CN111117082A - High-temperature-resistant rubber and plastic product and preparation method thereof - Google Patents
High-temperature-resistant rubber and plastic product and preparation method thereof Download PDFInfo
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- CN111117082A CN111117082A CN202010008293.3A CN202010008293A CN111117082A CN 111117082 A CN111117082 A CN 111117082A CN 202010008293 A CN202010008293 A CN 202010008293A CN 111117082 A CN111117082 A CN 111117082A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
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Abstract
The invention belongs to the technical field of rubber and plastic products, and provides a high-temperature-resistant rubber and plastic product and a preparation method thereof. A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight: 15-20 parts of ethylene propylene diene monomer, 4-7 parts of a foaming agent, 8-15 parts of aluminum tripolyphosphate, 3-5 parts of reinforcing carbon black, 13-18 parts of rubber operating oil, 0.3-0.5 part of an active agent, 0.1-0.3 part of stearic acid, 10-12 parts of a filler, 3-5 parts of protective wax, 2-4 parts of an accelerator and 0.1-0.3 part of a vulcanizing agent, wherein the active agent consists of the following components in parts by weight: 5-10 parts of yttrium oxide, 13-25 parts of zinc oxide, 8-20 parts of octahydroxybutyl cage-like silsesquioxane and 2-7 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt. In the preparation method of the high-temperature resistant rubber and plastic product, the discharge temperature of the rubber material in the banburying process is set as 140 ℃, and the incremental temperature of 8 sections in the vulcanization foaming process is set as 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃ and 175 ℃. Through the technical scheme, the problem that the use of the rubber and plastic product is influenced due to low heat-resistant temperature in the prior art is solved.
Description
Technical Field
The invention belongs to the technical field of rubber and plastic products, and relates to a high-temperature-resistant rubber and plastic product and a preparation method thereof.
Background
The rubber-plastic heat-insulating product is prepared by using nitrile rubber and polyvinyl chloride resin as main materials, adding other auxiliary materials, blending at high temperature, adding a vulcanizing agent and a foaming agent, and vulcanizing and foaming to obtain a closed-cell elastic material. The service temperature of the rubber and plastic products produced at present can only reach 110 ℃ at most, and the service environment of the rubber and plastic products is limited.
Disclosure of Invention
The invention provides a high-temperature-resistant rubber and plastic product and a preparation method thereof, and solves the problem that the use of the rubber and plastic product is influenced due to low heat-resistant temperature in the prior art.
The technical scheme of the invention is realized as follows:
a high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
15-20 parts of ethylene propylene diene monomer, 4-7 parts of foaming agent, 8-15 parts of aluminum tripolyphosphate, 3-5 parts of reinforcing carbon black, 13-18 parts of rubber operating oil, 0.3-0.5 part of activator, 0.1-0.3 part of stearic acid, 10-12 parts of filler, 3-5 parts of protective wax, 2-4 parts of accelerator and 0.1-0.3 part of vulcanizing agent,
the active agent comprises the following components in parts by weight:
5-10 parts of yttrium oxide, 13-25 parts of zinc oxide, 1-4 parts of octahydroxybutyl cage-like silsesquioxane and 2-7 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt.
As a further technical scheme, the paint comprises the following components in parts by weight:
18 parts of ethylene propylene diene monomer, 5 parts of foaming agent, 12 parts of aluminum tripolyphosphate, 4 parts of reinforcing carbon black, 15 parts of rubber operating oil, 0.4 part of active agent, 0.2 part of stearic acid, 11 parts of filler, 4 parts of protective wax, 3 parts of accelerator and 0.2 part of vulcanizing agent,
the active agent comprises the following components in parts by weight:
8 parts of yttrium oxide, 19 parts of zinc oxide, 2.3 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 5 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt.
As a further technical scheme, the preparation method of the active agent comprises the following steps:
mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; and heating the mixed powder to 200-240 ℃ for reaction to obtain the active agent.
As a further technical scheme, the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is one or a mixture of multiple of coarse whiting powder, talcum powder and quartz powder in any proportion, and the fineness is 400-2000 meshes.
A preparation method of a high-temperature-resistant rubber and plastic product comprises the following steps:
s1, blending ethylene propylene diene monomer, a foaming agent, aluminum tripolyphosphate, reinforcing carbon black, rubber operating oil, a filler, protective wax, an active agent and stearic acid, and discharging when the blended material reaches 140 ℃ to obtain a mixed rubber material;
s2, cooling the mixed rubber material, re-refining, discharging, and cooling to obtain a rubber sheet;
s3, adding a vulcanizing agent and an accelerant into the rubber sheet, uniformly mixing, and then discharging to obtain rubber strips;
and S4, extruding and molding the rubber strip, vulcanizing and foaming, and cooling to obtain the high-temperature-resistant rubber and plastic product.
As a further technical proposal, the sulfuration foaming in the step S4 is carried out under 8 stages of increasing temperatures, wherein the 8 stages of increasing temperatures are 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃ and 175 ℃ respectively.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the specific formula and the preparation method enable the prepared high-temperature-resistant rubber and plastic product to have good high temperature resistance, the heat-resistant temperature is up to 155 ℃, the tensile strength is up to 25.8MPa, the Shore hardness is up to 65.5A, the change rate of the thermal oxidation aging tensile strength is as low as-1.4% at 100 ℃ for 168h, and meanwhile, the compression permanent deformation of the prepared high-temperature-resistant rubber and plastic product at 25 ℃, 60 ℃ and 100 ℃ is smaller, so that the high-temperature-resistant rubber and plastic product prepared by the embodiment of the invention has good heat resistance, good mechanical property and solves the problem that the use of the rubber and plastic product is influenced by low heat-resistant temperature in the prior art.
2. According to the invention, the high-temperature resistant rubber and plastic product is added with the activator, the activator is composed of yttrium oxide, zinc oxide, octahydroxybutyl cage-like silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt, and the preparation method is characterized in that the components are mixed and then react at 200-240 ℃, so that the heat resistance temperature and the mechanical property of the rubber and plastic product are obviously improved. Under the temperature of 200-240 ℃, yttrium oxide, zinc oxide and hydroxyl in octahydroxybutyl cage-like silsesquioxane react to form a stable organic-inorganic hybrid material which is well dispersed in an ethylene-propylene-diene monomer matrix, so that the agglomeration phenomenon of the yttrium oxide and the zinc oxide in the ethylene-propylene-diene monomer matrix is effectively avoided, the addition of heptasodium salt of diethylenetriamine pentamethylenephosphonic acid further promotes the dispersion of the organic-inorganic hybrid material in the ethylene-propylene-diene monomer matrix, and improves the interface combination of the organic-inorganic hybrid material and the ethylene-propylene-diene monomer matrix, so that the reinforcing effect of the yttrium oxide, the zinc oxide and the octahydroxybutyl cage-like silsesquioxane on rubber is better exerted, the hardness, the ageing resistance and the heat resistance of a rubber and plastic product are improved, and meanwhile, the yttrium oxide, the zinc oxide and the hydroxyl in the ethylene-propylene-diene monomer copolymer are better utilized to reinforce the rubber, and the rubber product has, The zinc oxide, the octahydroxybutyl polyhedral oligomeric silsesquioxane and the diethylene triamine pentamethylene phosphonic acid heptasodium salt are compatible with each other, so that the crystallization performance of the ethylene propylene diene monomer rubber in a stretching state is promoted, the movement of a high polymer chain segment is limited, and the tensile strength of a rubber and plastic product is improved.
3. In the preparation method of the high-temperature-resistant rubber and plastic product, the discharge temperature of the rubber material in the banburying process of the step S1 is set to be 140 ℃, so that the mechanical property and the high temperature resistance of the high-temperature-resistant rubber and plastic product are improved. The discharge temperature is set to be 140 ℃, compared with 145 ℃, the mechanical property and the high temperature resistance of the high temperature resistant rubber plastic product are improved while the energy consumption is saved, compared with 135 ℃, the mechanical property and the high temperature resistance of the high temperature resistant rubber plastic product are also improved, meanwhile, the production stability is improved, and unexpected effects are achieved.
4. In the preparation method of the high-temperature-resistant rubber and plastic product, in the step S4 vulcanization foaming process, the incremental temperature of the section 8 is set to 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃ and 175 ℃, so that the vulcanization and the foaming are synchronous, the foam structure is improved, and the high temperature resistance and the aging resistance of the rubber and plastic product are obviously improved.
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, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
15 parts of ethylene propylene diene monomer, 4 parts of foaming agent, 8 parts of aluminum tripolyphosphate, 3 parts of reinforcing carbon black, 13 parts of rubber operating oil, 0.3 part of active agent, 0.1 part of stearic acid, 10 parts of filler, 3 parts of protective wax, 2 parts of accelerator and 0.1 part of vulcanizing agent,
the activating agent comprises the following components in parts by weight: 8 parts of yttrium oxide, 19 parts of zinc oxide, 2.3 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 5 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt; the preparation method of the activating agent comprises the following steps: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; heating the mixed powder to 200-240 ℃ for reaction for 2 hours to obtain an active agent; the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is coarse whiting powder, and the fineness is 400-2000 meshes;
the preparation method comprises the following steps:
s1, weighing the components according to the formula; putting ethylene propylene diene monomer, a foaming agent, aluminum tripolyphosphate, reinforcing carbon black, rubber operating oil, a filler, protective wax, an active agent and stearic acid into an internal mixer for blending, and discharging materials when the blended material reaches 140 ℃ to obtain a mixed rubber material;
s2, conveying the mixed rubber material to an open mill for cooling and re-refining, then discharging, cooling and standing for 24 hours to obtain a rubber sheet;
s3, adding a vulcanizing agent and an accelerant into the rubber sheet, uniformly mixing in an open mill, and then discharging to obtain rubber strips;
s4, extruding and molding the rubber strip by an extruder, conveying the rubber strip to an oven for vulcanization foaming, wherein the temperature of the oven is 8 sections of increasing temperature, namely 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃ and 175 ℃, and cooling to obtain the high-temperature resistant rubber-plastic product.
Example 2
A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
20 parts of ethylene propylene diene monomer, 7 parts of foaming agent, 15 parts of aluminum tripolyphosphate, 5 parts of reinforcing carbon black, 18 parts of rubber operating oil, 0.5 part of active agent, 0.3 part of stearic acid, 12 parts of filler, 5 parts of protective wax, 4 parts of accelerator and 0.3 part of vulcanizing agent,
the activating agent comprises the following components in parts by weight: 8 parts of yttrium oxide, 19 parts of zinc oxide, 2.3 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 5 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt; the preparation method of the activating agent comprises the following steps: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; heating the mixed powder to 200-240 ℃ for reaction for 2 hours to obtain an active agent; the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is coarse whiting powder, and the fineness is 400-2000 meshes;
the preparation method is the same as that of example 1.
Example 3
A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
18 parts of ethylene propylene diene monomer, 5 parts of foaming agent, 12 parts of aluminum tripolyphosphate, 4 parts of reinforcing carbon black, 15 parts of rubber operating oil, 0.4 part of active agent, 0.2 part of stearic acid, 11 parts of filler, 4 parts of protective wax, 3 parts of accelerator and 0.2 part of vulcanizing agent,
the activating agent comprises the following components in parts by weight: 8 parts of yttrium oxide, 19 parts of zinc oxide, 2.3 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 5 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt; the preparation method of the activating agent comprises the following steps: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; heating the mixed powder to 200-240 ℃ for reaction for 2 hours to obtain an active agent; the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is coarse whiting powder, and the fineness is 400-2000 meshes;
the preparation method is the same as that of example 1.
Example 4
A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
16 parts of ethylene propylene diene monomer, 6 parts of foaming agent, 13 parts of aluminum tripolyphosphate, 3 parts of reinforcing carbon black, 17 parts of rubber operating oil, 0.5 part of active agent, 0.3 part of stearic acid, 12 parts of filler, 3 parts of protective wax, 4 parts of accelerator and 0.1 part of vulcanizing agent,
the activating agent comprises the following components in parts by weight: 8 parts of yttrium oxide, 19 parts of zinc oxide, 2.3 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 5 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt; the preparation method of the activating agent comprises the following steps: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; heating the mixed powder to 200-240 ℃ for reaction for 2 hours to obtain an active agent; the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is talcum powder, and the fineness is 400-2000 meshes;
the preparation method is the same as that of example 1.
Example 5
A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
19 parts of ethylene propylene diene monomer, 5 parts of foaming agent, 10 parts of aluminum tripolyphosphate, 5 parts of reinforcing carbon black, 14 parts of rubber operating oil, 0.3 part of active agent, 0.1 part of stearic acid, 10 parts of filler, 5 parts of protective wax, 2 parts of accelerator and 0.3 part of vulcanizing agent,
the activating agent comprises the following components in parts by weight: 8 parts of yttrium oxide, 19 parts of zinc oxide, 2.3 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 5 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt; the preparation method of the activating agent comprises the following steps: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; heating the mixed powder to 200-240 ℃ for reaction for 2 hours to obtain an active agent; the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is quartz powder, and the fineness is 400-2000 meshes;
the preparation method is the same as that of example 1.
Example 6
A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
18 parts of ethylene propylene diene monomer, 5 parts of foaming agent, 12 parts of aluminum tripolyphosphate, 4 parts of reinforcing carbon black, 15 parts of rubber operating oil, 0.4 part of active agent, 0.2 part of stearic acid, 11 parts of filler, 4 parts of protective wax, 3 parts of accelerator and 0.2 part of vulcanizing agent,
the activating agent comprises the following components in parts by weight: 5 parts of yttrium oxide, 13 parts of zinc oxide, 1 part of octahydroxybutyl polyhedral oligomeric silsesquioxane and 2 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt; the preparation method of the activating agent comprises the following steps: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; heating the mixed powder to 200-240 ℃ for reaction for 2 hours to obtain an active agent; the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is a mixture of heavy calcium powder and talcum powder in a mass ratio of 1:1, and the fineness is 400-2000 meshes;
the preparation method is the same as that of example 1.
Example 7
A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
18 parts of ethylene propylene diene monomer, 5 parts of foaming agent, 12 parts of aluminum tripolyphosphate, 4 parts of reinforcing carbon black, 15 parts of rubber operating oil, 0.4 part of active agent, 0.2 part of stearic acid, 11 parts of filler, 4 parts of protective wax, 3 parts of accelerator and 0.2 part of vulcanizing agent,
the activating agent comprises the following components in parts by weight: 10 parts of yttrium oxide, 25 parts of zinc oxide, 4 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 7 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt; the preparation method of the activating agent comprises the following steps: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; heating the mixed powder to 200-240 ℃ for reaction for 2 hours to obtain an active agent; the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is a mixture of coarse whiting powder, talcum powder and quartz powder in a mass ratio of 1:1:1, and the fineness is 400-2000 meshes;
the preparation method is the same as that of example 1.
Example 8
A high-temperature-resistant rubber and plastic product comprises the following components in parts by weight:
18 parts of ethylene propylene diene monomer, 5 parts of foaming agent, 12 parts of aluminum tripolyphosphate, 4 parts of reinforcing carbon black, 15 parts of rubber operating oil, 0.4 part of active agent, 0.2 part of stearic acid, 11 parts of filler, 4 parts of protective wax, 3 parts of accelerator and 0.2 part of vulcanizing agent,
the activating agent comprises the following components in parts by weight: 8 parts of yttrium oxide, 19 parts of zinc oxide, 2.3 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 5 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt; the preparation method of the activating agent comprises the following steps: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; heating the mixed powder to 200-240 ℃ for reaction for 2 hours to obtain an active agent; the foaming agent is azodicarbonamide, the rubber operating oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is talcum powder, and the fineness is 400-2000 meshes;
the preparation method is the same as that of example 1.
Comparative example 1
The activating agent in the formula of the high-temperature resistant rubber and plastic product is yttrium oxide, other components in the formula are the same as those in example 3, and the preparation method is the same as that in example 1.
Comparative example 2
The high temperature resistant rubber and plastic product has zinc oxide as activator, the same components as in example 3 and the same preparation process as in example 1.
Comparative example 3
A high temperature resistant rubber and plastic product, the preparation method of the activating agent in the formula comprises: mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain an activator; the other components in the formulation were the same as in example 3, and the preparation method was the same as in example 1.
Comparative example 4
The formula of the high-temperature-resistant rubber-plastic product is the same as that in example 3, in the preparation method, in step S1, discharging is carried out when the temperature of the mixed material reaches 145 ℃, so as to obtain a mixed rubber material; the rest of the procedure was the same as in example 1.
Comparative example 5
The formula of the high-temperature-resistant rubber-plastic product is the same as that in example 3, in the preparation method, in step S1, discharging is carried out when the temperature of the mixed material reaches 135 ℃, so as to obtain a mixed rubber material; the rest of the procedure was the same as in example 1.
Comparative example 6
The formula of the high-temperature-resistant rubber and plastic product is the same as that in example 3, in the preparation method, step S4 is to extrude the rubber strip by an extruder, send the rubber strip to an oven for vulcanization foaming, and cool the rubber strip at 8 sections of increasing temperatures of 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃ and 165 ℃ to obtain the high-temperature-resistant rubber and plastic product; the rest of the procedure was the same as in example 1.
The following performance tests were performed on the high-temperature resistant rubber-plastic products prepared in examples 1 to 8 and comparative examples 1 to 6:
1. tensile strength: the tensile strength and elongation at break of the samples were tested according to the test methods specified in GB/T528-1998 determination of tensile stress strain Properties of vulcanizates or thermoplastic rubbers;
2. shore hardness: testing the Shore hardness of the sample according to a test method specified in the Shore Durometer method (Shore hardness) of the first part of the test method for press-in hardness of vulcanized rubber or thermoplastic rubber GB/T531.1-2008;
3. compression set: according to the test method specified in GB/T7759-1996 determination of compression set at normal temperature, high temperature and low temperature of vulcanized rubber and thermoplastic rubber, the compression set of the sample at 25 ℃, 60 ℃ and 100 ℃ is respectively tested;
4. aging resistance, heat resistance: testing the aging resistance and the heat-resistant temperature of a sample according to a testing method specified in GB/T3512-2014 vulcanized rubber or thermoplastic rubber hot air accelerated aging and heat-resistant test;
the test results are given in the following table:
TABLE 1 Performance test results of the high temperature resistant rubber and plastic products prepared in examples 1-8 and comparative examples 1-6
From the data in the above table, it can be seen that the high temperature resistant rubber and plastic products prepared in embodiments 1 to 8 of the present invention have good high temperature resistance, a heat resistance temperature of up to 155 ℃, a high tensile strength, a high hardness, and good aging resistance, the tensile strength of up to 25.8MPa, the shore hardness of up to 65.5A, and a rate of change of the thermal oxidative aging tensile strength of 100 ℃ x 168h of as low as-1.4%, and meanwhile, the high temperature resistant rubber and plastic products prepared in embodiments 1 to 8 have smaller compression permanent deformation at 25 ℃, 60 ℃, and 100 ℃.
Compared with the high-temperature resistant rubber and plastic products in the embodiments 1 to 8, the high-temperature resistant rubber and plastic products prepared in the comparative examples 1 to 3 have low tensile strength, low hardness, small compression permanent deformation, and poor aging resistance and heat resistance, because the active agent in the raw material of the high-temperature resistant rubber and plastic product in the comparative example 1 is yttrium oxide, the active agent in the raw material of the high-temperature resistant rubber and plastic product in the comparative example 2 is zinc oxide, and the preparation method of the active agent in the raw material of the high-temperature resistant rubber and plastic product in the comparative example 3 is direct mixing, the invention shows that the active agent is added into the raw material of the high-temperature resistant rubber and plastic product, and consists of yttrium oxide, zinc oxide, octahydroxybutyl cage-like silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt, and the preparation method is that the components are mixed and then react at 200 to 240 ℃, so that the heat resistance. Under the temperature of 200-240 ℃, yttrium oxide, zinc oxide and hydroxyl in octahydroxybutyl cage-like silsesquioxane react to form a stable organic-inorganic hybrid material which is well dispersed in an ethylene-propylene-diene monomer matrix, so that the agglomeration phenomenon of the yttrium oxide and the zinc oxide in the ethylene-propylene-diene monomer matrix is effectively avoided, the addition of heptasodium salt of diethylenetriamine pentamethylenephosphonic acid further promotes the dispersion of the organic-inorganic hybrid material in the ethylene-propylene-diene monomer matrix, and improves the interface combination of the organic-inorganic hybrid material and the ethylene-propylene-diene monomer matrix, so that the reinforcing effect of the yttrium oxide, the zinc oxide and the octahydroxybutyl cage-like silsesquioxane on rubber is better exerted, the hardness, the ageing resistance and the heat resistance of a rubber and plastic product are improved, and meanwhile, the yttrium oxide, the zinc oxide and the hydroxyl in the ethylene-propylene-diene monomer copolymer are better utilized to reinforce the rubber, and the rubber product has, The zinc oxide, the octahydroxybutyl polyhedral oligomeric silsesquioxane and the diethylene triamine pentamethylene phosphonic acid heptasodium salt are compatible with each other, so that the crystallization performance of the ethylene propylene diene monomer rubber in a stretching state is promoted, the movement of a high polymer chain segment is limited, and the tensile strength of a rubber and plastic product is improved.
Compared with the high-temperature-resistant rubber and plastic products in the embodiments 1 to 8, the high-temperature-resistant rubber and plastic products prepared in the comparative examples 4 to 5 are relatively poor in mechanical property and high-temperature resistance, because the high-temperature-resistant rubber and plastic product in the comparative example 4 is discharged when the temperature of the mixed material reaches 145 ℃ in the step S1, and the high-temperature-resistant rubber and plastic product in the comparative example 5 is discharged when the temperature of the mixed material reaches 135 ℃ in the step S1, the invention is proved that the discharge temperature of the rubber material in the banburying process is set to be 140 ℃, and the mechanical property and the high-temperature resistance of the high-temperature-resistant rubber. The discharge temperature is set to be 140 ℃, compared with 145 ℃, the mechanical property and the high temperature resistance of the high temperature resistant rubber plastic product are improved while the energy consumption is saved, compared with 135 ℃, the mechanical property and the high temperature resistance of the high temperature resistant rubber plastic product are also improved, meanwhile, the production stability is improved, and unexpected effects are achieved.
Compared with the high-temperature-resistant rubber and plastic products in the embodiments 1 to 8, the high-temperature-resistant rubber and plastic product prepared in the comparative example 6 has relatively poor high temperature resistance and aging resistance, because the 8-stage increasing temperature of the high-temperature-resistant rubber and plastic product in the comparative example 6 in the vulcanization foaming process is set to 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃ and 165 ℃, which indicates that in the invention, the 8-stage increasing temperature in the vulcanization foaming process is set to 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃ and 175 ℃, so that vulcanization and foaming are synchronous, thereby improving the cell structure and remarkably improving the high temperature resistance and aging resistance of the rubber and plastic product.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The high-temperature-resistant rubber and plastic product is characterized by comprising the following components in parts by weight:
15-20 parts of ethylene propylene diene monomer, 4-7 parts of foaming agent, 8-15 parts of aluminum tripolyphosphate, 3-5 parts of reinforcing carbon black, 13-18 parts of rubber operating oil, 0.3-0.5 part of activator, 0.1-0.3 part of stearic acid, 10-12 parts of filler, 3-5 parts of protective wax, 2-4 parts of accelerator and 0.1-0.3 part of vulcanizing agent,
the active agent comprises the following components in parts by weight:
5-10 parts of yttrium oxide, 13-25 parts of zinc oxide, 1-4 parts of octahydroxybutyl cage-like silsesquioxane and 2-7 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt.
2. The high-temperature-resistant rubber-plastic product according to claim 1, which comprises the following components in parts by weight:
18 parts of ethylene propylene diene monomer, 5 parts of foaming agent, 12 parts of aluminum tripolyphosphate, 4 parts of reinforcing carbon black, 15 parts of rubber operating oil, 0.4 part of active agent, 0.2 part of stearic acid, 11 parts of filler, 4 parts of protective wax, 3 parts of accelerator and 0.2 part of vulcanizing agent,
the active agent comprises the following components in parts by weight:
8 parts of yttrium oxide, 19 parts of zinc oxide, 2.3 parts of octahydroxybutyl polyhedral oligomeric silsesquioxane and 5 parts of diethylene triamine pentamethylene phosphonic acid heptasodium salt.
3. The high temperature resistant rubber-plastic product according to claim 1 or 2, wherein the preparation method of the active agent comprises the following steps:
mixing yttrium oxide, zinc oxide, octahydroxybutyl polyhedral oligomeric silsesquioxane and diethylene triamine pentamethylene phosphonic acid heptasodium salt to obtain mixed powder; and heating the mixed powder to 200-240 ℃ for reaction to obtain the active agent.
4. The high-temperature-resistant rubber and plastic product as claimed in claim 3, wherein the foaming agent is azodicarbonamide, the rubber process oil is aromatic oil, the accelerator is dithiocarbamate, the vulcanizing agent is benzoyl peroxide, the filler is one or more of coarse whiting powder, talcum powder and quartz powder which are mixed in any proportion, and the fineness is 400-2000 meshes.
5. The preparation method of the high-temperature-resistant rubber and plastic product is characterized by comprising the following steps of:
s1, blending ethylene propylene diene monomer, a foaming agent, aluminum tripolyphosphate, reinforcing carbon black, rubber operating oil, a filler, protective wax, an active agent and stearic acid, and discharging when the blended material reaches 140 ℃ to obtain a mixed rubber material;
s2, cooling the mixed rubber material, re-refining, discharging, and cooling to obtain a rubber sheet;
s3, adding a vulcanizing agent and an accelerant into the rubber sheet, uniformly mixing, and then discharging to obtain rubber strips;
and S4, extruding and molding the rubber strip, vulcanizing and foaming, and cooling to obtain the high-temperature-resistant rubber and plastic product.
6. The method as claimed in claim 5, wherein the vulcanization foaming in step S4 is sequentially carried out at 8 stages of increasing temperatures, wherein the 8 stages of increasing temperatures are 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 160 ℃, 170 ℃ and 175 ℃.
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