CN115819823B - Preparation method, product and application of water-lubricated nitrile rubber surface polymer brush - Google Patents
Preparation method, product and application of water-lubricated nitrile rubber surface polymer brush Download PDFInfo
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- CN115819823B CN115819823B CN202211447115.6A CN202211447115A CN115819823B CN 115819823 B CN115819823 B CN 115819823B CN 202211447115 A CN202211447115 A CN 202211447115A CN 115819823 B CN115819823 B CN 115819823B
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- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 119
- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000004073 vulcanization Methods 0.000 claims abstract description 20
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- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 230000006837 decompression Effects 0.000 claims abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000003712 anti-aging effect Effects 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 238000005461 lubrication Methods 0.000 abstract description 15
- 229920001971 elastomer Polymers 0.000 abstract description 14
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- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 239000013543 active substance Substances 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical group [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a water-lubricated nitrile rubber surface polymer brush, which comprises the following steps: s1, preparing nitrile rubber compound by adopting a mechanical blending method; s2, performing vulcanization molding on the nitrile rubber compound prepared in the step S1 to obtain vulcanized nitrile rubber; s3, placing the vulcanized nitrile rubber in excessive polyisocyanate with terminal NCO groups, reacting to obtain a product with the terminal NCO groups covered on the surface, taking out and centrifuging the product, wiping the product in nitrogen or inert atmosphere, and placing the product in excessive polyol subjected to decompression and water removal to react to obtain the water-lubricated nitrile rubber surface polymer brush. The invention also discloses a corresponding product and application. The invention accurately finds out the reactive sites on the NBR surface, provides possibility for chemical surface grafting of the rubber, solves the problem of poor surface hydrophilicity of the vulcanized nitrile rubber in the prior art, and improves the water lubrication tribological performance of the vulcanized nitrile rubber.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method, a product and application of a nitrile rubber surface high polymer brush with excellent water lubrication tribological performance.
Background
Nitrile rubber (Nitrile butadiene rubber, NBR) is widely used in the field of water lubricated bearings due to its excellent tribological properties, good silt containment and vibration damping properties. However, under the heavy load and low speed working conditions, the nitrile rubber bearing is not easy to completely form a hydrodynamic film between the nitrile rubber bearing and the shaft, and a partial area is in a boundary lubrication and even dry friction state, so that serious abrasion and vibration noise are generated, the safety and the service life of a ship shafting are reduced, and hidden danger is brought to the stealth performance of an underwater vehicle.
Related researches show that the material with higher hydrophilicity is favorable for forming a water film, so that the material has better water lubrication characteristics and lower vibration noise, and therefore, students try to carry out hydrophilic modification on the polymer material to obtain better water lubrication tribology performance. The polymer brush (chemical grafting modification) is formed by polymerizing monomers on the initiation points of the surface of the polymer to generate a orderly-arranged chain-shaped layer to form a layer of film, and the grafted layer can be highly stretched in corresponding lubricating liquid to form a hydration layer, so that the shearing strength is greatly reduced, and the inter-chain molecules have stronger osmotic pressure repulsive force and can bear higher load, thereby having excellent lubricating effect.
However, in the prior art, polymer brushes are mainly synthesized on the surface of a film or a fabric, and the tribological properties of the polymer brushes in specific lubricating fluids are studied. However, the water lubricated bearings have high requirements on the mechanical properties of the material, and the surface grafted polymer brushes have little effect on them. Therefore, how to find chemically reactive sites on the surface of vulcanized rubber and successfully graft hydrophilic segments to the surface thereof becomes a research difficulty and key technology.
Disclosure of Invention
Aiming at one or more of the defects or improvement requirements of the prior art, the invention provides a preparation method, a product and application of a water-lubricated nitrile rubber surface polymer brush, which accurately searches the reactive sites on the NBR surface, provides possibility for chemical surface grafting of the rubber, solves the problem of poor hydrophilicity of the vulcanized nitrile rubber surface in the prior art, and improves the water-lubricated tribological property of the vulcanized nitrile rubber.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a method for preparing a water-lubricated nitrile rubber surface polymer brush, comprising the steps of:
s1, preparing nitrile rubber compound by adopting a mechanical blending method;
s2, performing vulcanization molding on the nitrile rubber compound prepared in the step S1 to obtain vulcanized nitrile rubber;
s3, placing the vulcanized nitrile rubber in excessive polyisocyanate with terminal NCO groups, reacting to obtain a product with the terminal NCO groups covered on the surface, taking out and centrifuging the product, wiping the product in nitrogen or inert atmosphere, and placing the product in excessive polyol subjected to decompression and water removal to react to obtain the water-lubricated nitrile rubber surface polymer brush.
As a further improvement of the present invention, in step S3, the reaction conditions of the vulcanized nitrile rubber and the polyisocyanate are: the reaction temperature is 50-70 ℃, the rotor rotating speed is 200-500 rpm, and the reaction time is 20-40 min.
As a further development of the invention, in step S3, the reaction conditions of the product with terminal NCO groups on the surface and the polyol are: the reaction temperature is 70-100 ℃, and the oil bath is used for heating; the rotation speed of the rotor is 400 rpm-600 rpm, and the reaction time is 2 h-4 h.
As a further improvement of the present invention, in step S3, the polyisocyanate includes one or more of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate.
As a further improvement of the present invention, in step S3, the polyol includes one or more of polyethylene glycol, polyphenylene oxide, polyethylene oxide, polycaprolactone, and polybutylacrylate.
As a further improvement of the invention, in the step S1, the nitrile rubber compound comprises 100 parts of nitrile rubber, 4-7 parts of zinc oxide, 1-2 parts of stearic acid, 3-6 parts of an anti-aging agent, 1-4 parts of dioctyl phthalate, 0.5-1 part of sulfur, 1-3 parts of an accelerator and 40-60 parts of carbon black.
As a further improvement of the invention, in step S2, the preparation conditions of the vulcanized nitrile rubber are determined according to the vulcanization curve measured by the nitrile rubber compound; preferably, the reaction temperature is 100-200 ℃, the specific pressure is 10-30 Mpa, and the time is 20-50 min.
As a further improvement of the present invention, in step S2, a nitrile rubber is vulcanized and molded using a tablet press.
According to a second aspect of the invention, there is provided a water-lubricated nitrile rubber surface polymer brush prepared according to the preparation method.
According to a third aspect of the invention there is provided the use of the water lubricated nitrile rubber surface polymer brush as a water lubricated bearing material.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
according to the invention, the polyisocyanate intermediate containing the terminal NCO active group is introduced to react with acrylonitrile cyano on the surface of NBR in an active hydrogen transfer manner to generate an amide structure, and the polyol is used to end-cap the other terminal NCO group of the polyisocyanate intermediate to prepare the polymer brush with the hydrophilic chain segment on the surface, so that the reactive active site on the surface of NBR is accurately found, the possibility is provided for the chemical surface grafting of the rubber, the problem of poor surface hydrophilicity of the vulcanized nitrile rubber in the prior art is solved, and the water lubrication tribological property of the vulcanized nitrile rubber is improved.
Drawings
FIG. 1 is an SEM image of the surface polymer brush of nitrile rubber of example 1 of the present invention;
FIG. 2 is an SEM image of the surface of nitrile rubber of example 1 of the present invention after abrasion of the polymer brush.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The preparation method of the water-lubricated nitrile rubber surface polymer brush comprises the following steps:
s1, preparing nitrile rubber compound by adopting a mechanical blending method;
s2, performing vulcanization molding on the nitrile rubber compound prepared in the step S1 to obtain vulcanized nitrile rubber;
s3, placing the vulcanized nitrile rubber in excessive polyisocyanate with terminal NCO groups, reacting to obtain a product with the terminal NCO groups covered on the surface, taking out and centrifuging the product, wiping the product in nitrogen or inert atmosphere, and placing the product in excessive polyol subjected to decompression and water removal to react to obtain a final product, namely the water-lubricated nitrile rubber surface polymer brush.
Specifically, in the step S1, the nitrile rubber compound comprises 100 parts of nitrile rubber, 4-7 parts of zinc oxide, 1-2 parts of stearic acid, 3-6 parts of an anti-aging agent, 1-4 parts of dioctyl phthalate, 0.5-1 part of sulfur, 1-3 parts of an accelerator and 40-60 parts of carbon black.
The anti-aging agent and the accelerator may be rubber anti-aging agents and accelerators in the prior art, and in the preferred embodiment of the present invention, the anti-aging agent NA and the accelerator DM are selected. In addition, the formulation materials of the nitrile rubber compound are all commercially available.
In addition, the mechanical blending method is to add raw rubber on an open mill, add active agent, carbon black, plasticizer and anti-aging agent in sequence after the raw rubber is wrapped by a roller, add vulcanizing agent and accelerator after mixing uniformly, mix uniformly again, thin and pass, lower piece, stand for 24 hours and return to the mill. The mechanical blending method is a mixing method commonly used in the prior art, and is not described herein.
In step S2, the preparation conditions of the vulcanized nitrile rubber are determined according to the vulcanization curve of the nitrile rubber compound, and the vulcanization curve is preferably tested by a rubber processing analyzer 。 In a preferred embodiment, the reaction temperature is 100-200 ℃, the specific pressure is 10-30 Mpa, and the time is 20-50 min.
In step S3, the reaction conditions of the vulcanized nitrile rubber and the polyisocyanate are: the reaction temperature is 50-70 ℃, the rotor rotating speed is 200-500 rpm, and the reaction time is 20-40 min.
Further, in step S3, the reaction conditions of the product having terminal NCO groups on the surface and the polyol are: the reaction temperature is 70-100 ℃, and the oil bath is used for heating; the rotation speed of the rotor is 400 rpm-600 rpm, and the reaction time is 2 h-4 h.
Preferably, the polyisocyanate comprises one or more of Hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI).
Preferably, the polyol comprises one or more of polyethylene glycol (PEG), polyphenylene oxide (PPO), polyethylene oxide (PEO), polycaprolactone (PCL), polybutyl acrylate (PBA).
In addition, the inert atmosphere includes helium, neon, argon, krypton, xenon, and the like; nitrogen is preferably used.
The invention provides a preparation process which is simple in process and can effectively improve the water lubrication tribological performance of the nitrile rubber. The nitrile rubber matrix is adopted to react with polyisocyanate with terminal NCO groups in an active hydrogen transfer way, then polyol is utilized to block the other terminal NCO group of the polyisocyanate, a polymer brush with hydrophilic chain segments on the surface is prepared, the reactive sites on the NBR surface are accurately found, the possibility is provided for chemical surface grafting of the rubber, the problem of poor hydrophilicity of the vulcanized nitrile rubber surface in the prior art is solved, and the water lubrication tribological property of the vulcanized nitrile rubber is improved.
For better illustration and understanding of the technical scheme of the invention, the following specific embodiments are provided:
example 1
(1) The nitrile rubber compound is prepared by adopting a mechanical blending method, and the formula is as follows: 100 parts of nitrile rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 4 parts of an anti-aging agent, 2 parts of dioctyl phthalate, 1 part of sulfur, 2 parts of an accelerator and 50 parts of carbon black;
(2) Standing the mixed rubber for 24 hours at room temperature, testing the vulcanization curve, determining the vulcanization condition, setting the temperature to 160 ℃, the specific pressure to 20Mpa, and the time to 30 minutes, and vulcanizing and molding the nitrile rubber by selecting a die with the thickness of 16.5mm multiplied by 6.5mm multiplied by 10mm on a tablet press;
(3) The vulcanized nitrile rubber was placed in a flask containing 50mL of hexamethylene diisocyanate, the temperature was set at 60℃and the rotation speed of the rotor was 400rpm, and reacted for 30 minutes to obtain a product having terminal NCO groups on the surface. Taking out the mixture, centrifuging the mixture, wiping the mixture in a nitrogen atmosphere, putting the mixture into a three-neck flask filled with 50mL of polyethylene glycol subjected to reduced pressure and water removal, heating the mixture in an oil bath at 80 ℃, stirring the mixture at 500rpm, and reacting the mixture for 3 hours to obtain a final product.
Example 2
(1) The nitrile rubber compound is prepared by adopting a mechanical blending method, and the formula is as follows: 100 parts of nitrile rubber, 6 parts of zinc oxide, 2 parts of stearic acid, 3 parts of an anti-aging agent, 2 parts of dioctyl phthalate, 0.5 part of sulfur, 2 parts of an accelerator and 40 parts of carbon black;
(2) Standing the rubber compound at room temperature for 24 hours, testing the vulcanization curve, determining the vulcanization condition, setting the temperature to 180 ℃, the specific pressure to 10Mpa, and the time to 40 minutes, and vulcanizing and molding the nitrile rubber by selecting a die of 16.5mm multiplied by 6.5mm multiplied by 10mm on a tablet press;
(3) The vulcanized nitrile rubber was placed in a flask containing 50mL of toluene diisocyanate, the temperature was set at 50℃and the rotation speed of the rotor was 250rpm, and reacted for 40 minutes to obtain a product having terminal NCO groups on the surface. Taking out the mixture, centrifuging the mixture, wiping the mixture in a nitrogen atmosphere, putting the mixture into a three-neck flask filled with 50mL of polyphenylene oxide subjected to reduced pressure and water removal, heating the mixture in an oil bath at 70 ℃, stirring the mixture at 500rpm, and reacting the mixture for 4 hours to obtain a final product.
Example 3
(1) The nitrile rubber compound is prepared by adopting a mechanical blending method, and the formula is as follows: 100 parts of nitrile rubber, 4 parts of zinc oxide, 1 part of stearic acid, 3 parts of an anti-aging agent, 1 part of dioctyl phthalate, 1 part of sulfur, 3 parts of an accelerator and 60 parts of carbon black;
(2) Standing the rubber compound at room temperature for 24 hours, testing the vulcanization curve, determining the vulcanization condition, setting the temperature to 200 ℃, the specific pressure to 20Mpa, and the time to 20 minutes, and vulcanizing and molding the nitrile rubber by selecting a die with the thickness of 16.5mm multiplied by 6.5mm multiplied by 10mm on a tablet press;
(3) The vulcanized nitrile rubber is placed in a flask filled with 50mL of diphenylmethane diisocyanate, the temperature is set at 60 ℃, the rotation speed of a rotor is 500rpm, and the reaction is carried out for 25 minutes, so that a product with the surface covered with terminal NCO groups is obtained. Taking out the polyethylene oxide powder, centrifuging, drying in a nitrogen atmosphere, putting the polyethylene oxide powder into a three-neck flask filled with 50mL of polyethylene oxide subjected to reduced pressure and water removal, heating in an oil bath at 100 ℃, stirring at 600rpm, and reacting for 2 hours to obtain a final product.
Example 4
(1) The nitrile rubber compound is prepared by adopting a mechanical blending method, and the formula is as follows: 100 parts of nitrile rubber, 7 parts of zinc oxide, 2 parts of stearic acid, 5 parts of an anti-aging agent, 3 parts of dioctyl phthalate, 1 part of sulfur, 3 parts of an accelerator and 50 parts of carbon black;
(2) Standing the rubber compound at room temperature for 24 hours, testing the vulcanization curve, determining the vulcanization condition, setting the temperature to 100 ℃, the specific pressure to 20Mpa, and the time to 50 minutes, and vulcanizing and molding the nitrile rubber by selecting a die with the thickness of 16.5mm multiplied by 6.5mm multiplied by 10mm on a tablet press;
(3) The vulcanized nitrile rubber was placed in a flask containing 50mL of isophorone diisocyanate, the temperature was set at 70℃and the rotor speed was 300rpm, and reacted for 20 minutes to obtain a product having terminal NCO groups on the surface. Taking out the mixture, centrifuging the mixture, wiping the mixture in a nitrogen atmosphere, putting the mixture into a three-neck flask filled with 50mL of polybutyl acrylate subjected to reduced pressure and water removal, heating the mixture in an oil bath at 90 ℃, stirring the mixture at 500rpm, and reacting the mixture for 3 hours to obtain a final product.
Example 5
(1) The nitrile rubber compound is prepared by adopting a mechanical blending method, and the formula is as follows: 100 parts of nitrile rubber, 5 parts of zinc oxide, 2 parts of stearic acid, 6 parts of an anti-aging agent, 4 parts of dioctyl phthalate, 1 part of sulfur, 1 part of an accelerator and 50 parts of carbon black;
(2) Standing the mixed rubber for 24 hours at room temperature, testing the vulcanization curve, determining the vulcanization condition, setting the temperature to 160 ℃, the specific pressure to 20Mpa, and the time to 30 minutes, and vulcanizing and molding the nitrile rubber by selecting a die with the thickness of 16.5mm multiplied by 6.5mm multiplied by 10mm on a tablet press;
(3) The vulcanized nitrile rubber was placed in a flask containing 50mL of hexamethylene diisocyanate, the temperature was set at 60℃and the rotation speed of the rotor was 200rpm, and reacted for 35 minutes to obtain a product having terminal NCO groups on the surface. Taking out the mixture, centrifuging the mixture, wiping the mixture in a nitrogen atmosphere, putting the mixture into a three-neck flask filled with 50mL of polyphenylene oxide subjected to reduced pressure and water removal, heating the mixture in an oil bath at 80 ℃, stirring the mixture at 400rpm, and reacting the mixture for 3 hours to obtain a final product.
Example 6
(1) The nitrile rubber compound is prepared by adopting a mechanical blending method, and the formula is as follows: 100 parts of nitrile rubber, 5 parts of zinc oxide, 1 part of stearic acid, 5 parts of anti-aging agent, 2 parts of dioctyl phthalate, 1 part of sulfur, 2 parts of accelerator and 50 parts of carbon black;
(2) Standing the mixed rubber for 24 hours at room temperature, testing the vulcanization curve, determining the vulcanization condition, setting the temperature to 160 ℃, the specific pressure to 20Mpa, and the time to 30 minutes, and vulcanizing and molding the nitrile rubber by selecting a die with the thickness of 16.5mm multiplied by 6.5mm multiplied by 10mm on a tablet press;
(3) The vulcanized nitrile rubber was placed in a flask containing 50mL of toluene diisocyanate, the temperature was set at 60℃and the rotation speed of the rotor was 250rpm, and reacted for 30 minutes to obtain a product having terminal NCO groups on the surface. Taking out the mixture, centrifuging the mixture, wiping the mixture in a nitrogen atmosphere, putting the mixture into a three-neck flask filled with 50mL of polyethylene glycol subjected to reduced pressure and water removal, heating the mixture in an oil bath at 80 ℃, stirring the mixture at 500rpm, and reacting the mixture for 3 hours to obtain a final product.
The nitrile rubber matrix and the surface grafted polymer brush of example 1 were characterized and tested for performance to provide the following test examples:
test example 1
And (3) observing the surface of the nitrile rubber material grafted with the polymer brush by adopting a Scanning Electron Microscope (SEM), wherein the polymer brush of the polyol is uniformly distributed as shown in figure 1, and a layer of continuous film is formed on the surface of the nitrile rubber.
Test example 2
Water contact angle test; the water contact angle of the sample is measured according to GB/T30693-2014 by adopting an OCA-25 water contact angle measuring instrument, 10 different positions are respectively selected for the nitrile rubber matrix and the nitrile rubber of the surface graft polymer brush, the average value of the test results is calculated, and the results are shown in Table 1.
TABLE 1 Water contact Angle of materials
| Material | Water contact angle (°) |
| Nitrile rubber matrix | 103.95 |
| Nitrile rubber with surface grafted with polymer brush | 72.04 |
The result shows that the water contact angle of the polymer brush is obviously reduced and is smaller than 90 degrees, and the hydrophilicity of the material is improved.
Test example 3
Friction and wear performance test: the test was performed using a UMT-TL model friction tester. After the test sample is installed, a ring-block friction and wear test is carried out, the size of a plastic standard test sample is 16.5mm multiplied by 6.5mm multiplied by 10mm, the material of a tin-grinding bronze ring is ZCUSn10Zn2, the size phi is 35.00mm multiplied by 8.75mm, the loading force is set to be 100N, the rotating speeds are respectively 0.045, 0.090, 0.180, 0.270, 0.360, 0.540, 0.900, 1.500 and 1.800m/s, and the friction time is 600s.
The results show that the friction coefficient of the nitrile rubber with the surface grafted with the polymer brush is obviously reduced under the water lubrication condition, and the lubrication state is more stable, as shown in table 2.
Table 2 coefficient of friction of materials under Water lubrication conditions
| Rotating speed (m/s) | Nitrile rubber matrix | Nitrile rubber with surface grafted with polymer brush |
| 0.045 | 0.24158 | 0.12304 |
| 0.090 | 0.31435 | 0.18955 |
| 0.180 | 0.6305 | 0.22998 |
| 0.270 | 0.52185 | 0.13864 |
| 0.360 | 0.38629 | 0.1014 |
| 0.540 | 0.24942 | 0.08817 |
| 0.900 | 0.15413 | 0.04715 |
| 1.500 | 0.09339 | 0.03723 |
| 1.800 | 0.08727 | 0.03313 |
Further, the surface morphology of the material was observed by Scanning Electron Microscopy (SEM), and as shown in fig. 2, most of the area of the surface of the grafted polymer-brushed nitrile rubber was smooth, and almost no microscopic abrasion behavior occurred.
Test example 4
Collecting friction vibration signals: the vibration acceleration sensor is realized by a Pulse system, a 4519 type vibration acceleration sensor and a 3676 type module. A B & K4519 type sensor is arranged above a friction base of the testing machine, can record the vibration condition above the tangential direction of a friction surface, stores a friction vibration acceleration signal of a test sample block by being connected with a 3676 type module, and analyzes the friction vibration acceleration signal in a computer by using MATLAB software. Vibration signals of the friction tests 296s-305s are collected, and the 300s signal is taken for analysis, wherein the collection frequency is 65536Hz.
As shown in Table 3, the total vibration level of the nitrile rubber with the surface grafted polymer brush was reduced to a different extent under water lubrication conditions, and the vibration energy was lower.
Table 3 Total vibration level (dB) of materials under water lubrication condition
| Rotating speed (m/s) | Nitrile rubber matrix | Nitrile rubber with surface grafted with polymer brush |
| 0.045 | 97.968 | 97.758 |
| 0.090 | 98.624 | 97.945 |
| 0.180 | 104.591 | 102.291 |
| 0.270 | 113.585 | 108.284 |
| 0.360 | 118.281 | 116.243 |
| 0.540 | 123.28 | 119.717 |
| 0.900 | 127.751 | 125.635 |
| 1.500 | 133.187 | 131.852 |
| 1.800 | 134.245 | 132.838 |
In summary, by testing and analyzing the tribological conditions of the rubber before and after surface modification in water environment, the nitrile rubber grafted with the polymer brush on the surface has obviously reduced water contact angle and lower friction coefficient due to grafting of the hydrophilic chain segment, improves microscopic abrasion, has different vibration energy degrees lower than the nitrile rubber before modification, and shows excellent vibration damping performance. The invention provides a thinking for applying the molecular brush surface modification technology to the water lubrication bearing material, and provides a reliable basis for designing and preparing the polymer material with good water lubrication and vibration reduction performance.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the water-lubricated nitrile rubber surface polymer brush is characterized by comprising the following steps of:
s1, preparing nitrile rubber compound by adopting a mechanical blending method;
s2, performing vulcanization molding on the nitrile rubber compound prepared in the step S1 to obtain vulcanized nitrile rubber;
s3, placing the vulcanized nitrile rubber in excessive polyisocyanate with terminal NCO groups, reacting to obtain a product with the terminal NCO groups covered on the surface, taking out and centrifuging the product, wiping the product in nitrogen or inert atmosphere, and placing the product in excessive polyol subjected to decompression and water removal to react to obtain the water-lubricated nitrile rubber surface polymer brush.
2. The method for preparing the water-lubricated acrylonitrile-butadiene rubber surface polymer brush according to claim 1, wherein in the step S3, the reaction conditions of the vulcanized acrylonitrile-butadiene rubber and the polyisocyanate are as follows: the reaction temperature is 50-70 ℃, the rotor rotating speed is 200-500 rpm, and the reaction time is 20-40 min.
3. The method for preparing the polymer brush on the surface of the water-lubricated nitrile rubber according to claim 1, wherein in the step S3, the reaction conditions of the product with terminal NCO groups and the polyol are as follows: the reaction temperature is 70-100 ℃, and the oil bath is used for heating; the rotation speed of the rotor is 400 rpm-600 rpm, and the reaction time is 2 h-4 h.
4. The method for preparing the water-lubricated nitrile rubber surface polymer brush according to claim 1, wherein in the step S3, the polyisocyanate comprises one or more of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
5. The method for preparing a polymer brush on a surface of a water-lubricated nitrile rubber according to claim 1, wherein in the step S3, the polyhydric alcohol comprises one or more of polyethylene glycol, polyphenylene oxide, polyethylene oxide, polycaprolactone and polybutyl acrylate.
6. The method for preparing the water-lubricated surface polymer brush for the nitrile rubber according to claim 1, wherein in the step S1, the nitrile rubber compound comprises 100 parts of nitrile rubber, 4-7 parts of zinc oxide, 1-2 parts of stearic acid, 3-6 parts of an anti-aging agent, 1-4 parts of dioctyl phthalate, 0.5-1 part of sulfur, 1-3 parts of an accelerator and 40-60 parts of carbon black.
7. The method for preparing a water-lubricated acrylonitrile-butadiene rubber surface polymer brush according to claim 1, wherein in the step S2, the preparation conditions of the vulcanized acrylonitrile-butadiene rubber are determined according to the vulcanization curve measured by the acrylonitrile-butadiene rubber compound; the reaction temperature is 100-200 ℃, the specific pressure is 10-30 Mpa, and the reaction time is 20-50 min.
8. The method for preparing the water-lubricated nitrile rubber surface polymer brush according to claim 1, wherein in the step S2, the nitrile rubber is vulcanized and molded by a tablet press.
9. A water-lubricated nitrile rubber surface polymer brush produced according to the production method of any one of claims 1 to 8.
10. Use of the water-lubricated nitrile rubber surface polymer brush of claim 9 as a water-lubricated bearing material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053700A (en) * | 2000-08-09 | 2002-02-19 | Aoki Anzengutsu Seizo Kk | Rubber composition, shoe sole using the same rubber composition and shoe |
| JP2015183082A (en) * | 2014-03-24 | 2015-10-22 | 住友ゴム工業株式会社 | Surface modification method and surface modified elastic material |
| CN114369295A (en) * | 2021-12-09 | 2022-04-19 | 中国科学院兰州化学物理研究所 | Modified nitrile rubber water-lubricating composite material and preparation method thereof |
| CN114729076A (en) * | 2019-11-26 | 2022-07-08 | 默克专利股份有限公司 | Non-thiol nitrogen-based hydrophobic polymer brush materials and their use for substrate surface modification |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053700A (en) * | 2000-08-09 | 2002-02-19 | Aoki Anzengutsu Seizo Kk | Rubber composition, shoe sole using the same rubber composition and shoe |
| JP2015183082A (en) * | 2014-03-24 | 2015-10-22 | 住友ゴム工業株式会社 | Surface modification method and surface modified elastic material |
| CN114729076A (en) * | 2019-11-26 | 2022-07-08 | 默克专利股份有限公司 | Non-thiol nitrogen-based hydrophobic polymer brush materials and their use for substrate surface modification |
| CN114369295A (en) * | 2021-12-09 | 2022-04-19 | 中国科学院兰州化学物理研究所 | Modified nitrile rubber water-lubricating composite material and preparation method thereof |
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