CN114989509A - Environment-friendly oil-resistant high-strength NBR rubber sheet and preparation method thereof - Google Patents

Environment-friendly oil-resistant high-strength NBR rubber sheet and preparation method thereof Download PDF

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CN114989509A
CN114989509A CN202210941525.XA CN202210941525A CN114989509A CN 114989509 A CN114989509 A CN 114989509A CN 202210941525 A CN202210941525 A CN 202210941525A CN 114989509 A CN114989509 A CN 114989509A
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nbr rubber
montmorillonite
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CN114989509B (en
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庞坤
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Shandong Moncee Sensor Co ltd
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Abstract

The invention relates to the technical field of rubber plates, and discloses an environment-friendly oil-resistant high-strength NBR rubber plate and a preparation method thereof. The environment-friendly oil-resistant high-strength NBR rubber plate is prepared by taking montmorillonite as a reinforcing agent, grafting an anti-aging agent with double bonds and coupling groups on hydroxylated montmorillonite, inserting NBR rubber into modified montmorillonite, adding other auxiliaries, mixing and vulcanizing to prepare modified NBR rubber, and finally performing surface modification on the modified NBR rubber to obtain the environment-friendly oil-resistant high-strength NBR rubber plate. The environment-friendly oil-resistant high-strength NBR rubber sheet is environment-friendly, and has good oil resistance, mechanical properties and wear resistance.

Description

Environment-friendly oil-resistant high-strength NBR rubber sheet and preparation method thereof
Technical Field
The invention relates to the technical field of rubber plates, in particular to an environment-friendly oil-resistant high-strength NBR rubber plate and a preparation method thereof.
Background
The rubber industry is one of the important basic industries of national economy, not only provides daily and medical light industrial rubber products which are indispensable to daily life for people, but also provides various rubber production equipment or rubber parts for heavy industries such as mining, traffic, building, machinery, electronics and emerging industries. For example, chinese patent CN110223862B discloses a safety carpet and a production process thereof, rubber is used as a protective layer of the safety carpet, and for example, chinese patent CN204307823U discloses a wear-resistant rubber sieve plate, and rubber is made into a wear-resistant sieve plate.
When the rubber plate in the prior art is used as the main material of the safety carpet, the rubber main material needs to have higher characteristics in the aspects of strength, wear resistance, oil resistance and the like in consideration of the fact that the safety carpet is greatly concentrated in the operation area of large stamping mechanical equipment with severe operation environment in the application scene of the industrial field, so that the service life and the functional sensitivity of the safety carpet under different working conditions can be furthest improved, and the overall product performance of the safety carpet is further improved.
Nitrile Butadiene Rubber (NBR), a rubber, is a copolymer polymerized from acrylonitrile and butadiene monomers, and is mainly produced by a low-temperature emulsion polymerization method. The nitrile rubber can be used in air at 120 ℃ or oil at 150 ℃ for a long time, and in addition, because the nitrile rubber also has good water resistance, air tightness and excellent bonding performance, the nitrile rubber is widely used for manufacturing various oil-resistant rubber products, various oil-resistant gaskets, sleeves, flexible packages, flexible rubber tubes, printing and dyeing rubber rollers, cable rubber materials and the like.
For example, Chinese patent CN105153499B discloses a preparation method of NBR/MXDP high temperature and high wear resistant rubber material, the tensile strength and wear resistance of vulcanized rubber can be greatly improved by adding ternary nylon, the aging inhibitor adopts NAPM, and the aging resistance of vulcanized rubber is obviously improved, but carbon black is used as a reinforcing agent in Chinese patent CN105153499B, so that the processing pollution is large, the pollution of processing places is serious, the cleanness is difficult to keep, the mixing process needs a long time, and the energy consumption is large.
For another example, chinese patent CN103724731B discloses an NBR rubber sealing material for garbage disposers and a preparation method thereof, which comprises the following specific components in parts by weight: 100 parts of nitrile rubber, 1-1.5 parts of plasticizer, 5 parts of activator, 2-5 parts of anti-aging agent, 20-35 parts of carbon black, 10-18 parts of softening plasticizer, 2.25-2.5 parts of accelerator and 2.71 parts of vulcanizing agent; however, the antioxidant in CN103724731B is directly mixed and kneaded, which causes migration and uneven distribution of the antioxidant, thereby affecting the vulcanization efficiency and the properties of the final rubber.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
the step (1) comprises the preparation of an anti-aging agent and the preparation of hydroxylated montmorillonite:
preparing an anti-aging agent: mixing 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine according to the mass ratio of 1.5-1.8:1, adding triethylamine under the protection of nitrogen, heating to 110-130 ℃, reacting for 5-7h, adding diethyl ether, filtering, and distilling under the conditions of 0.08-0.1MPa and 145-150 ℃ to obtain the anti-aging agent;
preparation of hydroxylated montmorillonite: mixing sodium-based montmorillonite with ultrapure water to obtain slurry, adding long-chain alkyl quaternary ammonium salt into the slurry, stirring for 1.5-2.5h at the rotating speed of 3000-4000r/min, and performing suction filtration, washing, drying and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of the long-chain alkyl quaternary ammonium salt to the sodium-based montmorillonite is 40-60: 100;
step (2) preparation of modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing the anti-aging agent and ethanol according to the mass ratio of 1:1, spraying the mixture into the high-speed mixer, stirring the mixture for 5-10min at the rotating speed of 600-1000r/min, discharging, and drying, washing and drying to obtain modified montmorillonite, wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1;
step (3) preparation of the modified NBR rubber plate: adjusting the roll gap of a two-roll open mill, adding NBR rubber, and plastifying at 30 DEG C5-15min, triangular wrapping, adding modified montmorillonite and adhesive RH, mixing at 35 deg.C for 15-35min, triangular wrapping, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide, and dioctyl phthalate, mixing at 40 deg.C for 15-35min, triangular wrapping, thinly passing, slicing, standing for 3-5h, and measuring the optimal vulcanization time t with a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine to obtain a modified NBR rubber plate; wherein the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide and the dioctyl phthalate is 100:15-30:1-3:5:2:1.5:1.5: 10;
step (4), preparation of the environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 5-8 days, taking out, washing and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Preferably, the triethylamine in the step (1) is added according to a mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the triethylamine of 1.5-1.8: 0.8-1.
Preferably, in the step (1), the mixing conditions of the sodium montmorillonite and the ultrapure water are as follows: the stirring temperature is 60 ℃, the stirring speed is 3000-; the mass-volume ratio of the sodium montmorillonite to the ultrapure water is 0.2 g/mL; the washing liquid used for washing comprises ultrapure water; the drying temperature is as follows: 105 ℃ and 108 ℃.
Preferably, the long-chain alkyl quaternary ammonium salt comprises one of dioctadecyl dihydroxyethyl ammonium bromide, octadecyl methyl dihydroxyethyl ammonium bromide and hexadecyl trihydroxyethyl ammonium bromide.
Preferably, in the step (2), the drying conditions are as follows: drying at 120 deg.C for 2 hr; the washing conditions were: washing with ethanol for 5 times; the drying conditions were: drying at 120 deg.C for 1-2 hr.
Preferably, the adhesive RH in the step (3) is formed by mixing resorcinol withThe hexamethylene tetramine complex is formed by complexing according to the molar ratio of 1: 1; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%.
Preferably, in the step (3), the roller spacing of the two-roller open mill is adjusted to 2 mm; triangular bags are respectively packed for 6 times in the plastication and mixing processes; the number of thin pass operations is: passing through the thin layer for 5 times; the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for optimal time t 90 The specific result of the test of the rotor-free vulcanizing machine is set.
Furthermore, the invention also discloses an environment-friendly oil-resistant high-strength NBR rubber plate prepared by the preparation method of the environment-friendly oil-resistant high-strength NBR rubber plate.
Furthermore, the environment-friendly oil-resistant high-strength NBR rubber sheet can be applied to safety carpets.
Compared with the prior art, the invention has the beneficial effects that:
according to the reinforcing agent montmorillonite in the environment-friendly oil-resistant high-strength NBR rubber sheet, sodium montmorillonite is modified by using the long-chain quaternary ammonium salt, so that on one hand, the montmorillonite can be subjected to hydroxylation treatment; on the other hand, the quaternary ammonium salt cations can exchange with aluminum ions, silicon ions and the like between montmorillonite layers, and the compatibility of the modified montmorillonite and organic matters is greatly enhanced, so that the NBR rubber can be better intercalated in the montmorillonite; in addition, for the quaternary ammonium salt, the longer the alkyl molecular chain is, the larger the interlayer spacing of the modified montmorillonite is, and the better the intercalation effect is, so the quaternary ammonium salt adopted by the invention is one of dioctadecyl dihydroxyethyl ammonium bromide, octadecyl methyl dihydroxyethyl ammonium bromide and hexadecyl trihydroxyethyl ammonium bromide.
Coupling groups in the anti-aging agent can be combined with hydroxyl groups in hydroxylated montmorillonite, and the anti-aging agent is used as a connecting intermediate to connect the montmorillonite with the NBR rubber, so that the crosslinking density of the whole system is further increased; the greater the crosslinking density, the better the mechanical properties and oil resistance.
In addition, in the preparation of the environment-friendly oil-resistant high-strength NBR rubber sheet, the anti-aging agent with carbon-carbon double bonds and coupling groups is synthesized, and because the anti-aging agent contains the carbon-carbon double bonds, the anti-aging agent and unsaturated bonds of the NBR rubber can be subjected to addition reaction during high-temperature vulcanization, the crosslinking density of the NBR rubber sheet and the anti-aging agent can be increased, the vulcanization efficiency is improved, and the conditions of migration and uneven distribution caused by direct mixing of the anti-aging agent can be reduced. Sulfur also has initiating effect as vulcanizing agent and promoting effect on addition.
The reinforcing agent in the environment-friendly oil-resistant high-strength NBR rubber sheet material replaces the carbon black which is generally applicable in the past with the modified montmorillonite, the lamellar orientation of the montmorillonite enables oil molecules to not directly pass through the rubber in the process of moving in the rubber, and only can bypass the lamellar structure along a curve, so that the moving distance of the oil molecules in the rubber is increased, the reinforcing agent has the effect of blocking the movement of the oil molecules, and the oil resistance is improved while the strength is increased; meanwhile, the problems that carbon black is used as a reinforcing agent, the processing pollution is large, the pollution of processing places is serious, the cleanness is difficult to keep, the mixing needs a long time in the mixing process, and the energy consumption is wasted are solved; meanwhile, the selected accelerator is an environment-friendly accelerator N-tert-butyl-2-benzothiazole sulfonamide, so that the whole processing process is more energy-saving and environment-friendly.
After the surface modification is carried out on the environment-friendly oil-resistant high-strength NBR rubber plate, the oil resistance and the mechanical property are improved, meanwhile, the surface of the NBR rubber plate after the surface modification is compact and flat, has no flaws such as cracks and cavities, and the like, and is integrated with a matrix, so that the NBR rubber plate after the surface modification has good wear resistance.
Drawings
FIG. 1 is a schematic diagram of the process for preparing a modified NBR rubber sheet according to the invention;
FIG. 2 is a schematic diagram of a preparation process of the environment-friendly oil-resistant high-strength NBR rubber sheet;
FIG. 3 is a schematic diagram of the synthesis of an antioxidant according to the present invention;
FIG. 4 is a comparison graph of Shore hardness tests of rubber plates of examples of the present invention and comparative examples;
FIG. 5 is a comparison graph of tensile strength tests of rubber sheets of examples of the present invention and comparative examples;
FIG. 6 is a graph comparing the elongation at break test of rubber sheets of examples of the present invention and comparative examples;
FIG. 7 is a comparison graph of the volume change rate test after IRM903 # oil immersion for rubber sheets of examples of the invention and comparative examples;
FIG. 8 is a graph comparing hardness change tests after IRM903 # oil immersion of rubber sheets of examples of the present invention and comparative examples;
FIG. 9 is a comparison of rubber plate roller wear tests for examples of the invention and comparative examples.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
The embodiment discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 5 hours at 110 ℃, adding diethyl ether, filtering, and distilling at 0.08MPa and 145 ℃ to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.5:1: 0.8.
Preparation of hydroxylated montmorillonite: mixing sodium montmorillonite with ultrapure water, heating to 60 ℃, and stirring at the rotating speed of 3000r/min for 2h to obtain slurry, wherein the mass-volume ratio of the sodium montmorillonite to the ultrapure water is 0.2 g/mL; adding dioctadecyl dihydroxyethyl ammonium bromide into the slurry, stirring for 1.5h at the rotating speed of 3000r/min, filtering, washing a filter cake with ultrapure water, drying at 105 ℃, and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of the dioctadecyl dihydroxyethyl ammonium bromide to the sodium-based montmorillonite is 40: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 600r/min for 5min, discharging, vacuum drying at 120 ℃ for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 1h at constant temperature to obtain modified montmorillonite; wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roll distance of a double-roll open mill to 2mm, adding NBR rubber, plastifying at 30 ℃ for 5min, triangulating for 6 times, adding modified montmorillonite and RH (RH) adhesive, mixing at 35 ℃ for 15min, triangulating for 6 times, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide and dioctyl phthalate according to the proportion, mixing at 40 ℃ for 15min, triangulating for 6 times, thinly passing for 5 times, discharging, standing for 3h, and measuring the optimal vulcanization time t by using a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 16min to obtain the modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 16 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide and the dioctyl phthalate is 100:15:1:5:2:1.5:1.5: 10.
(4) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 5 days, taking out, washing with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Example 2
The embodiment discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 7 hours at 130 ℃, adding diethyl ether, filtering, and distilling at 0.09MPa and 145 ℃ to obtain the anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.8:1: 1.
Preparation of hydroxylated montmorillonite: mixing sodium-based montmorillonite with ultrapure water, heating to 60 ℃, and stirring at the rotating speed of 4000r/min for 2 hours to obtain slurry, wherein the mass-volume ratio of the sodium-based montmorillonite to the ultrapure water is 0.2 g/mL; adding dioctadecyl dihydroxyethyl ammonium bromide into the slurry, stirring for 2.5h at the rotating speed of 4000r/min, carrying out suction filtration, washing a filter cake by using ultrapure water, drying at the temperature of 108 ℃, and grinding to obtain hydroxylated montmorillonite, wherein the mass ratio of the dioctadecyl dihydroxyethyl ammonium bromide to the sodium montmorillonite is 60: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 1000r/min for 10min, discharging, drying at 120 ℃ in vacuum for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 2h at constant temperature to obtain modified montmorillonite, wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roller spacing of a two-roller open mill to 2mm, adding NBR rubber, plasticating for 15min at the temperature of 30 ℃, triangulating for 6 times, adding modified montmorillonite and adhesive RH, mixing for 35min at the temperature of 35 ℃, triangulating for 6 times, then adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide and dioctyl phthalate according to the proportion, mixing for 35min at the temperature of 40 ℃, triangulating for 6 times, thinly passing for 5 times, discharging, standing for 5h, and measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 25min to obtain the modified NBR rubber plate; wherein the vulcanization conditions are as follows: under the conditions of 143 ℃ of temperature and 10MPa of pressureVulcanizing for 25 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide and the dioctyl phthalate is 100:30:3:5:2:1.5:1.5: 10.
(4) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 8 days, taking out, washing with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Example 3
The embodiment discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 5.5h at 115 ℃, adding diethyl ether, filtering, and distilling at 148 ℃ under 0.09MPa to obtain the anti-aging agent. Wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.6:1: 0.85.
Preparation of hydroxylated montmorillonite: mixing sodium montmorillonite with ultrapure water, heating to 60 ℃, and stirring at the rotating speed of 3200r/min for 2h to obtain slurry, wherein the mass-volume ratio of the sodium montmorillonite to the ultrapure water is 0.2 g/mL; adding dioctadecyl dihydroxyethyl ammonium bromide into the slurry, stirring for 1.8h at the rotating speed of 3200r/min, carrying out suction filtration, washing a filter cake by using ultrapure water, drying at 106 ℃, and grinding to obtain hydroxylated montmorillonite, wherein the mass ratio of the dioctadecyl dihydroxyethyl ammonium bromide to the sodium montmorillonite is 45: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 700r/min for 6min, discharging, drying at 120 ℃ in vacuum for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 1.3h at constant temperature to obtain the modified montmorillonite, wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roll distance of a double-roll open mill to 2mm, adding NBR rubber, plastifying for 8min at 30 ℃, triangularly packaging for 6 times, adding modified montmorillonite and adhesive RH, mixing for 20min at 35 ℃, triangularly packaging for 6 times, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide and dioctyl phthalate according to the proportion, mixing for 20min at 40 ℃, triangularly packaging for 6 times, thinly passing for 5 times, discharging, standing for 3.5h, and measuring the optimal vulcanization time t by using a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 18min to obtain the modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 18 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tert-butyl-2-benzothiazole sulfonamide to the dioctyl phthalate is 100:20:1.5:5:2:1.5:1.5: 10.
(4) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% of KI aqueous solution and 18wt% of KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 6 days, taking out the modified NBR rubber plate, washing the modified NBR rubber plate with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Example 4
The embodiment discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 6 hours at 120 ℃, adding diethyl ether, filtering, and distilling at 150 ℃ under 0.1MPa to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.7:1: 0.9.
Preparation of hydroxylated montmorillonite: mixing sodium montmorillonite with ultrapure water, heating to 60 ℃, and stirring at the rotating speed of 3500r/min for 2h to obtain slurry, wherein the mass-volume ratio of the sodium montmorillonite to the ultrapure water is 0.2 g/mL; adding dioctadecyl dihydroxyethyl ammonium bromide into the slurry, stirring for 2h at the rotating speed of 3500r/min, filtering, washing a filter cake with ultrapure water, drying at 107 ℃, and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of the dioctadecyl dihydroxyethyl ammonium bromide to the sodium montmorillonite is 50: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 800r/min for 7min, discharging, vacuum drying at 120 ℃ for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 1.5h at constant temperature to obtain modified montmorillonite; wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roller spacing of a two-roller open mill to 2mm, adding NBR rubber, plasticating for 10min at 30 ℃, triangulating for 6 times, adding modified montmorillonite and adhesive RH, mixing for 25min at 35 ℃, triangulating for 6 times, then adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide and dioctyl phthalate according to the proportion, mixing for 25min at 40 ℃, triangulating for 6 times, thinly passing for 5 times, discharging, standing for 4h, and measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 19min to obtain the modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 19 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide and the dioctyl phthalate is 100:25:2:5:2:1.5:1.5: 10.
(4) Environment-friendly oil-resistant high-strength NBR rubber sheetPreparation: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 7 days, taking out, washing with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Example 5
The embodiment discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber plate, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 6.5h at 125 ℃, adding diethyl ether, filtering, and distilling at 147 ℃ under 0.08MPa to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.75:1: 0.95.
Preparation of hydroxylated montmorillonite: mixing sodium montmorillonite with ultrapure water, heating to 60 ℃, and stirring at the rotating speed of 3700r/min for 2 hours to obtain slurry, wherein the mass-volume ratio of the sodium montmorillonite to the ultrapure water is 0.2 g/mL; adding dioctadecyl dihydroxyethyl ammonium bromide into the slurry, stirring for 2h at the rotating speed of 3700r/min, carrying out suction filtration, washing a filter cake by ultrapure water, drying at 107 ℃, and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of the dioctadecyl dihydroxyethyl ammonium bromide to the sodium-based montmorillonite is 55: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 900r/min for 8min, discharging, vacuum drying at 120 ℃ for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 2h at constant temperature to obtain modified montmorillonite; wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roller spacing of a two-roller open mill to 2mm, adding NBR rubber, plasticating for 12min at 30 ℃, wrapping for 6 times by a triangle, addingAdding modified montmorillonite and binder RH, mixing at 35 deg.C for 30min, making into triangular bag for 6 times, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide, and dioctyl phthalate, mixing at 40 deg.C for 30min, making into triangular bag for 6 times, passing through for 5 times, slicing, standing for 4.5 hr, and measuring the optimal vulcanization time t with rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 23min to obtain the modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 23 min; optimum vulcanization time t 90 The time required for the vulcanization degree to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide and the dioctyl phthalate is 100:28:2.5:5:2:1.5:1.5: 10.
(4) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 8 days, taking out, washing with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Example 6
The embodiment discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber plate, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 6 hours at 120 ℃, adding diethyl ether, filtering, and distilling at 150 ℃ under 0.1MPa to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.7:1: 0.9.
Preparation of hydroxylated montmorillonite: mixing sodium-based montmorillonite with ultrapure water, heating to 60 ℃, and stirring at a rotation speed of 3500r/min for 2h to obtain slurry, wherein the mass-to-volume ratio of the sodium-based montmorillonite to the ultrapure water is 0.2 g/mL; adding octadecyl methyl dihydroxyethyl ammonium bromide into the slurry, stirring at the rotating speed of 3500r/min for 2h, performing suction filtration, washing a filter cake with ultrapure water, drying at 107 ℃, and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of the octadecyl methyl dihydroxyethyl ammonium bromide to the sodium montmorillonite is 50: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 800r/min for 7min, discharging, vacuum drying at 120 ℃ for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 1.5h at constant temperature to obtain modified montmorillonite; wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roll distance of a two-roll open mill to 2mm, adding NBR rubber, plasticating for 10min at 30 ℃, triangularly packaging for 6 times, adding modified montmorillonite and adhesive RH, mixing for 25min at 35 ℃, triangularly packaging for 6 times, adding zinc oxide, stearic acid, sulfur, N-tertiary butyl-2-benzothiazole sulfonamide and dioctyl phthalate according to the proportion, mixing for 25min at 40 ℃, triangularly packaging for 6 times, thinly passing for 5 times, feeding sheets, standing for 4h, and measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 19min to obtain the modified NBR rubber plate; wherein the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 19 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tert-butyl-2-benzothiazole sulfonamide to the dioctyl phthalate is 100:25:2:5:2:1.5:1.5: 10.
(4) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% of KI aqueous solution and 18wt% of KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 7 days, taking out the modified NBR rubber plate, washing the modified NBR rubber plate with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Example 7
The embodiment discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 6 hours at 120 ℃, adding diethyl ether, filtering, and distilling at 150 ℃ under 0.1MPa to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.7:1: 0.9.
Preparation of hydroxylated montmorillonite: mixing sodium montmorillonite with ultrapure water, heating to 60 ℃, and stirring at the rotating speed of 3500r/min for 2h to obtain slurry, wherein the mass-volume ratio of the sodium montmorillonite to the ultrapure water is 0.2 g/mL; adding hexadecyl trihydroxyethyl ammonium bromide into the slurry, stirring at the rotating speed of 3500r/min for 2h, performing suction filtration, washing a filter cake with ultrapure water, drying at 107 ℃, and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of the hexadecyl trihydroxyethyl ammonium bromide to the sodium montmorillonite is 50: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 800r/min for 7min, discharging, vacuum drying at 120 ℃ for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 1.5h at constant temperature to obtain modified montmorillonite; wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roller spacing of a two-roller open mill to 2mm, adding NBR rubber, plasticating for 10min at 30 ℃, triangulating for 6 times, adding modified montmorillonite and adhesive RH, mixing for 25min at 35 ℃, triangulating for 6 times, then adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide and dioctyl phthalate according to the proportion, mixing for 25min at 40 ℃, triangulating for 6 times, thinly passing for 5 times, discharging, standing for 4h, and measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 For 19min in a plate vulcanizing machineVulcanizing and tabletting to obtain a modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 19 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide and the dioctyl phthalate is 100:25:2:5:2:1.5:1.5: 10.
(4) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% of KI aqueous solution and 18wt% of KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 7 days, taking out the modified NBR rubber plate, washing the modified NBR rubber plate with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Comparative example 1
The comparative example discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 6 hours at 120 ℃, adding diethyl ether, filtering, and distilling at 150 ℃ under 0.1MPa to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.7:1: 0.9.
(2) Preparing a modified NBR rubber plate: adjusting the roll distance of a double-roll open mill to 2mm, adding NBR rubber, plasticating for 10min at 30 ℃, triangularly packaging for 6 times, adding sodium-based montmorillonite and adhesive RH, mixing for 25min at 35 ℃, triangularly packaging for 6 times, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide, dioctyl phthalate and anti-aging agent according to the proportion, mixing for 25min at 40 ℃, triangularly packaging for 6 times, thinly passing for 5 times, placing for 4h, measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 19min to obtain the modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 19 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the sodium-based montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tert-butyl-2-benzothiazole sulfonamide, the dioctyl phthalate and the anti-aging agent is 100:23.3:2:5:2:1.5:1.5:10: 1.7.
(3) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 7 days, taking out, washing with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Comparative example 2
The comparative example discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 6 hours at 120 ℃, adding diethyl ether, filtering, and distilling at 150 ℃ under 0.1MPa to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.7:1: 0.9.
Preparation of hydroxylated montmorillonite: mixing sodium montmorillonite with ultrapure water, heating to 60 ℃, and stirring at the rotating speed of 3500r/min for 2h to obtain slurry, wherein the mass-volume ratio of the sodium montmorillonite to the ultrapure water is 0.2 g/mL; adding dioctadecyl dihydroxyethyl ammonium bromide into the slurry, stirring for 2h at the rotating speed of 3500r/min, filtering, washing a filter cake with ultrapure water, drying at 107 ℃, and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of dioctadecyl dihydroxyethyl ammonium bromide to sodium-based montmorillonite is 50: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 800r/min for 7min, discharging, vacuum drying at 120 ℃ for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 1.5h at constant temperature to obtain modified montmorillonite; wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roll distance of a two-roll open mill to 2mm, adding NBR rubber, plasticating for 10min at 30 ℃, triangularly packaging for 6 times, adding modified montmorillonite and adhesive RH, mixing for 25min at 35 ℃, triangularly packaging for 6 times, adding zinc oxide, stearic acid, sulfur, N-tertiary butyl-2-benzothiazole sulfonamide and dioctyl phthalate according to the proportion, mixing for 25min at 40 ℃, triangularly packaging for 6 times, thinly passing for 5 times, feeding sheets, standing for 4h, and measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 19min to obtain the modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 19 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide and the dioctyl phthalate is 100:25:2:5:2:1.5:1.5: 10.
Comparative example 3
The comparative example discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 6 hours at 120 ℃, adding diethyl ether, filtering, and distilling at 150 ℃ under 0.1MPa to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.7:1: 0.9.
(2) Preparation of modified NBR rubber plate: adjusting the roller spacing of a two-roller open mill to 2mm, adding NBR rubber, plasticating at 30 ℃ for 10min, triangulating for 6 times, adding carbon black and an adhesive RH, mixing at 35 ℃ for 25min, triangulating for 6 times, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide, dioctyl phthalate and an anti-aging agent according to the proportion, and mixingMixing at 40 deg.C for 25min, making triangular bag for 6 times, passing through for 5 times, discharging, standing for 4h, and measuring the optimal vulcanization time t with rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 19min to obtain the modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 19 min; optimum vulcanization time t 90 The time required for the vulcanization degree to reach 90%; the mass ratio of the NBR rubber, the carbon black, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide, the dioctyl phthalate and the anti-aging agent is 100:23.3:2:5:2:1.5:1.5:10: 1.7.
(3) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 7 days, taking out, washing with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Comparative example 4
The comparative example discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) the preparation method comprises the following steps of preparing an anti-aging agent and preparing hydroxylated montmorillonite:
preparing an anti-aging agent: adding triethylamine into 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine under the protection of nitrogen, reacting for 6 hours at 120 ℃, adding diethyl ether, filtering, and distilling at 150 ℃ under 0.1MPa to obtain an anti-aging agent; wherein the mass ratio of the 2- (chloromethyl) propenyl trimethoxy silane to the p-aminodiphenylamine to the triethylamine is 1.7:1: 0.9.
Preparation of hydroxylated montmorillonite: mixing sodium-based montmorillonite with ultrapure water, heating to 60 ℃, and stirring at a rotation speed of 3500r/min for 2h to obtain slurry, wherein the mass-to-volume ratio of the sodium-based montmorillonite to the ultrapure water is 0.2 g/mL; adding dioctadecyl dihydroxyethyl ammonium bromide into the slurry, stirring for 2h at the rotating speed of 3500r/min, filtering, washing a filter cake with ultrapure water, drying at 107 ℃, and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of the dioctadecyl dihydroxyethyl ammonium bromide to the sodium-based montmorillonite is 50: 100.
(2) Preparing modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying, stirring at the rotating speed of 800r/min for 7min, discharging, vacuum drying at 120 ℃ for 2h, washing with ethanol for 5 times, and drying at 120 ℃ for 1.5h at constant temperature to obtain modified montmorillonite; wherein the mass ratio of the hydroxylated montmorillonite to the anti-aging agent is 14: 1.
(3) Preparing a modified NBR rubber plate: adjusting the roll distance of a double-roll open mill to 2mm, adding NBR rubber, plastifying at 30 ℃ for 10min, triangulating for 6 times, adding modified montmorillonite, mixing at 35 ℃ for 25min, triangulating for 6 times, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfenamide and dioctyl phthalate in proportion, mixing at 40 ℃ for 25min, triangulating for 6 times, thinly passing for 5 times, discharging, standing for 4h, and measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 19min to obtain the modified NBR rubber plate; wherein the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 19 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber, the modified montmorillonite, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide to the dioctyl phthalate is 100:25:5:2:1.5:1.5: 10.
(4) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 7 days, taking out, washing with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
Comparative example 5
The comparative example discloses a preparation method of an environment-friendly oil-resistant high-strength NBR rubber sheet, which comprises the following steps:
(1) preparation of modified NBR rubber plate: the roll gap of a two-roll mill is adjusted to 2mm, and N is addedPlasticating BR rubber at 30 ℃ for 10min, performing triangular wrapping for 6 times, adding sodium-based montmorillonite and RH as adhesive, conducting mixing at 35 ℃ for 25min, performing triangular wrapping for 6 times, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfonamide, dioctyl phthalate and antioxidant 4010 in proportion, conducting mixing at 40 ℃ for 25min, performing triangular wrapping for 6 times, performing thin passing for 5 times, discharging, standing for 4h, and measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine for 19min to obtain the modified NBR rubber plate; wherein, the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for 19 min; optimum vulcanization time t 90 The time required for the degree of vulcanization to reach 90%; the mass ratio of the NBR rubber to the sodium-based montmorillonite to the adhesive RH to the zinc oxide to the stearic acid to the sulfur to the N-tert-butyl-2-benzothiazole sulfonamide to the dioctyl phthalate to the anti-aging agent 4010 is 100:23.3:2:5: 1.5:1.5:10: 1.7.
(2) Preparing an environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% KI aqueous solution and 18wt% KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 7 days, taking out, washing with deionized water, and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
In all the above examples and comparative examples, the adhesive RH was prepared by complexing a complex of resorcinol and hexamethylenetetramine at a molar ratio of 1: 1; sodium-based montmorillonite, available from Shanghai spectral vibration Biotechnology Ltd, under the brand name Clara; n-tert-butyl-2-benzothiazole sulfonamide is an environment-friendly accelerator with CAS number 95-31-8, and is provided by Hubei Jiulong chemical Co., Ltd; dioctyl phthalate is softener dioctyl phthalate, CAS number 117-81-7, provided by Shandong Qianxiang chemical Co., Ltd.; the average grain diameter of the ground hydroxylated montmorillonite is 50 μm; the double-roll open mill is SK160 multiplied by 320B of Yongchun machinery factory; the plate vulcanizing machine is XLB-D model of Chaozhou Hongqiao rubber machinery Co; the rotorless cure instrument was model MDR2000 from Shanghainegjie machines and equipments, Inc., and the sample cure curve was determined according to GB/T16584-1996.
Examples of the experiments
The performance tests were performed on the environment-friendly oil-resistant high-strength NBR rubber sheets prepared in examples 1 to 7, comparative example 1, comparative example 3, comparative example 4, and comparative example 5 of the present invention and the modified NBR rubber sheet prepared in comparative example 2.
Testing I, hardness testing: shore hardness measurements were performed according to the national standard GB/T531.1-2008, each test specimen was tested at three different locations, and the median was taken as the final result. The tensile strength and the elongation at break are performed according to the national standard GB/T528-2009. The test results are shown in table 1:
TABLE 1
Figure 877285DEST_PATH_IMAGE001
As can be seen from the test results in Table 1, the environmental-friendly oil-resistant high-strength NBR rubber sheets of examples 1 to 7 have mechanical properties superior to those of the rubber sheets of comparative examples 1 to 5; wherein, the comparative examples 1-5 are based on the example 4, the anti-aging agent synthesized in the comparative example 1 is not grafted on montmorillonite, and is directly added into a mixing roll through mixing; the rubber sheet in comparative example 2 was not subjected to the final immersion treatment; the reinforcing agent in comparative example 3 replaces the modified montmorillonite with carbon black; comparative example 4 no binder RH was added during the mixing process, and comparative example 5 replaced the antioxidant synthesized by the present invention with conventional antioxidant 4010 and modified montmorillonite directly with sodium montmorillonite.
And in the second test, the oil resistance is tested according to GB/T1690-2010, and IRM903 # oil is selected under the condition of 100 ℃ multiplied by 70 h. The test results are shown in table 2:
TABLE 2
Figure 997688DEST_PATH_IMAGE002
From the test results in table 2, after the environment-friendly oil-resistant high-strength NBR rubber sheet in the embodiment of the invention is soaked in IRM903 # oil for 70 hours, the volume change rate is below 5%, the hardness change is between-5 and-1, and both the volume change rate and the hardness change are small, which indicates that the oil resistance is excellent.
And thirdly, testing the wear resistance, namely performing roller abrasion on the test sample according to GB/T9867-2008 'determination of the wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller type abrasion machine method)'. The test results are shown in table 3:
TABLE 3
Figure 43004DEST_PATH_IMAGE003
As shown in the test results in Table 3, the environment-friendly oil-resistant high-strength NBR rubber sheet material disclosed by the invention has excellent oil resistance and mechanical properties, and also has very good wear resistance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. The preparation method of the environment-friendly oil-resistant high-strength NBR rubber sheet is characterized by comprising the following steps of:
the step (1) comprises the preparation of an anti-aging agent and the preparation of hydroxylated montmorillonite:
preparing an anti-aging agent: mixing 2- (chloromethyl) propenyl trimethoxy silane and p-aminodiphenylamine according to the mass ratio of 1.5-1.8:1, adding triethylamine under the protection of nitrogen, heating to 110-130 ℃, reacting for 5-7h, adding diethyl ether, filtering, and distilling under the conditions of 0.08-0.1MPa and 145-150 ℃ to obtain the anti-aging agent;
preparation of hydroxylated montmorillonite: mixing sodium-based montmorillonite with ultrapure water to obtain slurry, adding long-chain alkyl quaternary ammonium salt into the slurry, stirring for 1.5-2.5h at the rotating speed of 3000-4000r/min, and performing suction filtration, washing, drying and grinding to obtain hydroxylated montmorillonite; wherein the mass ratio of the long-chain alkyl quaternary ammonium salt to the sodium-based montmorillonite is 40-60: 100;
step (2) preparation of modified montmorillonite: adding hydroxylated montmorillonite into a high-speed mixer, mixing an anti-aging agent and ethanol according to the mass ratio of 1:1, spraying the mixture into the high-speed mixer, stirring the mixture for 5-10min at the rotating speed of 600-;
preparing the modified NBR rubber plate in the step (3): adjusting the roll spacing of a two-roll open mill, adding NBR rubber, plastifying for 5-15min at 30 ℃, packaging in a triangular bag, adding modified montmorillonite and adhesive RH, mixing for 15-35min at 35 ℃, packaging in a triangular bag, adding zinc oxide, stearic acid, sulfur, N-tert-butyl-2-benzothiazole sulfenamide and dioctyl phthalate in proportion, mixing for 15-35min at 40 ℃, packaging in a triangular bag, thinly passing, discharging, standing for 3-5h, and measuring the optimal vulcanization time t by a rotor-free vulcanizer 90 Vulcanizing and tabletting on a flat vulcanizing machine to obtain a modified NBR rubber plate; wherein the mass ratio of the NBR rubber, the modified montmorillonite, the adhesive RH, the zinc oxide, the stearic acid, the sulfur, the N-tertiary butyl-2-benzothiazole sulfonamide and the dioctyl phthalate is 100:15-30:1-3:5:2:1.5:1.5: 10;
step (4), preparation of the environment-friendly oil-resistant high-strength NBR rubber sheet: the same volume of 30wt% H 2 SO 4 And mixing the aqueous solution, 32wt% of KI aqueous solution and 18wt% of KBr aqueous solution to obtain a mixed oxidation modified solution, soaking the modified NBR rubber plate in the mixed oxidation modified solution for 5-8 days, taking out, washing and drying to obtain the environment-friendly oil-resistant high-strength NBR rubber plate.
2. The method for preparing the environment-friendly oil-resistant high-strength NBR rubber sheet as claimed in claim 1, wherein the triethylamine in the step (1) is added in a ratio of 1.5-1.8:0.8-1 by mass of 2- (chloromethyl) propenyl trimethoxy silane to triethylamine.
3. The method for preparing the environment-friendly oil-resistant high-strength NBR rubber sheet material as claimed in claim 1, wherein in the step (1), the mixing conditions of the sodium montmorillonite and the ultrapure water are as follows: the stirring temperature is 60 ℃, the stirring speed is 3000-; the mass-volume ratio of the sodium montmorillonite to the ultrapure water is 0.2 g/mL; the washing liquid used for washing comprises ultrapure water; the drying temperature is as follows: 105 ℃ and 108 ℃.
4. The method for preparing the environment-friendly oil-resistant high-strength NBR rubber sheet material as claimed in claim 1, wherein the long-chain alkyl quaternary ammonium salt comprises one of dioctadecyl dihydroxyethyl ammonium bromide, octadecyl methyl dihydroxyethyl ammonium bromide, and hexadecyl trihydroxyethyl ammonium bromide.
5. The method for preparing the environment-friendly oil-resistant high-strength NBR rubber sheet as claimed in claim 1, wherein in the step (2), the drying conditions are as follows: drying at 120 deg.C for 2 hr; the washing conditions were: washing with ethanol for 5 times; the drying conditions were: drying at 120 deg.C for 1-2 hr.
6. The method for preparing the environment-friendly oil-resistant high-strength NBR rubber sheet as claimed in claim 1, wherein the adhesive RH in the step (3) is formed by complexing a complex of resorcinol and hexamethylenetetramine in a molar ratio of 1: 1.
7. The method for preparing the environment-friendly oil-resistant high-strength NBR rubber sheet as claimed in claim 1, wherein in the step (3), the roll gap of the two-roll mill is adjusted to 2 mm; performing triangular bag formation for 6 times in the plastication and mixing processes; the number of thin pass operations is: passing through the thin layer for 5 times; the vulcanization conditions are as follows: vulcanizing at 143 deg.C and 10MPa for optimal time t 90 The specific result of the test of the rotor-free vulcanizing machine is set.
8. An environment-friendly oil-resistant high-strength NBR rubber sheet prepared by the preparation method according to any one of claims 1 to 7.
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Publication number Priority date Publication date Assignee Title
CN108976515A (en) * 2018-07-26 2018-12-11 合肥旭亚新材料科技有限公司 A kind of low temperature resistant nitrile rubber
CN110845775A (en) * 2019-12-11 2020-02-28 戴洪卫 Wear-resistant and compression-resistant high-performance rubber and preparation method thereof
CN112940362A (en) * 2021-02-03 2021-06-11 广东贝洛新材料科技有限公司 High-temperature-resistant and hot-oil-resistant nitrile rubber material and preparation method thereof
US20220073668A1 (en) * 2018-12-27 2022-03-10 Arlanxeo Deutschland Gmbh Pulverulent mixture of precrosslinked nitrile rubbers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108976515A (en) * 2018-07-26 2018-12-11 合肥旭亚新材料科技有限公司 A kind of low temperature resistant nitrile rubber
US20220073668A1 (en) * 2018-12-27 2022-03-10 Arlanxeo Deutschland Gmbh Pulverulent mixture of precrosslinked nitrile rubbers
CN110845775A (en) * 2019-12-11 2020-02-28 戴洪卫 Wear-resistant and compression-resistant high-performance rubber and preparation method thereof
CN112940362A (en) * 2021-02-03 2021-06-11 广东贝洛新材料科技有限公司 High-temperature-resistant and hot-oil-resistant nitrile rubber material and preparation method thereof

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