CN113185756A - Magnetic sensitive rubber composition and preparation method thereof - Google Patents
Magnetic sensitive rubber composition and preparation method thereof Download PDFInfo
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- CN113185756A CN113185756A CN202110500318.6A CN202110500318A CN113185756A CN 113185756 A CN113185756 A CN 113185756A CN 202110500318 A CN202110500318 A CN 202110500318A CN 113185756 A CN113185756 A CN 113185756A
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- C08L7/00—Compositions of natural rubber
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Abstract
The invention discloses a magnetic-sensitive rubber composition and a preparation method thereof, wherein the magnetic-sensitive rubber composition comprises the following components: the rubber composition comprises a rubber matrix, an active agent, a reinforcing agent, an accelerator, an anti-aging agent, a vulcanizing agent, magnetic particles, a plasticizer and tackifying resin, wherein the rubber matrix comprises natural rubber and butadiene rubber. The magnetic-sensitive rubber composition has good low-temperature resistant flexibility and mechanical property, the low-temperature brittleness temperature is below-70 ℃, and no crack is generated after 30 ten thousand times of flexing.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a magnetic-sensitive rubber composition and a preparation method thereof.
Background
The magneto-sensitive rubber is one of magneto-rheological materials, can also be called as a magneto-rheological elastomer, and is a novel functional material and an intelligent material with the rheological property controllable by an external magnetic field. The material has high response speed, good reversibility (after the magnetic field is removed, the initial state is recovered), and continuous change of mechanical, electrical, magnetic and other properties of the material can be controlled by adjusting the size of the magnetic field, so the material has wide application prospects in the fields of aerospace, automobiles, vibration control and the like. When an airplane is in high altitude, the temperature is extremely low, the requirement on the low temperature resistance of rubber parts is high, and the current magnetic-sensitive rubber composition has poor low temperature resistance and yield resistance and is difficult to meet the use requirements of rubber parts such as aerospace shock absorbers.
Therefore, the existing magnetosensitive rubber composition is in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a magnetic-sensitive rubber composition and a preparation method thereof, wherein the magnetic-sensitive rubber composition has good low temperature resistance and yield resistance, and also has good mechanical properties.
In one aspect of the invention, a magnetically sensitive rubber composition is provided. According to an embodiment of the present invention, the magnetosensitive rubber composition comprises: the rubber composition comprises a rubber matrix, an active agent, a reinforcing agent, an accelerator, an anti-aging agent, a vulcanizing agent, magnetic particles, a plasticizer and tackifying resin, wherein the rubber matrix comprises natural rubber and butadiene rubber.
According to the magnetic-sensitive rubber composition disclosed by the embodiment of the invention, the natural rubber and the butadiene rubber are used as the rubber matrix, and the natural rubber has good wear resistance, very high elasticity, high tensile strength at break and high elongation, is one of the rubbers with the best comprehensive performance, and is wide in application; the butadiene rubber is the rubber with the highest elasticity in all the prior rubbers, the glass transition temperature of the butadiene rubber is low and is about-105 ℃, the molecular chain segment of the butadiene rubber can move freely at a very low temperature, so that the butadiene rubber can show high elasticity in a very wide temperature range and can be maintained even at-40 ℃, the butadiene rubber has higher elasticity and hardening resistance at the low temperature, the low-temperature performance of the butadiene rubber can be improved when the butadiene rubber is combined with natural rubber, and the butadiene rubber product has good dynamic crack generation resistance, so the yielding resistance is excellent. Secondly, when more butadiene rubber is added in general, the puncture resistance of the product is poor, and the application adds tackifying resin to improve the puncture resistance; meanwhile, the plasticizer capable of reducing the glass transition temperature of the rubber is added, so that the processing performance of the rubber can be improved, the brittleness temperature of the rubber can be effectively reduced, and the rubber product can be used in an extremely cold environment. In addition, the physical and mechanical properties of the rubber can be improved by adding the reinforcing agent; the addition of the activator can improve the vulcanization efficiency under the action of the accelerator and can also improve the physical property and the aging resistance of the rubber; the aging reaction of the rubber can be delayed by adding the anti-aging agent, and the service life of the rubber is prolonged. Therefore, the magnetic-sensitive rubber composition has good low-temperature resistant flexibility and mechanical property, the low-temperature brittleness temperature is below-70 ℃, and no crack is generated after 30 ten thousand times of flexing.
In addition, the magnetic-sensitive rubber composition according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, the magnetic-sensitive rubber composition includes 100 parts by weight of the rubber matrix, 4 to 8 parts by weight of the activator, 30 to 60 parts by weight of the reinforcing agent, 1 to 3 parts by weight of the accelerator, 2 to 4 parts by weight of the antioxidant, 1 to 2 parts by weight of the vulcanizing agent, 200 to 600 parts by weight of the magnetic particles, 1 to 5 parts by weight of the plasticizer, and 1 to 3 parts by weight of the tackifying resin. Therefore, the magnetic-sensitive rubber composition has good low-temperature resistance and yield resistance, and also has good mechanical properties.
In some embodiments of the present invention, the rubber matrix comprises 50 to 70 parts by weight of natural rubber and 30 to 50 parts by weight of butadiene rubber. Therefore, the magnetic-sensitive rubber composition has good low-temperature resistance and yield resistance, and also has good mechanical properties.
In some embodiments of the invention, the cis content of the butadiene rubber is not less than 96 wt%. Therefore, the magnetic-sensitive rubber composition has good low-temperature resistance and yield resistance, and also has good mechanical properties.
In some embodiments of the invention, the tackifying resin comprises at least one of a Koresin super tackifying resin, a t-butyl phenolic tackifying resin, and an octyl phenolic resin. This improves the puncture resistance of the rubber.
In some embodiments of the present invention, the Koresin super tackifying resin is a condensate of butyl phenol and acetylene, and at least one of the following conditions is satisfied: the softening point is 135-150 ℃ (ring and ball method/DIN 52011); the dropping point is 140-160 ℃ (DIN 51801); the density (20 ℃) is 1.02-1.04 g/cm3. This improves the puncture resistance of the rubber.
In some embodiments of the invention, the tert-butyl phenolic tackifying resin satisfies at least one of the following conditions: the softening point is 135-150 ℃ (ring and ball method/DIN 52011); free phenol is less than or equal to 2.0 wt%; the heating loss is less than or equal to 0.50 wt%. This improves the puncture resistance of the rubber.
In some embodiments of the invention, the octyl phenol-formaldehyde resin satisfies at least one of the following conditions: the softening point is 85-100 ℃ (ring and ball method/DIN 52011); the content of hydroxymethyl is less than or equal to 1.00 wt%; the heating loss is less than or equal to 0.50 wt%. This improves the puncture resistance of the rubber.
In some embodiments of the invention, the active agent is nano zinc oxide or a mixture of nano zinc oxide and stearic acid. Therefore, the rubber vulcanization accelerator can act with an accelerator to improve vulcanization efficiency, and can also improve the physical properties and aging resistance of rubber.
In some embodiments of the present invention, the nano zinc oxide includes 70 to 80 wt% of primary particles having a particle size of not more than 100nm and 20 to 30 wt% of primary particles having a particle size of more than 100 nm. Therefore, the rubber vulcanization accelerator can act with an accelerator to improve vulcanization efficiency, and can also improve the physical properties and aging resistance of rubber.
In some embodiments of the present invention, the reinforcing agent includes carbon black or a mixture of carbon black and white carbon. This improves the physical and mechanical properties of the rubber.
In some embodiments of the invention, the accelerator is accelerator NS. Therefore, the vulcanizing process can be shortened, and the use efficiency of the vulcanizing agent and the quality and performance of rubber can be improved.
In some embodiments of the present invention, the antioxidant comprises antioxidant 6PPD and antioxidant RD, and the mass ratio of antioxidant 6PPD to antioxidant RD is 1: (1-2). Therefore, the aging reaction of the rubber can be delayed, and the service life of the rubber is prolonged.
In some embodiments of the invention, the vulcanizing agent is sulfur.
In some embodiments of the present invention, the magnetic particles comprise at least one of modified carbonyl iron powder, modified nickel carbonyl powder, unmodified carbonyl iron powder, and unmodified nickel carbonyl powder, preferably modified carbonyl iron powder.
In some embodiments of the invention, the plasticizer comprises at least one of dibutyl phthalate, dioctyl sebacate, dibutyl sebacate, and dioctyl adipate. Can improve the processing property of rubber and effectively reduce the brittleness temperature of the rubber, so that the rubber product can be used in extremely cold environment.
In some embodiments of the invention, the adhesive further comprises 1-10 parts by weight of a self-repairing agent, wherein the self-repairing agent is liquid nitrile rubber-phenolic resin. This can improve the fatigue resistance of the rubber.
In some embodiments of the invention, at least one of an antioxidant, an antiozonant, and a protective wax is further included. Thereby, the service life of the rubber can be prolonged.
In a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned magnetosensitive rubber composition. According to an embodiment of the invention, the method comprises:
(1) mixing natural rubber, butadiene rubber, magnetic particles, a reinforcing agent, an activator, an anti-aging agent, a plasticizer and tackifying resin, performing first mixing, and standing after rubber discharge so as to obtain master batch;
(2) mixing the master batch with a vulcanizing agent and an accelerator for second mixing and rubber discharging so as to obtain a rubber compound;
(3) injecting the rubber compound into a mold, and carrying out pre-structuring treatment under a magnetic field so as to ensure that the magnetic particles are directionally arranged to obtain the rubber compound after pre-structuring treatment;
(4) and vulcanizing the pre-structured rubber compound to obtain the magnetic-sensitive rubber composition.
According to the method for preparing the magnetic-sensitive rubber composition, natural rubber, butadiene rubber, magnetic particles, a reinforcing agent, an activator, an anti-aging agent, a plasticizer and tackifying resin are mixed for first mixing, and standing is carried out after rubber discharge to obtain master batch; mixing the master batch with a vulcanizing agent and an accelerator for second mixing, and discharging rubber to obtain a mixed rubber; then injecting the rubber compound into a mold, and carrying out pre-structuring treatment under a magnetic field to ensure that the magnetic particles are directionally arranged to obtain the pre-structured rubber compound; and finally, vulcanizing the pre-structured rubber compound to obtain the magnetic-sensitive rubber composition. The magnetic-sensitive rubber composition prepared by the method has good low-temperature resistant and flexing-resistant performances and good mechanical properties, and the low-temperature brittleness temperature of the magnetic-sensitive rubber composition is below-70 ℃, and no crack is generated after 30 ten thousand times of flexing.
In addition, the method for preparing the above-mentioned magnetic-sensitive rubber composition according to the above-mentioned embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, further comprising adding a self-healing agent in step (1). This can improve the fatigue resistance of the rubber.
In some embodiments of the present invention, further comprising adding at least one of an antioxidant, an antiozonant, and a protective wax in step (1). Thereby, the service life of the rubber can be prolonged.
In some embodiments of the present invention, in the step (1), the first mixing time is 3 to 5 minutes, the temperature is 150 to 160 ℃, and the standing time is 4 to 8 hours.
In some embodiments of the present invention, in the step (2), the second mixing time is 1 to 3 minutes, and the temperature is 95 to 105 ℃.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a process for preparing a magnetosensitive rubber composition according to one embodiment of the present invention.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In a first aspect of the present invention, a magnetosensitive rubber composition is provided. According to an embodiment of the present invention, the magnetosensitive rubber composition includes: the rubber composition comprises a rubber matrix, an active agent, a reinforcing agent, an accelerator, an anti-aging agent, a vulcanizing agent, magnetic particles, a plasticizer and tackifying resin, wherein the rubber matrix comprises natural rubber and butadiene rubber.
The inventor finds that by adopting natural rubber and butadiene rubber as rubber matrixes, the natural rubber has good wear resistance, very high elasticity, breaking strength and elongation, is one of the rubbers with the best comprehensive performance, and is widely applied; the butadiene rubber is the rubber with the highest elasticity in all the prior rubbers, the glass transition temperature of the butadiene rubber is low and is about-105 ℃, the molecular chain segment of the butadiene rubber can move freely at a very low temperature, so that the butadiene rubber can show high elasticity in a very wide temperature range and can be maintained even at-40 ℃, the butadiene rubber has higher elasticity and hardening resistance at the low temperature, the low-temperature performance of the butadiene rubber can be improved when the butadiene rubber is combined with natural rubber, and the butadiene rubber product has good dynamic crack generation resistance, so the yielding resistance is excellent. Secondly, when more butadiene rubber is added in general, the puncture resistance of the product is poor, and the application adds tackifying resin to improve the puncture resistance; meanwhile, the plasticizer capable of reducing the glass transition temperature of the rubber is added, so that the processing performance of the rubber can be improved, the brittleness temperature of the rubber can be effectively reduced, and the rubber product can be used in an extremely cold environment. In addition, the physical and mechanical properties of the rubber can be improved by adding the reinforcing agent; the addition of the activator can improve the vulcanization efficiency under the action of the accelerator and can also improve the physical property and the aging resistance of the rubber; the aging reaction of the rubber can be delayed by adding the anti-aging agent, and the service life of the rubber is prolonged. Therefore, the magnetic-sensitive rubber composition has good low-temperature resistant flexibility and mechanical property, the low-temperature brittleness temperature is below-70 ℃, and no crack is generated after 30 ten thousand times of flexing.
Further, the magnetic-sensitive rubber composition comprises 100 parts by weight of a rubber matrix, 4-8 parts by weight of an activator, 30-60 parts by weight of a reinforcing agent, 1-3 parts by weight of an accelerator, 2-4 parts by weight of an anti-aging agent, 1-2 parts by weight of a vulcanizing agent, 200-600 parts by weight of magnetic particles, 1-5 parts by weight of a plasticizer and 1-3 parts by weight of a tackifying resin. The inventor finds that if the magnetic particles are excessively added, the defects such as voids of the magnetic-sensitive rubber are greatly increased, so that the magnetic-sensitive rubber has poor mechanical properties and short service life. If the magnetic particles are added too little, the magneto-rheological effect of the magneto-sensitive rubber is poor, and active control cannot be realized; meanwhile, if the reinforcing agent is added too much, the rubber hardness is increased, the elongation at break is reduced, and the use requirement of a rubber product cannot be met, and if the reinforcing agent is added too little, the reinforcing effect cannot be achieved; in addition, if the active agent, the vulcanizing agent and the accelerator are added too much, the vulcanization process of the rubber is accelerated, the control in industrial production is not easy, and if the active agent is added too little, the vulcanization is slow, the time is wasted, the energy is consumed, and the cost is increased; if the anti-aging agent is added too much, the surface of the rubber is easy to generate a frosting phenomenon, the surface of the rubber is not smooth, the attractiveness of a rubber product is influenced, and if the anti-aging agent is added too little, the anti-aging effect cannot be achieved, the rubber product is easy to age, and the service life is short; if the plasticizer is added too much, the hardness, tensile stress and tensile strength of the rubber material are small, so that the normal use of the product is influenced, and if the plasticizer is added too little, the rubber material is too hard, so that the normal use of the material is also influenced, and the effect of reducing the brittle temperature of the rubber is limited; if the tackifying resin is added too much, the rubber viscosity is larger, the processing is difficult, and if the tackifying resin is added too little, the rubber viscosity is insufficient, the creep deformation of semi-finished parts is easily caused, air bubbles are remained among all the parts, the serious consequences are caused in the use process of the rubber product, and the improvement effect on the puncture resistance of the rubber is limited. Therefore, the obtained rubber has good low-temperature resistant flexibility resistance, mechanical property and processability by adopting the composition of the magnetic-sensitive rubber composition.
Further, the rubber matrix comprises 50-70 parts by weight of natural rubber and 30-50 parts by weight of butadiene rubber. The inventor finds that if the butadiene rubber is excessively added, the tensile strength and the tearing strength of the rubber are low, and the rubber product is not resistant to puncture and is easy to scratch; if the amount of butadiene rubber is too small, the low temperature resistance of the rubber is poor. Therefore, the rubber matrix composition is beneficial to improving the low-temperature resistance and yield resistance of the rubber.
Further, the cis content of the above-mentioned butadiene rubber is not less than 96% by weight. The inventors have found that if the cis content of the butadiene rubber is too low, it may result in poor low temperature resistance of the rubber product.
It should be noted that the specific type of the above tackifying resin is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the tackifying resin includes Koresin super tackifying resin, t-butyl phenolic tackifying resinAt least one of a fat and an octyl phenolic resin. Further, the Koresin super tackifying resin is a condensate of butyl phenol and acetylene, and at least one of the following conditions is satisfied: the softening point is 135-150 ℃ (ring and ball method/DIN 52011); the dropping point is 140-160 ℃ (DIN 51801); the density (20 ℃) is 1.02-1.04 g/cm3. The inventor finds that if the softening point of the Koresin super tackifying resin is too high, the Koresin is not easy to soften in the rubber processing process and has poor processability; if the softening point of the Koresin super tackifying resin is too low, the resin is softened in the rubber too early, and molecular chains may be broken along with the processing of the rubber, so that the resin cannot perform the tackifying function. Meanwhile, if the dropping point of the Koresin super tackifying resin is too high, the Koresin is not easy to melt in the rubber processing process, the processing performance is poor, and the unmelted resin particles are easy to cause defects in rubber, so that the mechanical property of a rubber product is influenced; if the dropping point of the Koresin super tackifying resin is too low, the resin is melted in the rubber too early, and molecular chains may be broken along with the processing of the rubber, so that the resin cannot perform the tackifying function. In addition, too high or too low a density of the Koresin super tackifier resin affects the specific gravity of the rubber. Therefore, the rubber has good mechanical property and processability by adopting the physical property parameters of the Koresin super tackifying resin. Further, the tert-butyl phenolic tackifying resin satisfies at least one of the following conditions: the softening point is 135-150 ℃ (ring and ball method/DIN 52011); free phenol is less than or equal to 2.0 wt%; the heating loss is less than or equal to 0.50 wt%. The inventor finds that if the softening point of the tert-butyl phenolic tackifying resin is too high, the tert-butyl phenolic tackifying resin is not easy to soften in the rubber processing process and has poor processability; if the softening point of the tert-butyl phenolic tackifying resin is too low, the resin is softened in the rubber too early, molecular chains can be broken along with the processing of the rubber, and the tackifying effect cannot be achieved. Meanwhile, if the content of free phenol in the tert-butyl phenolic tackifying resin is too high, phenol pollutants in rubber products can exceed standards, and the environment is polluted. In addition, if the heating loss of the tert-butyl phenolic tackifying resin is too high, the resin contains more moisture or other impurities, and the service performance of rubber products is influenced. Therefore, the physical parameters of the tert-butyl phenolic tackifying resin can ensure that the rubber has good mechanical property,Processing performance and service performance, and is environment-friendly. Further, the octyl phenol resin satisfies at least one of the following conditions: the softening point is 85-100 ℃ (ring and ball method/DIN 52011); the content of hydroxymethyl is less than or equal to 1.00 wt%; the heating loss is less than or equal to 0.50 wt%. The inventor finds that if the softening point of the octyl phenolic resin is too high, the octyl phenolic resin is not easy to soften in the rubber processing process and has poor processability; if the softening point of the octyl phenolic resin is too low, the resin is softened in the rubber too early, and molecular chains can be broken along with the processing of the rubber, so that the tackifying effect cannot be achieved; meanwhile, if the content of hydroxymethyl in the octyl phenolic resin is too high, the branched chain part of the resin is more, and the rubber processability is poor. In addition, if the heating loss of the octyl phenolic resin is too high, the resin contains more moisture or other impurities, and the service performance of the rubber product is influenced. Therefore, the rubber has good mechanical property, processability and usability by adopting the physical property parameters of the octyl phenolic resin.
The specific types of the activator, the reinforcing agent, the accelerator, the anti-aging agent, the vulcanizing agent, the magnetic particles and the plasticizer can be selected by those skilled in the art according to actual needs, for example, the activator is nano zinc oxide or a mixture of nano zinc oxide and stearic acid, and when the activator is nano zinc oxide, the nano zinc oxide is 4 to 5 parts by weight; when the active agent is a mixture of nano zinc oxide and stearic acid, the nano zinc oxide accounts for 2-5 parts by weight, preferably 2-4 parts by weight, and the balance is stearic acid. The inventor finds that if the nano zinc oxide is added too much, the redundant zinc oxide can agglomerate, so that the rubber has more defects and poor mechanical property and fatigue resistance, and if the nano zinc oxide is added too little, the rubber cannot be effectively activated; in addition, if stearic acid is added too much, blooming may occur. Therefore, the composition of the active agent is beneficial to improving the mechanical property and fatigue resistance of the magnetic-sensitive rubber; and on the other hand, the phenomenon of frost can be avoided. Preferably, the active agent is a mixture of nano zinc oxide and stearic acid. The inventor finds that zinc oxide and stearic acid react to generate soluble zinc salt, the solubility of the zinc oxide in rubber is improved, the zinc oxide and the accelerator react to form a complex with good solubility in the rubber, the accelerator and sulfur are activated, and the vulcanization efficiency is improved; the zinc salt can also be chelated with the crosslinking bond, so that the weak bond is protected, the short crosslinking bond is generated by vulcanization, a new crosslinking bond is added, and the crosslinking density is improved. Furthermore, the nano zinc oxide comprises 70-80 wt% of primary particles with the particle size of not more than 100nm and 20-30 wt% of primary particles with the particle size of more than 100 nm. The inventors found that if the proportion of primary particles having a particle size of not more than 100nm is too large, that is, the proportion of small particles is too large, zinc oxide agglomerates and the rubber contains many defects, and mechanical properties and fatigue resistance are deteriorated, whereas if the proportion of primary particles having a particle size of not more than 100nm is too small, that is, the proportion of large particles is too large, voids are generated in the rubber, and mechanical properties and fatigue resistance are deteriorated. Therefore, the nano zinc oxide particle size composition is beneficial to improving the mechanical property and the fatigue resistance of the magnetic sensitive rubber; the reinforcing agent comprises carbon black or a mixture of carbon black and white carbon black, when the reinforcing agent is a mixture of carbon black and white carbon black, the mixing ratio of carbon black and white carbon black is not particularly limited, and can be selected by a person skilled in the art according to actual needs; the accelerant is accelerant NS; the antioxidant comprises antioxidant 6PPD and antioxidant RD, and further the mass ratio of antioxidant 6PPD to antioxidant RD is 1: (1-2), the inventor finds that the antioxidant 6PPD has excellent protection effect on ozone cracking and flex fatigue aging, has better protection effect on heat, oxygen, copper, manganese and other harmful metals, the antioxidant RD has excellent protection effect on aging caused by heat and oxygen, but has poorer protection effect on flex aging, and the combined use of the antioxidants can ensure that the rubber product has better aging resistance; the vulcanizing agent is sulfur; the magnetic particles comprise at least one of modified carbonyl iron powder, modified carbonyl nickel powder, unmodified carbonyl iron powder and unmodified carbonyl nickel powder, preferably modified carbonyl iron powder, wherein the modification mode is that the carbonyl iron powder or the carbonyl nickel powder and vinyl trimethoxy silane (the mass ratio of the carbonyl iron powder or the carbonyl nickel powder to the vinyl trimethoxy silane is 98:2) are respectively dispersed in a mixed solution consisting of absolute ethyl alcohol and a small amount of distilled water, and the two are mixed after ultrasonic dispersion for a period of time; mechanically stirring, and carrying out water bath reaction at 70-80 ℃ for a certain time; and drying at 70-80 ℃ to obtain the modified carbonyl iron powder or modified carbonyl nickel powder. The inventor finds that the modified magnetic particles have abundant hydroxyl and carboxyl on the surface, are easy to chemically react with other additives in rubber compound, and are combined more firmly; the plasticizer includes at least one of dibutyl phthalate, dioctyl sebacate, dibutyl sebacate, and dioctyl adipate.
In addition, the magnetic-sensitive rubber composition further comprises 1-10 parts by weight of a self-repairing agent, the self-repairing agent is liquid nitrile rubber-phenolic resin, and the preparation process is the same as that of the patent application with the application number of 202010598109.5. The inventor finds that if the self-repairing agent is excessively added, the excessive self-repairing agent plays the role of resin, so that the hardness of the rubber material is reduced, and the use requirement of a rubber product cannot be met; if the self-repairing agent is added too little, the self-repairing agent cannot generate a chelate with the magnetic particles sufficiently, and the good effect of improving the fatigue resistance of the rubber cannot be achieved. Therefore, the fatigue resistance of the magnetic-sensitive rubber can be improved by adding the self-repairing agent in the proportion of the application.
Further, the above-mentioned magnetic-sensitive rubber composition may further include at least one of an antioxidant, an antiozonant, and a protective wax. Thereby, the service life of the rubber can be prolonged. It should be noted that the specific types and mixing ratios of the antioxidant, the antiozonant and the protective wax are not particularly limited, and those skilled in the art can select them according to actual needs.
In a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned magnetosensitive rubber composition. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing natural rubber, butadiene rubber, magnetic particles, reinforcing agent, activator, anti-aging agent, plasticizer and tackifying resin for first mixing, placing after rubber discharge
In the step, natural rubber, butadiene rubber, magnetic particles, a reinforcing agent, an activator, an anti-aging agent, a plasticizer and tackifying resin are mixed for first mixing, and the mixture is placed after rubber discharge, so that the masterbatch is obtained. The inventor finds that by adopting natural rubber and butadiene rubber as rubber matrixes, the natural rubber has good wear resistance, very high elasticity, breaking strength and elongation, is one of the rubbers with the best comprehensive performance, and is widely applied; the butadiene rubber is the rubber with the highest elasticity in all the prior rubbers, the glass transition temperature of the butadiene rubber is low and is about-105 ℃, the molecular chain segment of the butadiene rubber can move freely at a very low temperature, so that the butadiene rubber can show high elasticity in a very wide temperature range and can be maintained even at-40 ℃, the butadiene rubber has higher elasticity and hardening resistance at the low temperature, the low-temperature performance of the butadiene rubber can be improved when the butadiene rubber is combined with natural rubber, and the butadiene rubber product has good dynamic crack generation resistance, so the yielding resistance is excellent. Secondly, when more butadiene rubber is added in general, the puncture resistance of the product is poor, and the application adds tackifying resin to improve the puncture resistance; meanwhile, the plasticizer capable of reducing the glass transition temperature of the rubber is added, so that the processing performance of the rubber can be improved, the brittleness temperature of the rubber can be effectively reduced, and the rubber product can be used in an extremely cold environment. In addition, the physical and mechanical properties of the rubber can be improved by adding the reinforcing agent; the addition of the activator can improve the vulcanization efficiency under the action of the accelerator and can also improve the physical property and the aging resistance of the rubber; the aging reaction of the rubber can be delayed by adding the anti-aging agent, and the service life of the rubber is prolonged.
Further, the first mixing time is 3-5 minutes, the temperature is 150-160 ℃, and the standing time is 4-8 hours. The inventor finds that if the first mixing time is too long, the rubber is over-mixed, which not only wastes energy, but also deteriorates the rubber performance; if the first mixing time is too short, the additive is poorly dispersed in the rubber. Meanwhile, if the temperature is too high, scorching of the rubber may occur, and the performance is deteriorated; if the temperature is too low, the additive may not be subjected to a chemical reaction well, and the additive may not exert its own effect. In addition, if the standing time is too short, various additives and fillers are not uniformly dispersed in the rubber. Therefore, the first mixing condition of the magnetic-sensitive rubber composition can ensure that various additives and fillers are uniformly dispersed in rubber, and the obtained magnetic-sensitive rubber composition has good performance.
Preferably, a self-healing agent is added during the first mixing process. The inventors have found that self-healing agents can improve the fatigue resistance of magnetically sensitive rubber compositions. Preferably, at least one of an antioxidant, an antiozonant, and a protective wax may also be added during the first mixing process. Thereby, the service life of the rubber can be prolonged.
It should be noted that the specific types and mixing ratios of the natural rubber, the butadiene rubber, the magnetic particles, the reinforcing agent, the activator, the antioxidant, the self-repairing agent, the antioxidant, the antiozonant and the protective wax are the same as those described above, and are not described herein again.
S200: mixing the master batch with a vulcanizing agent and an accelerant for secondary mixing, and discharging rubber
In the step, the master batch is mixed with a vulcanizing agent and an accelerant for secondary mixing and rubber discharge to obtain the rubber compound. Further, the second mixing time is 1 to 3 minutes, and the temperature is 95 to 105 ℃. The inventors found that, if the second mixing time is too short, the vulcanizing agent and the accelerator are poorly dispersed in the rubber; if the second mixing time is too long, the rubber molecular chain is broken, and the mechanical property of the rubber is deteriorated. Meanwhile, if the second mixing temperature is too low, the rubber is difficult to eat, the vulcanization is not melted, and the dispersion in the rubber is poor; if the second mixing temperature is too high, the rubber is vulcanized and even scorched, which results in poor rubber performance. Therefore, the vulcanizing agent and the accelerator can be uniformly dispersed in the rubber by adopting the second mixing condition, and the obtained magnetic-sensitive rubber composition has good performance. It should be noted that the specific types and mixing ratios of the above-mentioned vulcanizing agents and accelerators are the same as those described above and will not be described herein again.
The type of the apparatus for performing the first mixing and the second mixing is not particularly limited, and may be selected by those skilled in the art according to actual needs, and may be, for example, an internal mixer.
S300: injecting the rubber compound into a mould, and carrying out pre-structuring treatment under a magnetic field
In the step, the rubber compound is injected into a mold, and pre-structuring treatment is carried out under a magnetic field, so that the magnetic particles can be directionally arranged, and the pre-structured rubber compound is obtained. The inventors have found that a pre-structuring treatment allows for a subsequent vulcanization to give anisotropic magneto-sensitive rubber compositions which generally have a higher magneto-rheological effect and a higher change in the magneto-modulus than isotropic magneto-sensitive rubber compositions.
S400: vulcanizing the pre-structured rubber compound
In the step, the pre-structured rubber compound is vulcanized to obtain the magnetic-sensitive rubber composition. It should be noted that the vulcanization time and vulcanization temperature are not particularly limited, and those skilled in the art can select the vulcanization time and vulcanization temperature according to actual needs, for example, the vulcanization temperature is 161 ℃ and the vulcanization time is 15 min. Preferably, the vulcanization is carried out in three portions at 161 ℃ for 10min, 15min and 20min, respectively. The type of the apparatus for carrying out the vulcanization molding is not particularly limited, and may be selected by those skilled in the art according to actual needs, and may be, for example, a steam flat vulcanizing agent.
The inventor finds that a master batch is obtained by mixing natural rubber, butadiene rubber, magnetic particles, a reinforcing agent, an activator, an anti-aging agent, a plasticizer and tackifying resin for first mixing, and standing after rubber discharge; mixing the master batch with a vulcanizing agent and an accelerator for second mixing, and discharging rubber to obtain a mixed rubber; then injecting the rubber compound into a mold, and carrying out pre-structuring treatment under a magnetic field to ensure that the magnetic particles are directionally arranged to obtain the pre-structured rubber compound; and finally, vulcanizing the pre-structured rubber compound to obtain the magnetic-sensitive rubber composition. The magnetic-sensitive rubber composition prepared by the method has good low-temperature resistant and flexing-resistant performances and good mechanical properties, and the low-temperature brittleness temperature of the magnetic-sensitive rubber composition is below-70 ℃, and no crack is generated after 30 ten thousand times of flexing. It should be noted that the features and advantages described above for the magnetic-sensitive rubber composition are also applicable to the method for preparing the magnetic-sensitive rubber composition, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
The specific types and amounts of the components are shown in Table 1
Step 1: mixing natural rubber, butadiene rubber, magnetic particles, a reinforcing agent, an active agent, an anti-aging agent, a self-repairing agent, tackifying resin and a plasticizer in an internal mixer for first mixing for 3-4 minutes, discharging rubber at the temperature of 150-160 ℃, and standing a rubber sheet for 4 hours to obtain a master batch;
step 2: mixing the master batch with a vulcanizing agent and an accelerator for second mixing for 2-3 minutes, and discharging rubber at the temperature of 95-105 ℃ to obtain a mixed rubber;
and step 3: injecting the rubber compound into a mold, and performing pre-structuring treatment under a magnetic field to obtain the pre-structured rubber compound;
and 4, step 4: and vulcanizing the pre-structured rubber compound on a steam flat vulcanizing agent, wherein the vulcanization molding temperature is 161 ℃, and the vulcanization molding time is 10 minutes, 15 minutes and 20 minutes respectively, and obtaining the magnetic-sensitive rubber composition after the vulcanization is finished.
Example 2
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
Example 3
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
Example 4
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
Example 5
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
Example 6
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
Comparative example 1
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
Comparative example 2
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
Comparative example 3
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
Comparative example 4
The specific types and amounts of the respective components are shown in Table 1, and the preparation method is the same as that of example 1.
TABLE 1
Note: the cis content of the butadiene rubber in Table 1 is not less than 96 wt%;
the softening point of the Koresin super tackifying resin is 135-145 ℃ (ring and ball method/DIN 52011); the dropping point is 150-160 ℃ (DIN 51801); the density (20 ℃) is 1.02-1.04 g/cm3；
The softening point of the tert-butyl phenolic tackifying resin is 135-150 ℃ (a ring and ball method/DIN 52011); free phenol is less than or equal to 1.0 wt%; the heating decrement is less than or equal to 0.30 wt%;
the softening point of the octyl phenolic resin is 90-100 ℃ (ring and ball method/DIN 52011); the content of hydroxymethyl is less than or equal to 0.7 wt%; the heating decrement is less than or equal to 0.30 wt%;
the nano zinc oxide comprises 70-80 wt% of primary particles with the particle size of not more than 100nm and 20-30 wt% of primary particles with the particle size of more than 100 nm.
The magnetic-sensitive rubber compositions obtained in examples 1 to 6 and comparative examples 1 to 4 were characterized with respect to tensile hardness, elongation at break, brittle temperature and flex resistance, and the results are shown in Table 2:
brittle temperature evaluation method: the cold well is filled with a freezing medium (industrial ethanol) in an amount such that the distance from the lower end of the holder to the liquid surface is 75 + -10 mm. The sample is clamped vertically on the clamp, the sample is frozen, and a time sequence control switch (or a stopwatch is pressed) is started for timing. The sample freezing time was defined as 3.0. + -. 0.5 min. During freezing of the sample, the temperature of the freezing medium should not fluctuate by more than + -1 deg.C. The lifting gripper is lifted and the impactor is caused to impact the sample within a half second. The sample was removed, bent in the direction of impact to 180 °, and observed carefully for the presence of damage. After the samples are impacted (each sample is only quasi-impacted once), if the samples are damaged, the temperature of the freezing medium is increased, otherwise, the temperature of the freezing medium is reduced, and the test is continued. By trial and error, at least two minimum temperatures at which the test specimen does not fail and at least one maximum temperature at which the test specimen fails are determined, and the test is terminated when the two results differ by no more than 1 ℃.
Others were tested according to national standards.
TABLE 2
As can be seen from the characterization data in Table 2, the yield resistance of comparative example 1 is weaker than that of examples 1 to 6 because no butadiene rubber is added, and further, the tensile strength and elongation at break of the magnetic-sensitive rubber compositions obtained in comparative examples 1 to 4 are weaker than those of examples 1 to 6 and the brittle temperature is higher because no tackifier resin and plasticizer are added in comparative example 2, no plasticizer is added in comparative example 3, and no tackifier resin is added in comparative example 4.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A magnetically sensitive rubber composition, comprising: the rubber composition comprises a rubber matrix, an active agent, a reinforcing agent, an accelerator, an anti-aging agent, a vulcanizing agent, magnetic particles, a plasticizer and tackifying resin, wherein the rubber matrix comprises natural rubber and butadiene rubber.
2. The magnetic-sensitive rubber composition according to claim 1, wherein the magnetic-sensitive rubber composition comprises 100 parts by weight of the rubber matrix, 4 to 8 parts by weight of the activator, 30 to 60 parts by weight of the reinforcing agent, 1 to 3 parts by weight of the accelerator, 2 to 4 parts by weight of the antioxidant, 1 to 2 parts by weight of the vulcanizing agent, 200 to 600 parts by weight of the magnetic particles, 1 to 5 parts by weight of the plasticizer, and 1 to 3 parts by weight of the tackifier resin.
3. The magnetic-sensitive rubber composition according to claim 1 or 2, wherein the rubber matrix comprises 50 to 70 parts by weight of natural rubber and 30 to 50 parts by weight of butadiene rubber;
optionally, the cis content of the butadiene rubber is not less than 96 wt%.
4. The magnetically sensitive rubber composition of claim 1, wherein the tackifying resin comprises at least one of a Koresin super tackifying resin, a t-butyl phenolic tackifying resin, and an octyl phenolic resin;
optionally, the Koresin super tackifying resin is a condensate of butyl phenol and acetylene, and at least one of the following conditions is satisfied:
the softening point is 135-150 ℃, and the characterization method of the softening point adopts a ring and ball method/DIN 52011;
the dropping point is 140-160 ℃, and the characterization method of the dropping point adopts DIN 51801;
the density at 20 ℃ is 1.02-1.04 g/cm3；
Optionally, the tert-butyl phenolic tackifying resin satisfies at least one of the following conditions:
the softening point is 135-150 ℃, and the characterization method of the softening point adopts a ring and ball method/DIN 52011;
free phenol is less than or equal to 2.0 wt%;
the heating decrement is less than or equal to 0.50 wt%;
optionally, the octyl phenol-formaldehyde resin satisfies at least one of the following conditions:
the softening point is 85-100 ℃, and the characterization method of the softening point adopts a ring and ball method/DIN 52011;
the content of hydroxymethyl is less than or equal to 1.00 wt%;
the heating loss is less than or equal to 0.50 wt%.
5. The magnetosensitive rubber composition of claim 1, wherein the active agent is nano zinc oxide or a mixture of nano zinc oxide and stearic acid;
optionally, the nano zinc oxide comprises 70-80 wt% of primary particles with the particle size of not more than 100nm and 20-30 wt% of primary particles with the particle size of more than 100 nm;
optionally, the reinforcing agent comprises carbon black or a mixture of carbon black and white carbon black;
optionally, the accelerator is accelerator NS;
optionally, the antioxidant comprises antioxidant 6PPD and antioxidant RD, and the mass ratio of antioxidant 6PPD to antioxidant RD is 1: (1-2);
optionally, the vulcanizing agent is sulfur;
optionally, the magnetic particles comprise at least one of modified carbonyl iron powder, modified nickel carbonyl powder, unmodified carbonyl iron powder and unmodified nickel carbonyl powder, preferably modified carbonyl iron powder;
optionally, the plasticizer comprises at least one of dibutyl phthalate, dioctyl sebacate, dibutyl sebacate, and dioctyl adipate.
6. The magnetic-sensitive rubber composition according to claim 1 or 2, further comprising 1-10 parts by weight of a self-repairing agent, wherein the self-repairing agent is a liquid nitrile rubber-phenolic resin.
7. The magnetosensitive rubber composition according to claim 1, further comprising at least one of an antioxidant, an antiozonant, and a protective wax.
8. A method for preparing the magnetic-sensitive rubber composition according to any one of claims 1 to 7, comprising:
(1) mixing natural rubber, butadiene rubber, magnetic particles, a reinforcing agent, an activator, an anti-aging agent, a plasticizer and tackifying resin, performing first mixing, and standing after rubber discharge so as to obtain master batch;
(2) mixing the master batch with a vulcanizing agent and an accelerator for second mixing and rubber discharging so as to obtain a rubber compound;
(3) injecting the rubber compound into a mold, and carrying out pre-structuring treatment under a magnetic field so as to ensure that the magnetic particles are directionally arranged to obtain the rubber compound after pre-structuring treatment;
(4) and vulcanizing the pre-structured rubber compound to obtain the magnetic-sensitive rubber composition.
9. The method of claim 8, further comprising adding a self-healing agent in step (1).
10. The method of claim 8 or 9, further comprising adding at least one of an antioxidant, an antiozonant, and a protective wax in step (1);
optionally, in the step (1), the first mixing time is 3-5 minutes, the temperature is 150-160 ℃, and the standing time is 4-8 hours;
optionally, in the step (2), the second mixing time is 1 to 3 minutes, and the temperature is 95 to 105 ℃.
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