Rapidly-vulcanized high-temperature-resistant carboxylic acid type acrylate rubber as well as preparation method and application thereof

Abstract

The invention provides rapidly-vulcanized high-temperature-resistant carboxylic acid type acrylate rubber as well as a preparation method and application thereof, and belongs to the technical field of chemical materials. The carboxylic acid type acrylate rubber is obtained by vulcanizing carboxylic acid type acrylate raw rubber, and the carboxylic acid type acrylate raw rubber is prepared from the following raw materials in parts by weight: 85 to 97 parts of acrylate monomer, 1 to 5 parts of carboxylic acid type monomer and 1 to 5 parts of 3-hydroxy-1-adamantyl methacrylate. By introducing the adamantane heat-resistant functional monomer and the carboxylic acid type monomer, the carboxylic acid type acrylate rubber with excellent high-temperature aging resistance and oil resistance is prepared, the crosslinking density and vulcanization speed of the carboxylic acid type acrylate rubber are effectively improved, and the mechanical property of the carboxylic acid type acrylate rubber is not influenced; the rubber sealing product has a better application market, and the requirements of more use scenes are met.

Description

Technical Field

[0001] This invention belongs to the field of chemical materials technology, specifically relating to a rapidly vulcanizing high-temperature resistant carboxylic acid acrylate rubber, its preparation method, and its uses. Background Technology

[0002] Acrylic rubber, due to its saturated main chain structure, possesses properties such as heat resistance, UV radiation resistance, and ozone resistance. Its polar ester groups on the side chains also provide excellent oil resistance. It can operate in high-temperature environments of 150-175℃, and its heat resistance is second only to fluororubber and silicone rubber. Because of its good resistance to oils such as engine oil, lubricating oil, and automatic transmission fluid, acrylic rubber is widely used in various seals, gaskets, liners, and pipes, and is known as a "high-performance automotive adhesive."

[0003] Acrylic rubbers come in various types, which can be classified according to the type of monomer with the vulcanization point into active chlorine type, carboxylic acid type, epoxy type, etc.; and according to different temperature resistance grades of the rubber compound into standard type, cold-resistant type, cold-resistant improved type, ultra-cold-resistant type, heat-resistant improved type, etc. Different types of acrylic rubbers have different mechanical properties and advantages and disadvantages. Among them, carboxylic acid type rubbers have excellent compression set properties and are valued in various application fields.

[0004] In recent years, with the development of lightweight and energy-efficient automobiles, temperatures in high-temperature environments have increased, placing higher demands on the high-temperature resistance of rubber materials and promoting the continuous development of high-temperature resistant rubber materials. However, due to the poor flowability of carboxylic acid acrylates, there are problems such as short storage time of the compound, easy scorching, low operational safety during vulcanization, slow vulcanization speed, long vulcanization time, and difficulty in curing, which limit the application of carboxylic acid acrylates. In order to broaden the application fields of carboxylic acid acrylates, meet the needs of more application scenarios, and reduce the greenhouse effect and the use of perfluorinated and polyfluoroalkyl substances, it is necessary to modify them to improve their vulcanization performance and high-temperature resistance.

[0005] There are generally two methods to improve the high-temperature resistance of carboxylic acid acrylate rubber: one is to add heat-resistant fillers, and the other is to introduce heat-resistant monomers into the polymer. Although adding heat-resistant fillers can improve the heat resistance of rubber to a certain extent, this method is accompanied by problems such as poor filler dispersibility, limited material processing performance, and slowed vulcanization rate. Introducing heat-resistant monomers can improve its heat resistance and processing performance while maintaining the original properties of the rubber, but it has the disadvantages of high addition amount of heat-resistant monomers and low vulcanization rate.

[0006] Therefore, there is an urgent need to develop a more efficient modification method to further improve the vulcanization speed and high-temperature resistance of carboxylic acid acrylates to meet practical application requirements. Summary of the Invention

[0007] The purpose of this invention is to provide a rapidly vulcanized, high-temperature resistant carboxylic acid acrylate rubber, its preparation method, and its applications.

[0008] The present invention provides a carboxylic acid type acrylate raw rubber, which is prepared from raw materials comprising the following parts by weight: 85-97 parts of acrylate monomer, 1-5 parts of carboxylic acid type monomer, and 1-5 parts of 3-hydroxy-1-adamantyl methacrylate.

[0009] Furthermore, it is prepared from raw materials comprising the following parts by weight: 85 parts of acrylate monomer, 5 parts of carboxylic acid monomer, and 2 parts of 3-hydroxy-1-adamantyl methacrylate.

[0010] Further, the acrylate monomer includes at least one of alkyl acrylate, alkoxyalkyl acrylate, cycloalkyl acrylate, alkyl methacrylate, alkoxyalkyl methacrylate, and cycloalkyl methacrylate; the carboxylic acid monomer includes at least one of butenedioic acid mono-chain alkyl ester, butenedioic acid monoester with an alicyclic structure, butenedioic acid monoaromatic ester, pentenedioic acid monoalkyl ester, hexenedioic acid monoalkyl ester, itaconic acid, itaconic acid monobutyl ester, and citraconic acid monoester.

[0011] Furthermore, it is prepared from raw materials comprising the following parts by weight: 35 parts ethyl acrylate, 60 parts n-butyl acrylate, 5 parts carboxylic acid monomer, and 2 parts 3-hydroxy-1-adamantyl methacrylate.

[0012] This invention also provides a method for preparing carboxylic acid type acrylate raw rubber, comprising the following steps: Water and emulsifier are mixed and stirred to form an emulsion. Then, acrylate monomers, carboxylic acid monomers, and 3-hydroxy-1-adamantyl methacrylate are weighed and mixed according to the specified weight parts, and 0.4-0.6 volumes of the emulsion are added. The mixture is stirred evenly to obtain a monomer mixture. Subsequently, the remaining volume of the emulsion is passed through an inert gas, and 0.08-0.12 volumes of the monomer mixture are added to it for emulsification. Then, 0.2-0.4 volumes of initiator solution are added to initiate the polymerization reaction. When the solution turns blue, the remaining monomer mixture and initiator solution are added dropwise to allow the reaction to proceed. Finally, an inhibitor is added and the mixture is cooled to room temperature. The rubber latex is then coagulated, the rubber particles are washed, and dried to obtain carboxylic acid acrylate raw rubber.

[0013] Further, in the emulsion, the emulsifier comprises 1-5 parts and water comprises 250-350 parts; the initiator and the polymerization inhibitor are independently 0.1-1% of the sum of the masses of the acrylate monomer, the carboxylic acid monomer and 3-hydroxy-1-adamantyl methacrylate; the temperature of the reaction system when the initiator solution is added is 70-80°C; the temperature of the reaction system after the solution turns blue is 85-95°C; the emulsifier includes at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium allyloxyhydroxypropyl sulfonate, allyloxynonylphenol ether, alkylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether; the initiator includes at least one of potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyramidine hydrochloride, tert-butyl hydroperoxide-ascorbic acid, ammonium persulfate-sodium bisulfite or hydrogen peroxide-ferrous sulfate; the polymerization inhibitor includes at least one of p-benzoquinone, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, and methylhydroquinone.

[0014] The present invention also provides a carboxylic acid type acrylate rubber, which comprises the following raw materials in parts by weight: 90-110 parts of carboxylic acid type acrylate raw rubber, 0-70 parts of filler, 0.1-2 parts of vulcanizing agent, 0-4 parts of vulcanization accelerator, 0-5 parts of internal release agent, and 0-2 parts of antioxidant.

[0015] Further, it comprises the following raw materials in parts by weight: 100 parts of carboxylic acid type acrylate raw rubber, 50 parts of filler, 0.6 parts of vulcanizing agent, 2 parts of vulcanization accelerator, 3 parts of internal release agent, and 1 part of antioxidant; the filler includes at least one of barium sulfate, calcium silicate, carbon black, diatomaceous earth, silica powder, and white carbon black; the vulcanizing agent includes at least one of hexamethylenediamine, hexamethylenediamine carbamate, and N,N'-dicinnamaldehyde-1,6-hexanediamine; the vulcanization accelerator includes at least one of guanidine, tetramethylguanidine, dibutylguanidine, diphenylguanidine, di-o-tolylguanidine, and N,N'-di-o-tolylguanidine; the internal release agent includes at least one of WB222, stearic acid, zinc stearate, and ammonium stearate.

[0016] The present invention also provides a method for preparing carboxylic acid type acrylate rubber, wherein the raw carboxylic acid type acrylate rubber is first fully plasticized, then the remaining raw materials are added, mixed and sheeted, and vulcanized to obtain carboxylic acid type acrylate rubber.

[0017] This invention also provides the use of carboxylic acid acrylate raw rubber and carboxylic acid acrylate rubber in rubber sealing products, wherein the rubber sealing products are preferably heat-resistant and oil-resistant rubber sealing products. This invention introduces the heat-resistant functional monomer 3-hydroxy-1-adamantyl methacrylate and a carboxylic acid monomer to prepare a carboxylic acid acrylate rubber with excellent high-temperature aging resistance and oil resistance. Without affecting its mechanical properties, the crosslinking density and vulcanization speed of the carboxylic acid acrylate rubber are effectively improved. Experiments show that after aging at 200℃ for 336 hours, it still exhibits excellent retention rates of thermal aging tensile strength, elongation at break, and low compression set, with a tensile strength reduction rate of only 28%, an elongation at break reduction rate of only 30%, and a compression set rate of only 31%. After aging in ASTM903 hot oil at 150℃ for 70 hours, it also exhibits excellent retention rates of thermal aging tensile strength and elongation at break, with a tensile strength reduction rate of only 10% and an elongation at break reduction rate of only 13%.

[0018] This invention enables the preparation of carboxylic acid acrylate rubber that can be rapidly vulcanized and has both high-temperature aging resistance and oil resistance, making it more applicable in rubber sealing products and expanding its application fields to meet the needs of more usage scenarios.

[0019] Obviously, based on the above description of the present invention, and according to common technical knowledge and conventional methods in the field, various other modifications, substitutions or alterations can be made without departing from the basic technical concept of the present invention.

[0020] The following detailed embodiments further illustrate the above-described content of the present invention. However, this should not be construed as limiting the scope of the present invention to the following embodiments. All technologies implemented based on the above-described content of the present invention fall within the scope of the present invention. Detailed Implementation

[0021] The raw materials and equipment used in this invention are all known products, obtained by purchasing commercially available products.

[0022] Example 1: Preparation of carboxylic acid type acrylate rubber (1) 0.50 g (3 mmol) of 1,3-adamantanediol was prepared into a 4% solution with n-hexane. Under an ice bath at 0 °C, a 4% methacryloyl chloride solution with a stoichiometric ratio of 1:1 was added to the solution. The reaction was carried out for 1 h with a dropping rate of 2 mL / min. The mixture was then stirred at room temperature for 2 h. After the reaction was completed, the solvent was removed by rotary evaporation. The white product was washed with ethyl acetate and dried under vacuum at 25 °C for 12 h to obtain 3-hydroxy-1-adamantane methacrylate with a yield of 90%.

[0023] (2) Add 3 parts of OP-10 emulsifier and 300 parts of deionized water to mixing tank 2 and stir for 30 min to prepare an emulsion; take 1 / 2 volume of the emulsion into mixing tank 1, weigh 35 parts of ethyl acrylate, 60 parts of n-butyl acrylate, 5 parts of itaconic acid monobutyl ester, and 1 part of 3-hydroxy-1-adamantyl methacrylate according to the weight ratio and add them to mixing tank 1, and homogenize and stir at 3000 rpm for 20 min to obtain a monomer mixture; add the remaining 1 / 2 volume of emulsion in mixing tank 2 into the reactor, and purge the reactor with nitrogen to replace the air; then, add to the reactor One-tenth of the volume of the monomer mixture was emulsified for 30 minutes and heated to 80°C. Then, one-third of the volume of potassium persulfate solution (1 part potassium persulfate and 99 parts water) was added dropwise to the reactor to initiate the polymerization reaction. The mass of potassium persulfate was 0.6% of the total mass of the monomers. When the solution in the reactor turned blue, the remaining mixed monomer solution and potassium persulfate solution were added dropwise simultaneously over 2 hours. After the addition was completed, the temperature was raised to 90°C and stirred for 2 hours. Then, 1% of p-benzoquinone (the mass of the monomers was equal to the total mass of each monomer) was added. The mixture was cooled to room temperature, coagulated, the particles were washed, and dried to obtain carboxylic acid type acrylate raw rubber.

[0024] (3) Weigh out 100 parts by weight of carboxylic acid type acrylate raw rubber, 50 parts of N550, 1 part of stearic acid, 0.6 parts of hexamethylenediamine carbamate, 2 parts of N,N'-di-o-tolueneguanidine, 2 parts of WB222, and 1 part of 445; first, plasticize the carboxylic acid type acrylate raw rubber on a two-roll mill for 3 minutes at a roller speed of 40 r•min. -1 Add the remaining raw materials, and rotate the roller at 40 r / min. -1 After being mixed evenly, the mixture is sheeted out to obtain test pieces. Finally, it is vulcanized on a flat vulcanizing machine under the following conditions: first stage vulcanization: 180℃×5min, vulcanization pressure is 16MPa; second stage vulcanization: 170℃×4h, vulcanization pressure is 16MPa, to obtain carboxylic acid type acrylic rubber.

[0025] Example 2: Preparation of carboxylic acid type acrylate rubber Refer to Example 1, except that: 2 parts of 3-hydroxy-1-adamantyl methacrylate.

[0026] Example 3: Preparation of carboxylic acid type acrylate rubber Referring to Example 1, the only difference is that: 3 parts of 3-hydroxy-1-adamantyl methacrylate.

[0027] Example 4: Preparation of carboxylic acid type acrylate rubber Referring to Example 1, the only difference is that: 4 parts of 3-hydroxy-1-adamantyl methacrylate.

[0028] Example 5: Preparation of carboxylic acid type acrylate rubber Referring to Example 1, the only difference is that 5 parts of 3-hydroxy-1-adamantyl methacrylate were used.

[0029] Comparative Example 1: Preparation of Carboxylic Acid Type Acrylic Rubber Referring to Example 1, the only difference is that 3-hydroxy-1-adamantyl methacrylate is not added.

[0030] Comparative Example 2: Preparation of Carboxylic Acid Type Acrylic Rubber Referring to Example 1, the only difference is that 2 parts of 3-hydroxy-1-adamantyl methacrylate are used, and itaconic acid monobutyl ester is not added.

[0031] Experimental Example 1: Performance Testing of Carboxylic Acid Type Acrylic Rubber 1. Experimental subjects The carboxylic acid type acrylate rubbers prepared in Examples 1-5 and Comparative Examples 1-2.

[0032] 2. Experimental Methods Vulcanization performance test: (1) Vulcanization test: Test standard: GB / T16584-1996; Test conditions: Test equipment GT-M3000A, conditions MDR 180℃@20min, Arc0.5; Minimum torque (M) L ), N•m (kgf•cm): characterizes the creep property of rubber compound. The lower the ML, the better the creep property, and vice versa. Maximum torque (M) H N•m (kgf•cm): Characterizes the shear modulus, hardness, tensile strength, and crosslinking density of the rubber compound; M H The higher the value, the greater the shear modulus, hardness, tensile strength, and crosslinking density of the vulcanizate; M H -M L The difference between the highest and lowest torque reflects the degree of cross-linking; the larger the difference, the higher the degree of cross-linking.

[0033] Remaining scorch time (TS2): Characterizes the time that the rubber compound can flow in the mold cavity. The shorter the TS2, the more likely the rubber compound will become stuck, and the more likely the product will be defective due to insufficient material during production. Conversely, the longer the TS2, the higher the operational safety, but the lower the production efficiency and the higher the cost.

[0034] (2) Positive vulcanization time test: According to GB / T 9869-2014, a rotorless vulcanizer is used for testing, and the positive vulcanization time (TC) is determined based on the test results. 90 ); TC 90 Torque increased to ML +90% (M H -M L The time (TC) is the optimal vulcanization point, used to evaluate the primary vulcanization conditions of the rubber compound during molding production. 90 An excessively long vulcanization time indicates a slow vulcanization rate, which will result in low product hardness and low production efficiency.

[0035] Mechanical property testing: (1) Hardness test: The hardness of the vulcanized rubber was tested using a Shore hardness tester in accordance with GB / T 531.2-2009.

[0036] (2) Tensile properties test: According to GB / T528-2009, the tensile properties (tensile strength and elongation at break) of the vulcanizate before and after aging are tested on a universal testing machine.

[0037] (3) Compression deformation test: The test shall be conducted in accordance with GB / T 1683-2018 using a compression permanent deformation mold.

[0038] (4) Oil resistance test: The oil resistance is tested in accordance with ASTM D471.

[0039] 3. Experimental Results The carboxylic acid acrylate rubber in Example 5 was hard and brittle, and no mechanical property tests were conducted. The carboxylic acid acrylate rubber in Comparative Example 2 had poor initial mechanical properties, and no subsequent aging, compression set, and oil resistance tests were conducted.

[0040] As shown in Table 1, the vulcanization performance test results of Examples 1-4, compared with Comparative Example 1, show that M... H -M L Both increase, TC 90 The decrease in both values ​​indicates that the addition of 3-hydroxy-1-adamantyl methacrylate promotes the crosslinking of carboxylic acid acrylate rubber, effectively increasing the crosslinking density and vulcanization rate of carboxylic acid acrylate rubber.

[0041] Meanwhile, in Example 5, the addition of 5 parts of 3-hydroxy-1-adamantyl methacrylate resulted in an excessively high crosslinking density of the carboxylic acid acrylate rubber, which was not conducive to the balance between its hardness and elasticity. This indicates that the addition of 1 to 4 parts of 3-hydroxy-1-adamantyl methacrylate can better improve the crosslinking density and vulcanization speed while ensuring the mechanical properties of the carboxylic acid acrylate rubber.

[0042] The results of the vulcanization performance test of Comparative Example 2 show that crosslinking reaction can also occur with the addition of only 3-hydroxy-1-adamantyl methacrylate, but its vulcanization effect is poor. The addition of itaconic acid monobutyl ester in Example 2 significantly improved the crosslinking density and vulcanization speed of carboxylic acid acrylate rubber.

[0043] The results of vulcanization performance tests show that 3-hydroxy-1-adamantyl methacrylate and itaconic acid monobutyl ester are both indispensable, and the two together improve the crosslinking density and vulcanization speed of acrylate rubber.

[0044] As shown in Table 2, the mechanical property test results of Examples 2-4, compared with Comparative Example 1, show that the hardness and tensile strength of the carboxylic acid acrylate rubber are improved. The reduction rate of tensile strength and elongation at break after aging at 200℃ for 336h is reduced. The compression set after aging at 200℃ for 70h is reduced. The reduction rate of tensile strength and elongation at break after aging in ASTM903 hot oil at 150℃ for 70h is also reduced. This indicates that the addition of 3-hydroxy-1-adamantyl methacrylate improves the initial hardness and strength of the carboxylic acid acrylate rubber, while significantly improving its high-temperature aging resistance and oil resistance.

[0045] In Examples 1-4, with increasing amounts of 3-hydroxy-1-adamantyl methacrylate, the tensile strength and elongation at break of the carboxylic acid acrylate rubber after aging at 200°C for 336 hours initially decreased and then increased; the compression set after aging at 200°C for 70 hours initially decreased and then increased; and the tensile strength and elongation at break after aging in ASTM903 hot oil at 150°C for 70 hours initially decreased and then increased. Among these, the carboxylic acid acrylate rubber in Example 2 exhibited the lowest rates of decrease in tensile strength and elongation at break after aging at 200°C for 336 hours, the lowest rates of decrease in compression set after aging at 200°C for 70 hours, and the lowest rate of decrease in tensile strength after aging in ASTM903 hot oil at 150°C for 70 hours. This indicates that the carboxylic acid acrylate rubber prepared by adding 2 parts of 3-hydroxy-1-adamantyl methacrylate has the best high-temperature aging resistance and oil resistance.

[0046] Comparative Example 2 shows that without the addition of itaconic acid monobutyl ester, a carboxylic acid type acrylate rubber with good mechanical properties cannot be obtained.

[0047] Mechanical property test results show that 3-hydroxy-1-adamantyl methacrylate and itaconic acid monobutyl ester together improve the mechanical properties of acrylate rubber and have excellent high-temperature aging resistance and oil resistance; among them, the carboxylic acid type acrylate rubber with 2 parts of 3-hydroxy-1-adamantyl methacrylate as a heat-resistant monomer has the best high-temperature aging resistance and oil resistance.

[0048] Table 1. Vulcanization test results of the carboxylic acid type acrylate rubbers prepared in Examples 1-5 and Comparative Examples 1-2. Note: min:s means minutes:seconds, such as 1:17 means 1 minute and 17 seconds.

[0049] Table 2. Mechanical property test results of the carboxylic acid type acrylate rubbers prepared in Examples 1-5 and Comparative Examples 1-2. In summary, this invention, by introducing the heat-resistant functional monomer 3-hydroxy-1-adamantyl methacrylate and a carboxylic acid monomer, produces a carboxylic acid-type acrylate rubber with excellent high-temperature aging resistance and oil resistance. It also effectively improves the crosslinking density and vulcanization speed of the carboxylic acid-type acrylate rubber without affecting its mechanical properties. Specifically, adding 2 parts of 3-hydroxy-1-adamantyl methacrylate significantly increases the crosslinking density and vulcanization speed of the carboxylic acid-type acrylate rubber. The resulting carboxylic acid-type acrylate rubber exhibits excellent retention rates of thermal aging tensile strength, elongation at break, and low compression set after aging at 200℃ for 336 hours, with tensile strength decreasing by only 28%, elongation at break decreasing by only 30%, and compression set decreasing by only 31%. After aging in ASTM903 hot oil at 150℃ for 70 hours, it also exhibits excellent retention rates of thermal aging tensile strength and elongation at break, with tensile strength decreasing by only 10% and elongation at break decreasing by only 13%. This invention can produce carboxylic acid-based acrylate rubber with good mechanical properties. It can effectively improve the crosslinking density, vulcanization speed, high temperature aging resistance and oil resistance of carboxylic acid-based acrylate rubber, making the application field of carboxylic acid-based acrylate rubber wider and meeting the needs of more application scenarios.

Claims

1. A carboxylic acid type acrylate raw rubber, characterized in that, It is made from raw materials comprising the following parts by weight: 85-97 parts of acrylate monomer, 1-5 parts of carboxylic acid monomer, and 1-5 parts of 3-hydroxy-1-adamantyl methacrylate.

2. The carboxylic acid type acrylate raw rubber according to claim 1, characterized in that, It is made from raw materials comprising the following parts by weight: 85 parts acrylate monomer, 5 parts carboxylic acid monomer, and 2 parts 3-hydroxy-1-adamantyl methacrylate.

3. The carboxylic acid type acrylate raw rubber according to any one of claims 1 to 2, characterized in that, The acrylate monomers include at least one of alkyl acrylate, alkoxyalkyl acrylate, cycloalkyl acrylate, alkyl methacrylate, alkoxyalkyl methacrylate, and cycloalkyl methacrylate; the carboxylic acid monomers include at least one of mono-chain alkyl esters of butenedioic acid, mono-butenedioic acid with an alicyclic structure, mono-aromatic esters of butenedioic acid, mono-alkyl pentenedioic acid, mono-alkyl hexenedioic acid, itaconic acid, monobutyl itaconic acid, and mono-citric acid.

4. The carboxylic acid type acrylate raw rubber according to claim 3, characterized in that, It is made from the following raw materials in parts by weight: 35 parts ethyl acrylate, 60 parts n-butyl acrylate, 5 parts carboxylic acid monomer, and 2 parts 3-hydroxy-1-adamantyl methacrylate.

5. The method for preparing carboxylic acid type acrylate raw rubber according to any one of claims 1 to 4, characterized in that, Includes the following steps: Mix water and emulsifier and stir to form an emulsion; then, weigh acrylate monomer, carboxylic acid monomer and 3-hydroxy-1-adamantyl methacrylate according to the weight parts and mix them, and add 0.4~0.6 volumes of emulsion, mix and stir evenly to obtain monomer mixture; Subsequently, the remaining volume of emulsion was passed through an inert gas, and 0.08~0.12 volumes of monomer mixture were added to it for emulsification. Then, 0.2~0.4 volumes of initiator solution were added to initiate the polymerization reaction. When the solution turned blue, the remaining monomer mixture and initiator solution were added dropwise to react. Finally, after adding a polymerization inhibitor, the mixture was cooled to room temperature, and the rubber latex was coagulated, the rubber particles were washed, and dried to obtain carboxylic acid type acrylate raw rubber.

6. The preparation method according to claim 5, characterized in that, In the emulsion, the emulsifier comprises 1-5 parts and water comprises 250-350 parts; the initiator and the polymerization inhibitor are independently 0.1-1% of the sum of the masses of the acrylate monomer, the carboxylic acid monomer and the 3-hydroxy-1-adamantyl methacrylate; the temperature of the reaction system when the initiator solution is added is 70-80°C; the temperature of the reaction system after the solution turns blue is 85-95°C; the emulsifier includes at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium allyloxyhydroxypropyl sulfonate, allyloxynonylphenol ether, alkylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether; the initiator includes at least one of potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutyramidine hydrochloride, tert-butyl hydroperoxide-ascorbic acid, ammonium persulfate-sodium bisulfite or hydrogen peroxide-ferrous sulfate; the polymerization inhibitor includes at least one of p-benzoquinone, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, and methylhydroquinone.

7. A carboxylic acid type acrylate rubber, characterized in that, It comprises the following raw materials in parts by weight: 90-110 parts of carboxylic acid type acrylate raw rubber, 0-70 parts of filler, 0.1-2 parts of vulcanizing agent, 0-4 parts of vulcanization accelerator, 0-5 parts of internal release agent, and 0-2 parts of antioxidant.

8. The carboxylic acid type acrylate rubber according to claim 7, characterized in that, It comprises the following raw materials in parts by weight: 100 parts of carboxylic acid type acrylate raw rubber, 50 parts of filler, 0.6 parts of vulcanizing agent, 2 parts of vulcanization accelerator, 3 parts of internal release agent, and 1 part of antioxidant; the filler includes at least one of barium sulfate, calcium silicate, carbon black, diatomaceous earth, silica powder, and white carbon black; the vulcanizing agent includes at least one of hexamethylenediamine, hexamethylenediamine carbamate, and N,N'-dicinnamaldehyde-1,6-hexanediamine; the vulcanization accelerator includes at least one of guanidine, tetramethylguanidine, dibutylguanidine, diphenylguanidine, di-o-tolylguanidine, and N,N'-di-o-tolylguanidine; the internal release agent includes at least one of WB222, stearic acid, zinc stearate, and ammonium stearate.

9. The method for preparing the carboxylic acid type acrylate rubber according to claims 7-8, characterized in that, First, the raw carboxylic acid acrylate rubber is fully plasticized, then the remaining raw materials are added, mixed and sheeted, and vulcanized to obtain carboxylic acid acrylate rubber.

10. The use of the carboxylic acid type acrylate raw rubber according to any one of claims 1 to 4 and the carboxylic acid type acrylate rubber according to any one of claims 7 to 8 in rubber sealing products, wherein the rubber sealing products are preferably heat-resistant and oil-resistant rubber sealing products.

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