CN110092946B - Non-migration type anti-aging agent and preparation method and application thereof - Google Patents
Non-migration type anti-aging agent and preparation method and application thereof Download PDFInfo
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Abstract
A non-migration type anti-aging agent and a preparation method and application thereof relate to the technical field of high-performance rubber products, and the preparation method of the non-migration type anti-aging agent comprises the following steps: the method comprises the following steps: adding white carbon black and an anti-aging agent into a solvent, and performing ultrasonic dispersion to form uniform dispersion liquid; step two: adding the dispersion liquid obtained in the step one into an atomizer, wherein the temperature of the atomizer is room temperature, and the atmosphere is air or inert gas; step three: atomizing and spraying the dispersion liquid through the atomizer in the step two, and collecting a product after spray drying, namely the non-migratory antioxidant. The non-migration type anti-aging agent prepared by the method not only keeps the primary particle size effect of the white carbon black, but also realizes function enhancement, and has anti-aging performance and reinforcing performance.
Description
Technical Field
The invention belongs to the technical field of high-performance rubber products, and particularly relates to a non-migration type anti-aging agent with an anti-aging function and a reinforcing function, and a preparation method and application thereof.
Background
It is known that diene rubber materials having a large number of unsaturated carbon-carbon double bonds (e.g., natural rubber, styrene butadiene rubber, etc.) are excellent in high elasticity and are irreplaceable in many industrial fields. However, carbon-carbon double bonds and methyl groups in rubber molecular chains are easy to degrade and age under the combined action of heat and oxygen, so that rubber products are prematurely failed, a large amount of rubber resources are wasted every year, and even the safety of human beings is threatened. Therefore, it is very important to extend the service life of the rubber product by delaying its thermal oxidation aging process.
In order to improve the thermal-oxidative aging resistance of rubber products, adding a chemical anti-aging agent such as aromatic amine or phenol derivatives into a rubber matrix is one of the simplest methods for preventing rubber materials from thermal-oxidative aging. However, these antioxidant compounds have low molecular weights and are liable to migrate from the rubber matrix, thereby reducing the protective effect of the antioxidants, and the migrated antioxidants cause considerable environmental pollution. At present, researchers have proposed many methods for preparing non-migratory antioxidants, such as increasing the relative molecular weight of the antioxidant, grafting the antioxidant to a polymer chain, and allowing the antioxidant to be released continuously from a capsule or hollow material (e.g., halloysite, carbon nanotubes), but the methods are generally inefficient and difficult to be applied on a large scale.
White carbon black is commonly used as a rubber reinforcing filler, and a white carbon black reinforced rubber product has at least three advantages: the environment-friendly performance is high, and the problem of black pollution is well solved; the energy-saving performance is realized, the rolling resistance is reduced by 22-35%, and the fuel consumption can be reduced by about 1% when the rolling resistance is reduced by 6%; the safety and comfort are realized, and the green tire has excellent wet skid resistance and grip. However, white carbon black as a reinforcing agent still has some defects: 1) the surface of the white carbon black is weakly acidic and has strong hydrophilicity, and the white carbon black is easy to adsorb compounding agents and the like in rubber, so that the problems of vulcanization delay, crosslinking density reduction and the like can be caused, and the reinforcing performance is seriously influenced; 2) the white carbon black is easy to agglomerate and is difficult to be uniformly dispersed in the rubber matrix.
Disclosure of Invention
One of the objects of the present invention is to provide a method for preparing a non-migratory antioxidant, which has both anti-aging and reinforcing properties.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a non-migration type antioxidant is characterized by comprising the following steps:
the method comprises the following steps: adding white carbon black and an anti-aging agent into a solvent, and performing ultrasonic dispersion to form uniform dispersion liquid;
step two: adding the dispersion liquid obtained in the step one into an atomizer, wherein the temperature of the atomizer is room temperature, and the atmosphere is air or inert gas;
step three: atomizing and spraying the dispersion liquid through the atomizer in the step two, and collecting a product after spray drying, namely the non-migratory antioxidant.
Wherein the mass ratio of the white carbon black to the anti-aging agent is (0.05-0.5) to 1.
Preferably, the mass ratio of the white carbon black to the anti-aging agent is (0.09-0.3): 1.
wherein the white carbon black is one or more of precipitated silica, fumed silica, superfine silica gel, coupling agent modified white carbon black or other surface modified white carbon black.
Wherein the anti-aging agent is one or more of amine and phenol.
Preferably, the anti-aging agent is one or more of ketoamine, N-phenyl-alpha-aniline, N-phenyl-beta-naphthylamine, N-phenyl-N '-isopropyl-p-phenylenediamine, p-phenylenediamine and N-N' -diphenyl-p-phenylenediamine.
Wherein the ultrasonic dispersion time in the first step is 0.1-3 hours, and the ultrasonic power is 50-800 watts; and in the third step, the spray drying temperature is 110-250 ℃.
In the first step, the mass ratio of the white carbon black to the solvent is (0.001-0.2): 1.
on the other hand, the invention also provides the non-migration type antioxidant prepared by the preparation method, and the non-migration type antioxidant can be applied to rubber products.
Compared with the prior art, the invention has at least the following advantages: 1. the non-migration type anti-aging agent prepared by the invention contains common components of rubber products, and other compounding agents except for the rubber product formula process are not introduced, so that uncontrollable performance influence on the products is not generated. 2. The surface grafting reaction based on the primary structure of the white carbon black is adopted, the anti-aging agent can be uniformly coated and grafted on the surface of the primary structure of the white carbon black, the grafting rate is high, the local grafting modification of the aggregate of the white carbon black is avoided, and the prepared non-migratory anti-aging agent has small surface energy, is easy to disperse and does not agglomerate. 3. The invention adopts a spray drying method, and the procedures of activation, secondary dispersion, grafting, drying and the like of the anti-aging agent and the white carbon black are all completed in the spray drying process, belonging to one-pot one-step reaction, and having simple process and being suitable for molding production.
Drawings
FIG. 1 is a scanning electron micrograph of a non-migrating antioxidant prepared in example 1 of the present invention.
FIG. 2 is an infrared spectrum of a non-migrating antioxidant prepared in example 1 of the present invention.
FIG. 3 is a digital photograph of an aged test sample prepared in example 2 of the present invention.
FIG. 4 is a digital photograph of a weathering test sample prepared in example 3 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the differences between the present invention and the prior art, the present invention will be further described with reference to the following specific embodiments.
The following examples are generally based on the following ideas: under the action of an atomizer, white carbon black aggregates are dissociated to form a primary structure, and a graft with good migration resistance is formed through the grafting reaction of the primary structure and the anti-aging agent molecules, so that the non-migration anti-aging agent which is easy to disperse is obtained. The non-migration type anti-aging agent not only keeps the primary particle size effect of the white carbon black, but also realizes function enhancement, and has anti-aging performance and reinforcing performance.
The specific implementation steps comprise: (1) pre-dispersing the anti-aging agent and the white carbon black: dispersing an antioxidant compound and a white carbon black raw material in a solvent, and performing ultrasonic dispersion for 0.1-3 hours to form a uniform dispersion liquid; (2) grafting reaction of the antioxidant and white carbon black: and atomizing and spraying the dispersion liquid of the anti-aging agent and the white carbon black in air or inert gas, controlling the spray drying temperature to be 110-250 ℃, and collecting a spray drying product, namely the non-migration type anti-aging agent. In the process, the white carbon black aggregate can realize primary structure dispersion through the ultrasonic action, and then the anti-aging agent can be adsorbed and uniformly coated on the surface of the white carbon black with the primary structure under the action of the atomizer to form vaporific anti-aging agent coated white carbon black liquid drops. The temperature of the grafting reaction (i.e. the spray drying temperature) can be determined according to the types of the anti-aging agent and the white carbon black and the reaction temperature in industrial production, and it should be noted that the solvent cannot be well volatilized at too low temperature, the grafting rate is low, and the decomposition of the anti-aging agent can be caused at too high temperature. The spray drying is carried out in the atmosphere of air or inert gas, on one hand, the product can be better dispersed and dried through gas flow, and on the other hand, the atmosphere can be adjusted to adapt to different anti-aging agent reaction conditions. In addition, the mass ratio of the white carbon black to the solvent is preferably controlled to be (0.001-0.2): 1, controlling the mass ratio of the anti-aging agent to the white carbon black to be (0.05-0.5): 1, preferably (0.09-0.3): 1; the anti-aging agent can be one or more selected from thermal oxidation resistant anti-aging agent, ozone resistant anti-aging agent, harmful metal ion action inhibitor, anti-fatigue anti-aging agent and anti-ultraviolet radiation anti-aging agent according to functional classification; one or more of anti-aging agents such as amines, ketoamine, N-phenyl-alpha-aniline, N-phenyl-beta-naphthylamine, N-phenyl-N '-isopropyl-p-phenylenediamine, N-N' -diphenyl-p-phenylenediamine, phenolic agents and the like can be selected according to chemical components; the white carbon black can be selected and combined in conventional white carbon black and modified white carbon black, for example, precipitated silica, fumed silica, ultrafine silica gel and the like can be selected, and coupling agent modified white carbon black or other surface modified white carbon black can be selected.
Example 1:
the preparation method of the non-migration type antioxidant in the embodiment comprises the following steps:
(1) preparing white carbon black aggregates, p-phenylenediamine and deionized water into suspension with a certain concentration according to a mass ratio of 1: 2: 100, and performing ultrasonic dispersion for 5 minutes to obtain uniform dispersion liquid;
(2) preparing a non-migration type anti-aging agent by adopting a spray dryer: adding the dispersion liquid obtained in the step (1) into a spray bottle, spraying by using a medical atomizer, and introducing argon to spray atomized liquid drops into a quartz tube which is preheated to 150 ℃.
(3) Collecting the non-migration type antioxidant prepared by spray drying.
Product characterization: the appearance of a scanning electron microscope is as shown in figure 1, aggregates are already dispersed, and the primary structure dissociation degree of the white carbon black is loose; the infrared spectrum is represented as figure 2, and the white carbon black (SiO) after grafting modification2) The infrared image shows the-NH absorption peak (1650 cm) from p-phenylenediamine-1) And absorption peak (2260 cm) corresponding to-CN grafted by ring opening of p-phenylenediamine-1). The preparation of the non-migration type antioxidant grafted by p-phenylenediamine and white carbon black is proved to be successful.
And (3) performance testing: the prepared non-migratory antioxidant is applied to a rubber product, in order to compare the performance difference of the non-migratory antioxidant with the existing antioxidant, samples used in performance test comprise three groups, the basic formula (mass fraction) of the three groups of samples comprises 100 parts of natural rubber, 5 parts of zinc oxide, 1 parts of promoter CZ, 2 parts of sulfur, 2 parts of stearic acid and 40 parts of white carbon black, and in the three groups of samples, the using amount of the antioxidant is changed, wherein the content of the antioxidant in the sample group without the antioxidant is 0, the content of the antioxidant in the sample group with the antioxidant added is 4010, and the content of the antioxidant in the sample group with the non-migratory antioxidant added in the embodiment is 2. Mixing the above materials on a double-roller open mill by conventional method, standing for 1 day, and vulcanizing at 150 deg.C on a flat vulcanizing machine. The mechanical property test is carried out on three groups of samples which are not added with the anti-aging agent, the anti-aging agent 4010NA and the non-migratory anti-aging agent and are not aged, and the result is that the test result of the added non-migratory anti-aging agent is obviously superior to the test result of the added anti-aging agent 4010NA and the sample which is not added with the anti-aging agent, which shows that the non-migratory anti-aging agent involved in the embodiment can play a better reinforcing role. As the invention relates to the anti-aging agent, the test result of the anti-aging agent after thermal oxidation aging is focused. The thermal-oxidative aging is carried out for 48 hours at the temperature of 100 ℃, and the mechanical properties of three groups of samples are shown in the table 1.
Table 1 mechanical properties of three sets of samples after aging for 48 h.
From the above table, it can be seen that the film performance of the film with the non-migratory antioxidant is better than the film without the antioxidant and the common 4010NA antioxidant, which shows that the non-migratory antioxidant involved in the present example has better anti-aging performance.
Example 2:
the preparation method of the non-migration type antioxidant in the embodiment comprises the following steps:
(1) the white carbon black prepared by the vapor phase method and the silane coupling agent Si69 are stirred for 30 minutes at 145 ℃ according to the mass ratio of 100: 20. Extracting and drying to obtain the coupling agent modified white carbon black.
(2) Preparing modified white carbon black, p-aminodiphenylamine and deionized water into suspension with a certain concentration according to a mass ratio of 1: 2: 100, and performing ultrasonic dispersion for 5 minutes to obtain uniform dispersion liquid;
(3) adding the dispersion liquid obtained in the step (1) into a spray bottle, spraying by using a medical atomizer, and introducing argon to spray atomized liquid drops into a quartz tube which is preheated to 150 ℃.
And (3) performance testing: the prepared non-migratory antioxidant is applied to a rubber product, in order to compare the performance difference of the non-migratory antioxidant and the existing antioxidant, samples used in performance test comprise three groups, wherein the basic formula (mass fraction) of the three groups of samples comprises 100 parts of natural rubber, 5 parts of zinc oxide, CZ 1, 2 parts of sulfur, 2 parts of stearic acid, 40 parts of white carbon black, and the addition mode of the antioxidant refers to example 1. Mixing the above materials on a double-roller open mill by conventional method, standing for 1 day, and vulcanizing at 145 deg.C on a flat vulcanizing machine.
Three groups of samples which are not added with the anti-aging agent, the anti-aging agent 4010NA and the non-migratory anti-aging agent and are not aged are subjected to mechanical property test, and the test result is consistent with that of the embodiment 1. In addition, the digital photos of the product after the 2 groups of samples added with the anti-aging agent 4010NA and the non-migrating anti-aging agent of the embodiment are subjected to thermo-oxidative aging for 48 hours at the temperature of 100 ℃ and tensile strength tests are carried out on a universal tensile testing machine are shown in the attached figure 3. After 48 hours of thermo-oxidative aging, the film added with the conventional antioxidant is subjected to tensile stress, so that a great deal of antioxidant is separated out from the surface, and the tensile strength is 13.4 MPa. After the rubber sheet of the non-migrating anti-aging agent is aged for 48 hours, the anti-aging agent migration phenomenon (as shown in figure 3, the surface is still smooth) does not occur even under the action of tensile stress, the tensile strength is still as high as 22.6MPa, and the fact that the performance of the non-migrating anti-aging agent is superior to that of the micromolecular anti-aging agent 4010NA is proved.
Example 3:
the preparation method of the non-migration type antioxidant in the embodiment comprises the following steps:
(1) pretreating white carbon black and a coupling agent KH560 in a toluene solvent by a gas phase method, and stirring and refluxing for 5 hours at 90 ℃ according to the mass ratio of the white carbon black to Si69 of 100: 40. Extracting and drying to obtain the coupling agent modified white carbon black.
(2) Preparing modified white carbon black, p-aminodiphenylamine and deionized water into suspension with a certain concentration according to a mass ratio of 1: 2: 100, and performing ultrasonic dispersion for 5 minutes to obtain uniform dispersion liquid;
(3) adding the dispersion liquid obtained in the step (1) into a spray bottle, spraying by using a medical atomizer, introducing argon gas, and spraying atomized liquid drops into a quartz tube which is preheated to 150 ℃ for drying.
And (3) performance testing: the prepared non-migratory antioxidant is applied to a rubber product, in order to compare the performance difference of the non-migratory antioxidant and the existing antioxidant, samples used in performance test comprise three groups, wherein the basic formula (mass fraction) of the three groups of samples comprises 100 parts of natural rubber, 5 parts of zinc oxide, CZ 1, 2 parts of sulfur, 2 parts of stearic acid, 40 parts of white carbon black, and the addition mode of the antioxidant refers to example 1. Mixing the above materials on a double-roller open mill by conventional method, standing for 1 day, and vulcanizing at 150 deg.C on a flat vulcanizing machine.
Mechanical property tests were carried out on three groups of samples which were not aged, added with the anti-aging agent 4010NA and added with the non-migrating anti-aging agent, as in example 2, and the test results were also the same as in example 1. The photo of the product after aging by thermal oxidation at 100 ℃ for 48h and tensile strength test in a universal tensile testing machine is shown in figure 4. After 48 hours of thermo-oxidative aging, a layer of white micromolecule substance can be seen on the surface of the rubber sheet of the conventional anti-aging agent under the action of tensile stress, and the anti-aging agent is proved to have obvious migration and volatilization and the tensile strength of 13.8 MPa. After the rubber sheet of the non-migrating anti-aging agent is aged for 48 hours, the migration phenomenon of the anti-aging agent does not occur even under the action of tensile stress (as shown in figure 4, the surface is still smooth), the tensile strength is still as high as 25.5MPa, and the fact that the performance of the non-migrating anti-aging agent is superior to that of the micromolecular anti-aging agent 4010NA is proved.
Example 4:
the preparation method of the non-migration type antioxidant in the embodiment comprises the following steps:
(1) the white carbon black and the high molecular substance which are prepared by the vapor phase method are subjected to surface modification, and are mixed for 5 hours in a torque rheometer at 160 ℃ according to the mass ratio of the white carbon black to the epoxy natural rubber ENR of 100: 120. And extracting and drying to obtain the ENR modified white carbon black.
(2) Preparing modified white carbon black, p-aminodiphenylamine and deionized water into suspension with a certain concentration according to a mass ratio of 1: 2: 100, and performing ultrasonic dispersion for 5 minutes to obtain uniform dispersion liquid;
(3) adding the dispersion liquid obtained in the step (1) into a spray bottle, spraying by using a medical atomizer, introducing argon gas, and spraying atomized liquid drops into a quartz tube which is preheated to 150 ℃ for drying.
And (3) performance testing: the prepared non-migratory antioxidant is applied to a rubber product, in order to compare the performance difference of the non-migratory antioxidant and the existing antioxidant, samples used in performance test comprise three groups, wherein the basic formula (mass fraction) of the three groups of samples comprises 100 parts of natural rubber, 5 parts of zinc oxide, CZ 1, 2 parts of sulfur, 2 parts of stearic acid, 40 parts of white carbon black, and the addition mode of the antioxidant refers to example 1. Mixing the above materials on a double-roller open mill by conventional method, standing for 1 day, and vulcanizing at 150 deg.C on a flat vulcanizing machine.
Three groups of samples which are not added with the anti-aging agent, the anti-aging agent 4010NA and the non-migratory anti-aging agent and are not aged are subjected to mechanical property test, and the test results are also consistent with those in the embodiment 1. Three groups of samples without the anti-aging agent, with the anti-aging agent 4010NA and with the non-migration anti-aging agent of the embodiment are subjected to thermo-oxidative aging for 48 hours at the temperature of 100 ℃, and the mechanical properties are shown in Table 2. After aging, the film performance of the non-migration antioxidant grafted with p-aminodiphenylamine modified by ENR is superior to that of the other two groups of films, and the advantages of the non-migration antioxidant in rubber products involved in the embodiment are proved.
TABLE 2 mechanical properties of three groups of samples after aging for 48h
The above embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Some of the drawings and descriptions of the present invention have been simplified to facilitate the understanding of the improvements over the prior art by those skilled in the art, and some other elements have been omitted from this document for the sake of clarity, and it should be appreciated by those skilled in the art that such omitted elements may also constitute the subject matter of the present invention.
Claims (3)
1. A preparation method of a non-migration type antioxidant is characterized by comprising the following steps:
the method comprises the following steps: adding ENR modified white carbon black and p-aminodiphenylamine in a mass ratio of 0.5:1 into deionized water to obtain a mixed solution, wherein the ENR modified white carbon black is prepared by mixing white carbon black and epoxy natural rubber ENR in a mass ratio of 100:120 in a 160 ℃ torque rheometer for 5 hours, and then extracting and drying; carrying out ultrasonic dispersion on the mixed solution to form uniform dispersion liquid;
step two: adding the dispersion liquid obtained in the step one into an atomizer, wherein the temperature of the atomizer is room temperature, and the atmosphere is air or inert gas;
step three: and atomizing and spraying the dispersion liquid by using an atomizer in the second step, drying at the spray drying temperature of 150 ℃, and collecting the product after spray drying, namely the non-migration type antioxidant.
2. The process for producing a non-migrating antioxidant according to claim 1, characterized in that: in the first step, the ultrasonic dispersion time is 0.1-3 hours, and the ultrasonic power is 50-800 watts.
3. The use of the non-migrating antioxidant prepared by the preparation method of claim 1 or 2 as an antioxidant directly added to rubber products.
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