CN114369295A - Modified nitrile rubber water-lubricating composite material and preparation method thereof - Google Patents
Modified nitrile rubber water-lubricating composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a modified nitrile rubber water-lubricated composite material and a preparation method thereof, belonging to the field of conductive rubber. The adhesive is prepared from the following components in parts by mass: 100 parts of butyronitrile raw rubber, 15-25 parts of carbon black, 2-5 parts of zinc oxide, 0.5-2 parts of stearic acid, 1-5 parts of sulfur, 0.5-0.8 part of tetramethyl thiuram disulfide, 0.1-0.5 part of N-cyclohexyl-2-benzothiazole sulfonamide and 10-30 parts of hydroxyl-terminated polybutadiene liquid rubber. The invention uses HTPB liquid rubber to modify NBR to prepare the NBR composite material containing HTPB, double bonds in the HTPB can generate crosslinking copolymerization with double bonds in NBR raw rubber under the action of a vulcanizing machine and an accelerator to form a more compact network structure, the crosslinking degree is increased, side chain hydroxyl groups are introduced, the microstructure is more compact, and the hardness, the strength and the wear resistance of the composite material can be improved.
Description
Technical Field
The invention relates to the technical field of conductive rubber, in particular to a modified nitrile rubber water-lubricating composite material and a preparation method thereof.
Background
Nitrile Butadiene Rubber (NBR) is a copolymer of butadiene and acrylonitrile, has good shock absorption performance, good processing property, good frictional wear performance, wear resistance of wear particles, fatigue wear performance and the like, is a water-lubricated bearing material mainly used at present, has the greatest advantages of insensitivity to silt and small bearing capacity, and is easy to generate high wear and even tear under the conditions of high load and low speed (boundary and mixed lubrication conditions).
Under boundary and mixed lubrication conditions, the macroscopic friction and wear performance of the composite material is directly related to the hardness, wear resistance, surface hydrophilicity and the like of the material, so that the defects of the nitrile rubber material when the nitrile rubber material is used as a water lubrication bearing material are overcome, the bearing capacity (hardness and strength) and the wear resistance of the nitrile rubber composite material need to be improved, the friction coefficient at low speed (a water film can be formed at low speed) needs to be reduced, and the nitrile rubber material needs to be modified. However, in the traditional modification method, fillers such as inorganic fibers and inorganic nanoparticles are added into the nitrile rubber, but the fillers can obviously reduce the elasticity of the material while increasing the hardness and strength of the nitrile rubber, so that the coating performance of the nitrile rubber on silt and the like is reduced, the wear resistance is reduced, the hydrophilic performance of the nitrile rubber is low, the hydrophilic performance cannot be improved by adding the inorganic fillers, and the friction coefficient of water lubrication at a low speed cannot be reduced.
Disclosure of Invention
In view of the above, the invention aims to provide a modified nitrile rubber water-lubricated composite material and a preparation method thereof. The conductive nitrile rubber provided by the invention has the advantages of high strength, low friction coefficient under water lubrication and excellent wear resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a modified nitrile rubber water-lubricated composite material which is prepared from the following components in parts by mass: 100 parts of butyronitrile raw rubber, 15-25 parts of carbon black, 2-5 parts of zinc oxide, 0.5-2 parts of stearic acid, 1-5 parts of sulfur, 0.5-0.8 part of tetramethyl thiuram disulfide, 0.1-0.5 part of N-cyclohexyl-2-benzothiazole sulfonamide and 10-30 parts of hydroxyl-terminated polybutadiene liquid rubber.
Preferably, the modified nitrile rubber water-lubricated composite material is prepared from the following components in parts by mass: 100 parts of nitrile raw rubber, 25 parts of carbon black, 5 parts of zinc oxide, 1.2 parts of stearic acid, 3 parts of sulfur, 0.6 part of tetramethyl thiuram disulfide, 0.3 part of N-cyclohexyl-2-benzothiazole sulfonamide and 15-20 parts of hydroxyl-terminated polybutadiene liquid rubber.
Preferably, the relative molecular weight of the hydroxyl-terminated polybutadiene liquid rubber is 3000-4300.
The invention also provides a preparation method of the modified nitrile rubber water-lubricated composite material, which comprises the following steps:
mixing the butyronitrile raw rubber with carbon black, zinc oxide and stearic acid in sequence, and banburying to obtain a banburying material;
mixing the internal mixing material with sulfur, tetramethyl thiuram disulfide and N-cyclohexyl-2-benzothiazole sulfonamide in sequence for open mixing to obtain NBR rubber compound;
and mixing the NBR rubber compound with hydroxyl-terminated polybutadiene liquid rubber, and then sequentially carrying out dynamic vulcanization and flat vulcanization to obtain the modified nitrile-butadiene rubber water-lubricated composite material.
Preferably, the temperature of the dynamic vulcanization is 140 ℃ and the time is up to no liquid material.
Preferably, the dynamic vulcanization is carried out under stirring conditions, the rotation speed of the stirring being 60 revolutions per minute.
Preferably, the dynamic vulcanization is carried out in a dual rotor torque rheometer.
Preferably, the vulcanizing temperature of the flat plate is 160-180 ℃, and the pressure is 10-12 MPa.
Preferably, the banburying temperature is 60 ℃ and the banburying time is 15-20 min.
Preferably, the open mill comprises triangular wrapping and rolling which are sequentially carried out.
The invention provides a modified nitrile rubber water-lubricated composite material which is prepared from the following components in parts by mass: 100 parts of butyronitrile raw rubber, 15-25 parts of carbon black, 2-5 parts of zinc oxide, 0.5-2 parts of stearic acid, 1-5 parts of sulfur, 0.5-0.8 part of tetramethyl thiuram disulfide, 0.1-0.5 part of N-cyclohexyl-2-benzothiazole sulfonamide and 10-30 parts of hydroxyl-terminated polybutadiene liquid rubber. The invention uses hydroxyl-terminated polybutadiene (HTPB) liquid rubber to modify nitrile rubber (NBR) to prepare NBR composite material containing HTPB, double bonds in the HTPB can generate crosslinking copolymerization with double bonds in NBR raw rubber under the action of a vulcanizer and an accelerant to form a more compact network structure, the crosslinking degree is increased, side chain hydroxyl groups are introduced to form a more compact microstructure, the hardness, the strength and the wear resistance of the composite material can be improved, the surface of the NBR rubber is changed from hydrophobic to hydrophilic, the surface contact angle is reduced, when the NBR composite material is used as a water lubricating material, a stable water film can be formed at a low rotating speed due to the hydrophilic performance of the surface, the friction coefficient under water lubrication, particularly under the low rotating speed, is greatly reduced, the strength of the NBR composite material is improved, hydrophilic hydroxyl groups (-OH) are introduced into the NBR rubber, and the friction coefficient under water lubrication is remarkably reduced, and the wear resistance of the NBR composite material is also improved.
Detailed Description
The invention provides a modified nitrile rubber water-lubricated composite material which is prepared from the following components in parts by mass: 100 parts of butyronitrile raw rubber, 15-25 parts of carbon black, 2-5 parts of zinc oxide, 0.5-2 parts of stearic acid, 1-5 parts of sulfur, 0.5-0.8 part of tetramethyl thiuram disulfide, 0.1-0.5 part of N-cyclohexyl-2-benzothiazole sulfonamide and 10-30 parts of hydroxyl-terminated polybutadiene liquid rubber.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
In the invention, the modified nitrile rubber water-lubricated composite material is preferably prepared from the following components in parts by mass: 100 parts of nitrile raw rubber, 25 parts of carbon black, 5 parts of zinc oxide, 1.2 parts of stearic acid, 3 parts of sulfur, 0.6 part of tetramethyl thiuram disulfide, 0.3 part of N-cyclohexyl-2-benzothiazole sulfonamide and 15-20 parts of hydroxyl-terminated polybutadiene liquid rubber.
In the invention, the relative molecular weight of the hydroxyl-terminated polybutadiene liquid rubber is preferably 3000-4300.
In the invention, the structure of the hydroxyl-terminated polybutadiene liquid rubber is shown as a formula 1, double bonds are contained in the structure, and two ends of the hydroxyl-terminated polybutadiene liquid rubber are hydroxyl groups.
The invention also provides a preparation method of the modified nitrile rubber water-lubricated composite material, which comprises the following steps:
mixing the butyronitrile raw rubber with carbon black, zinc oxide and stearic acid in sequence, and banburying to obtain a banburying material;
mixing the internal mixing material with sulfur, tetramethyl thiuram disulfide and N-cyclohexyl-2-benzothiazole sulfonamide in sequence for open mixing to obtain NBR rubber compound;
and mixing the NBR rubber compound with hydroxyl-terminated polybutadiene liquid rubber, and then sequentially carrying out dynamic vulcanization and flat vulcanization to obtain the modified nitrile-butadiene rubber water-lubricated composite material.
The invention mixes the butyronitrile raw rubber with carbon black, zinc oxide and stearic acid in turn, and carries out banburying to obtain a banburying material.
In the invention, the banburying temperature is preferably 60 ℃, and the banburying time is preferably 15-20 min.
In the present invention, the internal mixing is preferably carried out in an internal mixer.
The invention preferably preheats the internal mixer to 60 ℃, then puts in the butyronitrile raw rubber, sets the rotating speed at 60 r/min, and puts in turn carbon black, zinc oxide and stearic acid into the internal mixer.
In the invention, after the banburying is finished, the banburying preferably further comprises standing, and the standing time is preferably 30 min.
After an internal mix is obtained, the internal mix is sequentially mixed with sulfur, tetramethyl thiuram disulfide and N-cyclohexyl-2-benzothiazole sulfonamide for open milling to obtain the NBR rubber compound.
In the present invention, the open mill preferably includes triangular wrapping and rolling performed in sequence. In the invention, the times of triangular packaging and rolling are preferably 3 times.
In the present invention, the temperature of the open mill is preferably room temperature.
In the present invention, the open mill is preferably carried out in an open mill.
After the NBR rubber compound is obtained, the NBR rubber compound and hydroxyl-terminated polybutadiene liquid rubber are mixed and then are subjected to dynamic vulcanization and flat vulcanization in sequence to obtain the modified nitrile rubber water-lubricated composite material.
In the present invention, the temperature of the dynamic vulcanization is preferably 140 ℃ and the time is preferably up to no liquid material.
In the present invention, the dynamic vulcanization is preferably carried out in a dual rotor torque rheometer. In the invention, the dynamic vulcanization mainly comprises the step of adding HTPB liquid rubber into the NBR rubber compound, wherein the HTPB liquid rubber is subjected to a cross-linking reaction with the NBR rubber compound while being mixed at 140 ℃, so that the HTPB liquid rubber is uniformly dispersed in the NBR rubber compound, and the process can be realized by the double-rotor torque rheometer.
In the present invention, the dynamic vulcanization is preferably carried out under stirring conditions, and the rotation speed of the stirring is preferably 60 revolutions per minute.
In the invention, the vulcanizing temperature of the flat plate is preferably 160-180 ℃, and the pressure is preferably 10-12 MPa
In the present invention, the press vulcanization is preferably carried out in a press vulcanizer.
The application of the modified nitrile rubber water-lubricated composite material is not specially limited, and the modified nitrile rubber water-lubricated composite material can be applied in a manner known by persons skilled in the art, and is particularly applied to stern bearings of naval vessels, guide bearings of large-scale shaft vertical pumps, guide bearings of water turbines and the like.
In order to further illustrate the present invention, the modified nitrile rubber water-lubricated composite material and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1:
preheating an internal mixer to 60 ℃, then adding 100g of nitrile rubber raw rubber, setting the rotating speed to be 60 r/min, sequentially adding 25g of carbon black, 5g of zinc oxide and 1.2g of stearic acid into the internal mixer, mixing for 20min, and taking out. Standing for 30min, using an open mill, at room temperature, continuously adding 3g of sulfur, 0.6g of tetramethylthiuram disulfide and 0.3g N-cyclohexyl-2-benzothiazole sulfonamide, and obtaining the NBR rubber compound after triangular wrapping for 3 times and rolling for 3 times. Putting the rubber compound and 10g of HTPB liquid into a double-rotor torque rheometer tank, setting the temperature to be 140 ℃, stirring at the speed of 60 r/min, taking out the mixture when no liquid substance exists in the mixture, discharging the mixture by using an open mill, putting the rubber compound into a mold, and vulcanizing by using a flat vulcanizing machine, wherein the vulcanizing temperature is 160 ℃ and the vulcanizing pressure is 10 MPa.
The performance of the modified nitrile rubber water-lubricated composite material prepared in example 1 was tested, and the results were as follows:
tensile strength: 14.5 MPa;
hardness (shore a): 80;
wear resistance (dry frictional wear amount, 0.5MPa, 2.83m/s, 2 h): 5 mg;
material contact angle (drop size 5 μ L): 50.3 degrees.
The coefficient of friction under water lubrication conditions is shown in table 1.
TABLE 1 coefficient of friction of the modified nitrile rubber water-lubricated composite prepared in example 1
Example 2:
preheating an internal mixer to 60 ℃, then adding 100g of nitrile rubber raw rubber, setting the rotating speed to be 60 r/min, sequentially adding 25g of carbon black, 5g of zinc oxide and 1.2g of stearic acid into the internal mixer, mixing for 20min, and taking out. Standing for 30min, using an open mill, at room temperature, continuously adding 3g of sulfur, 0.6g of tetramethylthiuram disulfide and 0.3g N-cyclohexyl-2-benzothiazole sulfonamide, and obtaining the NBR rubber compound after triangular wrapping for 3 times and rolling for 3 times. Putting the rubber compound and 15g of HTPB liquid into a double-rotor torque rheometer tank, setting the temperature at 140 ℃, stirring at a speed of 60 rpm, taking out the mixture when no liquid substance exists in the mixture, discharging the mixture by using an open mill, putting the rubber compound into a mold, and vulcanizing by using a flat vulcanizing machine, wherein the vulcanizing temperature is 180 ℃ and the vulcanizing pressure is 12 MPa.
The performance of the modified nitrile rubber water-lubricated composite material prepared in example 2 was tested, and the results were as follows:
tensile strength: 17.5 MPa;
hardness (shore a): 83;
wear resistance (dry frictional wear amount, 0.5MPa, 2.83m/s, 2 h): 4.5 mg;
material contact angle (drop size 5 μ L): 42.5 degrees.
The friction coefficient under water lubrication conditions is shown in table 2.
TABLE 2 coefficient of friction of the modified nitrile rubber water-lubricated composite prepared in example 2
Example 3:
preheating an internal mixer to 60 ℃, then adding 100g of nitrile rubber raw rubber, setting the rotating speed to be 60 r/min, sequentially adding 25g of carbon black, 5g of zinc oxide and 1.2g of stearic acid into the internal mixer, mixing for 15min, and taking out. Standing for 30min, using an open mill, at room temperature, continuously adding 3g of sulfur, 0.6g of tetramethylthiuram disulfide and 0.3g N-cyclohexyl-2-benzothiazole sulfonamide, and obtaining the NBR rubber compound after triangular wrapping for 3 times and rolling for 3 times. Putting the rubber compound and 20g of HTPB liquid into a double-rotor torque rheometer tank, setting the temperature to be 140 ℃, stirring at the speed of 60 r/min, taking out the mixture when no liquid substance exists in the mixture, discharging the mixture by using an open mill, putting the rubber compound into a mold, and vulcanizing by using a flat vulcanizing machine, wherein the vulcanizing temperature is 170 ℃ and the vulcanizing pressure is 11 MPa.
The performance of the modified nitrile rubber water-lubricated composite material prepared in example 3 was tested, and the results were as follows:
tensile strength: 21.2 MPa;
hardness (shore a): 86;
wear resistance (dry frictional wear amount, 0.5MPa, 2.83m/s, 2 h): 3.2 mg;
material contact angle (drop size 5 μ L): 35.6 degrees.
The friction coefficient under water lubrication conditions is shown in table 3.
TABLE 3 coefficient of friction of modified nitrile rubber water-lubricated composite prepared in example 3
Comparative example 1:
no HTPB liquid rubber added: preheating an internal mixer to 60 ℃, then adding 100g of nitrile rubber raw rubber, setting the rotating speed to be 60 r/min, sequentially adding 25g of carbon black, 5g of zinc oxide and 1.2g of stearic acid into the internal mixer, mixing for 20min, and taking out. Standing for 30min, using an open mill, at room temperature, continuously adding 3g of sulfur, 0.6g of tetramethylthiuram disulfide and 0.3g N-cyclohexyl-2-benzothiazole sulfonamide, and obtaining the NBR rubber compound after triangular wrapping for 3 times and rolling for 3 times. Putting the rubber compound into a mold, and vulcanizing by using a flat vulcanizing machine, wherein the vulcanizing temperature is 160 ℃, and the vulcanizing pressure is 10 MPa.
The composite material prepared in comparative example 1 was tested for properties, and the results were as follows:
tensile strength: 12.5 MPa;
hardness (shore a): 78, a nitrogen source;
wear resistance (dry frictional wear amount, 0.5MPa, 2.83m/s, 2 h): 8.3 mg;
material contact angle (drop size 5 μ L): and (5) 55.6 degrees.
The friction coefficient under water lubrication conditions is shown in table 4.
TABLE 4 coefficient of friction of the modified nitrile rubber water-lubricated composite obtained in comparative example 1
Comparative example 2:
the method without dynamic vulcanization reaction:
preheating an internal mixer to 60 ℃, then adding 100g of nitrile rubber raw rubber, setting the rotating speed to be 60 r/min, sequentially adding 25g of carbon black, 5g of zinc oxide and 1.2g of stearic acid into the internal mixer, mixing for 20min, and taking out. Standing for 30min, using an open mill, at room temperature, continuously adding 3g of sulfur, 0.6g of tetramethylthiuram disulfide and 0.3g N-cyclohexyl-2-benzothiazole sulfonamide, and obtaining the NBR rubber compound after triangular wrapping for 3 times and rolling for 3 times. And (3) putting the rubber compound and 20g of HTPB liquid into an internal mixer for mechanical mixing, wherein the stirring speed is 60 r/min, and at the moment, the HTPB liquid cannot be uniformly mixed into an NBR rubber system, so that the modified nitrile rubber water-lubricated composite material cannot be prepared.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The modified nitrile rubber water-lubricated composite material is characterized by being prepared from the following components in parts by mass: 100 parts of butyronitrile raw rubber, 15-25 parts of carbon black, 2-5 parts of zinc oxide, 0.5-2 parts of stearic acid, 1-5 parts of sulfur, 0.5-0.8 part of tetramethyl thiuram disulfide, 0.1-0.5 part of N-cyclohexyl-2-benzothiazole sulfonamide and 10-30 parts of hydroxyl-terminated polybutadiene liquid rubber.
2. The modified nitrile rubber water-lubricated composite material as claimed in claim 1, which is prepared from the following components in parts by mass: 100 parts of nitrile raw rubber, 25 parts of carbon black, 5 parts of zinc oxide, 1.2 parts of stearic acid, 3 parts of sulfur, 0.6 part of tetramethyl thiuram disulfide, 0.3 part of N-cyclohexyl-2-benzothiazole sulfonamide and 15-20 parts of hydroxyl-terminated polybutadiene liquid rubber.
3. The modified nitrile rubber water-lubricated composite material as claimed in claim 1 or 2, wherein the relative molecular weight of the hydroxyl-terminated polybutadiene liquid rubber is 3000-4300.
4. The preparation method of the modified nitrile rubber water-lubricated composite material as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
mixing the butyronitrile raw rubber with carbon black, zinc oxide and stearic acid in sequence, and banburying to obtain a banburying material;
mixing the internal mixing material with sulfur, tetramethyl thiuram disulfide and N-cyclohexyl-2-benzothiazole sulfonamide in sequence for open mixing to obtain NBR rubber compound;
and mixing the NBR rubber compound with hydroxyl-terminated polybutadiene liquid rubber, and then sequentially carrying out dynamic vulcanization and flat vulcanization to obtain the modified nitrile-butadiene rubber water-lubricated composite material.
5. The method of claim 4, wherein the temperature of the dynamic vulcanization is 140 ℃ and the time is up to no liquid material.
6. The method according to claim 4 or 5, wherein the dynamic vulcanization is carried out under stirring conditions at a rotation speed of 60 rpm.
7. The method of claim 6, wherein the dynamic vulcanization is performed in a dual rotor torque rheometer.
8. The preparation method according to claim 4, wherein the temperature of the plate vulcanization is 160-180 ℃ and the pressure is 10-12 MPa.
9. The preparation method according to claim 4, wherein the banburying is carried out at 60 ℃ for 15-20 min.
10. The method of claim 4, wherein the open mill comprises triangular wrapping and rolling in sequence.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115819823A (en) * | 2022-11-18 | 2023-03-21 | 中国人民解放军海军工程大学 | Preparation method, product and application of water-lubricated nitrile rubber surface polymer brush |
| CN117447794A (en) * | 2023-12-26 | 2024-01-26 | 河北技投机械设备有限公司 | Ternary olefin copolymer composition for slurry pump, and preparation method and application thereof |
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| US5587433A (en) * | 1995-08-17 | 1996-12-24 | Sartomer Company, Inc. | Esters of hydroxy terminated polybutadiene compositions and methods for making same |
| CN106674644A (en) * | 2016-11-24 | 2017-05-17 | 中国科学院长春应用化学研究所 | Super wear-resistant water-lubricated bearing composite material and preparation method thereof |
| CN107383475A (en) * | 2017-07-31 | 2017-11-24 | 华南理工大学 | A kind of lignin/nitile-butadiene rubber composite material and preparation method thereof |
| CN109337146A (en) * | 2018-09-28 | 2019-02-15 | 青岛科技大学 | A kind of water lubriucated bearing composite material and preparation method |
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| JPS62241934A (en) * | 1986-04-14 | 1987-10-22 | Japan Synthetic Rubber Co Ltd | Powdered nitrile rubber and its composition |
| US5587433A (en) * | 1995-08-17 | 1996-12-24 | Sartomer Company, Inc. | Esters of hydroxy terminated polybutadiene compositions and methods for making same |
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| CN117447794A (en) * | 2023-12-26 | 2024-01-26 | 河北技投机械设备有限公司 | Ternary olefin copolymer composition for slurry pump, and preparation method and application thereof |
| CN117447794B (en) * | 2023-12-26 | 2024-03-12 | 河北技投机械设备有限公司 | Ternary olefin copolymer composition for slurry pump, and preparation method and application thereof |
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