flaky kaolin-wollastonite is preferably (0.3-0.7): 100, more preferably (0.4 to 0.6): 100.
in the present invention, the second modification is preferably performed under stirring; the rotational speed of the stirring is not particularly limited in the present invention, and may be carried out by a process well known to those skilled in the art. In the present invention, the temperature of the stirring is preferably 30℃and the time is preferably 30 minutes.
After the second modification is finished, the invention also preferably comprises the steps of dropwise adding a sulfuric acid solution with the mass concentration of 12% for pH value adjustment and aging after the temperature of the obtained product system is raised to 85 ℃; the adjusted pH is preferably 9.8; the dripping time of the sulfuric acid solution is preferably less than or equal to 40min. In the present invention, the aging is preferably standing for 30 minutes.
After the aging is completed, the present invention also preferably adds an acid to the resulting system to a pH of 4.7. The kind of the acid is not particularly limited in the present invention, and may be any kind known to those skilled in the art. In the present invention, the acid addition time is preferably not more than 30 minutes.
In the invention, the mass ratio of the hydroxyl silicone oil to the binary composite of the modified nano flaky kaolin-wollastonite is preferably (0.8-1.5): 100, more preferably (0.9 to 1.3): 100, most preferably (1.0 to 1.2): 100.
in the present invention, the aging time after adding the hydroxyl silicone oil is preferably 1 hour.
After the aging is finished, the invention also preferably comprises washing and drying which are sequentially carried out; the washing agent adopted by the washing is preferably ethanol, and the washing times are preferably more than or equal to 1; the drying process is not particularly limited, and may be performed by a process known to those skilled in the art.
After the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder is obtained, the invention also preferably comprises sieving and packaging which are sequentially carried out; the sieving is not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art; the packaging is preferably carried out using an automatic packaging machine.
The invention also provides the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder prepared by the preparation method.
The invention also provides application of the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder in the field of rubber reinforcement. The method of the present invention is not particularly limited, and may be carried out by a process well known to those skilled in the art.
The nano platy kaolin-wollastonite-hydroxyl silicone oil ternary composite powder, the preparation method and the application thereof provided by the invention are described in detail below by combining examples, but the nano platy kaolin-wollastonite-hydroxyl silicone oil ternary composite powder is not to be construed as limiting the protection scope of the invention.
Example 1
Coarse crushing raw kaolin ore and raw wollastonite ore respectively by a jaw crusher, then feeding the coarse kaolin ore and the raw wollastonite ore into a ring roller mill for drying and grinding to about 400-500 meshes, and sieving the coarse kaolin ore and the raw wollastonite ore by a 450-mesh sieve to obtain coarse kaolin powder (the particle size is 22 μm) and coarse needle-like wollastonite powder (the particle size is 25 μm);
mixing 1000g of kaolin coarse powder and 2500g of urea solution with the mass concentration of 76%, adding 20g of cellulose derivative (the cellulose derivative is cellulose acetate butyrate), stirring and dispersing, preserving heat for 4 hours at 90 ℃ in a drying box, and grinding and stirring (the rotation speed of a adopted grinding machine is 1000rpm, the time is 1 hour, and the feeding amount is 0.8L/min) to obtain nano flaky kaolin;
mixing the nano flaky kaolin and water to obtain nano flaky kaolin slurry with the solid content of 16%;
adding 52g of concentrated sulfuric acid with the mass concentration of 97% into 1000g of the nano flaky kaolin slurry, placing the mixture in a drying oven, preserving heat for 3 hours at the temperature of 95 ℃, adding 21g of hexadecyl trimethyl ammonium bromide, stirring for 20 minutes at the temperature of 60 ℃, performing azeotropic distillation treatment, drying for 30 minutes at the temperature of 120 ℃, depolymerizing and scattering to obtain the nano flaky kaolin with the specific surface area of 127m 2 Modified nano platy kaolin per gram;
mixing 450g of needle-shaped wollastonite coarse powder, 3g of pre-dispersing agent (the pre-dispersing agent is sodium polyacrylate) and 1000g of water to obtain pre-dispersing slurry of the needle-shaped wollastonite;
after the needle-shaped wollastonite pre-dispersion powder slurry is sent to a grinder to be ground to 20 mu m, 70g of modified nano flaky kaolin and 5g of sodium silicate are added to be ground for 1h, sieving is carried out, and drying is carried out in a constant-temperature microwave cyclone device (the temperature of microwave drying is 106 ℃, the air supply speed is 28m/s and the time is 70 min), so as to obtain a binary compound of the modified nano flaky kaolin-wollastonite;
mixing 500g of the binary compound of the modified nano flaky kaolin-wollastonite and a compound modifier comprising 3.5g of triethanolamine and 2g of diisopropanolamine, stirring for 30min at 30 ℃, heating to 85 ℃, dripping sulfuric acid with the mass concentration of 12% at a constant speed within 40min, adjusting the pH value to 9.8, aging for 30min, adding acid within 30min until the pH value of the system is 4.7, adding 5g of hydroxyl silicone oil, aging for 1h, washing for 8 times by ethanol, drying, screening by a 400-mesh sieve, collecting, and packaging by an automatic packaging machine to obtain the ternary compound powder of the nano flaky kaolin-wollastonite-hydroxyl silicone oil;
different batches of samples of the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder were tested, and the test results are shown in table 1:
TABLE 1 Properties of the ternary composite powder of nano flaky Kaolin-wollastonite-hydroxy silicone oil
| Batch of | 1 | 2 | 3 | 4 | 5 |
| Whiteness degree | 97.3 | 97.7 | 97.3 | 97.4 | 97.1 |
| Oil absorption value/mL/100 g | 35 | 34 | 35 | 34 | 34 |
| D97/μm | 3.46 | 3.42 | 3.41 | 3.43 | 3.45 |
| D50/μm | 1.73 | 1.69 | 1.71 | 1.68 | 1.65 |
| BET specific surface area/m 2 /g | 12.89 | 12.85 | 12.83 | 12.87 | 12.81 |
| Degree of activation/% | 98.75 | 98.79 | 98.73 | 98.81 | 98.82 |
As shown in Table 1, the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder prepared in different batches has stable indexes and meets the technical requirement indexes.
Example 2
Coarse crushing raw kaolin ore and raw wollastonite ore respectively by a jaw crusher, then feeding the coarse kaolin ore and the raw wollastonite ore into a ring roller mill for drying and grinding to about 400-500 meshes, and sieving the coarse kaolin ore and the raw wollastonite ore by a 450-mesh sieve to obtain coarse kaolin powder (the particle size is 23 μm) and coarse needle-like wollastonite powder (the particle size is 24 μm);
mixing 1000g of kaolin coarse powder and 2400g of urea solution with the mass concentration of 79%, adding 40g of cellulose derivative (the cellulose derivative is cellulose acetate butyrate), stirring and dispersing, preserving heat for 4 hours at 90 ℃ in a drying box, and grinding and stirring (the rotation speed of a adopted grinding machine is 1000rpm, the time is 1 hour, and the feeding amount is 0.8L/min) to obtain nano flaky kaolin;
mixing the nano flaky kaolin and water to obtain nano flaky kaolin slurry with the solid content of 21 wt%;
adding 60g of concentrated sulfuric acid with the mass concentration of 97% into 1000g of the nano flaky kaolin slurry, placing the mixture in a drying oven, preserving heat for 3 hours at the temperature of 95 ℃, adding 23g of hexadecyl trimethyl ammonium bromide, stirring for 20 minutes at the temperature of 60 ℃ at the constant temperature, drying for 30 minutes at the temperature of 120 ℃ after azeotropic distillation treatment, depolymerizing and scattering to obtain the nano flaky kaolin with the specific surface area of 125m 2 Modified nano platy kaolin per gram;
mixing 500g of needle-shaped wollastonite coarse powder, 2g of pre-dispersing agent (the pre-dispersing agent is phosphate) and 1000g of water to obtain pre-dispersing slurry of the needle-shaped wollastonite;
after the needle-shaped wollastonite pre-dispersion powder slurry is sent to a grinder to be ground to 20 mu m, 100g of modified nano flaky kaolin and 6g of sodium silicate are added to be ground for 1.5 hours, the mixture is sieved and dried in a constant-temperature microwave cyclone device (the temperature of microwave drying is 107 ℃, the air supply speed is 29m/s and the time is 70 min), and a binary compound of the modified nano flaky kaolin-wollastonite is obtained;
mixing 500g of the binary compound of the modified nano flaky kaolin-wollastonite and a compound modifier comprising 3g of triethanolamine and 2.5g of diisopropanolamine, stirring for 30min at 30 ℃, heating to 85 ℃, dripping sulfuric acid with the mass concentration of 12% at a constant speed within 40min, adjusting the pH value to 9.8, aging for 30min, adding acid within 30min until the pH value of the system is 4.7, adding 6g of hydroxyl silicone oil, aging for 1h, washing for 9 times by ethanol, drying, screening by a 400-mesh sieve, collecting, and packaging by an automatic packaging machine to obtain the ternary compound powder of the nano flaky kaolin-wollastonite-hydroxyl silicone oil;
samples of different batches of the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder were tested, and the test results are shown in table 2:
TABLE 2 Properties of the nano flaky kaolin-wollastonite-hydroxy silicone oil ternary composite powder of different batches
| Batch of | 1 | 2 | 3 | 4 | 5 |
| Whiteness degree | 97.6 | 97.3 | 97.5 | 97.7 | 97.3 |
| Oil absorption value/mL/100 g | 34 | 35 | 35 | 35 | 34 |
| D97/μm | 3.52 | 3.47 | 3.46 | 3.48 | 3.43 |
| D50/μm | 1.77 | 1.71 | 1.69 | 1.68 | 1.73 |
| BET specific surface area/m 2 /g | 12.82 | 12.81 | 12.85 | 12.79 | 12.76 |
| Degree of activation/% | 98.76 | 98.69 | 98.71 | 98.77 | 98.61 |
As shown in Table 2, the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder prepared in different batches has stable indexes and meets the technical requirement indexes.
Example 3
Coarse crushing raw kaolin ore and raw wollastonite ore respectively by a jaw crusher, then feeding the coarse kaolin ore and the raw wollastonite ore into a ring roller mill for drying and grinding to about 400-500 meshes, and sieving the coarse kaolin ore and the raw wollastonite ore by a 350-mesh sieve to obtain coarse kaolin powder (the particle size is 24 μm) and coarse needle-like wollastonite powder (the particle size is 23 μm);
mixing 1000g of kaolin coarse powder and 2800g of urea solution with the mass concentration of 81%, adding 60g of cellulose derivative (the cellulose derivative is cellulose acetate butyrate), stirring and dispersing, preserving heat for 4 hours at 90 ℃ in a drying box, and grinding and stirring (the rotation speed of a adopted grinding machine is 1000rpm, the time is 1 hour, and the feeding amount is 0.8L/min) to obtain nano flaky kaolin;
mixing the nano flaky kaolin and water to obtain nano flaky kaolin slurry with the solid content of 26 wt%;
70g of a concentration with a mass concentration of 97% is added into 1000g of the nano flaky kaolin slurryPlacing sulfuric acid in a drying oven, maintaining the temperature at 95deg.C for 3 hr, adding 27g hexadecyl trimethyl ammonium bromide, stirring at 60deg.C for 20min, azeotropic distilling, drying at 120deg.C for 30min, depolymerizing and scattering to obtain a specific surface area of 121m 2 Modified nano platy kaolin per gram;
mixing 600g of needle-shaped wollastonite coarse powder, 3g of pre-dispersing agent (the pre-dispersing agent is sodium polyacrylate) and 1000g of water to obtain pre-dispersing slurry of the needle-shaped wollastonite;
after the needle-shaped wollastonite pre-dispersion powder slurry is sent to a grinder to be ground to 20 mu m, 120g of modified nano flaky kaolin and 9g of sodium silicate are added to be ground for 2 hours, sieving is carried out, and drying is carried out in a constant-temperature microwave cyclone device (the temperature of microwave drying is 108 ℃, the air supply speed is 30m/s and the time is 70 min), so as to obtain a binary compound of the modified nano flaky kaolin-wollastonite;
mixing 500g of the binary compound of the modified nano flaky kaolin-wollastonite and a compound modifier comprising 4g of triethanolamine and 3.5g of diisopropanolamine, stirring for 30min at 30 ℃, heating to 85 ℃, dripping sulfuric acid with the mass concentration of 12% at a constant speed within 40min, adjusting the pH value to 9.8, aging for 30min, adding acid within 30min until the pH value of the system is 4.7, adding 7g of hydroxyl silicone oil, aging for 1h, washing for 10 times by ethanol, drying, screening by a 400-mesh sieve, collecting, and packaging by an automatic packaging machine to obtain the ternary compound powder of the nano flaky kaolin-wollastonite-hydroxyl silicone oil;
samples of different batches of the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder were tested, and the test results are shown in table 3:
TABLE 3 Properties of the nano flaky kaolin-wollastonite-hydroxy silicone oil ternary composite powder of different batches
As shown in Table 3, the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder prepared in different batches has stable indexes and meets the technical requirement indexes.
Application examples 1 to 3
The formula comprises the following components: 100 parts by weight of butadiene rubber, 30 parts by weight of nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder in any one of examples 1 to 3, 3.5 parts by weight of stearic acid, 1.5 parts by weight of accelerator DM, 1.5 parts by weight of anti-aging agent RD, 5 parts by weight of paraffin oil and 2 parts by weight of sulfur (wherein, the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder in example 1 corresponds to application example 1, example 2 corresponds to application example 2 and example 3 corresponds to application example 3);
the preparation method of the styrene-butadiene rubber comprises the following steps: mixing the raw materials in the formula, and then sequentially carrying out mixing (the temperature is 55 ℃ for 15 min) and vulcanization (the temperature is 170 ℃ for 20 min) to obtain the cis-butadiene styrene rubber.
Comparative application example 1
The formula comprises the following components: 100 parts of butadiene rubber, 30 parts of white carbon black, 3.5 parts of stearic acid, 1.5 parts of accelerator DM, 1.5 parts of anti-aging agent RD, 5 parts of paraffin oil and 2 parts of sulfur;
the preparation method of the styrene-butadiene rubber comprises the following steps: mixing the raw materials in the formula, and then sequentially carrying out mixing (the temperature is 55 ℃ for 15 min) and vulcanization (the temperature is 170 ℃ for 20 min) to obtain the cis-butadiene styrene rubber.
Comparative application example 2
The formula comprises the following components: 100 parts of butadiene rubber, 30 parts of common wollastonite, 3.5 parts of stearic acid, 1.5 parts of accelerator DM, 1.5 parts of anti-aging agent RD, 5 parts of paraffin oil and 2 parts of sulfur;
the preparation method of the styrene-butadiene rubber comprises the following steps: mixing the raw materials in the formula, and then sequentially carrying out mixing (the temperature is 55 ℃ for 15 min) and vulcanization (the temperature is 170 ℃ for 20 min) to obtain the cis-butadiene styrene rubber.
Test case
The tensile stress strain and the series strength properties of the cis-butadiene rubber described in application example 1 and comparative application examples 1-2 were tested according to the national standard GB/T528-2009;
the abrasion index of the cis-butadiene rubber described in application example 1 and comparative application examples 1 to 2 was measured using an acle abrasion tester according to the national standard GB/T1689-2014;
the test results are shown in table 4:
TABLE 4 Performance parameters of cis-styrene butadiene rubber described in application example 1 and comparative application examples 1 to 2
As can be seen from Table 4, the nano platy kaolin-wollastonite-hydroxyl silicone oil ternary composite powder prepared by the invention is added into butadiene rubber, needle-shaped wollastonite is adopted to be mixed with platy kaolin powder, the needle-shaped wollastonite is different in form and property, the effective specific surface area of the powder in contact with a rubber matrix is improved, white carbon black and common wollastonite are obtained by comparing the same proportion, and the mechanical property of the butadiene rubber is improved. And when the needle-shaped/sheet-shaped structural powder is compounded and filled, the powder can be reinforced simultaneously along the X axis and the Y-Z plane direction during the mixing and molding of the sizing material, and the reinforcing effect is more excellent when the powder is added into butadiene rubber. Further adopts hydroxyl silicone oil for modification, and the obtained modified acicular wollastonite-nano kaolin composite powder has good compatibility with rubber molecules, so that the mechanical property and the wear resistance of rubber products are improved. And the triethanolamine, the diisopropanolamine and the hydroxyl silicone oil are added for compound modification, and the modified powder is added into a rubber system, so that the anti-corrosion performance is excellent, and the service life of a rubber product can be prolonged.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder is characterized by comprising the following steps of:
after intercalation is carried out on the kaolin by adopting urea solution, the kaolin is first mixed with an organic dispersing agent to obtain nano flaky kaolin; the organic dispersing agent is a cellulose derivative;
secondly mixing the nano flaky kaolin and water to obtain nano flaky kaolin slurry;
activating the nano flaky kaolin slurry by using concentrated sulfuric acid, and then, third mixing with a cationic surfactant, and performing first modification to obtain modified nano flaky kaolin;
mixing and grinding the pre-dispersed slurry of the modified nano flaky kaolin, the inorganic silicon source and the needle-shaped wollastonite to obtain a binary compound of the modified nano flaky kaolin-wollastonite; the inorganic silicon source is sodium silicate;
fourthly, mixing a composite modifier of triethanolamine and diisopropanolamine with the binary composite of the modified nano flaky kaolin-wollastonite for the second modification, and adding hydroxyl silicone oil for aging to obtain ternary composite powder of the nano flaky kaolin-wollastonite-hydroxyl silicone oil;
the mass ratio of the modified nano flaky kaolin to the needle-shaped wollastonite is (15-25): 100;
the mass ratio of the hydroxyl silicone oil to the binary composite of the modified nano flaky kaolin-wollastonite is (0.8-1.5): 100.
2. the preparation method of claim 1, wherein the mass concentration of the urea solution is 75-85%;
the mass ratio of the kaolin to the urea solution is 1 (2-3);
the intercalation is carried out under the condition of grinding, the temperature of the grinding is 60-70 ℃, the rotating speed is 800-1000 rpm, and the time is 7.5-8.5 h.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the organic dispersant to the kaolin is (2-9): 100.
4. The preparation method of claim 1, wherein the nano flaky kaolin slurry has a solid content of 15-30%;
the mass ratio of the nano flaky kaolin slurry to the concentrated sulfuric acid is 100 (5-7);
the activation temperature is 85-95 ℃ and the activation time is 3-4 hours.
5. The method of preparation of claim 1 or 4, wherein the cationic surfactant comprises cetyltrimethylammonium bromide and/or octadecyl dimethylbenzyl ammonium chloride;
the mass ratio of the nano flaky kaolin slurry to the cationic surfactant is 100: (2-3);
the temperature of the first modification is 60-70 ℃ and the time is 20-30 min;
the specific surface area of the modified nano flaky kaolin is 120-130 m 2 /g。
6. The method of claim 1, wherein the needle wollastonite pre-dispersion slurry has a solids content of 45 to 60%;
the pre-dispersed slurry of the needle-shaped wollastonite comprises needle-shaped wollastonite, a pre-dispersing agent and water;
the pre-dispersion agent comprises sodium polyacrylate and/or phosphate; the mass ratio of the pre-dispersing agent to the needle-shaped wollastonite is (0.3-0.8): 100.
7. the method of claim 6, wherein the ratio of the mass of the inorganic silicon source to the total mass of the modified nano-platy kaolin and needle-like wollastonite is (0.8 to 1.3): 100.
8. the preparation method of claim 1, wherein the mass ratio of triethanolamine to diisopropanolamine in the triethanolamine and diisopropanolamine composite modifier is (0.6-0.9): (0.3 to 0.7);
the mass ratio of the triethanolamine to the binary composite of the modified nano flaky kaolin-wollastonite is (0.6-0.9): 100;
the mass ratio of the diisopropanolamine to the binary composite of the modified nano platy kaolin-wollastonite is (0.3-0.7): 100.
9. the nano flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder prepared by the preparation method of any one of claims 1-8.
10. The use of the nano platy kaolin-wollastonite-hydroxyl silicone oil ternary composite powder according to claim 9 in the field of rubber reinforcement.
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