A high temperature resistant carboxylic acid type acrylate rubber and a method for producing the same

Abstract

The invention discloses a high temperature resistant carboxylic acid type acrylate rubber and a manufacturing method thereof, comprising 35 to 80 parts by weight of acrylate monomer raw materials, 5 parts of carboxylic acid type monomer raw materials, 15 to 60 parts of monomer raw materials for improving the high temperature resistance of rubber, 3 parts of emulsifier and 250 parts of deionized water; the acrylate monomer raw materials are at least one of ethyl acrylate, butyl acrylate, methoxyethyl acrylate and ethoxyethyl acrylate; the carboxylic acid type monomer raw materials have cross-linking active groups, and the carboxylic acid type monomer raw materials are at least one of itaconic acid, monobutyl itaconic acid, acrylic acid, fumaric acid and monobutyl fumarate; the monomer raw materials for improving the high temperature resistance of rubber are at least one of styrene, acrylonitrile, methyl acrylate and methyl methacrylate. By adding monomer raw materials for improving the high temperature resistance of rubber, the high temperature resistance of the final rubber is increased, so that the application field of acrylate rubber is wider and can meet some special use requirements with high high temperature resistance requirements.

Description

Technical Field

[0001] The invention relates to the technical field of rubber, and in particular to a high-temperature resistant carboxylic acid type acrylate rubber and a preparation method thereof. Background Art

[0002] Acrylic rubber (ACM) is a type of elastic material made by copolymerizing acrylic esters with monomers that can provide cross-linking reactive groups. Its main chain is a saturated structure, so it has the properties of heat resistance, UV radiation resistance and ozone resistance; its side chain contains polar ester groups, so it also has excellent oil resistance. The main use of acrylic rubber is to make heat-resistant and oil-resistant seals and oil pipes, etc., mainly used in automobiles, motorcycles, power transformers and other fields.

[0003] The physical and mechanical properties of acrylic rubber are affected by many factors, including: the structure of the rubber (the raw material ratio of the polymer), the molecular weight of the rubber, the rubber compounding processing technology, etc.

[0004] There are different types of acrylic rubber. According to the type of monomer at the vulcanization point, the commonly used ones are: active chlorine type, carboxylic acid type, epoxy type, etc. According to the different temperature resistance grades of the rubber, it can be divided into: standard type, cold-resistant type, cold-resistant improved type, super cold-resistant type, heat-resistant improved type, etc.

[0005] Different types of acrylic rubbers have different compounding and processing technologies, and different types of acrylic rubbers have different mechanical properties and advantages and disadvantages. Among them, the advantage of carboxylic acid type rubber is that the compression permanent deformation performance of rubber is excellent, so it is valued in the application field.

[0006] Acrylic rubber is characterized by high temperature resistance and oil resistance. It can be used for a long time in hot oil at 150°C and can withstand a short-term temperature of 200°C (about 10 hours). The requirements for high temperature resistance of existing acrylic rubbers are gradually increasing during use. In order to make the application field of acrylic rubber wider and meet the needs of more usage scenarios, the present invention proposes a high temperature resistant carboxylic acid type acrylic rubber and a manufacturing method thereof. Summary of the invention

[0007] In view of the deficiencies of the prior art, the object of the present invention is to provide a high temperature resistant carboxylic acid type acrylate rubber and a method for manufacturing the same.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] The high-temperature resistant carboxylic acid type acrylate rubber described in the technical solution includes 35 to 80 parts by weight of acrylate monomer raw materials, 5 parts of carboxylic acid type monomer raw materials, 15 to 60 parts of monomer raw materials for improving the high-temperature resistance of the rubber material, 3 parts of emulsifier and 250 parts of deionized water.

[0010] In the above technical solution, preferably, the acrylic acid ester monomer raw material is at least one of ethyl acrylate, butyl acrylate, methoxyethyl acrylate and ethoxyethyl acrylate;

[0011] The carboxylic acid type monomer raw material has a cross-linking active group, and the carboxylic acid type monomer raw material is at least one of itaconic acid, monobutyl itaconate, acrylic acid, fumaric acid and monobutyl fumarate;

[0012] The monomer raw material for improving the high temperature resistance of the rubber material is at least one of styrene, acrylonitrile, methyl acrylate and methyl methacrylate.

[0013] In the above technical solution, preferably, the emulsifier is sodium lauryl sulfate.

[0014] The method for producing the high temperature resistant carboxylic acid type acrylate rubber described in the technical solution comprises the following steps:

[0015] S1. The selected acrylate monomer raw material, carboxylic acid monomer raw material and monomer raw material for improving the high temperature resistance of the rubber are added to a mixing tank, stirred and mixed evenly to prepare a mixed monomer raw material;

[0016] S2. Deionized water and an emulsifier are added to the reactor, stirred, and an emulsion is prepared. The emulsification time is 10 min and the temperature is raised to 30 to 40 ° C;

[0017] S3. Nitrogen is introduced into the reactor to replace the air;

[0018] S4. 30% of the mixed monomer raw material was added to the reactor and stirred to prepare a monomer emulsion;

[0019] S5. A peroxide initiator solution having a concentration of 0.02% was added to the reactor to initiate the polymerization reaction;

[0020] S6. After the reaction starts, the heat released by the polymerization reaction raises the temperature of the emulsion to 50 ℃ ~ 60 ℃, and the remaining 70% of the mixed monomer raw material is added dropwise to the reactor;

[0021] S7. After the addition is completed, the rubber latex in the reactor is heated to 80 ° C and kept warm for 1 hour;

[0022] S8. After the insulation is completed, the rubber latex is condensed, the rubber particles are washed and dried to form a rubber product;

[0023] S9. Compound, process, vulcanize and test the finished rubber.

[0024] In the above technical solution, preferably, the polymerization reaction in S5 is carried out at 30°C to 70°C.

[0025] In the above technical solution, preferably, the peroxide in S5 is ammonium persulfate.

[0026] Compared with the prior art, the high temperature resistant carboxylic acid type acrylate rubber and the manufacturing method thereof provided by the present invention have the following beneficial effects:

[0027] The present invention adds a monomer raw material for improving the high temperature resistance of the rubber to the traditional manufacturing method. Different homopolymers have different brittle temperatures. The homopolymer of the monomer raw material for improving the high temperature resistance of the rubber has a higher brittle temperature. Therefore, compared with the traditional rubber to which the monomer raw material for improving the high temperature resistance of the rubber is added, the high temperature resistance of the rubber finally manufactured is increased, thereby expanding the application field of acrylic rubber and meeting the needs of more usage scenarios. DETAILED DESCRIPTION

[0028] The present invention will be further described below in conjunction with embodiments:

[0029] The embodiment of the present invention provides a high-temperature resistant carboxylic acid type acrylate rubber and a manufacturing method thereof, comprising 35 to 80 parts by weight of an acrylate monomer raw material, 5 parts of a carboxylic acid type monomer raw material, 15 to 60 parts of a monomer raw material for improving the high-temperature resistance of the rubber, 3 parts of an emulsifier and 250 parts of deionized water.

[0030] The acrylic ester monomer raw material is at least one of ethyl acrylate, butyl acrylate, methoxyethyl acrylate and ethoxyethyl acrylate; various acrylic ester monomer raw materials have different high temperature resistance, low temperature resistance and oil resistance, and one or more can be selected to combine to adjust the performance indicators of the rubber product.

[0031] The carboxylic acid type monomer raw material has a cross-linking active group, and the carboxylic acid type monomer raw material is at least one of itaconic acid, monobutyl itaconate, acrylic acid, fumaric acid and monobutyl fumarate.

[0032] The monomer raw material for improving the high temperature resistance of the rubber is at least one of styrene, acrylonitrile, methyl acrylate and methyl methacrylate. The homopolymer of the monomer raw material for improving the high temperature resistance of the rubber has a high brittle temperature, and thus has good high temperature resistance. Among them, the brittle temperature of polystyrene is 100°C, the brittle temperature of polyacrylonitrile is 96°C, the brittle temperature of polymethyl methacrylate is 105°C, and the brittle temperature of polymethyl acrylate is 8°C, while the brittle temperature of polyethyl acrylate in the basic monomer raw material is -22°C, the brittle temperature of polybutyl acrylate is -56°C, the brittle temperature of polymethoxyethyl acrylate is about -25°C, and the brittle temperature of polyethoxyethyl acrylate is about -50°C. The higher the brittle temperature, the better the high temperature resistance. After the monomer for improving the high temperature resistance of the rubber is added to the components, the high temperature resistance of the rubber can be improved.

[0033] In order to better implement the invention, the emulsifier is sodium lauryl sulfate.

[0034] The present invention provides a method for producing a high temperature resistant carboxylic acid type acrylate rubber, comprising the following steps:

[0035] S1. The selected acrylate monomer raw material, carboxylic acid monomer raw material and monomer raw material for improving the high temperature resistance of the rubber are added to a mixing tank, stirred and mixed evenly to prepare a mixed monomer raw material;

[0036] S2. Deionized water and an emulsifier were added to the reactor, stirred, and an emulsion was prepared. The emulsification time was 10 min, and the temperature was raised to 30 to 40 ° C;

[0037] S3. Nitrogen is introduced into the reactor to replace the air;

[0038] S4. 30% of the mixed monomer raw material was added to the reactor and stirred to prepare a monomer emulsion;

[0039] S5. Add a 0.02% peroxide initiator solution into the reactor to initiate the polymerization reaction; the chemical structure of the acrylate monomer contains a double bond. Under the action of the free radicals of the initiator, the double bond is opened to form a cross-linking point. When the cross-linking points between the acrylate monomers are "linked" to each other, a macromolecular polymer is formed, and the polymer molecules become larger and larger during the reaction process. At the same time, the monomer raw material will also become a part of the polymer to improve the high temperature resistance of the rubber, thereby improving the high temperature resistance of the formed rubber;

[0040] S6. After the reaction starts, the heat released by the polymerization reaction raises the temperature of the emulsion to 50°C to 60°C, and the remaining 70% of the mixed monomer raw materials are dripped into the reactor; during the dripping process of the mixed monomer raw materials, the dripping speed is determined by the temperature of the emulsion, that is, when the temperature of the emulsion is lower than 50°C, the dripping speed of the mixed monomer raw materials is increased to increase the amount of heat released per unit time by the polymerization reaction, thereby increasing the temperature of the emulsion; when the temperature of the emulsion is higher than 60°C, the dripping speed of the mixed monomer raw materials is reduced to reduce the amount of heat released per unit time by the polymerization reaction, thereby reducing the temperature of the emulsion. When the molecular weight of the polymer reaches near the target value, a terminator can be added or the mixed monomer raw materials can be stopped to terminate the polymerization reaction, i.e., the target polymer is formed;

[0041] S7. After the addition is completed, the rubber latex in the reactor is heated to 80 ° C and kept warm for 1 hour to force the residual mixed monomer raw materials that have not completely reacted to undergo polymerization under high temperature conditions to reduce the residual monomer raw materials;

[0042] S8. After the insulation is completed, the rubber latex is condensed, the rubber particles are washed and dried to form a rubber product;

[0043] S9. Compound, process, vulcanize and test the finished rubber.

[0044] In order to better implement the present invention, the polymerization reaction in S5 is carried out at 30°C to 70°C.

[0045] In order to better implement the present invention, the peroxide in S5 is ammonium persulfate.

[0046] Example 1

[0047] The embodiment of the present invention provides a high-temperature resistant carboxylic acid type acrylate rubber, which includes, by weight, 75 parts of ethyl acrylate as an acrylate monomer raw material, 5 parts of monobutyl itaconate as a carboxylic acid type monomer raw material, 10 parts of methyl acrylate and 10 parts of styrene as monomer raw materials for improving the high-temperature resistance of the rubber material, 3 parts of an emulsifier and 250 parts of deionized water.

[0048] The present invention provides a method for producing a high temperature resistant carboxylic acid type acrylate rubber, comprising the following steps:

[0049] S1. 75 parts of ethyl acrylate, 5 parts of monobutyl itaconate, 10 parts of methyl acrylate and 10 parts of styrene were added to a mixing tank, stirred and mixed to prepare a mixed monomer raw material;

[0050] S2. 250 parts of deionized water and 3 parts of an emulsifier, sodium lauryl sulfate, were added to the reactor and stirred to form an emulsion. The emulsification time was 10 min and the temperature was raised to 30 to 40 ° C.

[0051] S3. Nitrogen is introduced into the reactor to replace the air;

[0052] S4. 30% of the mixed monomer raw material was added to the reactor and stirred to prepare a monomer emulsion;

[0053] S5. Add 0.02% ammonium persulfate as an initiator into the reactor to initiate the polymerization reaction. The polymerization reaction is carried out at 30°C to 70°C. The chemical structure of the acrylate monomer contains a double bond. Under the action of the free radicals of the initiator, the double bond is opened to form a cross-linking point. When the cross-linking points between the acrylate monomers are "linked" to each other, a macromolecular polymer is formed. The polymer molecules become larger and larger during the reaction process, and the monomer raw material will also become a part of the polymer to improve the high temperature resistance of the rubber, thereby improving the high temperature resistance of the formed rubber.

[0054] S6. After the reaction starts, the heat released by the polymerization reaction raises the temperature of the emulsion to 50°C to 60°C, and the remaining 70% of the mixed monomer raw materials are dripped into the reactor; during the dripping process of the mixed monomer raw materials, the dripping speed is determined by the temperature of the emulsion, that is, when the temperature of the emulsion is lower than 50°C, the dripping speed of the mixed monomer raw materials is increased to increase the amount of heat released per unit time by the polymerization reaction, thereby increasing the temperature of the emulsion; when the temperature of the emulsion is higher than 60°C, the dripping speed of the mixed monomer raw materials is reduced to reduce the amount of heat released per unit time by the polymerization reaction, thereby reducing the temperature of the emulsion. When the molecular weight of the polymer reaches near the target value, a terminator can be added or the mixed monomer raw materials can be stopped to terminate the polymerization reaction, i.e., the target polymer is formed;

[0055] S7. After the addition is completed, the rubber latex in the reactor is heated to 80 ° C and kept warm for 1 hour to force the residual mixed monomer raw materials that have not completely reacted to undergo polymerization under high temperature conditions to reduce the residual monomer raw materials;

[0056] S8. After the insulation is completed, the rubber latex is condensed, the rubber particles are washed and dried to form a rubber product;

[0057] S9. Compound, process, vulcanize and test the finished rubber.

[0058] Example 2

[0059] The embodiment of the present invention provides a high-temperature resistant carboxylic acid type acrylate rubber, which includes, by weight, 80 parts of ethyl acrylate as an acrylate monomer raw material, 5 parts of monobutyl itaconate as a carboxylic acid type monomer raw material, 10 parts of methyl acrylate and 5 parts of acrylonitrile as monomer raw materials for improving the high-temperature resistance of the rubber material, 3 parts of an emulsifier and 250 parts of deionized water.

[0060] The method for manufacturing a high temperature resistant carboxylic acid type acrylate rubber provided in this embodiment 2 is consistent with that in embodiment 1.

[0061] Example 3

[0062] The embodiment of the present invention provides a high-temperature resistant carboxylic acid type acrylate rubber, which includes, by weight, 35 parts of ethyl acrylate as an acrylate monomer raw material, 5 parts of monobutyl itaconate as a carboxylic acid type monomer raw material, 60 parts of methyl acrylate as a monomer raw material for improving the high-temperature resistance of the rubber, 3 parts of an emulsifier and 250 parts of deionized water.

[0063] The method for manufacturing a high temperature resistant carboxylic acid type acrylate rubber provided in this embodiment 3 is consistent with that in embodiment 1.

[0064] Example 4

[0065] The embodiment of the present invention provides a high-temperature resistant carboxylic acid type acrylate rubber, which includes, by weight, 75 parts of ethyl acrylate as an acrylate monomer raw material, 5 parts of monobutyl itaconate as a carboxylic acid type monomer raw material, 20 parts of methyl methacrylate as a monomer raw material for improving the high-temperature resistance of the rubber material, 3 parts of an emulsifier and 250 parts of deionized water.

[0066] The method for manufacturing a high temperature resistant carboxylic acid type acrylate rubber provided in this embodiment 4 is consistent with that in embodiment 1.

[0067] Example 5

[0068] The embodiment of the present invention provides a high-temperature resistant carboxylic acid type acrylate rubber, which includes, by weight, 75 parts of ethyl acrylate as an acrylate monomer raw material, 5 parts of monobutyl fumarate as a carboxylic acid type monomer raw material, 15 parts of methyl acrylate and 5 parts of styrene as monomer raw materials for improving the high-temperature resistance of the rubber, 3 parts of an emulsifier and 250 parts of deionized water.

[0069] The method for manufacturing a high temperature resistant carboxylic acid type acrylate rubber provided in this embodiment 5 is consistent with that in embodiment 1.

[0070] Comparative Example

[0071] In the comparative example, no monomer raw material for improving the high temperature resistance of the rubber is added. The acrylate monomer raw materials include 75 parts of ethyl acrylate and 20 parts of butyl acrylate, 5 parts of carboxylic acid monomer raw materials are monobutyl itaconate, 3 parts of emulsifier and 250 parts of deionized water.

[0072] The method for preparing a high temperature resistant carboxylic acid type acrylate rubber provided in this comparative example is consistent with that in Example 1.

[0073] Comparative Examples 1 to 5 were tested for performance:

[0074] Table 1

[0075]

[0076] It can be seen from Table 1 that the rubbers prepared in Examples 1 to 5 after adding monomer raw materials for improving the high temperature resistance of the rubber material have lower elongation change rates after heat aging at 150°C × 70h and 170°C × 70h than the rubber prepared in the comparative example, that is, the heat aging coefficient of the rubber is high, which improves the high temperature resistance of the rubber.

[0077] In summary, the present invention provides a high-temperature resistant carboxylic acid type acrylate rubber and a manufacturing method thereof, wherein a monomer raw material for improving the high-temperature resistance of the rubber material having a high brittle temperature is added, all the monomer raw materials are mixed and stirred to form a mixed monomer raw material, and then an emulsion prepared by mixing deionized water and an emulsifier is heated to 30°C to 40°C, 30% of the mixed monomer raw material is added to the emulsion while nitrogen is filled to remove the air in the reactor, and ammonium persulfate with a concentration of 0.02% is added to initiate a polymerization reaction in the reactor, and the remaining 70% of the mixed monomer raw material is added dropwise when the emulsion reaches a temperature range of 50°C to 60°C, and the dropping speed is controlled according to the temperature of the emulsion, the prepared rubber latex is heated to 80°C and kept warm for 1 hour, and a rubber product is prepared after the insulation is completed, the monomer raw material for improving the high-temperature resistance of the rubber material is polymerized with the carboxylic acid type monomer raw material and the acrylate monomer raw material to form a polymer, and the brittle temperature of the polymer is increased by the added monomer raw material for improving the high-temperature resistance of the rubber material, thereby improving the high-temperature resistance of the final rubber product.

[0078] In the description of the present invention, “plurality” means two or more than two, unless otherwise clearly and specifically defined.

[0079] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on these embodiments, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in this field can still combine, add, delete or make other adjustments to the features in the various embodiments of the present invention according to the circumstances without conflict, without making creative work, so as to obtain different other technical solutions that do not deviate from the concept of the present invention in essence, and these technical solutions also belong to the scope of protection of the present invention.

Claims

1. A high temperature resistant carboxylic acid type acrylate rubber, characterized in that: The method comprises 35 to 80 parts by weight of an acrylic acid ester monomer raw material, 5 parts by weight of a carboxylic acid monomer raw material, 15 to 60 parts by weight of a monomer raw material for improving the high temperature resistance of the rubber material, 3 parts by weight of an emulsifier and 250 parts by weight of deionized water; The carboxylic acid type monomer raw material has a cross-linking active group, and the carboxylic acid type monomer raw material is at least one of itaconic acid, monobutyl itaconate, acrylic acid, fumaric acid and monobutyl fumarate; The monomer raw material for improving the high temperature resistance of the rubber material is at least one of styrene, acrylonitrile, methyl acrylate and methyl methacrylate; The acrylic acid ester monomer raw material is at least one of ethyl acrylate, butyl acrylate, methoxyethyl acrylate and ethoxyethyl acrylate.

2. The high temperature resistant carboxylic acid type acrylate rubber according to claim 1, characterized in that: The emulsifier is sodium lauryl sulfate.

3. The method for producing a high temperature resistant carboxylic acid type acrylate rubber according to claim 1 or 2, characterized in that: The following steps are involved: S1. The selected acrylate monomer raw material, carboxylic acid monomer raw material and monomer raw material for improving the high temperature resistance of the rubber are added to a mixing tank, stirred and mixed evenly to prepare a mixed monomer raw material; S2. Add deionized water and emulsifier into the reactor, stir to make an emulsion, emulsify for 10 min and heat to 30~40°C; S3. Nitrogen is introduced into the reactor to replace the air; S4 was added to the reactor 30% of the mixed monomer raw materials, stirred to prepare a monomer emulsion; S5. A peroxide initiator solution having a concentration of 0.02% was added to the reactor to initiate the polymerization reaction; S6. After the reaction starts, the heat released by the polymerization reaction raises the temperature of the emulsion to 50°C to 60°C, and the remaining 70% of the mixed monomer raw material is added dropwise to the reactor; S7. After the addition is completed, the rubber latex in the reactor is heated to 80 ° C and kept warm for 1 hour; S8. After the insulation is completed, the rubber latex is condensed, the rubber particles are washed and dried to form a rubber product; S9. Compound, process, vulcanize and test the finished rubber.

4. The method for producing a high temperature resistant carboxylic acid type acrylate rubber according to claim 3, characterized in that: The polymerization reaction in S5 is carried out at 30°C to 70°C.

5. The method for producing a high temperature resistant carboxylic acid type acrylate rubber according to claim 3, characterized in that: The peroxide in S5 is ammonium persulfate.

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