CN115044114B - Wear-resistant rubber composition and preparation method thereof - Google Patents
Wear-resistant rubber composition and preparation method thereof Download PDFInfo
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- CN115044114B CN115044114B CN202210981939.5A CN202210981939A CN115044114B CN 115044114 B CN115044114 B CN 115044114B CN 202210981939 A CN202210981939 A CN 202210981939A CN 115044114 B CN115044114 B CN 115044114B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides a wear-resistant rubber composition and a preparation method thereof, and belongs to the technical field of rubber compositions. The preparation method of the wear-resistant rubber composition comprises the following steps: preparing a wear-resistant agent, preparing a wear-resistant reinforcing agent, modifying a filler, mixing and vulcanizing. Wherein, the steps of pretreatment and microwave treatment are arranged in the preparation of the wear-resistant agent; the steps of modification and grinding are arranged in the preparation of the wear-resistant reinforcing agent. The rubber composition has the tensile strength of 29.0-30.2MPa, the Shore hardness of 66-67A, the elongation at break of 363-374%, the 100% stress at definite elongation of 4.8-5.2MPa, and the abrasion loss of 182.3-191.6mm 3 。
Description
Technical Field
The invention relates to the field of rubber compositions, in particular to a wear-resistant rubber composition and a preparation method thereof.
Background
Rubber is a highly elastic polymeric material with reversible deformation. The elastic material is elastic at normal temperature, can generate large deformation under the action of small external force, and can recover the original shape after the external force is removed. Rubber is a completely amorphous polymer, often with a molecular weight greater than several hundred thousand.
In the prior art, rubber is converted from raw rubber to cooked rubber, which requires a vulcanization process. The vulcanization process is generally carried out by adding a vulcanizing agent. The vulcanizing agent has a great influence on the physical properties of the rubber product and is an important factor next to the crude rubber. Although curing agents, curing accelerators or peroxides may be conventionally used in many rubber articles in combination with conventional curing means, such as electron beam curing, microwave curing, and the like. However, depending on the raw rubber material, other rubber vulcanization systems such as magnesium oxide vulcanization, FKM polyol vulcanization, etc. are also used to obtain a better vulcanization effect. Meanwhile, according to different uses of rubber products, methods such as radiation vulcanization, electron beam vulcanization and the like can be adopted.
However, the rubber used only after vulcanization generally has poor wear resistance, is easily worn and has a short service life because of the addition of an overcombusting agent during vulcanization. At present, the method for improving the wear resistance of rubber is to add a wear-resistant additive during rubber vulcanization, so that the effect of enhancing the wear resistance of the rubber is achieved.
The inventor finds that the dispersibility of the existing wear-resistant auxiliary in rubber is not ideal, and a small amount of wear-resistant auxiliary needs to be added for many times in the adding process of the wear-resistant auxiliary so as to improve the dispersibility of the wear-resistant auxiliary in rubber as much as possible; meanwhile, the processing device is matched with technological means such as high temperature, high shearing rotating speed and the like, the processing process is complicated, and the loss of processing equipment is high. The inventors have also found that even with the aforementioned method, the abrasion resistance aid cannot be uniformly dispersed in the rubber. The uneven addition of the wear-resistant auxiliary agent can cause the weak performance of the rubber product, the overall performance of the rubber product is not ideal, and the service life of the rubber product cannot be effectively prolonged; in a harsh environment, particularly a low-temperature environment, the tensile strength, the elongation at break and the wear resistance of the rubber product are seriously reduced, the required performances cannot be maintained all the time, and huge potential safety hazards exist.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the wear-resistant rubber composition and the preparation method thereof, the wear-resistant auxiliary agent can be effectively dispersed in rubber, the overall performance of a rubber product is good, and the service life of the rubber product can be effectively prolonged; meanwhile, under a low-temperature environment, the tensile strength, the elongation at break and the wear resistance of the rubber product are stable, and the required performances can be stably maintained.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a wear-resistant rubber composition comprises the following steps: preparing a wear-resistant agent, preparing a wear-resistant reinforcing agent, modifying a filler, mixing and vulcanizing.
The method for preparing the wear-resisting agent comprises the following steps: pretreatment and microwave treatment.
The pretreatment method comprises the steps of putting clay and alpha-cellulose into a ball mill, controlling the ball-to-material ratio to be 6-8:1, ball milling at the rotating speed of 500-700rpm, and ball milling for 10-20min; then adding dibutyl phthalate and polyethylene wax, and continuing ball milling for 5-15min to obtain a ball grinding material; putting ball grinding materials, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 into a high-speed shearing machine, and shearing at 1000-1200rpm for 5-8min to obtain a pretreated substance;
in the pretreatment, the ratio of the weight parts of the clay, the alpha-cellulose, the dibutyl phthalate and the polyethylene wax is 2-3:1-2 and is 0.3-0.5;
in the pretreatment, the weight parts of the ball grinding material, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 are 50-60;
in the pretreatment, the particle size of the clay is 300-350 meshes; the clay comprises the following components in percentage by weight: 45.5 to 46.5 percent of silicon dioxide, 8.0 to 8.5 percent of aluminum oxide, 0.5 to 0.7 percent of calcium oxide, 0.5 to 0.8 percent of magnesium oxide, 0.2 to 0.25 percent of titanium dioxide and 0.1 to 0.4 percent of ferric oxide;
in the pretreatment, the specification of the alpha-cellulose is that the diameter is 15-20 μm, and the length is 70-90 μm;
in the pretreatment, the number average molecular weight of the polyethylene wax is 4000-5000;
in the pretreatment, the type of polyether polyol is HK-1301;
in the pretreatment, the specification of the nano cerium dioxide is that the average particle size is 80-100nm, and the specific surface area is 25-35m 2 /g。
The microwave treatment method comprises placing the pretreated material in a microwave generator, and performing microwave treatment for 3-8min under nitrogen atmosphere; then grinding for 10-20min at the rotating speed of 1500-2000rpm to prepare the wear-resisting agent;
in the microwave treatment, the microwave frequency is 2.2-2.5GHz, and the microwave power is 350-550W.
The method for preparing the wear-resistant reinforcing agent comprises the following steps: and (5) modifying and grinding.
The modification method comprises using 48K carbon fiber as anode and copper electrode as cathode, and controlling current density at 25-35mA/cm at 30-40 deg.C 2 Modifying for 80-100s; then, leaching the carbon fibers by using 10-15 times of deionized water, and drying for 1-2 hours at the temperature of 80-90 ℃ in an environment with the vacuum degree of 0.02-0.05 MPa; then chopping the carbon fiber into 1-3mm to obtain a modified substance;
in the modification, the electrolyte is 5-7% of ammonium bicarbonate solution by mass concentration.
The grinding method comprises mixing the modifier, polyimide, tea saponin and silane coupling agent KH-550, stirring at 700-900rpm for 10-20min, and grinding at 2000-2500rpm for 3-5min to obtain wear-resistant reinforcing agent;
in the grinding, the ratio of the modified substance to the polyimide to the tea saponin to the silane coupling agent KH-550 by weight parts is 80-90.
The filler modification method comprises the steps of putting calcium carbonate and mica powder into a high-speed mixer, stirring until the temperature of the materials is 95-105 ℃, and then continuously stirring for 20-30min at a stirring speed of 200-300 rpm; then adding glass fiber and titanate coupling agent 201, stirring at 400-500rpm for 10-20min, and drying at 70-80 ℃ under the condition that the vacuum degree is 0.01-0.03MPa until the moisture content is 0.1-0.5wt% to prepare the modified filler;
in the filler modification, the weight parts of calcium carbonate, mica powder, glass fiber and titanate coupling agent 201 are 60-80;
in the filler modification, the specification of the calcium carbonate is that the particle size is 3-8 mu m, and the specific surface area is 10-20m 2 /g；
In the filler modification, the particle size of the mica powder is 10-15 μm;
in the filler modification, the diameter of the glass fiber is 5-10 μm.
The mixing method comprises the steps of putting 70-80 parts by weight of styrene butadiene rubber, 30-40 parts by weight of butadiene rubber, 15-25 parts by weight of white carbon black, 5-10 parts by weight of carbon black, 10-20 parts by weight of epoxy resin, 3-4 parts by weight of wear-resisting agent, 10-20 parts by weight of wear-resisting reinforcing agent, 20-30 parts by weight of modified filler, 1-2 parts by weight of anti-aging agent MB, 1-2 parts by weight of stearic acid and 3-6 parts by weight of zinc oxide into a mixer, and stirring at 300-500rpm for 20-30min; then placing the mixture into a mixing mill, controlling the primary mixing pressure to be 3-5MPa, the primary mixing temperature to be 155-165 ℃ and the primary mixing rotating speed to be 50-70rpm, and carrying out primary mixing for 5-10min; then controlling the secondary mixing pressure to be 8-10MPa, the secondary mixing temperature to be 165-175 ℃, the secondary mixing rotating speed to be 80-90rpm, and carrying out secondary mixing for 3-5min to obtain a mixed material.
The vulcanization method comprises the steps of adding 1.5-2.5 parts of sulfur and 1-2 parts of accelerator TBBS into the mixture according to the parts by weight, and stirring at 120-150rpm for 5-10min; then controlling the vulcanization pressure to be 10-15MPa, the vulcanization temperature to be 160-170 ℃ and the vulcanization time to be 40-60min to prepare the wear-resistant rubber composition.
The wear-resistant rubber composition is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method of the wear-resistant rubber composition, the specific wear-resistant agent and the wear-resistant reinforcing agent are prepared and added into the wear-resistant rubber composition, and the raw materials are matched with each other, so that the dispersibility of the wear-resistant agent and the wear-resistant auxiliary agent in rubber is effectively improved; in addition, in the adding process of the wear-resistant agent, the rubber can be directly mixed with other raw materials without adopting a small amount of repeated adding modes, thereby effectively eliminating rubberThe weak performance in the rubber effectively improves the wear resistance of the rubber composition; meanwhile, the compatibility among the raw materials of the rubber composition is further enhanced through the arrangement of the modified filler, the overall performance of the rubber composition is further improved, and the service life of the rubber composition is prolonged; the prepared rubber composition has the tensile strength of 29.0-30.2MPa, the Shore hardness of 66-67A, the elongation at break of 363-374%, the 100% stress at definite elongation of 4.8-5.2MPa, and the abrasion loss of 182.3-191.6mm 3 。
(2) The wear-resistant rubber composition can keep good long-term integral performance, effectively eliminates potential safety hazards of the rubber composition, and can still reach 27.7-29.1MPa in tensile strength, 340-353% in elongation at break and 176.8-182.6mm in abrasion loss after standing for 25 days at-20 DEG C 3 。
(3) The wear-resistant rubber composition can keep good long-term overall performance, under the xenon lamp irradiation environment, after continuous irradiation for 90 days, the tensile strength of the rubber composition can still reach 27.5-28.9MPa, the elongation at break can still reach 336-350%, and the abrasion loss can still reach 173.2-178.1mm 3 。
(4) The preparation method of the wear-resistant rubber composition has the advantages of simple and efficient process and simple and convenient operation, and the prepared rubber composition has stable and uniform indexes and can meet the requirement of large-scale industrial production.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
A preparation method of the wear-resistant rubber composition comprises the following specific steps:
1. preparation of the anti-wear agent
1) Pretreatment of
Putting clay and alpha-cellulose into a ball mill, controlling the ball-to-material ratio to be 6:1, carrying out ball milling at the rotating speed of 500rpm for 10min; then adding dibutyl phthalate and polyethylene wax, and continuing ball milling for 5min to obtain a ball grinding material; putting the ball grinding material, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 into a high-speed shearing machine, and shearing at 1000rpm for 5min to obtain a pretreated substance.
Wherein the ratio of the clay to the alpha-cellulose to the dibutyl phthalate to the polyethylene wax in parts by weight is 2.
The weight parts of the ball grinding material, the polyether polyol, the nano cerium dioxide, the fatty alcohol-polyoxyethylene ether and the silane coupling agent KH-570 are as follows.
The particle size of the clay is 300 meshes; the clay comprises the following components in percentage by weight: 45.5% of silicon dioxide, 8.0% of aluminum oxide, 0.5% of calcium oxide, 0.5% of magnesium oxide, 0.2% of titanium dioxide and 0.1% of iron oxide.
The alpha-cellulose had a diameter of 15 μm and a length of 70 μm.
The number average molecular weight of the polyethylene wax is 4000.
The polyether polyol is HK-1301.
The average particle size of the nano cerium dioxide is 80nm, and the specific surface area is 25m 2 /g。
2) Microwave treatment
Placing the pretreated substance in a microwave generator, and performing microwave treatment for 3min under the condition of nitrogen atmosphere; then grinding for 10min at the rotating speed of 1500rpm to prepare the wear-resisting agent.
And in the microwave treatment, the microwave frequency is 2.2GHz, and the microwave power is 350W.
2. Preparation of wear-resistant reinforcing agent
1) Modification of
Using 48K carbon fiber as anode and copper electrode as cathode, controlling current density at 25mA/cm at 30 deg.C 2 Modifying for 80s; then, leaching the carbon fibers by using 10 times of volume of deionized water, placing the carbon fibers in an environment with the vacuum degree of 0.02MPa and drying the carbon fibers for 1 hour at the temperature of 80 ℃; and then, chopping the carbon fibers into 2mm by using a fiber cutting machine to obtain the modified substance.
The electrolyte is an ammonium bicarbonate solution with the mass concentration of 5%.
2) Grinding
And mixing the modifier, polyimide, tea saponin and a silane coupling agent KH-550, stirring at 700rpm for 10min, and grinding at 2000rpm for 3min to obtain the wear-resistant reinforcing agent.
Wherein, the weight ratio of the modifier to the polyimide to the tea saponin to the silane coupling agent KH-550 is 80.
3. Filler modification
Putting calcium carbonate and mica powder into a high-speed mixer, stirring until the temperature of the materials is 95 ℃, and then continuously stirring for 20min at a stirring speed of 200 rpm; then adding the glass fiber and the titanate coupling agent 201, stirring at 400rpm for 10min, and drying at 70 ℃ under the condition that the vacuum degree is 0.01MPa until the moisture content is 0.1wt% to obtain the modified filler.
Wherein, the weight ratio of calcium carbonate, mica powder, glass fiber and titanate coupling agent 201 is 60.
The specification of the calcium carbonate is that the particle size is 3 mu m, and the specific surface area is 10m 2 /g。
The specification of the mica powder is that the particle size is 10 mu m.
The diameter of the glass fiber is 5 μm.
4. Mixing the raw materials
According to the weight parts, 70 parts of butadiene styrene rubber, 30 parts of butadiene rubber, 15 parts of white carbon black, 5 parts of carbon black, 10 parts of epoxy resin, 3 parts of wear-resisting agent, 10 parts of wear-resisting reinforcing agent, 20 parts of modified filler, 1 part of anti-aging agent MB, 1 part of stearic acid and 3 parts of zinc oxide are put into a mixer and stirred for 20min at 300 rpm; then placing the mixture into a mixing mill, controlling the primary mixing pressure to be 3MPa, the primary mixing temperature to be 155 ℃, the primary mixing rotating speed to be 50rpm, and carrying out primary mixing for 5min; then, the secondary mixing pressure was controlled to 8MPa, the secondary mixing temperature was 165 ℃ and the secondary mixing rotation speed was 80rpm, and secondary mixing was performed for 3min to obtain a mixed material.
5. Vulcanization
Continuously adding 1.5 parts of sulfur and 1 part of accelerator TBBS (butyl-benzene) into the mixed material according to the parts by weight, and stirring at 120rpm for 5min; then controlling the vulcanization pressure to be 10MPa, the vulcanization temperature to be 160 ℃ and the vulcanization time to be 40min to prepare the wear-resistant rubber composition.
Example 2
A preparation method of a wear-resistant rubber composition comprises the following specific steps:
1. preparation of the anti-wear agent
1) Pretreatment of
Putting clay and alpha-cellulose into a ball mill, controlling the ball-to-material ratio to be 7:1, and carrying out ball milling at the rotating speed of 600rpm for 15min; then adding dibutyl phthalate and polyethylene wax, and continuing ball milling for 10min to obtain a ball grinding material; putting the ball grinding material, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 into a high-speed shearing machine, and shearing at 1100rpm for 7min to obtain a pretreated substance.
Wherein the ratio of the clay to the alpha-cellulose to the dibutyl phthalate to the polyethylene wax in parts by weight is 2.5.
The ball grinding material, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 are characterized in that the ratio of parts by weight of the ball grinding material to the polyether polyol to the nano cerium dioxide is 55.
The particle size of the clay is 320 meshes; the clay comprises the following components in percentage by weight: 46.1% of silicon dioxide, 8.2% of aluminum oxide, 0.6% of calcium oxide, 0.7% of magnesium oxide, 0.22% of titanium dioxide and 0.3% of iron oxide.
The alpha-cellulose had a diameter of 18 μm and a length of 80 μm.
The polyethylene wax has a number average molecular weight of 4500.
The polyether polyol is HK-1301.
The average particle size of the nano cerium dioxide is 90nm, and the specific surface area is 30m 2 /g。
2) Microwave treatment
Placing the pretreated substance in a microwave generator, and performing microwave treatment for 5min under the condition of nitrogen atmosphere; then grinding for 15min at the rotating speed of 1800rpm to prepare the wear-resisting agent.
And (3) performing microwave treatment, wherein the microwave frequency is 2.4GHz, and the microwave power is 450W.
2. Preparation of wear-resistant reinforcing agent
1) Modification of
Using 48K carbon fiber as anode and copper electrode as cathode, controlling current density at 30mA/cm at electrolyte temperature of 35 deg.C 2 Modifying for 90s; then, leaching the carbon fibers by using deionized water with the volume being 12 times that of the carbon fibers, placing the carbon fibers in an environment with the vacuum degree of 0.03MPa and drying the carbon fibers for 1.5 hours at the temperature of 85 ℃; and chopping the carbon fibers to 1mm by using a fiber cutting machine to obtain the modified substance.
The electrolyte is an ammonium bicarbonate solution with the mass concentration of 6%.
2) Grinding
Mixing the modifier, polyimide, tea saponin and a silane coupling agent KH-550, stirring at 800rpm for 15min, and grinding at 2200rpm for 4min to obtain the wear-resistant reinforcing agent.
Wherein the weight parts ratio of the modifier to the polyimide to the tea saponin to the silane coupling agent KH-550 is 85.
3. Filler modification
Putting calcium carbonate and mica powder into a high-speed mixer, stirring until the temperature of the materials is 100 ℃, and then continuously stirring for 25min at a stirring speed of 250 rpm; then adding glass fiber and titanate coupling agent 201, stirring at 450rpm for 15min, and drying at 75 ℃ under the condition that the vacuum degree is 0.02MPa until the moisture content is 0.3wt% to obtain the modified filler.
Wherein, the weight parts of the calcium carbonate, the mica powder, the glass fiber and the titanate coupling agent 201 are as follows.
The specification of the calcium carbonate is that the particle size is 5 mu m, and the specific surface area is 15m 2 /g。
The specification of the mica powder is that the particle size is 12 μm.
The diameter of the glass fiber is 8 μm.
4. Mixing the raw materials
According to parts by weight, 75 parts of styrene butadiene rubber, 35 parts of butadiene rubber, 20 parts of white carbon black, 8 parts of carbon black, 15 parts of epoxy resin, 3.5 parts of wear-resisting agent, 15 parts of wear-resisting reinforcing agent, 25 parts of modified filler, 1.5 parts of anti-aging agent MB, 1.5 parts of stearic acid and 5 parts of zinc oxide are put into a mixer and stirred for 25min at 400 rpm; then placing the mixture into a mixing mill, controlling the primary mixing pressure to be 4MPa, the primary mixing temperature to be 160 ℃, the primary mixing rotating speed to be 60rpm, and carrying out primary mixing for 8min; then, the secondary mixing pressure was controlled to 9MPa, the secondary mixing temperature was controlled to 170 ℃ and the secondary mixing speed was controlled to 85rpm, and secondary mixing was performed for 4min to obtain a mixed material.
5. Vulcanization
2 parts of sulfur and 1.5 parts of accelerator TBBS are continuously added into the mixture according to the parts by weight, and the mixture is stirred for 8min at 140 rpm; then controlling the vulcanization pressure to be 12MPa, the vulcanization temperature to be 165 ℃ and the vulcanization time to be 50min to prepare the wear-resistant rubber composition.
Example 3
A preparation method of a wear-resistant rubber composition comprises the following specific steps:
1. preparation of the anti-wear agent
1) Pretreatment of
Putting clay and alpha-cellulose into a ball mill, controlling the ball-to-material ratio to be 8:1, and carrying out ball milling at the ball milling rotation speed of 700rpm for 20min; then adding dibutyl phthalate and polyethylene wax, and continuing ball milling for 15min to obtain a ball grinding material; putting the ball grinding material, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 into a high-speed shearing machine, and shearing at 1200rpm for 8min to obtain a pretreated substance.
Wherein the ratio of the clay to the alpha-cellulose to the dibutyl phthalate to the polyethylene wax in parts by weight is 3.
The ball grinding material, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 are prepared from the following components in parts by weight of 60.
The particle size of the clay is 350 meshes; the clay comprises the following components in percentage by weight: 46.5% of silicon dioxide, 8.5% of aluminum oxide, 0.7% of calcium oxide, 0.8% of magnesium oxide, 0.25% of titanium dioxide and 0.4% of iron oxide.
The alpha-cellulose had a diameter of 20 μm and a length of 90 μm.
The polyethylene wax has the number average molecular weight of 5000.
The polyether polyol is HK-1301.
The average particle size of the nano cerium dioxide is 100nm, and the specific surface area is 35m 2 /g。
2) Microwave treatment
Placing the pretreated substance in a microwave generator, and performing microwave treatment for 8min under the condition of nitrogen atmosphere; then grinding for 20min at the rotating speed of 2000rpm to prepare the wear-resisting agent.
And (3) performing microwave treatment, wherein the microwave frequency is 2.5GHz, and the microwave power is 550W.
2. Preparation of wear-resistant reinforcing agent
1) Modification of
Using 48K carbon fiber as anode and copper electrode as cathode, controlling current density at 35mA/cm at electrolyte temperature of 40 deg.C 2 Modifying for 100s; then, leaching the carbon fibers by using deionized water with the volume of 15 times, placing the carbon fibers in an environment with the vacuum degree of 0.05MPa and drying the carbon fibers for 2 hours at the temperature of 90 ℃; and chopping the carbon fibers into 3mm by using a fiber cutting machine to obtain the modified product.
The electrolyte is an ammonium bicarbonate solution with the mass concentration of 7%.
2) Grinding
And mixing the modifier, polyimide, tea saponin and a silane coupling agent KH-550, stirring at 900rpm for 20min, and grinding at 2500rpm for 5min to obtain the wear-resistant reinforcing agent.
Wherein the weight parts ratio of the modifier to the polyimide to the tea saponin to the silane coupling agent KH-550 is (90).
3. Filler modification
Putting calcium carbonate and mica powder into a high-speed mixer, stirring until the temperature of the materials is 105 ℃, and then continuously stirring for 30min at the stirring speed of 300 rpm; then adding the glass fiber and the titanate coupling agent 201, stirring at 500rpm for 20min, and drying at 80 ℃ under the condition that the vacuum degree is 0.03MPa until the moisture content is 0.5wt% to obtain the modified filler.
Wherein, the weight ratio of the calcium carbonate, the mica powder, the glass fiber and the titanate coupling agent 201 is 80.
The specification of the calcium carbonate is that the particle size is 8 mu m, and the specific surface area is 20m 2 /g。
The specification of the mica powder is that the particle size is 15 mu m.
The diameter of the glass fiber is 10 μm.
4. Mixing the raw materials
According to the parts by weight, 80 parts of butadiene styrene rubber, 40 parts of butadiene rubber, 25 parts of white carbon black, 10 parts of carbon black, 20 parts of epoxy resin, 4 parts of wear-resisting agent, 20 parts of wear-resisting reinforcing agent, 30 parts of modified filler, 2 parts of anti-aging agent MB, 2 parts of stearic acid and 6 parts of zinc oxide are put into a mixer and stirred at 500rpm for 30min; then placing the mixture into a mixing mill, controlling the primary mixing pressure to be 5MPa, the primary mixing temperature to be 165 ℃ and the primary mixing rotating speed to be 70rpm, and carrying out primary mixing for 10min; then, the secondary mixing pressure was controlled to 10MPa, the secondary mixing temperature was controlled to 175 ℃, the secondary mixing speed was controlled to 90rpm, and secondary mixing was performed for 5min to obtain a mixed material.
5. Vulcanization
2.5 parts of sulfur and 2 parts of accelerator TBBS are continuously added into the mixture according to the parts by weight, and the mixture is stirred for 10min at 150 rpm; and then controlling the vulcanization pressure to be 15MPa, the vulcanization temperature to be 170 ℃ and the vulcanization time to be 60min to prepare the wear-resistant rubber composition.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is as follows: 1) In the step 1, in the step of preparing the wear-resisting agent, dibutyl phthalate, polyether polyol, nano cerium dioxide and fatty alcohol-polyoxyethylene ether are omitted in the step of pretreatment; 2) In the step 1 of preparing the wear-resistant agent, the microwave treatment step is omitted.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is as follows: 1) In the preparation of the wear-resistant reinforcing agent, the modification step is omitted, and the carbon fiber is directly used for the grinding step; 2) Calcium carbonate is used to replace the modified filler.
Test example 1
The rubber compositions obtained in examples 1 to 3 and comparative examples 1 to 2 were tested for tensile strength, hardness, elongation at break, 100% stress at definite elongation, and abrasion resistance.
The specific test results and reference standards are as follows:
test example 2
The rubber compositions obtained in examples 1 to 3 and comparative examples 1 to 2 were allowed to stand at-20 ℃ for 25 days, and then the tensile strength, hardness, elongation at break, 100% stress at definite elongation, and abrasion resistance of each rubber composition were measured.
The specific test results and reference standards are as follows:
test example 3
The rubber compositions obtained in examples 1 to 3 and comparative examples 1 to 2 were left to stand for 90 days under xenon-lamp irradiation, and the tensile strength, hardness, elongation at break, 100% stress at break, and abrasion resistance of each rubber composition were measured.
Wherein, the relevant parameters of xenon lamp irradiation are as follows: the irradiation intensity of the xenon lamp is 0.5W/m 2 The wavelength of the xenon lamp is 380nm, the ambient temperature is 40 ℃, the blackboard temperature is 75 ℃, and the ambient humidity is 55%.
The specific test results and reference standards are as follows:
all percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. The preparation method of the wear-resistant rubber composition is characterized by comprising the following steps: preparing a wear-resisting agent, preparing a wear-resisting reinforcing agent, modifying a filler, mixing and vulcanizing;
the method for preparing the wear-resisting agent comprises the following steps: pretreatment and microwave treatment;
the pretreatment method comprises the steps of putting clay and alpha-cellulose into a ball mill, controlling the ball-to-material ratio to be 6-8:1, ball milling at the rotating speed of 500-700rpm, and ball milling for 10-20min; then adding dibutyl phthalate and polyethylene wax, and continuing ball milling for 5-15min to obtain a ball grinding material; putting ball grinding materials, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 into a high-speed shearing machine, and shearing at 1000-1200rpm for 5-8min to obtain a pretreated substance;
in the pretreatment, the ratio of the weight parts of the clay, the alpha-cellulose, the dibutyl phthalate and the polyethylene wax is 2-3:1-2 and is 0.3-0.5;
in the pretreatment, the weight parts of the ball grinding material, polyether polyol, nano cerium dioxide, fatty alcohol-polyoxyethylene ether and a silane coupling agent KH-570 are 50-60;
in the pretreatment, the particle size of the clay is 300-350 meshes; the clay comprises the following components in percentage by weight: 45.5 to 46.5 percent of silicon dioxide, 8.0 to 8.5 percent of aluminum oxide, 0.5 to 0.7 percent of calcium oxide, 0.5 to 0.8 percent of magnesium oxide, 0.2 to 0.25 percent of titanium dioxide and 0.1 to 0.4 percent of ferric oxide;
in the pretreatment, the specification of the alpha-cellulose is that the diameter is 15-20 μm, and the length is 70-90 μm;
in the pretreatment, the number average molecular weight of the polyethylene wax is 4000-5000;
in the pretreatment, the type of polyether polyol is HK-1301;
in the pretreatment, the specification of the nano cerium dioxide is that the average particle size is 80-100nm, and the specific surface area is 25-35m 2 /g；
The microwave treatment method comprises placing the pretreated material in a microwave generator, and performing microwave treatment for 3-8min under nitrogen atmosphere; then grinding for 10-20min at the rotating speed of 1500-2000rpm to prepare the wear-resisting agent;
the method for preparing the wear-resistant reinforcing agent comprises the following steps: modifying and grinding;
the modification method comprises using 48K carbon fiber as anode and copper electrode as cathode, and controlling current density at 25-35mA/cm at 30-40 deg.C 2 Modifying for 80-100s; then, leaching the carbon fibers by using 10-15 times of deionized water, and drying for 1-2 hours at the temperature of 80-90 ℃ in an environment with the vacuum degree of 0.02-0.05 MPa; then chopping the carbon fiber into 1-3mm to obtain a modified substance;
in the modification, the electrolyte is 5-7% of ammonium bicarbonate solution by mass concentration;
the grinding method comprises mixing the modifier, polyimide, tea saponin and silane coupling agent KH-550, stirring at 700-900rpm for 10-20min, and grinding at 2000-2500rpm for 3-5min to obtain wear-resistant reinforcing agent;
in the grinding, the ratio of the modified substance to the polyimide to the tea saponin to the silane coupling agent KH-550 by weight parts is 80-90;
the filler modification method comprises the steps of putting calcium carbonate and mica powder into a high-speed mixer, stirring until the temperature of the materials is 95-105 ℃, and then continuously stirring for 20-30min at a stirring speed of 200-300 rpm; then adding glass fiber and titanate coupling agent 201, stirring at 400-500rpm for 10-20min, and drying at 70-80 ℃ under the condition that the vacuum degree is 0.01-0.03MPa until the moisture content is 0.1-0.5wt% to obtain the modified filler;
in the filler modification, the weight parts ratio of calcium carbonate, mica powder, glass fiber and titanate coupling agent 201 is (60-80);
in the filler modification, the specification of the calcium carbonate is that the particle size is 3-8 mu m, and the specific surface area is 10-20m 2 /g；
In the filler modification, the particle size of the mica powder is 10-15 μm;
in the filler modification, the diameter of the glass fiber is 5-10 μm;
the mixing method comprises the steps of putting 70-80 parts by weight of styrene butadiene rubber, 30-40 parts by weight of butadiene rubber, 15-25 parts by weight of white carbon black, 5-10 parts by weight of carbon black, 10-20 parts by weight of epoxy resin, 3-4 parts by weight of wear-resisting agent, 10-20 parts by weight of wear-resisting reinforcing agent, 20-30 parts by weight of modified filler, 1-2 parts by weight of anti-aging agent MB, 1-2 parts by weight of stearic acid and 3-6 parts by weight of zinc oxide into a mixer, and stirring at 300-500rpm for 20-30min; then placing the mixture into a mixing mill, controlling the primary mixing pressure to be 3-5MPa, the primary mixing temperature to be 155-165 ℃ and the primary mixing rotating speed to be 50-70rpm, and carrying out primary mixing for 5-10min; then controlling the secondary mixing pressure to be 8-10MPa, the secondary mixing temperature to be 165-175 ℃, and the secondary mixing rotating speed to be 80-90rpm, and carrying out secondary mixing for 3-5min to obtain a mixed material;
the vulcanization method comprises the steps of continuously adding 1.5-2.5 parts of sulfur and 1-2 parts of accelerator TBBS into the mixed material according to the parts by weight, and stirring at 120-150rpm for 5-10min; then controlling the vulcanization pressure to be 10-15MPa, the vulcanization temperature to be 160-170 ℃ and the vulcanization time to be 40-60min to prepare the wear-resistant rubber composition.
2. The method of claim 1, wherein the microwave frequency of the microwave treatment in the step of preparing the anti-abrasion agent is 2.2 to 2.5GHz, and the microwave power is 350 to 550W.
3. An abrasion-resistant rubber composition characterized by being produced by the production method according to claim 1 or claim 2.
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| US5756589A (en) * | 1996-09-19 | 1998-05-26 | Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
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| CN104788765A (en) * | 2015-04-22 | 2015-07-22 | 青岛国航祥玉技术服务有限公司 | High-strength wear-resisting rubber |
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| CN109456513B (en) * | 2018-09-28 | 2021-11-16 | 潍坊职业学院 | Wear-resistant tire rubber and preparation method thereof |
| CN111423620A (en) * | 2020-03-20 | 2020-07-17 | 河北旭龙液压密封件有限公司 | Rubber wear-resistant agent and preparation method thereof, wear-resistant and aging-resistant vulcanized rubber and preparation method and application thereof |
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