CN111171383A - Preparation method and application of porous load type rubber vulcanization accelerator - Google Patents
Preparation method and application of porous load type rubber vulcanization accelerator Download PDFInfo
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- CN111171383A CN111171383A CN202010086895.0A CN202010086895A CN111171383A CN 111171383 A CN111171383 A CN 111171383A CN 202010086895 A CN202010086895 A CN 202010086895A CN 111171383 A CN111171383 A CN 111171383A
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- vulcanization accelerator
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a preparation method and application of a porous load type rubber vulcanization accelerator. Adding an inorganic carrier into an electrolyte solution, uniformly stirring, and reacting at 600-900 ℃ for 6-10 hours to obtain a solid product, namely a product A; b. washing the product A, adding the product A and a zinc-containing compound with the mass of 0.5-5 times that of the inorganic carrier into deionized water to prepare a mixed solution, adjusting the pH value of the mixed solution to 8-12, and carrying out hydrothermal reaction at 120-180 ℃ for 6-10 hours to obtain a product B; c. and filtering, washing and drying the product B to obtain the porous load type rubber vulcanization accelerator. The invention overcomes the defects of low use efficiency, large use amount, precipitation in the use process, environmental pollution, single function, filler agglomeration and the like of the traditional accelerator, and provides the preparation method of the novel porous load type rubber vulcanization accelerator, which has the advantages of high efficiency, multiple functions, low cost, environmental friendliness and suitability for industrial production.
Description
Technical Field
The invention relates to the field of high-performance rubber additives, in particular to a preparation method and application of a porous load type rubber vulcanization accelerator.
Background
The rubber product is one of indispensable materials in the fields of automobile industry, aerospace, oil exploitation and the like. Rubber products generally need to be vulcanized and added with fillers to improve the mechanical properties, mechanical properties and aging resistance thereof so as to meet the use requirements. Silica (white carbon black) is an indispensable filler for preparing 'green tires', but the surface of the silica (white carbon black) has high active groups, so that the silica (white carbon black) is easy to agglomerate when added into rubber and cannot fully play a role. The vulcanization accelerator is one of the most important varieties in the rubber auxiliary industry, and can reduce the vulcanization temperature of rubber and shorten the vulcanization time, thereby improving the production efficiency. The prior industrial rubber vulcanization accelerator has the defects of low use efficiency, easy agglomeration, easy precipitation in the use process, environmental pollution and the like. With the continuous improvement of the use requirements of modern industry on rubber products, the preparation of the novel efficient, multifunctional and environment-friendly vulcanization accelerator reduces the consumption of the traditional accelerator, and becomes the development trend of the rubber industry, so that the research and development of a novel accelerator for replacing the traditional accelerator have important significance.
Disclosure of Invention
The invention aims to provide a preparation method of a porous supported rubber vulcanization accelerator. The invention overcomes the defects of low use efficiency, large use amount, precipitation in the use process, environmental pollution, single function, filler agglomeration and the like of the traditional accelerator, and provides the preparation method of the novel porous load type rubber vulcanization accelerator, which has the advantages of high efficiency, multiple functions, low cost, environmental friendliness and suitability for industrial production.
The technical scheme of the invention is as follows: a preparation method of a porous supported rubber vulcanization accelerator comprises the following steps:
a. adding silicon dioxide into the electrolyte solution, uniformly stirring, and reacting at 600-900 ℃ for 6-10 hours to obtain a solid product, namely product A;
b. washing the product A, adding the product A and a zinc-containing compound with the mass being 0.5-5 times that of silicon dioxide into deionized water to prepare a mixed solution, adjusting the pH value of the mixed solution, and performing hydrothermal reaction at 120-180 ℃ for 6-10 hours to obtain a product B;
c. and filtering, washing and drying the product B to obtain the porous load type rubber vulcanization accelerator.
In the step a of the preparation method of the porous supported rubber vulcanization accelerator, the mass ratio of the silicon dioxide to the electrolyte solution is 1: 2-4.
In the step a of the preparation method of the porous supported rubber vulcanization accelerator, the particle size of the silica is micron-sized or nanometer-sized.
In the step a of the preparation method of the porous supported rubber vulcanization accelerator, the electrolyte solution is a sodium chloride solution and/or a lithium chloride solution.
In the step a of the preparation method of the porous supported rubber vulcanization accelerator, the solution is uniformly stirred by adopting ultrasound and stirring, and the stirring time is 1-60 minutes.
In the step b of the preparation method of the porous supported rubber vulcanization accelerator, the zinc-containing compound is zinc acetate.
In the step b of the preparation method of the porous supported rubber vulcanization accelerator, the pH value is 8-12.
In the step b of the preparation method of the porous supported rubber vulcanization accelerator, the pH value is adjusted by ammonia water.
The porous supported rubber vulcanization accelerator prepared by the preparation method is used for preparing natural rubber or synthetic rubber.
Compared with the prior art, the porous supported rubber vulcanization accelerator has the advantages that the surface of silicon dioxide is ablated by an electrolyte solution at high temperature (600-900 ℃) to form porous silicon dioxide, and then the accelerator grows on the surface of the porous silicon dioxide, so that the agglomeration of fillers and the accelerator in a rubber matrix is effectively reduced, and the defects of low use efficiency, single function and easy precipitation of the accelerator are overcome. The whole preparation process is simple and efficient, does not need an organic solvent, and is suitable for industrial production.
When the porous load type rubber vulcanization accelerator is used for preparing rubber products, the normal vulcanization time of rubber can be obviously reduced, the use efficiency of the accelerator and an inorganic carrier is improved, the dispersion of a filler in a rubber matrix and the combination of an interface are improved, and the reinforcing effect of the filler on the rubber is improved.
The invention can reduce the using amount of the accelerant, inhibit the migration and precipitation of the accelerant in the using process, and protect the environment. Besides, the rubber vulcanization accelerator disclosed by the invention can enhance the interaction between a rubber molecular chain and the filler, synergistically reduce the agglomeration of the filler and the accelerator, weaken the Payne effect and improve the tensile strength of vulcanized rubber.
Drawings
FIG. 1 shows silicon dioxide (SiO)2) Porous silica (porous-SiO)2) And growing nano zinc oxide (ZnO-g-SiO) on the porous silicon dioxide2) The nitrogen adsorption curve and the pore size distribution diagram;
FIG. 2 shows nano-ZnO and porous SiO2) And growing nano zinc oxide (ZnO-g-SiO) on the porous silicon dioxide2) A Fourier infrared spectrogram of (1);
FIG. 3 shows nano-ZnO and porous SiO2) And growing nano zinc oxide (ZnO-g-SiO) on the porous silicon dioxide2) XRD spectrum of (1);
FIG. 4 shows the growth of nano zinc oxide (ZnO-g-SiO) on porous silica2) Scanning electron microscope images of;
FIG. 5 is a graph of a frequency sweep of the compound;
FIG. 6 is a bar graph of the tensile strength of the vulcanizate;
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1. A preparation method of a porous supported rubber vulcanization accelerator comprises the following steps:
a. adding 100g silicon dioxide into 300ml electrolyte solution prepared from 7.5g lithium chloride and 11.25g sodium chloride, stirring at room temperature for 30min, ultrasonic stirring for 30min, stirring, and reacting at 600 deg.C for 6 hr to obtain porous silicon dioxide product A;
b. washing the product A with 600ml of deionized water twice, adding the product A and 2 times of zinc acetate in the mass of the product A into 80ml of deionized water, ultrasonically mixing for 30min to prepare a mixed solution, adjusting the pH value of the mixed solution to 9 with ammonia water, and then carrying out hydrothermal reaction for 6 hours at 140 ℃ to obtain a product B;
c. and filtering, washing and drying the product B to obtain the porous load type rubber vulcanization accelerator.
The nitrogen adsorption curve and the pore size distribution of the porous supported rubber vulcanization accelerator prepared by the steps are shown in figure 1, and the figure shows that the specific surface area of silicon dioxide ablated by an electrolyte solution at high temperature is reduced, and the average pore size is increased; after the zinc oxide accelerant is further grown, the specific surface area is continuously reduced, and the average pore diameter is increased, which shows that the nano zinc oxide is successfully grown on the surface of the porous silicon dioxide. Fourier infrared spectrum and XRD spectrum are shown in figures 2 and 3, from which it can be found that the XRD curve of the porous supported rubber vulcanization accelerator simultaneously presents the characteristic diffraction peaks of silicon dioxide and zinc oxide, and the infrared curve also simultaneously presents the characteristic absorption peaks of silicon dioxide and zinc oxide, and moreover, the length of the XRD curve is 937cm-1And a new absorption peak appears, which can be regarded as a stretching vibration peak of Si-O-Zn, and shows that zinc oxide successfully grows in the porous silicon dioxide to form the porous load rubber vulcanization accelerator. FIG. 4 is a scanning electron microscope image of a porous rubber vulcanization accelerator-supported material.
The basic formulation for preparing natural rubber composites using the porous supported rubber vulcanization accelerators is shown in Table 1, and the vulcanization characteristics of the corresponding rubber compounds are shown in Table 2. As can be seen from Table 2, the addition of the porous supported rubber vulcanization accelerator greatly shortens the vulcanization time, and the torque of the rubber compound also obviously indicates that the processability of the rubber compound is improved.
TABLE 1
TABLE 2
FIG. 5 is a frequency scanning curve chart of the rubber compound, and it can be seen that the Payne effect of the porous load type rubber vulcanization is weaker, which shows that the Payne effect is more uniform in the rubber matrix and the processability is better. FIG. 6 is a bar graph of tensile strength of vulcanized rubber, and it can be seen that the mechanical properties of the porous supported rubber vulcanization accelerator are improved more significantly.
Example 2. A preparation method of a porous supported rubber vulcanization accelerator comprises the following steps:
a. adding silicon dioxide into the electrolyte solution, uniformly stirring, and reacting at 600-900 ℃ for 6-10 hours to obtain a solid product, namely product A;
b. washing the product A, adding the product A and a zinc-containing compound with the mass being 0.5-5 times that of silicon dioxide into deionized water to prepare a mixed solution, adjusting the pH value of the mixed solution, and performing hydrothermal reaction at 120-180 ℃ for 6-10 hours to obtain a product B;
c. and filtering, washing and drying the product B to obtain the porous load type rubber vulcanization accelerator.
In the step a, the mass ratio of the silicon dioxide to the electrolyte solution is 1: 2-4, so that the surface of the silicon dioxide is in a porous shape.
In the foregoing step a, the particle size of the silica is micron-sized or nanometer-sized.
In the foregoing step a, the electrolyte solution is a sodium chloride solution and/or a lithium chloride solution.
In the step a, the solution is uniformly stirred by adopting ultrasound and stirring, and the stirring time is 1-60 minutes.
In the foregoing step b, the zinc-containing compound is zinc acetate.
In the step b, the pH value is 8-12, so that the zinc oxide is grown on the surface of the product A.
In the step b, the pH value is adjusted by ammonia water.
The porous supported rubber vulcanization accelerator prepared by the preparation method is used for preparing natural rubber or synthetic rubber.
Claims (9)
1. The preparation method of the porous supported rubber vulcanization accelerator is characterized by comprising the following steps of:
a. adding silicon dioxide into the electrolyte solution, uniformly stirring, and reacting at 600-900 ℃ for 6-10 hours to obtain a solid product, namely product A;
b. washing the product A, adding the product A and a zinc-containing compound with the mass being 0.5-5 times that of silicon dioxide into deionized water to prepare a mixed solution, adjusting the pH value of the mixed solution, and performing hydrothermal reaction at 120-180 ℃ for 6-10 hours to obtain a product B;
c. and filtering, washing and drying the product B to obtain the porous load type rubber vulcanization accelerator.
2. The preparation method of the porous supported rubber vulcanization accelerator according to claim 1, wherein in step a, the mass ratio of the silica to the electrolyte solution is 1: 2-4.
3. The method for preparing the porous supported rubber vulcanization accelerator according to claim 1, wherein in step a, the particle size of the silica is in the micro-or nano-scale.
4. The method for preparing the porous supported rubber vulcanization accelerator according to claim 1, wherein in step a, the electrolyte solution is a sodium chloride solution and/or a lithium chloride solution.
5. The method for preparing the porous supported rubber vulcanization accelerator according to claim 1, wherein in the step a, the solution is uniformly stirred by ultrasound and stirring for 1 to 60 minutes.
6. The method for preparing the porous supported rubber vulcanization accelerator according to claim 1, wherein in step b, the zinc-containing compound is zinc acetate.
7. The method for preparing the porous supported rubber vulcanization accelerator according to claim 1, wherein in step b, the pH value is 8 to 12.
8. The method for preparing a porous supported rubber vulcanization accelerator according to claim 1, wherein in step b, the pH is adjusted with ammonia water.
9. A porous supported rubber vulcanization accelerator obtained by the production method according to any one of claims 1 to 8, wherein the porous supported rubber vulcanization accelerator is produced for use in the production of natural rubber or synthetic rubber.
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Citations (3)
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CN102225780A (en) * | 2011-04-19 | 2011-10-26 | 上海彭浦冶金辅料有限公司 | High-activity calcium oxide and production method thereof |
CN107814976A (en) * | 2017-11-01 | 2018-03-20 | 华东理工大学 | A kind of preparation method of rubber vulcanization activating agent |
CN109428065A (en) * | 2017-08-28 | 2019-03-05 | 内蒙古欣蒙碳纳米科技有限公司 | A kind of preparation method of nanometer rods composite negative pole material |
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2020
- 2020-02-11 CN CN202010086895.0A patent/CN111171383A/en active Pending
Patent Citations (3)
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CN102225780A (en) * | 2011-04-19 | 2011-10-26 | 上海彭浦冶金辅料有限公司 | High-activity calcium oxide and production method thereof |
CN109428065A (en) * | 2017-08-28 | 2019-03-05 | 内蒙古欣蒙碳纳米科技有限公司 | A kind of preparation method of nanometer rods composite negative pole material |
CN107814976A (en) * | 2017-11-01 | 2018-03-20 | 华东理工大学 | A kind of preparation method of rubber vulcanization activating agent |
Non-Patent Citations (2)
Title |
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姚光远 等: ""氯化钠助熔煅烧对硅藻精土结构、形貌及物化性能的影响"", 《硅酸盐通报》 * |
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