CN112812387A - Cold-resistant oil-resistant nitrile rubber for sealing element and preparation method thereof - Google Patents
Cold-resistant oil-resistant nitrile rubber for sealing element and preparation method thereof Download PDFInfo
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
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Abstract
The invention relates to the field of rubber, and discloses cold-resistant and oil-resistant nitrile rubber for a sealing element and a preparation method thereof, wherein the cold-resistant and oil-resistant nitrile rubber comprises the following steps: 50-60% of nitrile-butadiene rubber, 5-10% of modified nitrile-butadiene rubber, 5-10% of butadiene rubber, 1-5% of thermoplastic polyurethane elastomer, 0-0.5% of aramid short fiber, 1-3% of zinc oxide, 0.1-1.0% of stearic acid, 10-20% of inorganic reinforcing agent, 0.1-2% of anti-aging agent, 3-5% of softening oil, 1-3% of vulcanizing agent and 1-3% of accelerator. The nitrile rubber is doped with a proper amount of special modified nitrile rubber under the condition of reducing the content of acrylonitrile in a small amount, and the performances of elasticity, wear resistance, mechanical strength and the like of the rubber at a low temperature can be effectively improved on the premise of not influencing the oil resistance.
Description
Technical Field
The invention relates to the field of rubber, in particular to cold-resistant and oil-resistant nitrile rubber for a sealing element and a preparation method thereof.
Background
Nitrile rubber is a synthetic rubber made by copolymerizing butadiene and acrylonitrile. The more the acrylonitrile content in the nitrile rubber is, the better the oil resistance is. Therefore, the nitrile rubber is a universal oil-resistant rubber and is widely applied to hydraulic and pneumatic systems of petroleum machinery, vehicles, engineering machinery and the like. Among them, nitrile rubber is particularly suitable as a material for sealing members because of its excellent elasticity, good oil, odor and chemical corrosion resistance, and good compression set and heat resistance. But the properties of nitrile rubbers are significantly reduced at low temperatures. The brittleness temperature is only about-40 ℃, if the sealing gasket is used in an environment below-40 ℃, the elasticity, the wear resistance, the mechanical strength and the like can be greatly reduced, the sealing function is easy to lose effectiveness, and the use is directly influenced.
The Chinese invention patent CN201710908623.2 discloses a nitrile rubber (NBR) low-temperature cold-resistant sealing element and a preparation method thereof, wherein the sealing element comprises the following raw material components in parts by weight: 70-90 parts of nitrile butadiene rubber; 10-30 parts of butadiene rubber; 3-7 parts of zinc oxide; 0.5-1.5 parts of Stearic Acid (SA); 0.5-1.5 parts of anti-aging agent (MB); 0.5-1.5 parts of anti-aging agent (RD); 10-30 parts of N-550 carbon black; 30-50 parts of N-774 carbon black; 15-30 parts of a softener (TP-95); 3.5-7.5 parts of an accelerator. According to the invention, the proportion of each raw material component is optimized, particularly, the butadiene rubber is added into the formula, the butadiene rubber is synthetic rubber with a regular structure and polymerized by butadiene, the vulcanized butadiene rubber has excellent cold resistance, wear resistance and elasticity, and generates less heat under dynamic load. When the rubber is used with the butadiene-acrylonitrile rubber, the addition of the butadiene-acrylonitrile rubber can improve the wear resistance of the composite rubber mainly made of the butadiene-acrylonitrile rubber due to the fact that the mass portion of the butadiene-acrylonitrile rubber is less than that of the butadiene-acrylonitrile rubber, and the oil resistance is correspondingly reduced. The vulcanized butadiene rubber can improve the cold resistance of the composite rubber mainly made of butadiene-acrylonitrile rubber.
Although the above proposal can improve the performance of the rubber at low temperature, the essence is realized by reducing the proportion of acrylonitrile in the rubber, so that the oil resistance of the rubber is sacrificed when the low temperature performance is improved. Oil resistance refers to the ability of rubber to resist dissolution, swelling, cracking, deformation or reduction in physical properties caused by oils. Since the rubber seal needs to be constantly in contact with grease, the oil resistance of the rubber seal is also one of the key indicators.
In view of the above, there is a need to develop a nitrile rubber for a sealing member having both cold resistance and oil resistance.
Disclosure of Invention
In order to solve the technical problems, the invention provides cold-resistant oil-resistant nitrile rubber for a sealing element and a preparation method thereof. The nitrile rubber is doped with a proper amount of special modified nitrile rubber under the condition of reducing the content of acrylonitrile in a small amount, and the performances of elasticity, wear resistance, mechanical strength and the like of the rubber at a low temperature can be effectively improved on the premise of not influencing the oil resistance.
The specific technical scheme of the invention is as follows:
the cold-resistant oil-resistant nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
50-60% of nitrile-butadiene rubber,
5 to 10 percent of modified nitrile-butadiene rubber,
5 to 10 percent of cis-butadiene rubber,
1 to 5 percent of thermoplastic polyurethane elastomer,
0 to 0.5 percent of aramid short fiber,
1 to 3 percent of zinc oxide,
0.1 to 1.0 percent of stearic acid,
10 to 20 percent of inorganic reinforcing agent,
0.1 to 2 percent of anti-aging agent,
3 to 5 percent of softening oil,
1 to 3 percent of vulcanizing agent,
1 to 3 percent of accelerant.
As described in the background section, the nitrile rubber is obtained by copolymerizing butadiene and acrylonitrile, and the higher the acrylonitrile content is, the better the oil resistance is, but the higher the acrylonitrile content is, the lower the cold resistance of the rubber is, which is particularly shown in that the elasticity, the wear resistance, the mechanical strength and the like are greatly reduced, and the sealing function is easily lost when the rubber is used as a sealing member. In the prior art, the cold resistance of the rubber is usually improved by doping butadiene rubber, but the essence is realized by reducing the proportion of acrylonitrile in the rubber, so that the oil resistance of the rubber is sacrificed while the cold resistance is improved. That is, the cold resistance and the oil resistance are contradictory to some extent.
In order to overcome the technical problems, the invention develops a new way, the cold resistance of the rubber is not improved by greatly reducing the content of acrylonitrile, but the content of acrylonitrile is reduced by a small amount, and part of nitrile rubber is replaced by the modified nitrile rubber developed by the invention. The modified nitrile-butadiene rubber contains nano silicon dioxide @ metal organic framework material combined with butadiene and acrylonitrile in a copolymerization mode, on one hand, nano silicon dioxide particles can serve as reinforcing points to effectively improve the abrasion resistance and strength of the rubber at low temperature; on the other hand, the metal organic framework material can improve the oil resistance of rubber, and the principle is as follows: the oil resistance refers to the capability of resisting oil to cause dissolution, swelling, cracking, deformation or reduction of physical properties, so that the essence of poor oil resistance of rubber is that the rubber is easy to dissolve or swell (mainly swell) after contacting with oil, and when the metal organic framework material with the cage-shaped network structure is dispersed in the rubber, a large amount of tiny framework structures are constructed in a rubber matrix, so that the effect of covering the cage is achieved, the effect similar to the effect of a steel bar network in cement is achieved, the swelling resistance of the material can be effectively increased, and the rubber shows better oil resistance.
In addition, the addition of the modified nitrile rubber brings negative effects to a certain degree on the elasticity of rubber, so that the thermoplastic polyurethane elastomer with high elasticity characteristic is compounded in the material to compensate. In order to further solve the problem that the rubber is easy to embrittle and crack at low temperature, the invention is also compounded with a proper amount of aramid short fibers, and the aramid short fibers can effectively improve the toughness of the rubber and reduce the probability of low-temperature cracking of the rubber; and the aramid short fiber is taken as high-strength fiber, and can smoothly reinforce the wear resistance, the strength and the like of the rubber.
Preferably, the mass ratio of the butadiene to the acrylonitrile in the nitrile rubber is (70: 30) - (75: 25).
Preferably, the preparation method of the modified nitrile rubber comprises the following steps:
A) dispersing zinc chloride and 2-amino-4, 4' -biphenyldicarboxylic acid in a solvent, stirring for dissolving, adding o-toluic acid, adding hydrochloric acid, heating to 140-; dispersing the metal organic framework material in an alcohol-water solution, adding ethyl orthosilicate, adjusting the pH to 8-10, carrying out hydrolysis reaction for 2-4h, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material; dispersing the nano silicon dioxide @ metal organic framework material in an organic solvent, adding methacrylic anhydride, heating to react for 5-10h at 50-60 ℃, centrifugally separating a product, washing and drying to obtain the terminal alkenyl modified nano silicon dioxide @ metal organic framework material.
B) Adding water, tween and acrylonitrile into a reaction kettle in sequence, stirring uniformly, introducing butadiene under the protection of inert gas, cooling to 5-15 ℃, adding diisopropylbenzene hydroperoxide, sodium formaldehyde sulfoxylate and tert-dodecyl mercaptan in sequence, carrying out emulsion polymerization reaction for 5-10h at normal temperature, adding the alkenyl modified nano silicon dioxide @ metal organic framework material at intervals during the reaction, and adding a terminator after the reaction is finished to terminate the reaction to obtain the rubber latex.
C) Degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
In the step A), the metal organic framework material with the network cage-like structure is prepared by a hydrothermal reaction, and the framework structure of the metal organic framework material enables the metal organic framework material to have high porosity and is commonly used as a gas adsorption material at present. After the metal organic framework material is obtained, the metal organic framework material is soaked in an alcohol-water solution of tetraethoxysilane, and then tetraethoxysilane is hydrolyzed under an alkaline condition to generate silica sol, and a large amount of tetraethoxysilane is loaded in the metal organic framework material before hydrolysis, so that a large amount of silica sol is generated in situ in the metal organic framework material after hydrolysis, and the nano silica @ metal organic framework material is obtained. Further, the invention realizes the modification of the terminal alkenyl group of the material by combining the anhydride on the methacrylic anhydride with the amino group on the organic ligand in the nano-silica @ metal organic framework material, and the existence of the terminal alkenyl group endows the modified material with the capability of participating in subsequent copolymerization.
In the step B), acrylonitrile and butadiene are used as main raw materials, and the terminal alkenyl modified nano silicon dioxide @ metal organic framework material is used as a modified monomer for copolymerization to prepare the rubber latex, so that the modified material can be compounded in the rubber in a covalent bond combination mode (as a block distributed in the main chain of the polymer or as a short side chain). The modified material is inorganic material, so that the modified material is poor in rubber solubility with organic texture. Therefore, compared with the traditional physical blending mode, the chemically combined modified material is not easy to separate out from the rubber base material at the later stage, and has good stability.
In the step C), the modified nitrile-butadiene rubber is prepared from the rubber latex by a conventional process.
Preferably, in the step A), the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-methylbenzoic acid is 1: 1-2.
Preferably, in the step A), the addition amount of the hydrochloric acid is 1-3% by mass of the solvent.
Preferably, in the step A), the mass ratio of the metal organic framework material to the tetraethoxysilane is 1 to (0.5-1).
The mass ratio of the nano silicon dioxide @ metal organic framework material to the methacrylic anhydride is 1: 1-2.
In step a), in order to obtain better technical effects, the amounts of the metal organic framework material, the tetraethoxysilane and the methacrylic anhydride need to be strictly controlled.
Preferably, in the step A) and the step B), the mass ratio of the acrylonitrile to the butadiene to the terminal alkenyl modified nano silicon dioxide @ metal organic framework material is 1 to (1-5) to (0.1-1).
In step B), in order to obtain better technical effect, the dosage of acrylonitrile, butadiene and the terminal alkenyl modified nano silicon dioxide @ metal organic framework material needs to be strictly controlled.
Preferably, in the step B), the addition interval of the nano silicon dioxide @ metal organic framework material is 0.5-1.5h, and the nano silicon dioxide @ metal organic framework material is added at a constant speed.
In order to further improve the distribution uniformity of the modified material in the rubber substrate, the invention also strictly limits the adding mode to be constant-speed adding at intervals, so that the modified monomer can intermittently participate in the reaction in the process of molecular chain growth, and the modified monomer is distributed on the molecular chain as uniformly as possible.
Preferably, in step a), the aramid staple fibers have a length of 0.5 to 1.5 mm.
Preferably, in step a), the inorganic reinforcing agent is carbon black.
A preparation method of cold-resistant oil-resistant nitrile rubber for sealing elements comprises the following steps:
1) mixing butadiene acrylonitrile rubber and modified butadiene acrylonitrile rubber, and plasticating for 60-90min and 30-40 min.
2) Mixing other raw materials with the materials obtained in the step 1), filtering and forming to obtain a formed rubber blank.
3) And (3) putting the formed rubber blank into a mold, pressurizing, heating and pre-vulcanizing.
4) Taking out the rubber obtained by pre-vulcanization in the step 3), and placing the rubber in heating equipment for secondary vulcanization and tertiary vulcanization.
5) And (4) punching the rubber obtained in the step 4) to obtain a finished product.
Preferably, in step 3), the moldThe pressure is 175-185kgf/cm2The prevulcanization temperature is 150-160 ℃, and the time is 300-400 s.
Preferably, in the step 4), the secondary vulcanization temperature is 145-155 ℃, and the time is 20-40 min; the tertiary vulcanization temperature is 135-145 ℃, and the time is 1-2 h.
The invention adopts a three-step vulcanization scheme, and the whole process can be summarized as follows: the advantages of the method are that the activity of vulcanized molecular chains at high temperature is high during secondary vulcanization, severe crosslinking can occur, a highly networked main body structure is rapidly formed, then the temperature is immediately reduced for low-temperature vulcanization, and further crosslinking supplementation is carried out on the basis of the main body structure, so that the rubber performance is improved.
Compared with the prior art, the invention has the following technical effects: the nitrile rubber is doped with a proper amount of special modified nitrile rubber under the condition of reducing the content of acrylonitrile in a small amount, and the performances of elasticity, wear resistance, mechanical strength and the like of the rubber at a low temperature can be effectively improved on the premise of not influencing the oil resistance.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
The cold-resistant oil-resistant nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
50-60% of butadiene-acrylonitrile rubber (the mass ratio of butadiene to acrylonitrile is (70: 30) - (75: 25)),
5 to 10 percent of modified nitrile-butadiene rubber,
5 to 10 percent of cis-butadiene rubber,
1 to 5 percent of thermoplastic polyurethane elastomer,
0 to 0.5 percent of aramid short fiber (0.5 to 1.5mm),
1 to 3 percent of zinc oxide,
0.1 to 1.0 percent of stearic acid,
10 to 20 percent of inorganic reinforcing agent carbon black,
0.1 to 2 percent of anti-aging agent,
3 to 5 percent of softening oil,
1 to 3 percent of vulcanizing agent,
1 to 3 percent of accelerant.
Preferably, the preparation method of the modified nitrile rubber comprises the following steps:
A) dispersing zinc chloride and 2-amino-4, 4 '-biphenyldicarboxylic acid in a water solvent, stirring and dissolving, adding an o-methylbenzoic acid template agent, wherein the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-methylbenzoic acid is 1: 1-2. Adding hydrochloric acid with the mass of 1-3% of the solvent, heating to 140-; dispersing a metal organic framework material in an alcohol water solution, adding tetraethoxysilane, adjusting the pH to 8-10 according to the mass ratio of the metal organic framework material to the tetraethoxysilane of 1: 0.5-1, carrying out hydrolysis reaction for 2-4h, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material; dispersing the nano silicon dioxide @ metal organic framework material in an organic solvent DMF, adding methacrylic anhydride, heating and reacting for 5-10h at 50-60 ℃ with the mass ratio of the nano silicon dioxide @ metal organic framework material to the methacrylic anhydride being 1: 1-2, centrifugally separating a product, washing and drying to obtain the terminal alkenyl modified nano silicon dioxide @ metal organic framework material;
B) adding water, tween and acrylonitrile into a reaction kettle in sequence, stirring uniformly, introducing butadiene under the protection of inert gas, cooling to 5-15 ℃, adding an oxidant of diisopropylbenzene hydroperoxide, a reducing agent of sodium formaldehyde sulfoxylate and a molecular weight regulator of tert-decamercaptan in sequence, carrying out emulsion polymerization reaction for 5-10h at normal temperature, and adding the alkenyl modified nano silicon dioxide @ metal organic framework material at constant speed every 0.5-1.5h during the reaction, wherein the mass ratio of acrylonitrile, butadiene and the alkenyl modified nano silicon dioxide @ metal organic framework material is 1: 1-5: 0.1-1; adding a terminating agent to terminate the reaction after the reaction is finished to obtain rubber latex;
C) degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
A preparation method of cold-resistant oil-resistant nitrile rubber for sealing elements comprises the following steps:
1) mixing butadiene acrylonitrile rubber and modified butadiene acrylonitrile rubber, and plasticating for 60-90min and 30-40 min.
2) Mixing other raw materials with the materials obtained in the step 1), filtering and forming to obtain a formed rubber blank.
3) The molded rubber blank is put into a mold to be presulfurized by pressurizing and heating, wherein the mold pressure is 175-185kgf/cm2The prevulcanization temperature is 150-160 ℃, and the time is 300-400 s.
4) Taking out the rubber obtained by the pre-vulcanization in the step 3), and placing the rubber in heating equipment for secondary vulcanization (134 ℃ and 155 ℃ for 20-40min) and tertiary vulcanization (135 ℃ and 145 ℃ for 1-2 h).
5) And (4) punching the rubber obtained in the step 4) to obtain a finished product.
Example 1
The cold-resistant oil-resistant nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
55% of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 8% of modified nitrile-butadiene rubber, 7% of butadiene rubber, 3% of thermoplastic polyurethane elastomer, 0.5% of aramid short fiber (0.1mm), 2% of zinc oxide, 0.5% of stearic acid, 15% of inorganic reinforcing agent carbon black, 1% of anti-aging agent RD, 954% of softening oil, 2% of vulcanizing agent BIPB/TAIC and 2% of accelerator DM.
The preparation method comprises the following steps:
dispersing zinc chloride and 2-amino-4, 4 '-biphenyldicarboxylic acid in a water solvent, stirring for dissolving, adding an o-methylbenzoic acid template, wherein the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-methylbenzoic acid is 1: 1.5. Adding hydrochloric acid with the solvent mass of 2%, heating to 150 ℃, carrying out hydrothermal reaction for 12 hours, centrifugally separating a product, washing, drying and crushing to obtain a micron-sized metal organic framework material; dispersing a metal organic framework material in an alcohol-water solution, adding tetraethoxysilane, regulating the mass ratio of the metal organic framework material to the tetraethoxysilane to be 1: 0.8, regulating the pH to be 9, carrying out hydrolysis reaction for 3 hours, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material; dispersing the nano silicon dioxide @ metal organic framework material in an organic solvent DMF, adding methacrylic anhydride, heating and reacting for 8 hours at 55 ℃ with the mass ratio of the nano silicon dioxide @ metal organic framework material to the methacrylic anhydride being 1: 1.5, centrifugally separating a product, washing and drying to obtain the terminal alkenyl modified nano silicon dioxide @ metal organic framework material.
Adding water, tween and acrylonitrile into a reaction kettle in sequence, stirring uniformly, introducing butadiene under the protection of nitrogen, cooling to 10 ℃, adding a proper amount of oxidant namely diisopropylbenzene hydroperoxide, reducing agent sodium formaldehyde sulfoxylate and molecular weight regulator tert-deca-mercaptan in sequence, carrying out emulsion polymerization reaction for 8 hours at normal temperature, adding the alkenyl modified nano-silica @ metal organic framework material at constant speed every 1 hour during the reaction period, wherein the mass ratio of acrylonitrile, butadiene and the alkenyl modified nano-silica @ metal organic framework material is 1: 3: 0.5; and adding a terminator to terminate the reaction after the reaction is finished, thereby obtaining the rubber latex. Degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
Mixing butadiene acrylonitrile rubber and modified butadiene acrylonitrile rubber, and plasticating for 75min and butadiene acrylonitrile rubber for 35 min. Mixing other raw materials with the obtained material, filtering, and molding to obtain a molded rubber blank. Placing the formed rubber blank into a mold, pressurizing and heating for pre-vulcanization, wherein the mold pressure is 180kgf/cm2The prevulcanization temperature was 155 ℃ for 350 s. The rubber obtained from the prevulcanisation was taken out and placed in a heating apparatus for a second vulcanisation (150 ℃, 30min) and a third vulcanisation (140 ℃, 1.5 h). And punching the rubber obtained in the last step to obtain a finished product.
Example 2
The cold-resistant oil-resistant nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
60% of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 75: 25), 5% of modified nitrile-butadiene rubber, 10% of butadiene rubber, 1% of thermoplastic polyurethane elastomer, 0.4% of aramid short fiber (1.5mm), 3% of zinc oxide, 0.1% of stearic acid, 15% of inorganic reinforcing agent carbon black, 0.5% of anti-aging agent RD, 953% of softening oil TP, 1% of vulcanizing agent BIPB/TAIC and 1% of accelerator DM.
The preparation method comprises the following steps:
dispersing zinc chloride and 2-amino-4, 4 '-biphenyldicarboxylic acid in a water solvent, stirring for dissolving, adding an o-methylbenzoic acid template, wherein the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-methylbenzoic acid is 1: 1. Adding hydrochloric acid with the mass of 1% of the solvent, heating to 160 ℃, carrying out hydrothermal reaction for 10 hours, centrifugally separating the product, washing, drying and crushing to obtain a micron-sized metal organic framework material; dispersing a metal organic framework material in an alcohol-water solution, adding tetraethoxysilane, regulating the mass ratio of the metal organic framework material to the tetraethoxysilane to be 1: 0.5, regulating the pH to be 8, carrying out hydrolysis reaction for 2 hours, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material; dispersing the nano silicon dioxide @ metal organic framework material in an organic solvent DMF, adding methacrylic anhydride, heating and reacting the nano silicon dioxide @ metal organic framework material and the methacrylic anhydride for 10 hours at 50 ℃, centrifugally separating a product, washing and drying to obtain the terminal alkenyl modified nano silicon dioxide @ metal organic framework material.
Sequentially adding water, tween and acrylonitrile into a reaction kettle, uniformly stirring, introducing butadiene under the protection of inert gas, cooling to 5 ℃, sequentially adding an oxidant, namely diisopropylbenzene hydroperoxide, a reducing agent, namely sodium formaldehyde sulfoxylate and a molecular weight regulator, namely tert-decamercaptol, carrying out emulsion polymerization reaction for 5 hours at normal temperature, and adding the terminal alkenyl modified nano-silica @ metal organic framework material at a constant speed every 0.5 hour during the reaction, wherein the mass ratio of the acrylonitrile to the terminal alkenyl modified nano-silica @ metal organic framework material is 1: 0.1; and adding a terminator to terminate the reaction after the reaction is finished, thereby obtaining the rubber latex. Degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
Mixing butadiene acrylonitrile rubber and modified butadiene acrylonitrile rubber, and plasticating butadiene acrylonitrile rubber for 60min and butadiene acrylonitrile rubber for 30 min. Mixing other raw materials with the obtained material, filtering, and molding to obtain a molded rubber blank. Placing the formed rubber blank into a mold, pressurizing and heating for pre-vulcanization, wherein the mold pressure is 185kgf/cm2The prevulcanization temperature is 150 ℃ and 400s. The rubber obtained from the prevulcanisation was taken out and placed in a heating apparatus for a second vulcanisation (150 ℃, 40min) and a third vulcanisation (135 ℃, 2 h). And punching the rubber obtained in the last step to obtain a finished product.
Example 3
The cold-resistant oil-resistant nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
50% of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 10% of modified nitrile-butadiene rubber, 5% of thermoplastic polyurethane elastomer, 0.5% of aramid short fiber (0.5mm), 3% of zinc oxide, 1.0% of stearic acid, 12.5% of inorganic reinforcing agent carbon black, 2% of anti-aging agent RD, 955% of softening oil TP, 3% of vulcanizing agent BIPB/TAIC and 3% of accelerator DM.
The preparation method comprises the following steps:
dispersing zinc chloride and 2-amino-4, 4 '-biphenyldicarboxylic acid in a water solvent, stirring for dissolving, adding an o-methylbenzoic acid template, wherein the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-methylbenzoic acid is 1: 2. Adding hydrochloric acid with the solvent mass of 3%, heating to 150 ℃, carrying out hydrothermal reaction for 15h, centrifugally separating a product, washing, drying and crushing to obtain a micron-sized metal organic framework material; dispersing a metal organic framework material in an alcohol-water solution, adding tetraethoxysilane, regulating the mass ratio of the metal organic framework material to the tetraethoxysilane to be 1: 1, regulating the pH to be 10, carrying out hydrolysis reaction for 4 hours, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material; dispersing the nano silicon dioxide @ metal organic framework material in an organic solvent DMF, adding methacrylic anhydride, heating and reacting for 5 hours at 60 ℃ with the mass ratio of the nano silicon dioxide @ metal organic framework material to the methacrylic anhydride being 1: 2, centrifugally separating a product, washing and drying to obtain the terminal alkenyl modified nano silicon dioxide @ metal organic framework material.
Adding water, tween and acrylonitrile into a reaction kettle in sequence, stirring uniformly, introducing butadiene under the protection of inert gas, cooling to 15 ℃, adding an oxidant, namely diisopropylbenzene hydroperoxide, a reducing agent, namely sodium formaldehyde sulfoxylate, and a molecular weight regulator, namely tert-decamercaptol in sequence, carrying out emulsion polymerization reaction for 10 hours at normal temperature, adding the alkenyl modified nano-silica @ metal organic framework material at constant speed every 1.5 hours during the reaction, wherein the mass ratio of the acrylonitrile, the tween and the alkenyl modified nano-silica @ metal organic framework material is 1: 5: 1; and adding a terminator to terminate the reaction after the reaction is finished, thereby obtaining the rubber latex. Degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
Mixing butadiene acrylonitrile rubber and modified butadiene acrylonitrile rubber, and plasticating for 90min and 40 min. Mixing other raw materials with the obtained material, filtering, and molding to obtain a molded rubber blank. Placing the formed rubber blank into a mold, pressurizing and heating for pre-vulcanization, wherein the mold pressure is 180kgf/cm2The prevulcanization temperature is 160 ℃ and 300 s. The rubber obtained from the prevulcanisation was taken out and placed in a heating apparatus for a second vulcanisation (150 ℃, 20min) and a third vulcanisation (145 ℃, 1 h). And punching the rubber obtained in the last step to obtain a finished product.
Example 4
The cold-resistant oil-resistant nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
55% of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 10% of modified nitrile-butadiene rubber, 5% of thermoplastic polyurethane elastomer, 2% of zinc oxide, 0.5% of stearic acid, 17% of inorganic reinforcing agent carbon black, 0.5% of anti-aging agent RD, 953% of softening oil TP, 8% of vulcanizing agent BIPB/TAIC1 and 1% of accelerator DM.
The preparation method comprises the following steps:
dispersing zinc chloride and 2-amino-4, 4 '-biphenyldicarboxylic acid in a water solvent, stirring for dissolving, adding an o-methylbenzoic acid template, wherein the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-methylbenzoic acid is 1: 1.5. Adding hydrochloric acid with the solvent mass of 2%, heating to 150 ℃, carrying out hydrothermal reaction for 12 hours, centrifugally separating a product, washing, drying and crushing to obtain a micron-sized metal organic framework material; dispersing a metal organic framework material in an alcohol-water solution, adding tetraethoxysilane, regulating the mass ratio of the metal organic framework material to the tetraethoxysilane to be 1: 0.8, regulating the pH to be 9, carrying out hydrolysis reaction for 3 hours, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material; dispersing the nano silicon dioxide @ metal organic framework material in an organic solvent DMF, adding methacrylic anhydride, heating and reacting for 8 hours at 55 ℃ with the mass ratio of the nano silicon dioxide @ metal organic framework material to the methacrylic anhydride being 1: 1.5, centrifugally separating a product, washing and drying to obtain the terminal alkenyl modified nano silicon dioxide @ metal organic framework material.
Adding water, tween and acrylonitrile into a reaction kettle in sequence, stirring uniformly, introducing butadiene under the protection of nitrogen, cooling to 10 ℃, adding a proper amount of oxidant namely diisopropylbenzene hydroperoxide, reducing agent sodium formaldehyde sulfoxylate and molecular weight regulator tert-deca-mercaptan in sequence, carrying out emulsion polymerization reaction for 8 hours at normal temperature, adding the alkenyl modified nano-silica @ metal organic framework material at constant speed every 1 hour during the reaction period, wherein the mass ratio of acrylonitrile, butadiene and the alkenyl modified nano-silica @ metal organic framework material is 1: 3: 0.5; and adding a terminator to terminate the reaction after the reaction is finished, thereby obtaining the rubber latex. Degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
Mixing butadiene acrylonitrile rubber and modified butadiene acrylonitrile rubber, and plasticating for 75min and butadiene acrylonitrile rubber for 35 min. Mixing other raw materials with the obtained material, filtering, and molding to obtain a molded rubber blank. Placing the formed rubber blank into a mold, pressurizing and heating for pre-vulcanization, wherein the mold pressure is 175kgf/cm2The prevulcanization temperature was 155 ℃ for 350 s. The rubber obtained from the prevulcanisation was taken out and placed in a heating apparatus for a second vulcanisation (150 ℃, 35min) and a third vulcanisation (140 ℃, 2 h). And punching the rubber obtained in the last step to obtain a finished product.
Example 5
The cold-resistant oil-resistant nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
60% of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 5% of modified nitrile-butadiene rubber, 10% of butadiene rubber, 2% of thermoplastic polyurethane elastomer, 0.5% of aramid short fiber (1mm), 1% of zinc oxide, 1% of stearic acid, 11.5% of inorganic reinforcing agent carbon black, 1% of anti-aging agent RD, 955% of softening oil TP, 2% of vulcanizing agent BIPB/TAIC and 2% of accelerator DM.
The preparation method comprises the following steps:
dispersing zinc chloride and 2-amino-4, 4 '-biphenyldicarboxylic acid in a water solvent, stirring for dissolving, adding an o-methylbenzoic acid template, wherein the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-methylbenzoic acid is 1: 2. Adding hydrochloric acid with the solvent mass of 3%, heating to 150 ℃, carrying out hydrothermal reaction for 15h, centrifugally separating a product, washing, drying and crushing to obtain a micron-sized metal organic framework material; dispersing a metal organic framework material in an alcohol-water solution, adding tetraethoxysilane, regulating the mass ratio of the metal organic framework material to the tetraethoxysilane to be 1: 1, regulating the pH to be 10, carrying out hydrolysis reaction for 4 hours, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material; dispersing the nano silicon dioxide @ metal organic framework material in an organic solvent DMF, adding methacrylic anhydride, heating and reacting for 5 hours at 60 ℃ with the mass ratio of the nano silicon dioxide @ metal organic framework material to the methacrylic anhydride being 1: 2, centrifugally separating a product, washing and drying to obtain the terminal alkenyl modified nano silicon dioxide @ metal organic framework material.
Adding water, tween and acrylonitrile into a reaction kettle in sequence, stirring uniformly, introducing butadiene under the protection of inert gas, cooling to 15 ℃, adding an oxidant, namely diisopropylbenzene hydroperoxide, a reducing agent, namely sodium formaldehyde sulfoxylate, and a molecular weight regulator, namely tert-decamercaptol in sequence, carrying out emulsion polymerization reaction for 10 hours at normal temperature, adding the alkenyl modified nano-silica @ metal organic framework material at constant speed every 1.5 hours during the reaction, wherein the mass ratio of the acrylonitrile, the tween and the alkenyl modified nano-silica @ metal organic framework material is 1: 5: 1; and adding a terminator to terminate the reaction after the reaction is finished, thereby obtaining the rubber latex. Degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
Mixing and plastifying nitrile-butadiene rubber and modified nitrile-butadiene rubber 9Plasticate the butadiene rubber for 40min after 0 min. Mixing other raw materials with the obtained material, filtering, and molding to obtain a molded rubber blank. Placing the formed rubber blank into a mold, pressurizing and heating for pre-vulcanization, wherein the mold pressure is 180kgf/cm2The prevulcanization temperature is 160 ℃ and 300 s. The rubber obtained from the prevulcanisation was taken out and placed in a heating apparatus for a second vulcanisation (150 ℃, 20min) and a third vulcanisation (145 ℃, 1 h). And punching the rubber obtained in the last step to obtain a finished product.
Comparative example 1
The nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
63% of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 7% of butadiene rubber, 3% of thermoplastic polyurethane elastomer, 0.5% of aramid short fiber (0.1mm), 2% of zinc oxide, 0.5% of stearic acid, 15% of inorganic reinforcing agent carbon black, 1% of anti-aging agent RD, 954% of softening oil, 2% of vulcanizing agent BIPB/TAIC and 2% of accelerator DM.
The preparation method comprises the following steps: plasticating nitrile butadiene rubber for 75min and cis-butadiene rubber for 35 min. Mixing other raw materials with the obtained material, filtering, and molding to obtain a molded rubber blank. Placing the formed rubber blank into a mold, pressurizing and heating for pre-vulcanization, wherein the mold pressure is 200kgf/cm2The prevulcanization temperature is 155 ℃ and the time is 350 s. The rubber obtained from the prevulcanisation was taken out and placed in a heating apparatus for a second vulcanisation (190 ℃, 30min) and a third vulcanisation (140 ℃, 1.5 h). And punching the rubber obtained in the last step to obtain a finished product.
Comparative example 2
The nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
55% of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 15% of butadiene rubber, 3% of thermoplastic polyurethane elastomer, 0.5% of aramid short fiber (0.1mm), 2% of zinc oxide, 0.5% of stearic acid, 15% of inorganic reinforcing agent carbon black, 1% of anti-aging agent RD, 954% of softening oil, 2% of vulcanizing agent BIPB/TAIC and 2% of accelerator DM.
The preparation method comprises the following steps: plasticating nitrile butadiene rubber for 75min and cis-butadiene rubber for 35 min. Mixing other raw materials with the obtained material, filtering, and molding to obtain a molded rubber blank. And placing the formed rubber blank into a mold, pressurizing and heating for precuring, wherein the mold pressure is 180kgf/cm2, the precuring temperature is 155 ℃, and the time is 350 s. The rubber obtained from the prevulcanisation was taken out and placed in a heating apparatus for a second vulcanisation (150 ℃, 30min) and a third vulcanisation (140 ℃, 1.5 h). And punching the rubber obtained in the last step to obtain a finished product.
Comparative example 3
The nitrile rubber for the sealing element comprises the following raw materials in percentage by mass:
55% of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 8% of modified nitrile-butadiene rubber, 7% of butadiene rubber, 3% of thermoplastic polyurethane elastomer, 0.5% of aramid short fiber (0.1mm), 2% of zinc oxide, 0.5% of stearic acid, 15% of inorganic reinforcing agent carbon black, 1% of anti-aging agent RD, 954% of softening oil, 2% of vulcanizing agent BIPB/TAIC and 2% of accelerator DM.
The preparation method comprises the following steps:
dispersing zinc chloride and 2-amino-4, 4 '-biphenyldicarboxylic acid in a water solvent, stirring for dissolving, adding an o-methylbenzoic acid template, wherein the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-methylbenzoic acid is 1: 1.5. Adding hydrochloric acid with the solvent mass of 2%, heating to 150 ℃, carrying out hydrothermal reaction for 12 hours, centrifugally separating a product, washing, drying and crushing to obtain a micron-sized metal organic framework material; dispersing a metal organic framework material in an alcohol-water solution, adding tetraethoxysilane, regulating the mass ratio of the metal organic framework material to the tetraethoxysilane to be 1: 0.8, regulating the pH to be 9, carrying out hydrolysis reaction for 3 hours, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material.
Sequentially adding water, tween and acrylonitrile into a reaction kettle, uniformly stirring, introducing butadiene under the protection of nitrogen, cooling to 10 ℃, sequentially adding a proper amount of oxidant namely diisopropylbenzene hydroperoxide, reductant sodium formaldehyde sulfoxylate and molecular weight regulator namely tert-deca-mercaptan, carrying out emulsion polymerization reaction for 8 hours at normal temperature, and adding nano silicon dioxide @ metal organic framework material at a constant speed every 1 hour during the reaction period, wherein the mass ratio of acrylonitrile, tween and nano silicon dioxide @ metal organic framework material is 1: 3: 0.5; and adding a terminator to terminate the reaction after the reaction is finished, thereby obtaining the rubber latex. Degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
Mixing butadiene acrylonitrile rubber and modified butadiene acrylonitrile rubber, and plasticating for 75min and butadiene acrylonitrile rubber for 35 min. Mixing other raw materials with the obtained material, filtering, and molding to obtain a molded rubber blank. Placing the formed rubber blank into a mold, pressurizing and heating for pre-vulcanization, wherein the mold pressure is 180kgf/cm2The prevulcanization temperature is 155 ℃ and the time is 350 s. The rubber obtained from the prevulcanisation was taken out and placed in a heating apparatus for a second vulcanisation (150 ℃, 30min) and a third vulcanisation (140 ℃, 1.5 h). And punching the rubber obtained in the last step to obtain a finished product.
Performance testing
The products obtained in example 1 and comparative examples 1 to 3 were subjected to various performance tests, and the results were as follows:
| performance of | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Swelling rate of% | 23 | 36 | 45 | 32 |
| Brittleness temperature not higher than DEG C | -60 | -48 | -60 | -60 |
| Hardness, Shore A | 70 | 61 | 66 | 64 |
| Tensile strength, Mpa | 23.8 | 18.3 | 17.4 | 19.1 |
| Elongation at break, based on | 297 | 292 | 283 | 279 |
| Elasticity | 48 | 47 | 46 | 47 |
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The cold-resistant oil-resistant nitrile rubber for the sealing element is characterized by comprising the following raw materials in percentage by mass:
50-60% of nitrile-butadiene rubber,
5 to 10 percent of modified nitrile-butadiene rubber,
5 to 10 percent of cis-butadiene rubber,
1 to 5 percent of thermoplastic polyurethane elastomer,
0 to 0.5 percent of aramid short fiber,
1 to 3 percent of zinc oxide,
0.1 to 1.0 percent of stearic acid,
10 to 20 percent of inorganic reinforcing agent,
0.1 to 2 percent of anti-aging agent,
3 to 5 percent of softening oil,
1 to 3 percent of vulcanizing agent,
1 to 3 percent of accelerant.
2. The nitrile rubber according to claim 1, wherein: the mass ratio of butadiene to acrylonitrile in the nitrile rubber is (70: 30) - (75: 25).
3. The nitrile rubber according to claim 1, wherein: the preparation method of the modified nitrile-butadiene rubber comprises the following steps:
A) dispersing zinc chloride and 2-amino-4, 4' -biphenyldicarboxylic acid in a solvent, stirring for dissolving, adding o-toluic acid, adding hydrochloric acid, heating to 140-; dispersing the metal organic framework material in an alcohol-water solution, adding ethyl orthosilicate, adjusting the pH to 8-10, carrying out hydrolysis reaction for 2-4h, aging, washing and drying to obtain the nano silicon dioxide @ metal organic framework material; dispersing the nano silicon dioxide @ metal organic framework material in an organic solvent, adding methacrylic anhydride, heating to react for 5-10h at 50-60 ℃, centrifugally separating a product, washing and drying to obtain the terminal alkenyl modified nano silicon dioxide @ metal organic framework material;
B) sequentially adding water, tween and acrylonitrile into a reaction kettle, uniformly stirring, introducing butadiene under the protection of inert gas, cooling to 5-15 ℃, sequentially adding diisopropylbenzene hydroperoxide, sodium formaldehyde sulfoxylate and tert-dodecyl mercaptan, carrying out emulsion polymerization reaction for 5-10h at normal temperature, adding the alkenyl modified nano silicon dioxide @ metal organic framework material at intervals during the reaction, and adding a terminator to terminate the reaction after the reaction is finished to obtain rubber latex;
C) degassing rubber latex, removing unreacted monomers by flash evaporation, condensing the rubber latex into granular rubber by using salt solution, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
4. The nitrile rubber according to claim 3, wherein: in the step A), the step B) is carried out,
the mass ratio of the zinc chloride to the 2-amino-4, 4' -biphenyldicarboxylic acid to the o-toluic acid is 1 (1-2) to 1-2;
the addition amount of the hydrochloric acid is 1-3% of the mass of the solvent;
the mass ratio of the metal organic framework material to the tetraethoxysilane is 1 (0.5-1);
the mass ratio of the nano silicon dioxide @ metal organic framework material to methacrylic anhydride is 1 (1-2).
5. The nitrile rubber according to claim 3, wherein: in the step B), the step (A) is carried out,
the mass ratio of the acrylonitrile to the butadiene to the terminal alkenyl modified nano silicon dioxide @ metal organic framework material is 1 (1-5) to 0.1-1;
the addition interval of the nano silicon dioxide @ metal organic framework material is 0.5-1.5h, and the nano silicon dioxide @ metal organic framework material is added at a constant speed.
6. The nitrile rubber according to claim 1, wherein: the length of the aramid short fiber is 0.5-1.5 mm.
7. The nitrile rubber according to claim 1, wherein: the inorganic reinforcing agent is carbon black.
8. A process for the preparation of the nitrile rubber according to any of claims 1 to 7, characterized in that it comprises the following steps:
1) mixing butadiene acrylonitrile rubber and modified butadiene acrylonitrile rubber, plasticating for 60-90min, and plasticating for 30-40 min;
2) mixing other raw materials with the material obtained in the step 1), filtering and forming to obtain a formed rubber blank;
3) putting the formed rubber blank into a die, pressurizing, heating and pre-vulcanizing;
4) taking out the rubber obtained by pre-vulcanization in the step 3), and placing the rubber in heating equipment for secondary vulcanization and tertiary vulcanization;
5) and (4) punching the rubber obtained in the step 4) to obtain a finished product.
9. The method of claim 8, wherein: in the step 3), the mold pressure is 175-2The prevulcanization temperature is 150-160 ℃, and the time is 300-400 s.
10. The method of claim 8, wherein: in the step 4), the secondary vulcanization temperature is 145-155 ℃, and the time is 20-40 min; the tertiary vulcanization temperature is 135-145 ℃, and the time is 1-2 h.
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| CN115627040A (en) * | 2022-11-02 | 2023-01-20 | 国网黑龙江省电力有限公司电力科学研究院 | Sealing composite material capable of resisting low temperature of-50 ℃, preparation method and sensor |
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| US20060205881A1 (en) * | 2005-03-08 | 2006-09-14 | Michael Gozdiff | Blends of diene rubber with thermoplastic copolymer modifield with nitrile rubber |
| JP2008088241A (en) * | 2006-09-29 | 2008-04-17 | Jsr Corp | Oil- and weather-resistant rubber composition and its molded article |
| CN105885130A (en) * | 2015-01-13 | 2016-08-24 | 奉化联邦橡胶有限公司 | Composite low temperature resistant and oil resistant rubber seal material and preparation method thereof |
| CN107686573A (en) * | 2017-09-29 | 2018-02-13 | 天台亚耐气动密封件有限公司 | A kind of nitrile rubber（NBR）Cold-resistant seal of low temperature and preparation method thereof |
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| US20060205881A1 (en) * | 2005-03-08 | 2006-09-14 | Michael Gozdiff | Blends of diene rubber with thermoplastic copolymer modifield with nitrile rubber |
| JP2008088241A (en) * | 2006-09-29 | 2008-04-17 | Jsr Corp | Oil- and weather-resistant rubber composition and its molded article |
| CN105885130A (en) * | 2015-01-13 | 2016-08-24 | 奉化联邦橡胶有限公司 | Composite low temperature resistant and oil resistant rubber seal material and preparation method thereof |
| CN107686573A (en) * | 2017-09-29 | 2018-02-13 | 天台亚耐气动密封件有限公司 | A kind of nitrile rubber（NBR）Cold-resistant seal of low temperature and preparation method thereof |
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| CN115627040A (en) * | 2022-11-02 | 2023-01-20 | 国网黑龙江省电力有限公司电力科学研究院 | Sealing composite material capable of resisting low temperature of-50 ℃, preparation method and sensor |
| CN115627040B (en) * | 2022-11-02 | 2023-11-10 | 国网黑龙江省电力有限公司电力科学研究院 | Composite material resistant to low temperature of-50 ℃ for sealing, preparation method and sensor |
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