CN112679817A - Self-repairing rubber material and preparation method thereof - Google Patents
Self-repairing rubber material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-repairing rubber material which is characterized by being prepared from the following components in parts by weight: 40-50 parts of epoxidized natural rubber, 30-40 parts of methyl vinyl silicone rubber, 5-10 parts of benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, 8-12 parts of hyperbranched secondary thiol compound, 2-4 parts of hyperbranched polyamidoamine, 2-5 parts of pig hair fiber, 15-25 parts of inorganic filler, 2-3 parts of coupling agent, 1-3 parts of vulcanizing agent and 1-2 parts of photoinitiator. The invention also provides a preparation method of the self-repairing rubber material. The self-repairing rubber material provided by the invention has better comprehensive performance and performance stability, better self-repairing effect, and more excellent mechanical property, temperature resistance, impact resistance and aging resistance.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a self-repairing rubber material and a preparation method thereof.
Background
In recent years, with the development of science and technology and the improvement of living standard of people, the performance of rubber materials is continuously improved, and the rubber materials are more and more widely applied to various fields in the life of people and become an indispensable part in the daily life of people. However, in the process of forming and subsequent use of rubber material products, the rubber material products are inevitably subjected to external stimulation such as heat, mechanical, chemical and ultraviolet irradiation, so that local damage or microcracks are generated inside the materials, the local damage or microcracks are extremely difficult to detect and repair, the mechanical performance of the materials is reduced, the use is influenced if the local damage or microcracks are extremely difficult to detect and repair, the life safety of other people is threatened if the local damage or microcracks are light, and the use value and the safety of the rubber material products are greatly reduced. How to effectively find and repair local damage or microcracks in rubber materials is a problem that researchers in the industry have to face.
Self-healing refers to the ability of the material itself to self-judge, control and restore defects. The self-repairing material can be self-detected and can automatically repair micro-damage through a certain mechanism, so that the safety of the material is obviously improved, and the service life of the material is prolonged. Therefore, the self-repairing capability is endowed to the rubber material, which is an effective way to solve the problem that the use value and the safety of the rubber material are reduced due to local damage or microcrack.
The existing self-repairing rubber material realizes the self-repairing function by introducing a dynamic reversible covalent bond with reversible characteristics or a structural unit with reversible non-covalent bond interaction into a rubber macromolecule chain structure. On one hand, however, the self-repairing mechanism of the existing self-repairing high-rubber material is relatively single, and a material with good comprehensive performance and ideal self-repairing effect cannot be obtained; on the other hand, when the structural unit with reversible non-covalent bond interaction is introduced into a rubber high molecular chain, a cosolvent is generally required to be added into a reaction system for realization, which can cause the release of volatile compounds (VOC) and energy consumption and environmental problems in the preparation and use processes of the self-repairing rubber material. In addition, the self-repairing rubber materials on the market at present have the defects of poor mechanical strength, weak impact resistance, and further improved self-repairing performance and aging resistance.
For example, publication No. CN109111604A discloses a self-repairing rubber material, which is prepared by mixing and vulcanizing a rubber substrate, a self-repairing elastic prepolymer, carbon black, zinc oxide, stearic acid, an antioxidant, an accelerator and a vulcanizing agent, and can achieve a good self-repairing effect, and has a huge market application prospect and good economic and social benefits. However, the components of the rubber material are not well compatible, the toxicity is high, and the repeated self-repairing of the rubber can not be realized, so that the temperature resistance, the toughness and the tensile resistance can not be guaranteed, and the service life of the rubber material is reduced; and the processing and forming conditions are harsh, and the energy consumption is large.
Therefore, the development of the self-repairing rubber material with better comprehensive performance and performance stability, better self-repairing effect and more excellent mechanical property, temperature resistance, impact resistance and aging resistance meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the field of self-repairing materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the self-repairing rubber material which has better comprehensive performance and performance stability, better self-repairing effect and more excellent mechanical property, temperature resistance, impact resistance and aging resistance. Meanwhile, the invention also provides a preparation method of the self-repairing rubber material, and the preparation method is simple, low in equipment investment, low in energy consumption, high in preparation efficiency, green and environment-friendly in preparation process and suitable for continuous large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that the self-repairing rubber material is characterized by being prepared from the following components in parts by weight: 40-50 parts of epoxidized natural rubber, 30-40 parts of methyl vinyl silicone rubber, 5-10 parts of benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, 8-12 parts of hyperbranched secondary thiol compound, 2-4 parts of hyperbranched polyamidoamine, 2-5 parts of pig hair fiber, 15-25 parts of inorganic filler, 2-3 parts of coupling agent, 1-3 parts of vulcanizing agent and 1-2 parts of photoinitiator.
Preferably, the photoinitiator is at least one of benzophenone, benzoin ethyl ether and benzoin methyl ether.
Preferably, the vulcanizing agent is prepared by mixing tetramethylthiuram disulfide and zinc dibutyl dithiocarbamate according to the mass ratio of 3 (1-2).
Preferably, the coupling agent is selected from one or more of a silane coupling agent KH570, a silane coupling agent KH560 and a silane coupling agent KH 550.
Preferably, the inorganic filler is at least one of white carbon black, lignin, carbon black and coal powder.
Preferably, the particle size of the inorganic filler is 800-1200 meshes.
Preferably, the pig hair fiber is waste pig hair fiber, and the length of the pig hair fiber is 3-8 mm.
Preferably, the hyperbranched polyamidoamine is the hyperbranched polyamidoamine prepared by the method of example 1 in CN 103523885A.
Preferably, the hyperbranched secondary thiol compound is prepared by the preparation method of example 1 in application No. 201911087448.0.
Preferably, the preparation method of the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate comprises the following steps: adding benzophenone-4, 4 '-dicarboxylic acid and amino-terminated polyurethane into a high boiling point solvent, then adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into the solvent, carrying out reflux stirring reaction for 8-12 hours at the temperature of 160 ℃ in an inert gas atmosphere, carrying out rotary evaporation to remove the solvent and byproducts after the reaction is finished, and then carrying out water washing and drying in sequence to obtain the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate.
Preferably, the molar ratio of the benzophenone-4, 4' -dicarboxylic acid to the amino-terminated polyurethane to the high boiling point solvent to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine is 1:1 (8-12) to 0.8-1.2: 0.5.
Preferably, the amino-terminated polyurethane is prepared by the method of example 1 of patent CN102432804 a.
Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
Preferably, the grade of the methyl vinyl silicone rubber is H-110-6, and the methyl vinyl silicone rubber is purchased from Hengzheng Hengji silicone company; the molecular weight is 45-60 ten thousand, and the vinyl mass content is 0.9-1.1%.
Preferably, the epoxidized natural rubber is at least one of ENR-20 epoxidized natural rubber, ENR-25 epoxidized natural rubber, ENR-30 epoxidized natural rubber and ENR-40 epoxidized natural rubber.
Another object of the present invention is to provide a method for preparing the self-repairing rubber material, which comprises the following steps: mixing the components according to parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extruding; then, at room temperature, the self-repairing rubber material is prepared by the light irradiation of ultraviolet light with the wavelength of 250-350nm for 30-40 minutes.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1) the preparation method of the self-repairing rubber material provided by the invention is simple, low in equipment investment, low in energy consumption, high in preparation efficiency, green and environment-friendly in preparation process, and suitable for continuous large-scale production.
2) The self-repairing rubber material provided by the invention overcomes the defect that the existing self-repairing rubber material has a relatively single self-repairing mechanism and cannot obtain a material with good comprehensive performance and ideal self-repairing effect; when a rubber high-molecular chain is introduced, a structural unit with reversible non-covalent bond interaction is generally realized by adding a cosolvent into a reaction system, which can cause the defects of Volatile Organic Compound (VOC) release and energy consumption and environmental problems in the preparation and use processes of the self-repairing rubber material; the defects that the self-repairing rubber material on the market at present is poor in mechanical strength, weak in impact resistance and required to be further improved in self-repairing performance and ageing resistance are overcome; the components have synergistic effect, so that the prepared self-repairing rubber material has better comprehensive performance and performance stability, better self-repairing effect, and more excellent mechanical property, temperature resistance, impact resistance and aging resistance.
3) According to the self-repairing rubber material provided by the invention, the epoxy group on the epoxidized natural rubber can chemically react with the amino group on the hyperbranched polyamidoamine, the acid amino group and the carboxyl group on the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, and the thiol group on the hyperbranched secondary thiol compound can click-react with the vinyl groups on the epoxidized natural rubber and the methyl vinyl silicone rubber under the action of the photoinitiator to form a complex three-dimensional network structure, so that the comprehensive performance and the performance stability of the rubber material are effectively improved; due to the introduction of the hyperbranched molecular structure and the long side chain structure, the winding and curling of molecular chains can increase the space between the molecular chains, improve the elasticity and toughness of the rubber material, and when cracks are generated in the rubber matrix, the crack positions of the rubber can be healed more easily under the action of external force.
4) The benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate can provide excellent weather resistance and mechanical properties for rubber materials, a benzophenone structure is introduced to a molecular main chain of the polycondensate through polycondensation to form a macromolecular photoinitiator, when a rubber matrix cracks, the photoinitiator initiates a click reaction between thiol groups remained on hyperbranched secondary thiol compounds and unsaturated bonds remained on the rubber matrix nearby the cracks through illumination, cross-linked products are quickly generated, the cracks in the rubber are filled, and therefore the rubber is effectively repaired, and the original mechanical properties of the materials are restored or improved. The activity and stability of the macromolecular initiator can be improved through the autonomously synthesized macromolecular initiator, so that the rubber can be self-repaired for many times, and the cost performance of the rubber is improved.
5) According to the self-repairing rubber material provided by the invention, the epoxy group on the epoxidized natural rubber reacts with the hyperbranched polyamidoamine to generate hydroxyl, the amino on the hyperbranched polyamidoamine and the polyurethane structure are introduced, so that the rubber substrate contains a plurality of hydrogen bonds, the plurality of hydrogen bonds interact with each other to rearrange and repair micron-scale cracks and further bridge the cracks, the repeated self-repairing of the rubber is realized, and the good temperature resistance, toughness and tensile resistance of the rubber are maintained, so that the service life of the rubber material is effectively prolonged.
6) The self-repairing rubber material provided by the invention is added with the pig hair fiber, so that the mechanical property of the rubber can be effectively improved, and meanwhile, the waste pig hair is recycled, so that the waste is changed into valuable, the environmental problem is solved, the energy is saved, and the requirements of the basic national policy of sustainable development are met.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The hyperbranched polyamidoamines used in the following examples of the invention were the hyperbranched polyamidoamines prepared according to the method of example 1 in CN 103523885A; the hyperbranched secondary thiol compound is prepared by the preparation method of example 1 in application No. 201911087448.0; the amino-terminated polyurethane is prepared by the method of patent CN102432804A example 1; the methyl vinyl silicone rubber is H-110-6, and is purchased from Hengzheng Hengji Hengcheng organosilicon Co Ltd; other raw materials were all purchased commercially.
Example 1
The self-repairing rubber material is characterized by being prepared from the following components in parts by weight: 40 parts of epoxidized natural rubber, 30 parts of methyl vinyl silicone rubber, 5 parts of benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, 8 parts of hyperbranched secondary thiol compound, 2 parts of hyperbranched polyamidoamine, 2 parts of pig hair fiber, 15 parts of inorganic filler, 2 parts of coupling agent, 1 part of vulcanizing agent and 1 part of photoinitiator.
The photoinitiator is benzophenone; the vulcanizing agent is formed by mixing tetramethylthiuram disulfide and zinc dibutyl dithiocarbamate according to the mass ratio of 3: 1; the coupling agent is selected from a silane coupling agent KH 570.
The inorganic filler is white carbon black; the particle size of the inorganic filler is 800 meshes; the pig hair fiber is waste pig hair fiber, and the length of the pig hair fiber is 3 mm.
The preparation method of the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate comprises the following steps: adding benzophenone-4, 4 '-dicarboxylic acid and amino-terminated polyurethane into a high-boiling-point solvent, then adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into the solvent, carrying out reflux stirring reaction for 8 hours at 110 ℃ in an inert gas atmosphere, carrying out rotary evaporation to remove the solvent and byproducts after the reaction is finished, and then carrying out water washing and drying in sequence to obtain the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate.
The molar ratio of the benzophenone-4, 4' -dicarboxylic acid to the amino-terminated polyurethane to the high-boiling point solvent to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine is 1:1:8:0.8: 0.5; the high boiling point solvent is dimethyl sulfoxide; the inert gas is nitrogen.
The epoxidized natural rubber is ENR-20 epoxidized natural rubber.
The preparation method of the self-repairing rubber material is characterized by comprising the following steps of: mixing the components according to parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extruding; and then irradiating the mixture for 30 minutes under ultraviolet light with the wavelength of 250nm at room temperature to prepare the self-repairing rubber material.
Example 2
The self-repairing rubber material is characterized by being prepared from the following components in parts by weight: 43 parts of epoxidized natural rubber, 32 parts of methyl vinyl silicone rubber, 6 parts of benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, 9 parts of hyperbranched secondary thiol compound, 2.5 parts of hyperbranched polyamidoamine, 2.5 parts of pig hair fiber, 17 parts of inorganic filler, 2.3 parts of coupling agent, 1.5 parts of vulcanizing agent and 1.2 parts of photoinitiator.
The photoinitiator is benzoin ethyl ether; the vulcanizing agent is formed by mixing tetramethylthiuram disulfide and zinc dibutyl dithiocarbamate according to the mass ratio of 3: 1.2; the coupling agent is a silane coupling agent KH 560; the inorganic filler is lignin; the particle size of the inorganic filler is 900 meshes; the pig hair fiber is waste pig hair fiber, and the length of the pig hair fiber is 4 mm.
The preparation method of the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate comprises the following steps: adding benzophenone-4, 4 '-dicarboxylic acid and amino-terminated polyurethane into a high-boiling-point solvent, then adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into the solvent, carrying out reflux stirring reaction for 9 hours at 120 ℃ in an inert gas atmosphere, carrying out rotary evaporation to remove the solvent and byproducts after the reaction is finished, and then carrying out water washing and drying in sequence to obtain the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate.
The molar ratio of the benzophenone-4, 4' -dicarboxylic acid to the amino-terminated polyurethane to the high-boiling point solvent to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine is 1:1:9:0.9: 0.5; the high boiling point solvent is N, N-dimethylformamide; the inert gas is helium.
The epoxidized natural rubber is ENR-25 epoxidized natural rubber.
The preparation method of the self-repairing rubber material is characterized by comprising the following steps of: mixing the components according to parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extruding; and then irradiating the mixture for 33 minutes under ultraviolet light with the wavelength of 270nm at room temperature to prepare the self-repairing rubber material.
Example 3
The self-repairing rubber material is characterized by being prepared from the following components in parts by weight: 45 parts of epoxidized natural rubber, 35 parts of methyl vinyl silicone rubber, 7.5 parts of benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, 10 parts of hyperbranched secondary thiol compound, 3 parts of hyperbranched polyamidoamine, 3.5 parts of pig hair fiber, 20 parts of inorganic filler, 2.5 parts of coupling agent, 2 parts of vulcanizing agent and 1.5 parts of photoinitiator.
The photoinitiator is benzoin methyl ether; the vulcanizing agent is formed by mixing tetramethylthiuram disulfide and zinc dibutyl dithiocarbamate according to the mass ratio of 3: 1.5; the coupling agent is a silane coupling agent KH 550; the inorganic filler is carbon black; the particle size of the inorganic filler is 1000 meshes; the pig hair fiber is waste pig hair fiber, and the length of the pig hair fiber is 5 mm.
The preparation method of the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate comprises the following steps: adding benzophenone-4, 4 '-dicarboxylic acid and amino-terminated polyurethane into a high-boiling-point solvent, then adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into the solvent, carrying out reflux stirring reaction for 10 hours at 130 ℃ in an inert gas atmosphere, carrying out rotary evaporation to remove the solvent and byproducts after the reaction is finished, and then carrying out water washing and drying in sequence to obtain the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate.
The molar ratio of the benzophenone-4, 4' -dicarboxylic acid to the amino-terminated polyurethane to the high-boiling point solvent to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine is 1:1:10:1: 0.5; the high boiling point solvent is N, N-dimethylacetamide; the inert gas is neon.
The epoxidized natural rubber is ENR-30 epoxidized natural rubber.
The preparation method of the self-repairing rubber material is characterized by comprising the following steps of: mixing the components according to parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extruding; and then irradiating the mixture for 35 minutes under ultraviolet light with the wavelength of 300nm at room temperature to prepare the self-repairing rubber material.
Example 4
The self-repairing rubber material is characterized by being prepared from the following components in parts by weight: 48 parts of epoxidized natural rubber, 38 parts of methyl vinyl silicone rubber, 9 parts of benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, 11 parts of hyperbranched secondary thiol compound, 3.5 parts of hyperbranched polyamidoamine, 4.5 parts of pig hair fiber, 23 parts of inorganic filler, 2.8 parts of coupling agent, 2.8 parts of vulcanizing agent and 1.8 parts of photoinitiator.
The photoinitiator is formed by mixing benzophenone, benzoin ethyl ether and benzoin methyl ether according to the mass ratio of 1:2: 4; the vulcanizing agent is formed by mixing tetramethylthiuram disulfide and zinc dibutyl dithiocarbamate according to the mass ratio of 3: 1.8.
The coupling agent is formed by mixing a silane coupling agent KH570, a silane coupling agent KH560 and a silane coupling agent KH550 according to a mass ratio of 1:2: 4; the inorganic filler is formed by mixing white carbon black, lignin, carbon black and coal powder according to the mass ratio of 1:2:4: 3; the particle size of the inorganic filler is 1100 meshes; the pig hair fiber is waste pig hair fiber, and the length of the pig hair fiber is 7 mm.
The preparation method of the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate comprises the following steps: adding benzophenone-4, 4 '-dicarboxylic acid and amino-terminated polyurethane into a high-boiling-point solvent, then adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into the solvent, carrying out reflux stirring reaction for 11 hours at 150 ℃ in an inert gas atmosphere, carrying out rotary evaporation to remove the solvent and byproducts after the reaction is finished, and then carrying out water washing and drying in sequence to obtain the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate.
The molar ratio of the benzophenone-4, 4' -dicarboxylic acid to the amino-terminated polyurethane to the high-boiling point solvent to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine is 1:1:11:1.1: 0.5; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:1:2: 3; the inert gas is argon.
The epoxidized natural rubber is prepared by mixing ENR-20 epoxidized natural rubber, ENR-25 epoxidized natural rubber, ENR-30 epoxidized natural rubber and ENR-40 epoxidized natural rubber according to the mass ratio of 1:3:3: 2.
The preparation method of the self-repairing rubber material is characterized by comprising the following steps of: mixing the components according to parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extruding; and then irradiating the mixture for 39 minutes under ultraviolet light with the wavelength of 330nm at room temperature to prepare the self-repairing rubber material.
Example 5
The self-repairing rubber material is characterized by being prepared from the following components in parts by weight: 50 parts of epoxidized natural rubber, 40 parts of methyl vinyl silicone rubber, 10 parts of benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, 12 parts of hyperbranched secondary thiol compound, 4 parts of hyperbranched polyamidoamine, 5 parts of pig hair fiber, 25 parts of inorganic filler, 3 parts of coupling agent, 3 parts of vulcanizing agent and 2 parts of photoinitiator.
The photoinitiator is benzophenone; the vulcanizing agent is formed by mixing tetramethylthiuram disulfide and zinc dibutyl dithiocarbamate according to the mass ratio of 3: 2; the coupling agent is a silane coupling agent KH 550; the inorganic filler is coal powder; the particle size of the inorganic filler is 1200 meshes; the pig hair fiber is waste pig hair fiber, and the length of the pig hair fiber is 8 mm.
The preparation method of the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate comprises the following steps: adding benzophenone-4, 4 '-dicarboxylic acid and amino-terminated polyurethane into a high-boiling-point solvent, then adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into the solvent, carrying out reflux stirring reaction for 12 hours at 160 ℃ in an inert gas atmosphere, carrying out rotary evaporation to remove the solvent and byproducts after the reaction is finished, and then carrying out water washing and drying in sequence to obtain the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate.
The molar ratio of the benzophenone-4, 4' -dicarboxylic acid to the amino-terminated polyurethane to the high-boiling point solvent to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine is 1:1:12:1.2: 0.5; the high boiling point solvent is N-methyl pyrrolidone; the inert gas is nitrogen.
The epoxidized natural rubber is ENR-40 epoxidized natural rubber.
The preparation method of the self-repairing rubber material is characterized by comprising the following steps of: mixing the components according to parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extruding; and then irradiating the mixture for 40 minutes under ultraviolet light with the wavelength of 350nm at room temperature to prepare the self-repairing rubber material.
Comparative example 1
The present example provides a self-repairing rubber material, the formulation and preparation method of which are substantially the same as those in example 1, except that: no epoxidized natural rubber was added.
Comparative example 2
The present example provides a self-repairing rubber material, the formulation and preparation method of which are substantially the same as those in example 1, except that: no benzophenone-4, 4' -dicarboxylic acid/amino terminated polyurethane polycondensate was added.
Comparative example 3
The present example provides a self-repairing rubber material, the formulation and preparation method of which are substantially the same as those in example 1, except that: no hyperbranched secondary thiol compound was added.
Comparative example 4
The present example provides a self-repairing rubber material, the formulation and preparation method of which are substantially the same as those in example 1, except that: no hyperbranched polyamidoamine was added.
Comparative example 5
The present example provides a self-repairing rubber material, the formulation and preparation method of which are substantially the same as those in example 1, except that: no pig hair fiber was added.
The self-repairing rubber materials in the above examples 1-5 and comparative examples 1-5 are subjected to performance tests, the test results are shown in table 1, and the test methods refer to the standards GB/T529-2008, GB/T528-2009 and GB/T1681-1991 respectively. The self-repairing performance is that rubber which generates cracks in a stretching mode is placed on a flat plate at the temperature of 50 ℃ for 5 hours, the rubber is irradiated by 300nm ultraviolet light for 15 minutes, the stretching performance is tested again, the self-repairing performance is equal to the stretching strength/initial stretching strength multiplied by 100% after self-repairing, and the larger the numerical value is, the better the self-repairing performance is.
TABLE 1 self-repairing rubber Material Performance test results
| Detecting items | Tear Strength (KN/m) | Tensile Strength (MPa) | Impact rebound (%) | Self-healing Properties (%) |
| Example 1 | 27.5 | 19.6 | 68 | 84 |
| Example 2 | 27.9 | 20.0 | 72 | 86 |
| Example 3 | 28.3 | 20.4 | 76 | 88 |
| Example 4 | 28.6 | 20.7 | 79 | 90 |
| Example 5 | 28.8 | 21.0 | 81 | 91 |
| Comparative example 1 | 23.5 | 16.2 | 54 | 75 |
| Comparative example 2 | 24.2 | 16.6 | 56 | 76 |
| Comparative example 3 | 21.0 | 14.5 | 47 | 70 |
| Comparative example 4 | 23.3 | 15.4 | 50 | 79 |
| Comparative example 5 | 25.1 | 17.3 | 60 | 83 |
As can be seen from table 1, the self-repairing rubber material disclosed in the examples of the present invention has higher tensile strength, more excellent rebound resilience and tear resistance, and better self-repairing effect, which is a result of the synergistic effect of the components.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The self-repairing rubber material is characterized by being prepared from the following components in parts by weight: 40-50 parts of epoxidized natural rubber, 30-40 parts of methyl vinyl silicone rubber, 5-10 parts of benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate, 8-12 parts of hyperbranched secondary thiol compound, 2-4 parts of hyperbranched polyamidoamine, 2-5 parts of pig hair fiber, 15-25 parts of inorganic filler, 2-3 parts of coupling agent, 1-3 parts of vulcanizing agent and 1-2 parts of photoinitiator.
2. The self-repairing rubber material of claim 1, wherein the photoinitiator is at least one of benzophenone, benzoin ethyl ether and benzoin methyl ether; the vulcanizing agent is formed by mixing tetramethylthiuram disulfide and zinc dibutyl dithiocarbamate according to the mass ratio of 3 (1-2); the coupling agent is selected from one or more of a silane coupling agent KH570, a silane coupling agent KH560 and a silane coupling agent KH 550.
3. The self-repairing rubber material of claim 1, wherein the inorganic filler is at least one of white carbon black, lignin, carbon black and coal dust; the particle size of the inorganic filler is 800-1200 meshes.
4. The self-repairing rubber material of claim 1, wherein the pig hair fibers are waste pig hair fibers and have a length of 3-8 mm.
5. The self-repairing rubber material of claim 1, wherein the preparation method of the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate comprises the following steps: adding benzophenone-4, 4 '-dicarboxylic acid and amino-terminated polyurethane into a high boiling point solvent, then adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into the solvent, carrying out reflux stirring reaction for 8-12 hours at the temperature of 160 ℃ in an inert gas atmosphere, carrying out rotary evaporation to remove the solvent and byproducts after the reaction is finished, and then carrying out water washing and drying in sequence to obtain the benzophenone-4, 4' -dicarboxylic acid/amino-terminated polyurethane polycondensate.
6. The self-repairing rubber material of claim 5, wherein the molar ratio of the benzophenone-4, 4' -dicarboxylic acid, the amino-terminated polyurethane, the high boiling point solvent, the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and the 4-dimethylaminopyridine is 1:1 (8-12) to (0.8-1.2) to 0.5.
7. The self-healing rubber material of claim 5, wherein the high boiling point solvent is at least one of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.
8. The self-repairing rubber material of claim 1, wherein the epoxidized natural rubber is at least one of ENR-20 epoxidized natural rubber, ENR-25 epoxidized natural rubber, ENR-30 epoxidized natural rubber, ENR-40 epoxidized natural rubber.
9. The preparation method of the self-repairing rubber material according to any one of claims 1 to 8, characterized by comprising the following steps: mixing the components according to parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extruding; then, at room temperature, the self-repairing rubber material is prepared by the light irradiation of ultraviolet light with the wavelength of 250-350nm for 30-40 minutes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114350098A (en) * | 2022-03-03 | 2022-04-15 | 上海起帆电线电缆技术有限公司 | Heat-resistant environment-friendly cable material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114350098A (en) * | 2022-03-03 | 2022-04-15 | 上海起帆电线电缆技术有限公司 | Heat-resistant environment-friendly cable material and preparation method thereof |
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