CN111171400B - Rubber composition resisting hot oil aging and preparation method thereof - Google Patents
Rubber composition resisting hot oil aging and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
- C08L7/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention relates to the technical field of rubber, in particular to a rubber composition resisting hot oil aging and a preparation method thereof. The rubber composition prepared by the invention has higher hardness, excellent high temperature resistance, thermal aging resistance and tensile resistance, higher stability and better mechanical property, and the vulcanized rubber sheet of the prepared rubber composition has the tensile strength of more than or equal to 35MPa, the elongation at break of more than or equal to 980 percent, the 300 percent stress at definite elongation of more than or equal to 7MPa and the tear strength of more than or equal to 70 kN/m. In addition, the vulcanized rubber sheet of the rubber composition prepared by the invention also has excellent heat-resistant oil aging performance, after the vulcanized rubber sheet is soaked in oil at 100 ℃ for 72 hours, the reduction rate of the tensile strength is less than or equal to 10 percent, the weight gain rate of the vulcanized rubber sheet is less than or equal to 5 percent, the application range is wide, the vulcanized rubber sheet is particularly suitable for application in inner rubber and outer rubber of an automobile oil cooling pipe, and the vulcanized rubber sheet can be free of cracking or fracture after long-time hot oil circulation.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a rubber composition resisting hot oil aging and a preparation method thereof.
Background
Natural rubber has the advantages of high elasticity, good self-adhesion, good air tightness, good processing performance and the like, and is widely applied to various aspects of industry, agriculture, national defense, traffic, transportation, mechanical manufacturing, medicine and health fields, daily life and the like. However, natural rubber itself has some drawbacks such as poor oil resistance, poor mechanical properties, poor heat aging properties, etc., which limit the use of natural rubber. Therefore, the natural rubber needs to be modified to obtain a rubber material with good comprehensive performance to meet the social requirements.
Carbon Nanotubes (CNTs) are hollow tubular structures wound like a hexagonal network of graphite structure in which C atoms are aggregated under certain conditions. Carbon nanotubes can be viewed as seamless nanoscale cylinders made of single or multiple layers of graphene sheets that are rolled up in a certain degree of helicity. The carbon nano tube has large length-diameter ratio, nano tube diameter and a hollow nano structure, and the unique structures enable the carbon nano tube to have excellent physical and chemical properties and can be used as an excellent composite material reinforced rubber material. In recent years, research in the field of carbon nanotube-rubber has become more and more extensive, for example, carbon nanotube-natural rubber composite materials are prepared by mechanical mixing, organic solvent dissolution, emulsion and the like. However, the carbon nanotubes have a strong surface effect, are easily agglomerated and are unevenly dispersed in a rubber product, so that the structural uniformity of the composite material is poor, and the improvement range of the performance of the composite material is not large, thereby limiting the application range of the composite material. Patent CN201310721595.5 discloses a composite material of carbon nanotubes and rubber prepared by grinding carbon nanotubes and hydroxyl-terminated polybutadiene and mixing with rubber, although the dispersibility of carbon nanotubes in a rubber matrix is improved to a certain extent, the reinforcing effect of carbon nanotubes on rubber is poor, and the tensile strength of the prepared composite material is only 0.14 MPa.
In view of the above problems, the present invention aims to provide a rubber composition resistant to hot oil aging, which has excellent tensile properties, tear properties and hot oil aging resistance, and has a tensile strength of not less than 35 MPa.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a rubber composition resistant to hot oil aging, comprising 90 to 110 parts by weight of a rubber component, 6 to 10 parts by weight of a filler, and 1 to 3 parts by weight of a multifunctional coupling agent.
As a preferable technical scheme, the rubber composition comprises 100 parts of rubber component, 8 parts of filler and 2 parts of multifunctional coupling agent in parts by weight.
As a preferable embodiment, the rubber component is at least one selected from the group consisting of natural rubber latex, natural rubber, epoxidized natural rubber latex, epoxidized natural rubber, hydroxyethyl methacrylate rubber latex, and hydroxyethyl methacrylate rubber.
As a preferable technical scheme, the rubber composition resisting the hot oil aging comprises 90-110 parts of rubber component; the rubber component comprises 87-103 parts of natural rubber latex by dry weight and 3-7 parts of hydroxyethyl methacrylate rubber latex by dry weight.
As a preferable technical scheme, the preparation raw material of the filler comprises at least one of calcium carbonate, shell powder, argil, graphene and carbon nanotubes.
As a preferable technical scheme, in the preparation raw materials of the filler, the length of the carbon nano tube is 50-70 nm.
As a preferable technical scheme, in the preparation raw materials of the filler, the length of the carbon nano tube is 60 nm.
As a preferable technical scheme, the multifunctional coupling agent is at least one selected from JL-G terminal amino-hydroxyl alcohol ester coupling modifier, trimethoxy- [3- (ethylene oxide-2-yl methoxy) propyl ] silane and modified trimethoxy- [3- (ethylene oxide-2-yl methoxy) propyl ] silane.
As a preferable technical scheme, in the multifunctional coupling agent, the weight ratio of the JL-G terminal amino-hydroxyl alcohol ester coupling modifier to the modified trimethoxy- [3- (ethylene oxide-2-yl methoxy) propyl ] silane is 1: (1-3).
The second aspect of the present invention provides a method for preparing a rubber composition resistant to hot oil aging, comprising the steps of: mixing the filler and water, adding a multifunctional coupling agent, performing ultrasonic treatment for 20-40min, reacting at 65-75 ℃ for 1-2h, adding hydroxyethyl methacrylate rubber latex, performing ultrasonic treatment at 65-75 ℃ for 20-40min, adding natural rubber latex, reacting at 65-75 ℃ for 1-2h, and finally coagulating with acetic acid, tabletting, washing and drying to obtain the modified polyurethane.
Has the advantages that: the rubber composition prepared by the invention has higher hardness, excellent high temperature resistance, thermal aging resistance and tensile resistance, higher stability and better mechanical property, and the vulcanized rubber sheet of the prepared rubber composition has the tensile strength of more than or equal to 35MPa, the elongation at break of more than or equal to 980 percent, the 300 percent stress at definite elongation of more than or equal to 7MPa and the tear strength of more than or equal to 70 kN/m. In addition, the vulcanized rubber sheet of the rubber composition prepared by the invention also has excellent heat-resistant oil aging performance, after the vulcanized rubber sheet is soaked in oil at 100 ℃ for 72 hours, the reduction rate of the tensile strength is less than or equal to 10 percent, the weight gain rate of the vulcanized rubber sheet is less than or equal to 5 percent, the application range is wide, the vulcanized rubber sheet is particularly suitable for application in inner rubber and outer rubber of an automobile oil cooling pipe, and the vulcanized rubber sheet can be free of cracking or fracture after long-time hot oil circulation.
Detailed Description
The technical features in the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, but the scope of protection of the present invention is not limited thereto.
"preferred", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
The first aspect of the invention provides a rubber composition resisting hot oil aging, which comprises 90-110 parts of rubber component, 6-10 parts of filler and 1-3 parts of multifunctional coupling agent in parts by weight.
In a preferred embodiment, the rubber composition comprises 100 parts by weight of rubber component, 8 parts by weight of filler and 2 parts by weight of multifunctional coupling agent.
In a preferred embodiment, the rubber component is selected from at least one of natural rubber latex, natural rubber, epoxidized natural rubber latex, epoxidized natural rubber, hydroxyethyl methacrylate rubber latex, hydroxyethyl methacrylate rubber.
In a preferred embodiment, the rubber component is a natural rubber latex, a hydroxyethyl methacrylate rubber latex.
In a preferred embodiment, the heat-oil aging resistant rubber composition includes 90 to 110 parts by weight of a rubber component; the rubber component comprises 87-103 parts of natural rubber latex by dry weight and 3-7 parts of hydroxyethyl methacrylate rubber latex by dry weight.
In a preferred embodiment, the heat-oil aging resistant rubber composition includes 100 parts by weight of a rubber component; the rubber component comprises 95 parts of natural rubber latex by dry weight and 5 parts of hydroxyethyl methacrylate rubber latex by dry weight.
In a preferred embodiment, the natural latex is Hevea brasiliensis natural latex or concentrated natural latex concentrated by centrifugation to a total solids content of 60%.
In a more preferred embodiment, the natural rubber latex is concentrated natural rubber latex having a total solids content of 60% by centrifugal concentration.
In a preferred embodiment, the hydroxyethyl methacrylate rubber latex is milky hydroxyethyl methacrylate rubber prepared by graft copolymerization of natural rubber and hydroxyethyl methacrylate, or is prepared by graft copolymerization of concentrated natural rubber latex and hydroxyethyl methacrylate, so as to obtain the hydroxyethyl methacrylate latex with the grafting rate of 5-50% and the total solid content of 20-25%.
In a more preferred embodiment, the hydroxyethyl methacrylate rubber latex is prepared by graft copolymerization of concentrated natural latex, and has a grafting ratio of 5 to 50% and a total solid content of 20 to 25%.
In a more preferred embodiment, the hydroxyethyl methacrylate rubber latex is a concentrated natural latex prepared by graft copolymerization with a graft ratio of 10% and a total solid content of 20%.
In a preferred embodiment, the raw material for preparing the filler comprises at least one of calcium carbonate, shell powder, pottery clay, graphene and carbon nanotubes.
In a more preferred embodiment, the raw material for the filler comprises carbon nanotubes.
In a preferred embodiment, the method of making the filler comprises the steps of:
(a) reacting carbon nano tubes with a nitric acid aqueous solution at 70-80 ℃ for 12-18h, and then carrying out suction filtration, washing and drying to obtain a mixture 1;
(b) mixing the mixture 1, thionyl chloride and dimethylformamide, reacting at 70-80 ℃ for 15-20h, cooling, centrifuging at the rotating speed of 2200-;
(c) mixing the mixture 2, polyethylene glycol and toluene, adding a catalyst, reacting at 0 ℃ for 20-40min, then reacting at 90-110 ℃ for 1-3h, and finally filtering, washing and drying to obtain the catalyst.
In a more preferred embodiment, the filler is prepared by a process comprising the steps of:
(a) 4-6g of carbon nano tube and 20-40mL of 2-4mol/L nitric acid aqueous solution react for 15h at 75 ℃, and then are subjected to suction filtration, water washing and drying at 100 ℃ to obtain a mixture 1;
(b) mixing 4-6g of the mixture 1 with 80-120mL of thionyl chloride and 1-3mL of dimethylformamide, reacting at 75 ℃ for 18h, cooling, centrifuging at the rotating speed of 2500r/min for 1h, and performing suction filtration, washing with tetrahydrofuran and drying at 50 ℃ to obtain a mixture 2;
(c) mixing the mixture 2, polyethylene glycol and toluene, adding a catalyst, reacting at 0 ℃ for 30min, then at 100 ℃ for 2h, and finally filtering, washing and drying at 80 ℃ to obtain the catalyst.
In a more preferred embodiment, the filler is prepared by a process comprising the steps of:
(a) 5g of carbon nano tube and 30mL of nitric acid aqueous solution with the concentration of 3mol/L react for 15h at 75 ℃, and then mixture 1 is obtained after suction filtration, water washing and drying at 100 ℃;
(b) mixing 5g of the mixture 1 with 100mL of thionyl chloride and 2mL of dimethylformamide, reacting at 75 ℃ for 18h, cooling, centrifuging at the rotating speed of 2500r/min for 1h, performing suction filtration, washing with tetrahydrofuran, and drying at 50 ℃ to obtain a mixture 2;
(c) mixing the mixture 2, polyethylene glycol and toluene, adding 2 drops of catalyst, reacting at 0 deg.C for 30min, then at 100 deg.C for 2h, filtering, washing, and drying at 80 deg.C to obtain the final product.
The CAS number for dimethylformamide is 68-12-2.
In a preferred embodiment, the weight ratio of the mixture 2 to the polyethylene glycol is (1-3): 1.
in a more preferred embodiment, the weight ratio of mixture 2 to polyethylene glycol is 2: 1.
in a preferred embodiment, the mass-to-volume ratio of mixture 2 to toluene is 1: (8-12) g/mL.
In a more preferred embodiment, the mass to volume ratio of mixture 2 to toluene is 1: 10 g/mL.
In a preferred embodiment, the catalyst is dibutyl tin dilaurate.
In a preferred embodiment, the hydroxyl value of the polyethylene glycol is 150-550 mgKOH/g.
The Hydroxyl value (Hydroxyl value) is the number of milligrams of potassium hydroxide (KOH) corresponding to the Hydroxyl group in 1g of the sample, and is expressed as mgKOH/g.
In a preferred embodiment, the polyethylene glycol is selected from at least one of polyethylene glycol 200, polyethylene glycol 400, and polyethylene glycol 600.
In a more preferred embodiment, the polyethylene glycol is polyethylene glycol 400.
The CAS number of the polyethylene glycol is 25322-68-3.
In a preferred embodiment, the carbon nanotubes have a length of 50 to 70 nm.
In a more preferred embodiment, the carbon nanotubes have a length of 60 nm.
The carbon nanotubes are commercially available, including but not limited to from Jiangsu Aikang biomedical research and development Co.
Through a large number of experiments, the applicant finds that when the carbon nano tubes are added into the rubber component and modified by adopting the specific polyethylene glycol and the length of the carbon nano tubes is controlled to be 50-70nm, the excellent tensile property and tearing property of the rubber composition can be ensured, and meanwhile, the heat-resistant oil aging property of the rubber composition is improved. Presumably, the possible reasons are: on one hand, under specific conditions, the carbon nano tube has small impurity effect, and simultaneously, due to the introduction of alkyl groups with specific lengths, rubber molecular chains can form uniform cross-linking points on the surface of the carbon nano tube, so that the tensile property and the tearing property of the rubber composition are improved; on the other hand, under specific conditions, the carbon nano tube modified by the polyethylene glycol can form a specific three-dimensional network structure in a rubber matrix, and the relative movement of rubber molecular chains in the swelling process is hindered, so that the hot oil aging resistance of the rubber composition is improved.
In a preferred embodiment, the multifunctional coupling agent is selected from at least one of JL-G terminal amino hydroxyl alcohol ester coupling modifier, trimethoxy- [3- (oxiran-2-ylmethoxy) propyl ] silane, modified trimethoxy- [3- (oxiran-2-ylmethoxy) propyl ] silane.
In a preferred embodiment, the multifunctional coupling agent is JL-G amino-terminated hydroxyl alcohol ester coupling modifier, modified trimethoxy- [3- (oxiranyl-2-ylmethoxy) propyl ] silane.
The JL-G terminal amino hydroxyl alcohol ester coupling modifier is purchased from Nanjing Jinlaiwang plastic technology Co.
In a preferred embodiment, the process for the preparation of said modified trimethoxy- [3- (oxiran-2-ylmethoxy) propyl ] silane comprises the following steps: mixing trimethoxy- [3- (oxiran-2-yl methoxy) propyl ] silane, p-aminodiphenylamine, 1: (1-1.5) and reacting for 1-3h at the temperature of 130-150 ℃ under the protection of nitrogen.
In a more preferred embodiment, the process for the preparation of said modified trimethoxy- [3- (oxiran-2-ylmethoxy) propyl ] silane comprises the steps of: mixing trimethoxy- [3- (oxiran-2-yl methoxy) propyl ] silane, p-aminodiphenylamine, 1: 1.2, and reacting for 2 hours at 140 ℃ under the protection of nitrogen.
In a preferred embodiment, the weight ratio of the JL-G terminal amino-hydroxyl alcohol ester coupling modifier to the modified trimethoxy- [3- (oxiranyl-2-ylmethoxy) propyl ] silane is 1: (1-3).
In a more preferred embodiment, the weight ratio of the JL-G terminal amino hydroxyl alcohol ester coupling modifier to the modified trimethoxy- [3- (oxiranyl-2-ylmethoxy) propyl ] silane is 1: 2.
the CAS number of the trimethoxy- [3- (oxiranyl-2-yl methoxy) propyl ] silane is 25704-87-4.
The CAS number of the p-aminodiphenylamine is 101-54-2.
Through a large number of experiments, the applicant finds that when the JL-G terminal amino-hydroxyl alcohol ester coupling modifier and the modified trimethoxy- [3- (ethylene oxide-2-yl methoxy) propyl ] silane are compounded to cooperate with the filler in a system to jointly prepare the rubber composition, the prepared rubber composition has excellent mechanical property and heat oil aging resistance.
The second aspect of the present invention provides a method for preparing a rubber composition resistant to hot oil aging, comprising the steps of: mixing the filler and water, adding a multifunctional coupling agent, performing ultrasonic treatment for 20-40min, reacting at 65-75 ℃ for 1-2h, adding hydroxyethyl methacrylate rubber latex, performing ultrasonic treatment at 65-75 ℃ for 20-40min, adding natural rubber latex, reacting at 65-75 ℃ for 1-2h, and finally coagulating with acetic acid, tabletting, washing and drying to obtain the modified polyurethane.
In a preferred embodiment, the method for preparing the rubber composition resistant to hot oil aging comprises the following steps: mixing the filler and water, adding the multifunctional coupling agent, performing ultrasonic treatment for 30min, reacting at 70 ℃ for 1h, adding hydroxyethyl methacrylate rubber latex, performing ultrasonic treatment at 70 ℃ for 30min, adding natural rubber latex, reacting at 70 ℃ for 1h, and finally coagulating, tabletting, washing and drying by using acetic acid to obtain the modified polyurethane.
In a preferred embodiment, the weight ratio of the filler to the water is 1: (9-11).
In a more preferred embodiment, the weight ratio of filler to water is 1: 10.
in a preferred embodiment, the method for preparing a vulcanized rubber sheet of the rubber composition resistant to hot oil aging comprises the steps of: the rubber composition is prepared by uniformly mixing 95-105 parts of heat-oil-aging-resistant rubber composition, 1.5-2 parts of sulfur, 2-3 parts of zinc oxide, 0.1-0.3 part of zinc diethyldithiocarbamate, 0.5-1 part of zinc ethylmonophenyldithiocarbamate and 0.1-0.3 part of 2, 6-di-tert-butyl-4-methylphenol, and vulcanizing at the temperature of 140 ℃ and 160 ℃ for 10-30 min.
In a more preferred embodiment, the method for preparing a vulcanized rubber sheet of the rubber composition resistant to hot oil aging comprises the steps of: 100 parts of rubber composition resistant to heat oil aging, 1.8 parts of sulfur, 2.5 parts of zinc oxide, 0.2 part of zinc diethyldithiocarbamate, 0.8 part of zinc ethylphenyldithiocarbamate and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol are uniformly mixed and vulcanized for 20min at 150 ℃ to obtain the rubber composition.
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. In addition, all the raw materials are commercially available if not particularly limited.
Examples
Example 1
Example 1 of the present invention provides a rubber composition resistant to hot oil aging comprising, in parts by weight, 95 parts by dry weight of a natural rubber latex, 5 parts by dry weight of a hydroxyethyl methacrylate rubber latex, 8 parts by weight of a filler, and 2 parts by weight of a multifunctional coupling agent.
The natural latex is concentrated natural latex with the total solid content of 60 percent after centrifugal concentration.
The hydroxyethyl methacrylate rubber latex is prepared by concentrated natural latex through graft copolymerization, and has a grafting rate of 10% and a total solid content of 20%.
The preparation method of the filler comprises the following steps:
(a) 5g of carbon nano tube and 30mL of nitric acid aqueous solution with the concentration of 3mol/L react for 15h at 75 ℃, and then mixture 1 is obtained after suction filtration, water washing and drying at 100 ℃;
(b) mixing 5g of the mixture 1 with 100mL of thionyl chloride and 2mL of dimethylformamide, reacting at 75 ℃ for 18h, cooling, centrifuging at the rotating speed of 2500r/min for 1h, performing suction filtration, washing with tetrahydrofuran, and drying at 50 ℃ to obtain a mixture 2;
(c) mixing the mixture 2, polyethylene glycol and toluene, adding 2 drops of catalyst, reacting at 0 deg.C for 30min, then at 100 deg.C for 2h, filtering, washing, and drying at 80 deg.C to obtain the final product.
The weight ratio of the mixture 2 to the polyethylene glycol is 2: 1.
the mass-volume ratio of the mixture 2 to the toluene is 1: 10 g/mL.
The catalyst is dibutyl tin dilaurate.
The polyethylene glycol is polyethylene glycol 400.
The length of the carbon nano tube is 60 nm.
The multifunctional coupling agent is JL-G terminal amino-hydroxyl alcohol ester coupling modifier and modified trimethoxy- [3- (ethylene oxide-2-yl methoxyl) propyl ] silane.
The preparation method of the modified trimethoxy- [3- (oxiranyl-2-ylmethoxy) propyl ] silane comprises the following steps: mixing trimethoxy- [3- (oxiran-2-yl methoxy) propyl ] silane, p-aminodiphenylamine, 1: 1.2, and reacting for 2 hours at 140 ℃ under the protection of nitrogen.
The weight ratio of the JL-G terminal amino hydroxyl alcohol ester coupling modifier to the modified trimethoxy- [3- (ethylene oxide-2-methoxy) propyl ] silane is 1: 2.
the preparation method of the rubber composition with the hot oil aging resistance comprises the following steps: mixing the filler and water, adding the multifunctional coupling agent, performing ultrasonic treatment for 30min, reacting at 70 ℃ for 1h, adding hydroxyethyl methacrylate rubber latex, performing ultrasonic treatment at 70 ℃ for 30min, adding natural rubber latex, reacting at 70 ℃ for 1h, and finally coagulating, tabletting, washing and drying by using acetic acid to obtain the modified polyurethane.
The weight ratio of the filler to the water is 1: 10.
the preparation method of the vulcanized rubber sheet of the rubber composition with the thermal oil aging resistance comprises the following steps: 100 parts of rubber composition resistant to heat oil aging, 1.8 parts of sulfur, 2.5 parts of zinc oxide, 0.2 part of zinc diethyldithiocarbamate, 0.8 part of zinc ethylphenyldithiocarbamate and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol are uniformly mixed and vulcanized for 20min at 150 ℃ to obtain the rubber composition.
Example 2
Example 2 of the present invention provides a rubber composition resistant to hot oil aging comprising, in parts by weight, 87 parts by dry weight of a natural rubber latex, 3 parts by dry weight of a hydroxyethyl methacrylate rubber latex, 6 parts by weight of a filler, and 1 part by weight of a multifunctional coupling agent.
The natural latex is concentrated natural latex with the total solid content of 60 percent after centrifugal concentration.
The hydroxyethyl methacrylate rubber latex is prepared by concentrated natural latex through graft copolymerization, and has a grafting rate of 10% and a total solid content of 20%.
The preparation method of the filler comprises the following steps:
(a) 5g of carbon nano tube and 30mL of nitric acid aqueous solution with the concentration of 3mol/L react for 15h at 75 ℃, and then mixture 1 is obtained after suction filtration, water washing and drying at 100 ℃;
(b) mixing 5g of the mixture 1 with 100mL of thionyl chloride and 2mL of dimethylformamide, reacting at 75 ℃ for 18h, cooling, centrifuging at the rotating speed of 2500r/min for 1h, performing suction filtration, washing with tetrahydrofuran, and drying at 50 ℃ to obtain a mixture 2;
(c) mixing the mixture 2, polyethylene glycol and toluene, adding 2 drops of catalyst, reacting at 0 deg.C for 30min, then at 100 deg.C for 2h, filtering, washing, and drying at 80 deg.C to obtain the final product.
The weight ratio of the mixture 2 to the polyethylene glycol is 2: 1.
the mass-volume ratio of the mixture 2 to the toluene is 1: 10 g/mL.
The catalyst is dibutyl tin dilaurate.
The polyethylene glycol is polyethylene glycol 400.
The length of the carbon nanotube is 50 nm.
The multifunctional coupling agent is JL-G terminal amino-hydroxyl alcohol ester coupling modifier and modified trimethoxy- [3- (ethylene oxide-2-yl methoxyl) propyl ] silane.
The preparation method of the modified trimethoxy- [3- (oxiranyl-2-ylmethoxy) propyl ] silane comprises the following steps: mixing trimethoxy- [3- (oxiran-2-yl methoxy) propyl ] silane, p-aminodiphenylamine, 1: 1.2, and reacting for 2 hours at 140 ℃ under the protection of nitrogen.
The weight ratio of the JL-G terminal amino hydroxyl alcohol ester coupling modifier to the modified trimethoxy- [3- (ethylene oxide-2-methoxy) propyl ] silane is 1: 2.
the preparation method of the rubber composition with the hot oil aging resistance comprises the following steps: mixing the filler and water, adding the multifunctional coupling agent, performing ultrasonic treatment for 30min, reacting at 70 ℃ for 1h, adding hydroxyethyl methacrylate rubber latex, performing ultrasonic treatment at 70 ℃ for 30min, adding natural rubber latex, reacting at 70 ℃ for 1h, and finally coagulating, tabletting, washing and drying by using acetic acid to obtain the modified polyurethane.
The weight ratio of the filler to the water is 1: 10.
the preparation method of the vulcanized rubber sheet of the rubber composition with the thermal oil aging resistance comprises the following steps: 100 parts of rubber composition resistant to heat oil aging, 1.8 parts of sulfur, 2.5 parts of zinc oxide, 0.2 part of zinc diethyldithiocarbamate, 0.8 part of zinc ethylphenyldithiocarbamate and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol are uniformly mixed and vulcanized for 20min at 150 ℃ to obtain the rubber composition.
Example 3
Example 3 of the present invention provides a rubber composition resistant to hot oil aging comprising, by weight, 103 parts by dry weight of a natural rubber latex, 7 parts by dry weight of a hydroxyethyl methacrylate rubber latex, 10 parts by dry weight of a rubber latex
Filler and 3 parts of multifunctional coupling agent.
The natural latex is concentrated natural latex with the total solid content of 60 percent after centrifugal concentration.
The hydroxyethyl methacrylate rubber latex is prepared by concentrated natural latex through graft copolymerization, and has a grafting rate of 10% and a total solid content of 20%.
The preparation method of the filler comprises the following steps:
(a) 5g of carbon nano tube and 30mL of nitric acid aqueous solution with the concentration of 3mol/L react for 15h at 75 ℃, and then mixture 1 is obtained after suction filtration, water washing and drying at 100 ℃;
(b) mixing 5g of the mixture 1 with 100mL of thionyl chloride and 2mL of dimethylformamide, reacting at 75 ℃ for 18h, cooling, centrifuging at the rotating speed of 2500r/min for 1h, performing suction filtration, washing with tetrahydrofuran, and drying at 50 ℃ to obtain a mixture 2;
(c) mixing the mixture 2, polyethylene glycol and toluene, adding 2 drops of catalyst, reacting at 0 deg.C for 30min, then at 100 deg.C for 2h, filtering, washing, and drying at 80 deg.C to obtain the final product.
The weight ratio of the mixture 2 to the polyethylene glycol is 2: 1.
the mass-volume ratio of the mixture 2 to the toluene is 1: 10 g/mL.
The catalyst is dibutyl tin dilaurate.
The polyethylene glycol is polyethylene glycol 400.
The length of the carbon nanotube is 70 nm.
The multifunctional coupling agent is JL-G terminal amino-hydroxyl alcohol ester coupling modifier and modified trimethoxy- [3- (ethylene oxide-2-yl methoxyl) propyl ] silane.
The preparation method of the modified trimethoxy- [3- (oxiranyl-2-ylmethoxy) propyl ] silane comprises the following steps: mixing trimethoxy- [3- (oxiran-2-yl methoxy) propyl ] silane, p-aminodiphenylamine, 1: 1.2, and reacting for 2 hours at 140 ℃ under the protection of nitrogen.
The weight ratio of the JL-G terminal amino hydroxyl alcohol ester coupling modifier to the modified trimethoxy- [3- (ethylene oxide-2-methoxy) propyl ] silane is 1: 2.
the preparation method of the rubber composition with the hot oil aging resistance comprises the following steps: mixing the filler and water, adding the multifunctional coupling agent, performing ultrasonic treatment for 30min, reacting at 70 ℃ for 1h, adding hydroxyethyl methacrylate rubber latex, performing ultrasonic treatment at 70 ℃ for 30min, adding natural rubber latex, reacting at 70 ℃ for 1h, and finally coagulating, tabletting, washing and drying by using acetic acid to obtain the modified polyurethane.
The weight ratio of the filler to the water is 1: 10.
the preparation method of the vulcanized rubber sheet of the rubber composition with the thermal oil aging resistance comprises the following steps: 100 parts of rubber composition resistant to heat oil aging, 1.8 parts of sulfur, 2.5 parts of zinc oxide, 0.2 part of zinc diethyldithiocarbamate, 0.8 part of zinc ethylphenyldithiocarbamate and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol are uniformly mixed and vulcanized for 20min at 150 ℃ to obtain the rubber composition.
Example 4
The embodiment 4 of the invention provides a rubber composition resistant to hot oil aging and a preparation method thereof, and also provides a preparation method of a vulcanized rubber sheet of the rubber composition resistant to hot oil aging, which is the same as the embodiment 1 in the specific implementation mode, and is characterized in that the filler is carbon nanotubes, and the length of the carbon nanotubes is 60 nm.
Example 5
Example 5 of the present invention provides a rubber composition resistant to hot oil aging and a method for preparing the same, and further provides a method for preparing a vulcanized rubber sheet of the rubber composition resistant to hot oil aging, the specific embodiment of which is the same as example 1, except that the length of the carbon nanotubes is replaced with 30 nm.
Example 6
Example 6 of the present invention provides a rubber composition resistant to hot oil aging and a method for preparing the same, and further provides a method for preparing a vulcanized rubber sheet of the rubber composition resistant to hot oil aging, the specific embodiment of which is the same as example 1, except that the length of the carbon nanotubes is replaced with 90 nm.
Example 7
The embodiment 7 of the invention provides a rubber composition resistant to hot oil aging and a preparation method thereof, and also provides a preparation method of a vulcanized rubber sheet of the rubber composition resistant to hot oil aging, which is the same as the embodiment 1 in the specific implementation mode, except that the polyethylene glycol is polyethylene glycol 200.
Example 8
The embodiment 8 of the invention provides a rubber composition resistant to hot oil aging and a preparation method thereof, and also provides a preparation method of a vulcanized rubber sheet of the rubber composition resistant to hot oil aging, which is the same as the embodiment 1 in the specific implementation mode, except that the polyethylene glycol is polyethylene glycol 600.
Example 9
The embodiment 9 of the invention provides a rubber composition with thermal oil aging resistance and a preparation method thereof, and also provides a preparation method of a vulcanized rubber sheet of the rubber composition with thermal oil aging resistance, and the specific implementation mode is the same as that of the embodiment 1, except that the preparation method of the modified trimethoxy- [3- (ethylene oxide-2-yl methoxy) propyl ] silane comprises the following steps: mixing trimethoxy- [3- (oxiran-2-yl methoxy) propyl ] silane, p-aminodiphenylamine, 1: 1.2, and mixing to obtain the final product.
Performance evaluation
1. Mechanical properties
The vulcanized sheets of the rubber compositions prepared in examples 1 to 8, which were resistant to hot oil aging, were tested for tensile properties according to GB/T528-2009. If the tensile strength is more than or equal to 35MPa, the elongation at break is more than or equal to 980%, and the 300% stress at definite elongation is more than or equal to 7MPa, the product is marked as qualified, otherwise, the product is unqualified.
The vulcanized sheets of the rubber compositions prepared in examples 1 to 8, which were resistant to hot oil aging, were tested for tear properties according to GB/T529-. If the tearing strength is more than or equal to 70kN/m, the product is marked as qualified, otherwise, the product is unqualified.
2. Resistance to hot oil aging
The vulcanized sheets of the rubber compositions resistant to thermal oil aging prepared in examples 1 to 9 were tested for their resistance to thermal oil aging according to GB/T1690-2010. The oil used for the test is Dexron VI oil, and the test conditions are 100 ℃ multiplied by 72 h. If the reduction rate of the tensile strength is less than or equal to 10 percent and the weight gain rate of the vulcanized rubber sheet is less than or equal to 5 percent, recording as qualified, otherwise, recording as unqualified.
The results are shown in Table 1.
Table 1 results of performance testing
Experimental results show that the vulcanized rubber sheet of the rubber composition prepared by the invention has excellent mechanical properties, the tensile strength is more than or equal to 35MPa, the tensile elongation is more than or equal to 980%, the 300% stress at definite elongation is more than or equal to 7MPa, and the tearing strength is more than or equal to 70 kN/m. In addition, the vulcanized rubber sheet of the rubber composition prepared by the invention has excellent hot oil aging resistance, and after the vulcanized rubber sheet is soaked in oil at 100 ℃ for 72 hours, the reduction rate of the tensile strength is less than or equal to 10 percent, and the weight gain rate of the vulcanized rubber sheet is less than or equal to 5 percent.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. The use of some numerical ranges in the claims also includes sub-ranges within their range, and variations in these ranges are also to be construed as being covered by the appended claims where possible.
Claims (4)
1. The rubber composition with the heat oil aging resistance is characterized by comprising 90-110 parts by weight of rubber component, 6-10 parts by weight of filler and 1-3 parts by weight of multifunctional coupling agent;
the rubber component comprises 87-103 parts of natural rubber latex calculated by dry glue and 3-7 parts of hydroxyethyl methacrylate rubber latex calculated by dry glue;
in the preparation raw materials of the filler, the length of the carbon nano tube is 50-70 nm;
the preparation method of the filler comprises the following steps:
(a) reacting carbon nano tubes with a nitric acid aqueous solution at 70-80 ℃ for 12-18h, and then carrying out suction filtration, washing and drying to obtain a mixture 1;
(b) mixing the mixture 1, thionyl chloride and dimethylformamide, reacting at 70-80 ℃ for 15-20h, cooling, centrifuging at the rotating speed of 2200-;
(c) mixing the mixture 2, polyethylene glycol and toluene, adding a catalyst, reacting at 0 ℃ for 20-40min, then reacting at 90-110 ℃ for 1-3h, and finally filtering, washing and drying to obtain the catalyst;
the hydroxyl value of the polyethylene glycol is 150-550 mgKOH/g;
the polyethylene glycol is selected from polyethylene glycol 400;
in the multifunctional coupling agent, the weight ratio of the JL-G terminal amino-hydroxyl alcohol ester coupling modifier to the modified trimethoxy- [3- (ethylene oxide-2-yl methoxyl) propyl ] silane is 1: 1-3;
the preparation method of the modified trimethoxy- [3- (oxiranyl-2-ylmethoxy) propyl ] silane comprises the following steps: mixing trimethoxy- [3- (oxiran-2-yl methoxy) propyl ] silane, p-aminodiphenylamine, 1: 1-1.5, and reacting at 130-150 ℃ for 1-3h under the protection of nitrogen.
2. The rubber composition resistant to hot oil aging according to claim 1, comprising 100 parts by weight of the rubber component, 8 parts by weight of the filler, and 2 parts by weight of the multifunctional coupling agent.
3. The rubber composition resistant to hot oil aging according to claim 1, wherein the carbon nanotubes in the filler are 60nm in length.
4. A method for producing the hot oil aging resistant rubber composition according to any one of claims 1 to 3, comprising the steps of: mixing the filler and water, adding a multifunctional coupling agent, performing ultrasonic treatment for 20-40min, reacting at 65-75 ℃ for 1-2h, adding hydroxyethyl methacrylate rubber latex, performing ultrasonic treatment at 65-75 ℃ for 20-40min, adding natural rubber latex, reacting at 65-75 ℃ for 1-2h, and finally coagulating with acetic acid, tabletting, washing and drying to obtain the modified polyurethane.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456961A (en) * | 2009-01-07 | 2009-06-17 | 中国热带农业科学院农产品加工研究所 | Method for preparing reactive nano calcium carbonate-native rubber composite material |
| CN102838788A (en) * | 2012-09-26 | 2012-12-26 | 中国热带农业科学院农产品加工研究所 | Shell powder-natural rubber composite material and preparation method thereof |
| CN103539976A (en) * | 2013-10-29 | 2014-01-29 | 中国热带农业科学院农产品加工研究所 | Preparation method of reinforced natural rubber composite material by grafting hydroxyethyl methacrylate rubber with modified nano calcium carbonate |
| CN103554558A (en) * | 2013-10-29 | 2014-02-05 | 中国热带农业科学院农产品加工研究所 | Preparation method of hydroxyethyl methylacrylate rubber grafted and modified clay-enhanced natural rubber composite material |
| CN105348581A (en) * | 2015-12-10 | 2016-02-24 | 中国热带农业科学院农产品加工研究所 | Natural rubber-based flexible wave absorbing composite material and preparation method thereof |
| CN106084355A (en) * | 2015-08-29 | 2016-11-09 | 山东丰源轮胎制造股份有限公司 | Rubber composition and preparation method thereof, semi-steel radial tire |
| JP2019019192A (en) * | 2017-07-14 | 2019-02-07 | 住友ゴム工業株式会社 | Rubber material for tennis ball, and tennis ball |
-
2020
- 2020-02-05 CN CN202010080784.9A patent/CN111171400B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456961A (en) * | 2009-01-07 | 2009-06-17 | 中国热带农业科学院农产品加工研究所 | Method for preparing reactive nano calcium carbonate-native rubber composite material |
| CN102838788A (en) * | 2012-09-26 | 2012-12-26 | 中国热带农业科学院农产品加工研究所 | Shell powder-natural rubber composite material and preparation method thereof |
| CN103539976A (en) * | 2013-10-29 | 2014-01-29 | 中国热带农业科学院农产品加工研究所 | Preparation method of reinforced natural rubber composite material by grafting hydroxyethyl methacrylate rubber with modified nano calcium carbonate |
| CN103554558A (en) * | 2013-10-29 | 2014-02-05 | 中国热带农业科学院农产品加工研究所 | Preparation method of hydroxyethyl methylacrylate rubber grafted and modified clay-enhanced natural rubber composite material |
| CN106084355A (en) * | 2015-08-29 | 2016-11-09 | 山东丰源轮胎制造股份有限公司 | Rubber composition and preparation method thereof, semi-steel radial tire |
| CN105348581A (en) * | 2015-12-10 | 2016-02-24 | 中国热带农业科学院农产品加工研究所 | Natural rubber-based flexible wave absorbing composite material and preparation method thereof |
| JP2019019192A (en) * | 2017-07-14 | 2019-02-07 | 住友ゴム工業株式会社 | Rubber material for tennis ball, and tennis ball |
Non-Patent Citations (1)
| Title |
|---|
| Influence of aminosilane-functionalized carbon nanotubes on the rheometric, mechanical,electrical and thermal degradation properties of epoxidized natural rubber nanocomposites;Andikkadu M 等;《polymer international》;20131231;第62卷(第10期);第1433-1441页 * |
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