Organic modification of layered inorganic nanomaterials and rubber composites under acidic conditions and their preparation methods
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HAINAN NATURAL RUBBER IND GROUP
- Filing Date
- 2026-05-09
- Publication Date
- 2026-06-30
Smart Images
Figure CN122302597A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer composite materials technology, specifically relating to an organically modified layered inorganic nanomaterial, a rubber composite material, and a preparation method thereof under acidic conditions. Background Technology
[0002] Nanoclay is an important layered inorganic nanomaterial, showing great potential as a widely available and inexpensive nanofiller for polymer reinforcement. However, due to the thermodynamic incompatibility between the inherent hydrophilicity of its layered structure and the hydrophobicity of the rubber matrix, it is difficult to achieve uniform nanoscale dispersion of clay in the rubber matrix, and the interfacial bonding is weak.
[0003] Existing processes for preparing nano-clay rubber mainly include emulsion flocculation and co-current acid coagulation. Emulsion flocculation results in low water solubility of clay, limited nano-content, and numerous impurities, thus limiting material properties. Co-current acid coagulation suffers from low production efficiency, uneven dispersion leading to incomplete coagulation, significant clay loss during pressing and dehydration, and unstable product quality. Neither method fundamentally solves the two core scientific problems of "interfacial compatibility" and "nano-dispersion stability" between clay and rubber, nor does it achieve the crucial process of "synchronous curing" of the filler and the rubber matrix.
[0004] Chinese patent CN108503906A discloses a three-phase blending method in which organically modified nano-clay, natural fresh rubber latex, and coagulating acid are simultaneously flowed into a coagulation tank. This method solves the problem of long coagulation time and makes the nano-clay more uniformly dispersed. However, this method cannot effectively solve the interfacial compatibility between nano-clay and rubber. In addition, during the three-phase co-flow coagulation process, the coagulation processes of butyl pyridine latex and natural rubber latex influence each other, which may lead to incomplete coagulation or unstable coagulation process, thereby affecting the dispersion stability of nano-clay in the rubber matrix.
[0005] Therefore, the field needs to fundamentally solve the two core scientific problems of "interfacial compatibility" and "nano-dispersion stability" between nano-clay and rubber, effectively improve the dispersibility and compatibility of nano-clay in rubber matrix, solve problems such as incomplete solidification and serious clay loss during creping, and further improve the relevant properties of nano-clay rubber composites. Summary of the Invention
[0006] Based on this, the purpose of this invention is to provide an organically modified layered inorganic nanomaterial, a rubber composite material, and a preparation method thereof under acidic conditions, which can effectively solve the two core scientific problems of "interfacial compatibility" and "nano-dispersion stability" between layered inorganic nanomaterials and rubber, and improve the relevant properties of rubber composite materials.
[0007] To achieve the above objectives, the present invention adopts the following technical solution.
[0008] In a first aspect, the present invention provides an organically modified layered inorganic nanomaterial, obtained by modifying the layered inorganic nanomaterial with a polymer latex containing pyridine or nitrogen-containing aromatic rings under acidic conditions.
[0009] In some embodiments, the dry basis mass ratio of the layered inorganic nanomaterial to the polymer latex containing pyridine or nitrogen-containing aromatic rings is 1:(0.8-1.4).
[0010] In some embodiments, the dry basis mass ratio of the layered inorganic nanomaterial to the polymer latex containing pyridine or nitrogen-containing aromatic rings is 1:(0.8-1.2).
[0011] In some embodiments, the pH value of the acidic conditions is 4.8-5.2.
[0012] In some embodiments, the polymer latex containing pyridine or nitrogen-containing aromatic rings is selected from at least one of styrene-butadiene pyridine latex, pyridine-containing nitrile butadiene rubber latex, pyridine-modified natural latex, pyridine-styrene-butadiene-pyridine terpolymer latex, and pyridine-isoprene rubber latex.
[0013] In some embodiments, the polymer latex containing pyridine or nitrogen-containing aromatic rings is styrene-butadiene pyridine latex.
[0014] In some embodiments, the layered inorganic nanomaterial is nanoclay, preferably at least one of montmorillonite and bentonite.
[0015] In some embodiments, the acidic conditions are provided by at least one of organic acids, inorganic acids, acidic salts, and acidic buffer systems.
[0016] In some embodiments, the acidic conditions are provided by formic acid and / or acetic acid.
[0017] In some embodiments, the formic acid has a mass concentration of 0.2%-0.8%, and the acetic acid has a mass concentration of 1%-2%.
[0018] A second aspect of the present invention provides a method for preparing the organically modified layered inorganic nanomaterials as described above, comprising the following steps: (1) Mix the polymer latex of pyridine or aza-aromatic ring and the dispersion of layered inorganic nanomaterials evenly; (2) Add an acid regulator to the mixture in step (1) to adjust the pH value to 4.8-5.2, and then react at 20℃-35℃ for 25min-30min; (3) The reactants obtained in step (2) are homogenized or subjected to cell wall disruption treatment to obtain the final product.
[0019] In some embodiments, the solid content of the polymer latex containing pyridine or nitrogen-containing aromatic rings is 6%-12%.
[0020] In some embodiments, the mass concentration of the dispersion of the layered inorganic nanomaterial is 3%-6%.
[0021] In some embodiments, the homogenization pressure is 200-500 bar, and the time is 5-20 minutes.
[0022] In some embodiments, the cell disruption speed is 8000 r / min-12000 r / min, and the time is 20 s-60 s.
[0023] A third aspect of the present invention provides the application of the organically modified layered inorganic nanomaterials described above in the preparation of rubber composite materials.
[0024] In a fourth aspect, the present invention provides a rubber composite material prepared from the organically modified layered inorganic nanomaterials, natural fresh latex and coagulant as described above, in a mass ratio of (4-6):(100-120):(7.5-12.5); wherein the natural fresh latex is calculated as dry rubber.
[0025] In some embodiments, the mass ratio of the organically modified layered inorganic nanomaterial, natural fresh latex, and coagulant is (4-6):100:(7.5-12.5).
[0026] In some embodiments, the mass concentration of the coagulating acid is 0.3%-1.0%.
[0027] In some embodiments, the coagulating acid is selected from at least one of formic acid, acetic acid, and sulfuric acid.
[0028] A fifth aspect of the present invention provides a method for preparing the rubber composite material as described above, comprising the following steps: mixing a dispersion of the organically modified layered inorganic nanomaterial with natural fresh rubber latex, and then co-flowing it with the coagulating acid in two phases for coagulation and curing, thereby obtaining the final product.
[0029] In some embodiments, the solidification temperature is 20°C-35°C.
[0030] In some embodiments, the solidification temperature is 25°C-35°C.
[0031] Compared with the prior art, the present invention has the following beneficial effects.
[0032] This invention, based on extensive research, discovered that by premixing styrene-butadiene pyridine latex of appropriate mass concentration with layered inorganic nanomaterials through stirring, followed by the addition of acid, and by appropriate acidification, the pyridine groups of the latex are fully protonated to generate strong cationic properties. This allows the pyridine groups of the styrene-butadiene pyridine latex to intercalate into the interior of the layered inorganic nanomaterials with positive charges, thus undergoing cation exchange. Effective ion exchange and intercalation adsorption occur between the styrene-butadiene pyridine latex and the layered inorganic nanomaterials. After further treatment by cell disruption or homogenization, organically modified layered inorganic nanomaterials with expanded interlayer spacing and oleophilic surfaces are obtained. The nanomaterials undergo a transformation from hydrophilic to hydrophobic, fundamentally solving the interfacial compatibility problem.
[0033] When the organically modified layered inorganic nanomaterials are blended with rubber, they hydrophobically bond with the rubber molecular chains, avoiding the polarity problem after direct wet mixing, coagulation and drying of hydrophilic materials, as well as the problem of local agglomeration of materials after long-term use of masterbatch. This effectively solves the problems of dispersion and interfacial compatibility of layered inorganic nanomaterials, significantly reduces the filler loss rate, and ultimately obtains high-performance, highly consistent rubber composite materials. Attached Figure Description
[0034] Figure 1 This is a representative diagram illustrating the preparation of the organically modified layered inorganic nanomaterials of this invention.
[0035] Figure 2 A representative diagram illustrating the preparation of the rubber composite material of this invention. Detailed Implementation
[0036] The experimental methods described in the following embodiments of the present invention, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer.
[0037] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention.
[0038] The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, apparatus, product, or device that includes a series of steps is not limited to the steps or modules listed, but may optionally include steps not listed, or may optionally include other steps inherent to such process, method, product, or device.
[0039] The term "and / or" as used in this invention describes the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can represent three situations: A exists alone, A and B exist simultaneously, and B exists alone.
[0040] The following description is based on specific implementation methods.
[0041] All commonly used chemical reagents used in the following examples are commercially available products. Among them, the layered inorganic nanomaterial is nano-bentonite, purchased from Changchun Liu Fangzi Aisike Bentonite Co., Ltd., with the trade name OT55; the butadiene-pyridine latex is purchased from Zibo Zhangdian Dongfang Chemical Co., Ltd., with the trade name high-pyridine latex.
[0042] Example 1 This embodiment provides a rubber composite material, which is prepared by the following method: (1) Preparation of organically modified layered inorganic nanomaterials: The nano-bentonite was prepared at a mass concentration of 12.5%. The nano-bentonite was mixed with water and stirred in a reactor at 1200 rpm for 2 hours to form a nano-bentonite aqueous dispersion. After sedimentation, the upper dispersion was diluted with water to a concentration of 5% and pumped to a 10% concentration butadiene-pyridine latex (initial concentration of 40%, the same below) mixing tank to obtain a mixed solution. The dry matrix of the nano-bentonite aqueous dispersion and the butadiene-pyridine latex was controlled. The ratio of the two solutions is 5:5. A 0.4% formic acid solution is added under low-speed stirring at 750 rpm until the pH of the mixture reaches 5.0. Nano-bentonite and butyl-pyridine latex undergo an organic reaction in an acidic environment at 30°C for 26 minutes to obtain an organically modified nano-bentonite slurry. The modified nano-bentonite slurry is then added to a blender and dispersed at 10,000 rpm for 30 seconds to obtain a dispersion of organically modified layered inorganic nanomaterials.
[0043] (2) Two-phase blending: The dispersion of the prepared organic modified layered inorganic nanomaterials is mixed evenly with natural fresh latex and then coagulated with coagulant acid in a two-phase flow, and coagulated and cured at 30°C; the coagulant acid is a formic acid solution with a mass concentration of 0.50% and the mass ratio of the organic modified layered inorganic nanomaterials (based on the dry basis weight of the prepared organic modified layered inorganic nanomaterials dispersion, the same below) to natural fresh latex and coagulant acid is 5:100:10, wherein the natural fresh latex is based on dry latex.
[0044] Example 2 This embodiment provides a rubber composite material, which is prepared by the following method: (1) Preparation of organically modified layered inorganic nanomaterials: The nano-bentonite was prepared with a mass concentration of 15%. The nano-bentonite was mixed with water and stirred in a reactor at 1500 rpm for 1.5 h to form a nano-bentonite aqueous dispersion. After sedimentation, the upper dispersion was diluted with water to a concentration of 5% and pumped to a 10% concentration butadiene-pyridine latex mixing tank to obtain a mixed solution. The dry basis mass ratio of the nano-bentonite aqueous dispersion to butadiene-pyridine latex was controlled to be 5:4. A 0.4% formic acid solution was added under low-speed stirring at 750 rpm until the pH of the mixed solution was 5.0. The nano-bentonite and butadiene-pyridine latex underwent an organic reaction in an acidic environment at a reaction temperature of 25℃ for 28 min to obtain an organically modified nano-bentonite slurry. The modified nano-bentonite slurry was added to a wall-breaking machine and dispersed at 10000 rpm for 30 s to obtain a dispersion of organically modified layered inorganic nanomaterials.
[0045] (2) Two-phase blending: The dispersion of organically modified layered inorganic nanomaterials is mixed evenly with natural fresh latex and then coagulated with coagulant acid in a two-phase flow, and coagulated and cured at an ambient temperature of 25°C; the coagulating acid is a sulfuric acid solution with a mass concentration of 0.50%, and the mass ratio of organically modified layered inorganic nanomaterials to natural fresh latex and coagulating acid is 5:100:12, wherein the natural fresh latex is calculated as dry latex.
[0046] Example 3 This embodiment provides a rubber composite material, which is prepared by the following method: (1) Preparation of organically modified layered inorganic nanomaterials: The nano-bentonite was prepared with a mass concentration of 10%. The nano-bentonite was mixed with water and stirred in a reactor at 1400 rpm for 1 h to form a nano-bentonite aqueous dispersion. After sedimentation, the upper dispersion was diluted with water to a concentration of 5% and pumped to a 10% concentration butadiene-pyridine latex mixing tank to obtain a mixed solution. The dry basis mass ratio of the nano-bentonite aqueous dispersion to butadiene-pyridine latex was controlled to be 5:5. A 0.4% formic acid solution was added under low-speed stirring at 750 rpm until the pH of the mixed solution was 4.9. The nano-bentonite and butadiene-pyridine latex underwent an organic reaction in an acidic environment at a reaction temperature of 35℃ for 25 min to obtain an organically modified nano-bentonite slurry. The modified nano-bentonite slurry was added to a wall-breaking machine and dispersed at 10000 rpm for 30 s to obtain a dispersion of organically modified layered inorganic nanomaterials.
[0047] (2) Two-phase blending: The dispersion of organically modified layered inorganic nanomaterials is mixed evenly with natural fresh latex and then coagulated with coagulant acid in a two-phase flow, and coagulated and matured at an ambient temperature of 35°C; the coagulating acid is an acetic acid solution with a mass concentration of 0.50%, and the mass ratio of organically modified layered inorganic nanomaterials to natural fresh latex and coagulating acid is 5:100:8, wherein the natural fresh latex is calculated as dry latex.
[0048] The two-phase blending and co-flowing device is equipped with a mixing chamber. The natural fresh latex, which is a dispersion of organically modified layered inorganic nanomaterials, and coagulating acid are mixed evenly in the mixing chamber by impact. Then, the mixture flows into the coagulation tank through the co-flowing pipe, thereby improving the coagulation and mixing efficiency.
[0049] Example 4 This embodiment provides a rubber composite material, the preparation method of which is the same as that of Example 3, except that the dry basis mass ratio of nano-bentonite aqueous dispersion to butyl pyridine latex is controlled at 5:7 when preparing organically modified layered inorganic nanomaterials.
[0050] Example 5 This embodiment provides a rubber composite material, the preparation method of which is the same as that of Example 3, except that the mass ratio of organic modified layered inorganic nanomaterials to natural fresh rubber latex and coagulating acid is 5:120:8.
[0051] Example 6 This embodiment provides a rubber composite material, the preparation method of which is the same as that of Example 3, except that the solidification environment temperature is 20°C.
[0052] Comparative Example 1 This comparative example provides a rubber composite material, which is prepared by the following method: (1) Preparation of organically modified layered inorganic nanomaterials: The nano-bentonite was prepared with a mass concentration of 10%. The nano-bentonite was mixed with water and stirred in a reactor at 1400 rpm for 1 h to form a nano-bentonite aqueous dispersion. After sedimentation, the upper dispersion was diluted with water to a concentration of 5% and pumped into a 10% concentration butadiene-pyridine latex mixing tank. The dry basis mass ratio of the nano-bentonite aqueous dispersion to the butadiene-pyridine latex was controlled to be 5:5. The nano-bentonite and butadiene-pyridine latex underwent an organic reaction to obtain a dispersion of organically modified layered inorganic nanomaterials.
[0053] (2) Two-phase blending: Same as in Example 3.
[0054] Comparative Example 2 This comparative example provides a rubber composite material, which is prepared by the following method: (1) Preparation of organically modified layered inorganic nanomaterials: The nano-bentonite was prepared with a mass concentration of 10%. The nano-bentonite was mixed with water and stirred in a reactor at 1400 rpm for 1 h to form a nano-bentonite aqueous dispersion. After sedimentation, the upper dispersion was diluted with water to a concentration of 5% and pumped into a 10% concentration butadiene-pyridine latex mixing tank. The dry basis mass ratio of the nano-bentonite aqueous dispersion to the butadiene-pyridine latex was controlled to be 5:5. The nano-clay and butadiene-pyridine latex underwent an organic reaction to obtain a dispersion of organically modified layered inorganic nanomaterials.
[0055] (2) Three-phase blending: The dispersion of organic modified layered inorganic nanomaterials, natural fresh latex and coagulating acid are simultaneously flowed into the coagulation tank, and the three phases collide and mix. Under the condition of an ambient temperature of 35°C, the mixture is allowed to solidify. Other raw materials besides the dispersion of organic modified layered inorganic nanomaterials and the amount of each raw material are the same as in Example 3.
[0056] Comparative Example 3 This comparative example provides a rubber composite material, the preparation method of which is the same as in Example 3, except that the mass concentration of the nano-bentonite aqueous dispersion pumped into the butadiene-pyridine latex mixing tank is 12%.
[0057] Comparative Example 4 This comparative example provides a rubber composite material, which is the same as in Example 3 except that the pH value of the mixture in the nano-bentonite aqueous dispersion and the butadiene-pyridine latex mixing tank is 6.5 when a 0.4% formic acid solution is added.
[0058] Figure 1 This is a representative diagram illustrating the preparation of the organically modified layered inorganic nanomaterials of this invention.
[0059] Figure 2 A representative diagram illustrating the preparation of the rubber composite material of this invention.
[0060] The quality of the rubber composite materials prepared by blending the above embodiments and comparative examples was tested.
[0061] Tensile strength, elongation at break, and stress at 300% constant elongation are tested according to GB / T 528-2009; tear strength is tested according to GB / T 529-2008; ash content is tested according to GB / T 4498; and Akron abrasion is tested according to GB / T 1689-2014. Coagulation time: the time it takes for the latex to break down into granules and form a complete gel block. Cut resistance: the vulcanized sample is placed in a rubber dynamic cutting tester and continuously cut for 20 minutes at an impact speed of 120 rpm and a wheel speed of 720 rpm. The sample mass is weighed before and after the test, and the cutting mass is obtained by calculating the difference in mass before and after cutting. The percentage of weight loss is calculated using the following formula, and the percentage of weight loss characterizes the material's cut resistance. The test results are shown in Table 1.
[0062] Table 1 As shown in Table 1, the rubber composite material prepared by this invention has the characteristics of short solidification time, excellent mechanical properties, and good wear resistance. Taking Example 3 as an example, its solidification time is only 19 min, which is significantly shorter than the 1.6 h, 2.3 h, 1.8 h, and 50 min of Comparative Examples 1-4, indicating that the method of this invention can significantly improve the solidification efficiency of the rubber system. Meanwhile, the tensile strength of the rubber composite material obtained in Example 3 reaches 29.4 MPa, and the tear strength is 55 kN / m, both significantly better than the rubber composite materials obtained in the comparative examples, indicating that the organically modified layered inorganic nanomaterials of this invention are more uniformly dispersed in the rubber matrix, and the interfacial bonding is stronger. Furthermore, the Akron abrasion of Example 3 is 0.73 cm. 3 With a wear resistance of 1.06 km and a cutting performance of 8.52%, both exhibiting good wear resistance and cutting resistance.
[0063] Compared to Example 3, in Example 4, when preparing the organically modified layered inorganic nanomaterials, the dry basis mass ratio of the layered inorganic nanomaterials to butyl pyridine latex was 5:7. The relatively increased proportion of butyl pyridine latex reduced the effective loading of the layered inorganic nanomaterials in the rubber matrix, thus weakening the reinforcing effect of the rubber composite material. This manifested as a decrease in tensile strength from 29.4 MPa to 27.2 MPa, a decrease in tear strength from 55 kN / m to 54 kN / m, and a slight decrease in cutting performance. This indicates that the dry basis mass ratio of the layered inorganic nanomaterials to butyl pyridine latex affects the relevant properties of the final rubber composite material. In this invention, the dry basis mass ratio of the layered inorganic nanomaterials to the polymer latex containing pyridine or nitrogen-containing aromatic rings is 1:(0.8-1.4), preferably 1:(0.8-1.2), which ensures that the rubber composite material has good performance.
[0064] Compared to Example 3, in Example 5, the mass ratio of organically modified layered inorganic nanomaterials, natural fresh rubber latex, and coagulating acid is 5:120:8. The increased proportion of natural fresh rubber latex reduces the relative content of layered inorganic nanomaterials in the rubber matrix, thereby weakening the reinforcing effect of the layered inorganic nanomaterials on the rubber. This results in a decrease in tear strength from 55 kN / m to 51 kN / m and a decrease in 300% tensile stress from 3.59 MPa to 3.44 MPa. The present invention uses an organically modified layered inorganic nanomaterial, natural fresh rubber latex, and coagulating acid in a mass ratio of (4-6):(100-120):(7.5-12.5), preferably (4-6):100:(7.5-12.5), which ensures that the rubber composite material has good performance.
[0065] Compared with Example 3, the solidification temperature of Example 6 was 20°C. Under the lower temperature condition, the solidification rate of the rubber system decreased, and the dispersion stability of the organic modified layered inorganic nanomaterials in the rubber matrix was affected to a certain extent, resulting in a decrease in tear strength from 55kN / m to 48kN / m.
[0066] Compared with Example 3, in the preparation method of Comparative Example 1, the layered inorganic nanomaterials and butyl pyridine latex were not modified under acidic conditions, resulting in uneven dispersion of the layered inorganic nanomaterials in the rubber matrix. This caused a significant decrease in the tensile strength, tear strength and abrasion resistance of the rubber composite material, and the solidification time was significantly extended to 1.6 h.
[0067] Compared to Example 3, in Comparative Example 2, the layered inorganic nanomaterials and butyl-pyridine latex were not modified under acidic conditions, making it difficult to effectively improve the interfacial compatibility between the layered inorganic nanomaterials and rubber. Furthermore, the three-phase system exhibited unstable coagulation, leading to a prolonged coagulation time of 2.3 hours even with three-phase blending. Consequently, the tensile strength, tear strength, and abrasion resistance of the rubber composite material significantly decreased. This invention, by first pre-modifying the layered inorganic nanomaterials and butyl-pyridine latex under acidic conditions, followed by two-phase blending and coagulation with natural latex, effectively improves the interfacial compatibility between the layered inorganic nanomaterials and rubber. This allows the layered inorganic nanomaterials to form a stable and uniform dispersion structure in the rubber matrix, thereby significantly enhancing the overall performance of the rubber composite material and effectively reducing filler loss, resulting in a high-performance, highly consistent rubber composite material.
[0068] Compared with Example 3, the mass concentration of the aqueous dispersion of layered inorganic nanomaterials in the organic modification process of Comparative Example 3 was too high. Under high concentration conditions, the layered inorganic nanomaterials are prone to agglomeration, which affects their uniform dispersion in the rubber matrix, resulting in a decrease in the tensile strength, tear strength and wear resistance of the rubber composite material, and the solidification time is extended to 1.8h.
[0069] Compared with Example 3, the preparation method of Comparative Example 4 was modified under the condition of pH 6.5 of the mixture of layered inorganic nanomaterials and butyl pyridine latex. The acidic conditions were insufficient to effectively induce the demulsification of butyl pyridine latex and expose the positively charged pyridine groups, which led to a weakening of the interfacial interaction between the layered inorganic nanomaterials and the rubber, resulting in a decrease in the water dispersion effect of the layered inorganic nanomaterials, thereby reducing the mechanical properties and wear resistance of the rubber composite material.
[0070] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0071] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.
Claims
1. An organically modified layered inorganic nanomaterial, characterized in that, It is obtained by modifying layered inorganic nanomaterials with polymer latex containing pyridine or nitrogen-containing aromatic rings under acidic conditions.
2. The organically modified layered inorganic nanomaterial as described in claim 1, characterized in that, The dry basis mass ratio of the layered inorganic nanomaterial to the polymer latex containing pyridine or nitrogen-containing aromatic rings is 1:(0.8-1.4); and / or, The pH value of the acidic conditions is 4.8-5.
2.
3. The organically modified layered inorganic nanomaterial as described in claim 1 or 2, characterized in that, The polymer latex containing pyridine or nitrogen-containing aromatic rings is selected from at least one of styrene-butadiene pyridine latex, pyridine-containing nitrile butadiene rubber latex, pyridine-modified natural latex, pyridine-styrene-butadiene-pyridine terpolymer latex, and pyridine-isoprene rubber latex; preferably styrene-butadiene pyridine latex; and / or, The layered inorganic nanomaterial is nano-clay, preferably at least one selected from montmorillonite and bentonite; and / or The acidic conditions are provided by at least one of organic acid, inorganic acid, acidic salt, and acidic buffer system; preferably by formic acid and / or acetic acid; more preferably, the mass concentration of the formic acid is 0.2%-0.8%, and the mass concentration of the acetic acid is 1%-2%.
4. The method for preparing the organically modified layered inorganic nanomaterials according to any one of claims 1-3, characterized in that, Includes the following steps: (1) Mix the polymer latex of pyridine or aza-aromatic ring and the dispersion of layered inorganic nanomaterials evenly; (2) Add an acidic regulator to the mixture in step (1) to adjust the pH value to 4.8-5.2, and then react at 20℃-35℃ for 25min-30min; (3) Homogenize or break the cell walls of the reactants obtained in step (2) to obtain the final product.
5. The preparation method according to claim 4, characterized in that, The polymer latex containing pyridine or nitrogen-containing aromatic rings has a solid content of 6%-12%; and / or, The mass concentration of the dispersion of layered inorganic nanomaterials is 3%-6%; and / or, The homogenization pressure is 200-500 bar, and the time is 5-20 minutes; and / or, The cell wall breaking speed is 8000r / min-12000r / min, and the time is 20s-60s.
6. The application of the organically modified layered inorganic nanomaterials as described in any one of claims 1-3 in the preparation of rubber composite materials.
7. A rubber composite material, characterized in that, It is prepared by organically modified layered inorganic nanomaterials as described in any one of claims 1-3, natural fresh latex and coagulant in a mass ratio of (4-6):(100-120):(7.5-12.5); wherein the natural fresh latex is based on dry latex.
8. The rubber composite material as described in claim 7, characterized in that, The mass ratio of the organically modified layered inorganic nanomaterial, natural fresh latex, and coagulating acid is (4-6):100:(7.5-12.5); and / or, The mass concentration of the coagulating acid is 0.3%-1.0%; and / or, The coagulating acid is selected from at least one of formic acid, acetic acid, and sulfuric acid.
9. The method for preparing the rubber composite material as described in claim 7 or 8, characterized in that, Includes the following steps: The dispersion of the organically modified layered inorganic nanomaterial is mixed evenly with natural fresh latex, and then co-flowed with the coagulating acid to coagulate and mature, thus obtaining the final product.
10. The preparation method according to claim 9, characterized in that, The solidification temperature is 20℃-35℃.