CN113321857B - Aramid fiber pressing ring and preparation method thereof - Google Patents
Aramid fiber pressing ring and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of composite materials and discloses an aramid fiber pressing ring and a preparation method thereof. The modified nitrile-butadiene rubber contains nano silicon dioxide @ metal organic framework material copolymerized and combined with butadiene and acrylonitrile, so that the compression strength of rubber can be effectively improved, and the oil resistance of the rubber can be further improved. The aramid fiber pressing ring prepared by the method has stronger bonding force between the aramid fiber base cloth and the rubber layer, and further can improve the pressure resistance.
Description
Technical Field
The invention relates to the field of composite materials, in particular to an aramid fiber pressing ring and a preparation method thereof.
Background
The aramid fiber pressing ring is a product formed by combining aramid fiber base cloth and rubber bonded on the base cloth, and is mainly used on a shaft of an oil field drilling machine. Due to the special use scene of the aramid fiber pressing ring, the aramid fiber pressing ring needs to continuously work for 24 hours at the temperature of-20 to-100 ℃, is suitable for drilling fluid, acidizing fluid, pressure fluid, quartz sand and the like, and the working position vibrates, the plunger makes reciprocating linear motion, and the highest speed reaches 1 m/s. Therefore, it is required to have high compression resistance (at least 138MPa in compression strength) and oil resistance.
The development of the aramid fiber pressing ring comprises selection of base cloth, development of rubber material formulas, a frictioning and forming process of rubber and the base cloth, a vulcanization process of rubber products and the like. The aramid fiber cloth is also called Kevlar, is an aramid fiber material developed by DuPont in the United states, and has the characteristics of low density, high strength, good toughness, high temperature resistance and the like. At present, the aramid fiber base cloth with high performance is mature, and the main difficulties are the development of a high-strength and high-oil-resistance rubber material and the frictioning forming process of the aramid fiber base cloth and the rubber material. Nitrile rubber is a synthetic rubber made by copolymerizing butadiene and acrylonitrile. The more the acrylonitrile content in the nitrile-butadiene rubber is, the better the oil resistance is. Therefore, the nitrile rubber is a general oil-resistant rubber, but the high pressure resistance of the common nitrile rubber cannot meet the performance requirement of the aramid fiber pressing ring.
In conclusion, due to the fact that the aramid fiber pressing ring is complex in design and processing flow, severe in use environment and high in material requirement, few companies for producing aramid fiber pressing ring products at home and abroad are available at present, and therefore an aramid fiber pressing ring product with high pressure resistance and high oil resistance needs to be developed.
Disclosure of Invention
In order to solve the technical problems, the invention provides an aramid fiber pressing ring and a preparation method thereof. The modified nitrile-butadiene rubber contains nano silicon dioxide @ metal organic framework material copolymerized and combined with butadiene and acrylonitrile, so that the compression strength of rubber can be effectively improved, and the oil resistance of the rubber can be further improved. The aramid fiber pressing ring prepared by the method has stronger bonding force between the aramid fiber base cloth and the rubber layer, and further can improve the pressure resistance.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides an aramid fiber pressing ring which comprises an aramid fiber base cloth and a rubber layer which are bonded at intervals in an overlapping mode.
The rubber layer is nitrile rubber and comprises the following raw materials in parts by weight: 90-110 parts of modified nitrile-butadiene rubber containing nano silicon dioxide @ metal organic framework material, 5-15 parts of liquid nitrile-butadiene rubber, 5-15 parts of C5 petroleum resin, 3-7 parts of coumarone resin, 70-90 parts of white carbon black, 6-10 parts of barium sulfate, 3-7 parts of zinc oxide, 3-5 parts of light magnesium oxide, 0.4-0.8 part of microcrystalline wax, 2-3 parts of polyethylene glycol, 0.5-1.5 parts of stearic acid, 0.5-1.0 part of vulcanizing agent, 2-3 parts of anti-aging agent and 2-4 parts of accelerator.
Compared with other rubbers, the nitrile rubber has excellent oil resistance and better mechanical property when being selected and bonded on the aramid base cloth. Further, in order to overcome the defect of insufficient compression resistance of common nitrile rubber, the modified nitrile rubber contains nano silicon dioxide @ metal organic framework material combined with butadiene and acrylonitrile in a copolymerization mode, and on one hand, nano silicon dioxide particles can serve as reinforcing points to effectively improve the compression strength of rubber; on the other hand, the metal organic framework material can further 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 liquid nitrile rubber in the formulation serves to plasticize, and the C5 petroleum resin and the coumarone resin serve to tackify. Preferably, the vulcanizing agent is sulfur.
Preferably, the anti-aging agent is RD anti-aging agent and MB anti-aging agent with the mass ratio of (1-2) to 1.
Preferably, the accelerant is TMTD accelerant, CBS accelerant and DM accelerant which are mixed according to the mass ratio of (1-2) to 1 to (0.3-0.5).
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-methylbenzoic 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. 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).
Preferably, in the step A), the mass ratio of the nano silicon dioxide @ metal organic framework material to the methacrylic anhydride is 1 to (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 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.
In a second aspect, the invention provides a preparation method of an aramid fiber pressing ring, which comprises the following steps:
s1: and (3) dipping the aramid fiber base cloth in liquid nitrile rubber.
S2: firstly plasticating the modified nitrile-butadiene rubber, and then adding other raw materials for mixing together to obtain the rubber compound.
S3: coating the surface of the aramid fiber base cloth obtained in the step S1 with the mixed rubber obtained in the step S2; .
S4: and (3) sequentially carrying out pressure heating pre-vulcanization and secondary vulcanization on the product obtained in the step (S3).
S5: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
In S1, the aramid base fabric is dipped in liquid nitrile-butadiene rubber to adhere a thin layer of nitrile-butadiene rubber on the surface of the base fabric in advance; compared with the aramid fiber base cloth which is not subjected to impregnation treatment, the surface nitrile rubber and the modified nitrile rubber in the rubber compound can form cross-linking in the vulcanization process of S5, so that the binding force between the aramid fiber base cloth and the rubber layer is improved, the relatively micro displacement between the rubber layer and the aramid fiber base cloth under external force can be reduced, and the compressive strength of the aramid fiber ring is improved.
Preferably, in S1, the impregnation rate of the aramid base fabric after the impregnation treatment is 5 to 10%.
Preferably, in S2, the plastication time is 4-8 min; the mixing time is 15-25 min.
Preferably, S3The blade coating amount of the rubber compound is 180-220g/m2. Preferably, in S4, the precuring pressure is 90 to 110kgf/cm2The prevulcanization temperature is 150-160 ℃, and the time is 500-700 s; the secondary vulcanization temperature is 145-155 ℃, and the time is 50-70 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the modified nitrile rubber is selectively bonded on the aramid fiber base cloth, and the modified nitrile rubber contains nano silicon dioxide @ metal organic framework material combined with butadiene and acrylonitrile in a copolymerization manner, so that the compression strength of the rubber can be effectively improved, and the oil resistance of the rubber can be further improved.
(2) The aramid fiber pressing ring prepared by the method has stronger bonding force between the aramid fiber base cloth and the rubber layer, and further can improve the pressure resistance.
Drawings
Fig. 1 is a schematic structural diagram of an aramid press ring of the present invention.
The reference signs are: aramid fiber base cloth 1 and a rubber layer 2.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
An aramid fiber pressing ring comprises an aramid fiber base cloth and a rubber layer which are overlapped and bonded at intervals.
The rubber layer is nitrile rubber and comprises the following raw materials in parts by weight: 90-110 parts of modified nitrile rubber (the mass ratio of butadiene to acrylonitrile is (70: 30) - (75: 25)), 5-15 parts of liquid nitrile rubber, 5-15 parts of C5 petroleum resin, 3-7 parts of coumarone resin, 70-90 parts of white carbon black, 6-10 parts of barium sulfate, 3-7 parts of zinc oxide, 3-5 parts of light magnesium oxide, 0.4-0.8 part of microcrystalline wax, 2-3 parts of polyethylene glycol, 0.5-1.5 parts of stearic acid, 0.5-1.0 part of vulcanizing agent (sulfur), 1-2 parts of anti-aging agent (RD anti-aging agent and MB anti-aging agent) in the mass ratio of (1-2) to 1, and 2-4 parts of accelerator (TMTD accelerator, CBS accelerator and DM accelerator in the mass ratio of (1-2) to 1 (0.3-0.5).
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, thereby obtaining 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 an aramid fiber pressing ring comprises the following steps:
s1: and (3) dipping the aramid fiber base cloth in liquid nitrile rubber, wherein the dipping rate is controlled to be 5-10%.
S2: firstly plasticating the modified nitrile-butadiene rubber for 4-8min, then adding other raw materials and mixing for 15-25min to obtain the rubber compound.
S3: coating the surface of the aramid fiber base cloth obtained in the step S1 with the mixed rubber obtained in the step S2; the coating amount is 180-220g/m2。
S4: the product obtained in S3 was successively subjected to pressure heating precuring (90-110 kgf/cm)2150 ℃ and 160 ℃, 500 ℃ and 700) and secondary vulcanization (145 ℃ and 155 ℃, 50-70 min). S5: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
Example 1
An aramid fiber pressing ring is shown in figure 1 and comprises an aramid fiber base cloth 1(4 layers) and a rubber layer 2(3 layers) which are overlapped and bonded at intervals.
The rubber layer is nitrile rubber and comprises the following raw materials in parts by weight: 100 parts of modified nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 10 parts of liquid nitrile-butadiene rubber, 10 parts of C5 petroleum resin, 5 parts of coumarone resin, 80 parts of white carbon black, 8 parts of barium sulfate, 5 parts of zinc oxide, 4 parts of light magnesium oxide, 0.6 part of microcrystalline wax, 2.5 parts of polyethylene glycol, 1 part of stearic acid, 0.6 part of vulcanizing agent (sulfur), 2.5 parts of anti-aging agent (RD anti-aging agent and MB anti-aging agent in a mass ratio of 1.5: 1), and 2.9 parts of accelerator (TMTD accelerator, CBS accelerator and DM accelerator in a mass ratio of 1.5: 1: 0.4).
The preparation method of the modified nitrile-butadiene rubber 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.
A preparation method of an aramid fiber pressing ring comprises the following steps:
s1: and (3) dipping the aramid fiber base cloth in liquid nitrile rubber, wherein the dipping rate is controlled to be 8%.
S2: firstly plasticating the modified nitrile-butadiene rubber for 6min, then adding other raw materials and mixing for 10min to obtain the rubber compound.
S3: coating the surface of the aramid fiber base cloth obtained in the step S1 with the mixed rubber obtained in the step S2; the coating weight was 200g/m2。
S4: the product obtained in S3 was successively subjected to pressure heating precuring (100 kgf/cm)2155 ℃, 600s) and secondary vulcanization (150 ℃, 60 min).
S5: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
Example 2
An aramid fiber pressing ring comprises aramid fiber base cloth (4 layers) and a rubber layer (3 layers) which are overlapped and bonded at intervals.
The rubber layer is nitrile rubber and comprises the following raw materials in parts by weight: 90 parts of modified nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 75: 25), 5 parts of liquid nitrile-butadiene rubber, 5-parts of C5 petroleum resin, 3 parts of coumarone resin, 70 parts of white carbon black, 6-parts of barium sulfate, 3 parts of zinc oxide, 3 parts of light magnesium oxide, 0.4 part of microcrystalline wax, 2 parts of polyethylene glycol, 0.5 part of stearic acid, 0.5 part of vulcanizing agent (sulfur), 1 part of anti-aging agent (RD anti-aging agent and MB anti-aging agent in a mass ratio of 1: 1), and 2 parts of accelerant (TMTD accelerant, CBS accelerant and DM accelerant in a mass ratio of 1: 0.3).
The preparation method of the modified nitrile rubber 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. And degassing the rubber latex, removing unreacted monomers by flash evaporation, coagulating the rubber latex into granular rubber by using salt water, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
A preparation method of an aramid fiber pressing ring comprises the following steps:
s1: and (3) dipping the aramid fiber base cloth in liquid nitrile rubber, wherein the dipping rate is controlled to be 5%.
S2: firstly plasticating the modified nitrile-butadiene rubber for 4min, then adding other raw materials and mixing for 9min to obtain the rubber compound.
S3: coating the surface of the aramid fiber base cloth obtained in the step S1 with the mixed rubber obtained in the step S2; the coating weight was 200g/m2。
S4: the product obtained in S3 was successively subjected to pressure heating precuring (100 kgf/cm)2150 ℃ for 450s), and secondary vulcanization (145 ℃ for 70 min).
S5: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
Example 3
An aramid fiber pressing ring comprises aramid fiber base cloth (4 layers) and a rubber layer (3 layers) which are overlapped and bonded at intervals.
The rubber layer is nitrile rubber and comprises the following raw materials in parts by weight: 110 parts of modified nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is (72: 28), 15 parts of liquid nitrile-butadiene rubber, 15 parts of C5 petroleum resin, 7 parts of coumarone resin, 90 parts of white carbon black, 10 parts of barium sulfate, 7 parts of zinc oxide, 5 parts of light magnesium oxide, 0.8 part of microcrystalline wax, 3 parts of polyethylene glycol, 1.5 parts of stearic acid, 1.0 part of vulcanizing agent (sulfur), 2 parts of anti-aging agents (RD anti-aging agent and MB anti-aging agent in a mass ratio of 2: 1), and 4 parts of accelerators (TMTD accelerator, CBS accelerator and DM accelerator in a mass ratio of 2: 1: 0.5).
The preparation method of the modified nitrile-butadiene rubber 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.
A preparation method of an aramid fiber pressing ring comprises the following steps:
s1: and (3) dipping the aramid fiber base cloth in liquid nitrile rubber, wherein the dipping rate is controlled to be 10%.
S2: firstly plasticating the modified nitrile-butadiene rubber for 8min, then adding other raw materials and mixing for 11min to obtain the rubber compound.
S3: coating the surface of the aramid fiber base cloth obtained in the step S1 with the mixed rubber obtained in the step S2; blade coating amount of 200g/m2。
S4: the product obtained in S3 was successively subjected to pressure heating precuring (100 kgf/cm)2160 ℃ for 350s), secondary vulcanization (1)55℃，50min)。
S5: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
Comparative example 1 (different from example 1 in that a conventional nitrile rubber was used)
An aramid fiber pressing ring comprises aramid fiber base cloth (4 layers) and a rubber layer (3 layers) which are overlapped and bonded at intervals.
The rubber layer is nitrile rubber and comprises the following raw materials in parts by weight: 100 parts of nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 10 parts of liquid nitrile-butadiene rubber, 10 parts of C5 petroleum resin, 5 parts of coumarone resin, 80 parts of white carbon black, 8 parts of barium sulfate, 5 parts of zinc oxide, 4 parts of light magnesium oxide, 0.6 part of microcrystalline wax, 2.5 parts of polyethylene glycol, 1 part of stearic acid, 0.6 part of vulcanizing agent (sulfur), 2.5 parts of anti-aging agent (RD anti-aging agent and MB anti-aging agent in a mass ratio of 1.5: 1), and 2.9 parts of accelerator (TMTD accelerator, CBS accelerator and DM accelerator in a mass ratio of 1.5: 1: 0.4).
A preparation method of an aramid fiber pressing ring comprises the following steps:
s1: and (3) dipping the aramid fiber base cloth in liquid nitrile rubber, wherein the dipping rate is controlled to be 8%.
S2: firstly plasticating the modified nitrile-butadiene rubber for 6min, then adding other raw materials and mixing for 10min to obtain the rubber compound.
S3: coating the surface of the aramid fiber base cloth obtained in the step S1 with the mixed rubber obtained in the step S2; the coating weight was 200g/m2。
S4: the product obtained in S3 was successively subjected to pressure heating precuring (100 kgf/cm)2155 ℃ for 400s), secondary vulcanization (150 ℃ for 60 min).
S5: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
Comparative example 2 (differing from example 1 in that the nanosilica @ metal organic framework material was not modified with terminal alkenyl groups)
An aramid fiber pressing ring comprises aramid fiber base cloth (4 layers) and a rubber layer (3 layers) which are overlapped and bonded at intervals.
The rubber layer is nitrile rubber and comprises the following raw materials in parts by weight: 100 parts of modified nitrile-butadiene rubber (the mass ratio of butadiene to acrylonitrile is 70: 30), 10 parts of liquid nitrile-butadiene rubber, 10 parts of C5 petroleum resin, 5 parts of coumarone resin, 80 parts of white carbon black, 8 parts of barium sulfate, 5 parts of zinc oxide, 4 parts of light magnesium oxide, 0.6 part of microcrystalline wax, 2.5 parts of polyethylene glycol, 1 part of stearic acid, 0.6 part of vulcanizing agent (sulfur), 2.5 parts of anti-aging agent (RD anti-aging agent and MB anti-aging agent in a mass ratio of 1.5: 1), and 2.9 parts of accelerator (TMTD accelerator, CBS accelerator and DM accelerator in a mass ratio of 1.5: 1: 0.4).
The preparation method of the modified nitrile rubber 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. And degassing the rubber latex, removing unreacted monomers by flash evaporation, coagulating the rubber latex into granular rubber by using salt water, washing the granular rubber by using water, and drying the granular rubber to obtain the modified nitrile-butadiene rubber.
A preparation method of an aramid fiber pressing ring comprises the following steps:
s1: and (3) dipping the aramid fiber base cloth in liquid nitrile rubber, wherein the dipping rate is controlled to be 8%.
S2: firstly plasticating the modified nitrile-butadiene rubber for 6min, then adding other raw materials and mixing for 10min to obtain the rubber compound.
S3: coating the surface of the aramid fiber base cloth obtained in the step S1 with the mixed rubber obtained in the step S2; the coating weight was 200g/m2。
S4: the product obtained in S3 was successively subjected to pressure heating precuring (100 kgf/cm)2155 ℃ for 400s), secondary vulcanization (150 ℃ for 60 min).
S5: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
Comparative example 3 (difference from example 1 in that aramid base fabric was not subjected to prepreg treatment)
A preparation method of an aramid fiber pressing ring comprises the following steps:
s1: firstly plasticating the modified nitrile-butadiene rubber for 8min, then adding other raw materials and mixing for 15min to obtain the rubber compound.
S2: coating the surface of the aramid fiber base cloth with the mixed rubber obtained by S1 in a scraping manner; the coating weight was 200g/m2。
S3: the product obtained in S2 was successively subjected to pressure heating precuring (100 kgf/cm)2155 ℃ for 400s), secondary vulcanization (150 ℃ for 60 min).
S4: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
Performance testing
The same specification products obtained in example 1 and comparative examples 1 to 3 were subjected to each performance test, and the results were as follows:
| performance of | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Compressive strength, MPa | 203 | 138 | 168 | 182 |
| Swelling rate of% | 21 | 32 | 28 | 21 |
| Hardness, Er A | 73 | 58 | 62 | 72 |
As can be seen from the comparison of the data in the table above, compared with example 1, the ordinary nitrile rubber is adopted in comparative example 1 instead of the modified nitrile rubber, so that the indexes of compressive strength, hardness and swelling ratio (for representing oil resistance) are obviously inferior to those of example 1. The nano silica @ metal organic framework material in the comparative example 2 is not subjected to alkenyl-terminated modification treatment, so that the nano silica @ metal organic framework material cannot be compounded in the nitrile rubber in a covalent bond form, and the functionality of the nitrile rubber cannot be fully exerted. In contrast, in comparative example 3, since the aramid base fabric was not subjected to impregnation treatment, the swelling ratio and hardness were comparable to those of example 1, but the compressive strength was significantly inferior to that of example 1, and the aramid press rings were broken at a pressure of 182 MPa.
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 (6)
1. An aramid fiber pressing ring is characterized in that: comprises aramid fiber base cloth and a rubber layer which are overlapped and bonded at intervals; the rubber layer is nitrile rubber and comprises the following raw materials in parts by weight:
90-110 parts of modified nitrile-butadiene rubber,
5-15 parts of liquid nitrile-butadiene rubber,
5 to 15 portions of C5 petroleum resin,
3-7 parts of a coumarone resin,
70-90 parts of white carbon black,
6-10 parts of barium sulfate, namely barium sulfate,
3-7 parts of zinc oxide, namely zinc oxide,
3-5 parts of light magnesium oxide,
0.4 to 0.8 portion of microcrystalline wax,
2-3 parts of polyethylene glycol,
0.5 to 1.5 portions of stearic acid,
0.5 to 1.0 portion of vulcanizing agent,
2-3 parts of an anti-aging agent,
2-4 parts of an accelerator;
the mass ratio of butadiene to acrylonitrile in the liquid nitrile rubber is (70: 30) - (75: 25);
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;
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 the methacrylic anhydride is 1 (1-2);
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;
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;
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.
2. The aramid press ring of claim 1, wherein:
the vulcanizing agent is sulfur;
the anti-aging agent is RD anti-aging agent and MB anti-aging agent with the mass ratio of (1-2) to 1;
the accelerator comprises TMTD accelerator, CBS accelerator and DM accelerator with the mass ratio of (1-2) to 1 (0.3-0.5).
3. A method of making the aramid press ring of claim 1 or 2, comprising the steps of:
s1: dipping aramid fiber base cloth in liquid nitrile rubber;
s2: firstly plasticating the modified nitrile-butadiene rubber, and then adding other raw materials for mixing together to obtain mixed rubber;
s3: coating the surface of the aramid fiber base cloth obtained in the step S1 with the mixed rubber obtained in the step S2;
s4: sequentially carrying out pressurization, heating, pre-vulcanization and secondary vulcanization on the product obtained in the step S3;
s5: and (4) performing after-appearance post-treatment on the blank obtained after vulcanization to obtain a finished product.
4. The method of claim 3, wherein: in S1, the impregnation rate of the aramid base fabric after the impregnation treatment is 5-10%.
5. The method of claim 3, wherein:
in S2, plasticating time is 4-8 min; mixing for 15-25 min;
in S3, the coating weight of the rubber compound was 180-220g/m2。
6. The method of claim 3, wherein: in S4, the precuring pressure is 90-110kgf/cm2The prevulcanization temperature is 150-160 ℃, and the time is 500-700 s; the secondary vulcanization temperature is 145-155 ℃, and the time is 50-70 min.
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Effective date of registration: 20221206 Address after: 315300 Room 101, Building 1, No. 598 Gaoke Avenue, Cixi Hi tech Industrial Development Zone, Ningbo, Zhejiang Patentee after: Ningbo Degussa Sealing Technology Co.,Ltd. Address before: 315300 No. 398 Yiheng Road, Changhe Town Industrial Zone, Cixi City, Ningbo City, Zhejiang Province Patentee before: Ningbo Daqi Sealing Technology Co.,Ltd. |