Ultralow-temperature-resistant hydrogenated nitrile rubber tube rubber material and preparation method thereof

Abstract

The invention discloses an ultralow-temperature-resistant hydrogenated butadiene-acrylonitrile rubber tube rubber material and a preparation method thereof, and belongs to the technical field of butadiene-acrylonitrile rubber production. The ultralow-temperature-resistant hydrogenated butadiene-acrylonitrile rubber tube rubber material provided by the invention comprises the following raw materials in parts by mass: 100 parts of hydrogenated butadiene-acrylonitrile rubber, 65-80 parts of carbon black, 2-5 parts of zinc oxide, 1-2 parts of stearic acid, 8-12 parts of a low-temperature-resistant plasticizer, 1-3 parts of a vulcanizing agent, 1-2 parts of an accelerant and 2-5 parts of an anti-aging agent. The preparation method of the ultralow-temperature-resistant hydrogenated butadiene-acrylonitrile rubber tube rubber material comprises the following steps: adding hydrogenated butadiene-acrylonitrile rubber into an internal mixer, sequentially adding carbon black, zinc oxide, stearic acid and a low-temperature-resistant plasticizer, and continuously mixing for 4-5 minutes to obtain the rubber material; transferring the rubber material to an open mill, and adding a vulcanizing agent, an accelerant and an anti-aging agent to obtain a rubber compound; and vulcanizing the rubber compound, taking out the rubber material after vulcanization, and naturally cooling to room temperature to obtain the ultralow-temperature-resistant hydrogenated nitrile rubber tube rubber material.

Description

Technical Field

[0001] The invention belongs to the technical field of nitrile rubber production, and specifically relates to an ultra-low temperature resistant hydrogenated nitrile hose rubber material and a preparation method thereof. Background Art

[0002] As a key component for conveying various fluid media, the performance of hydrogenated nitrile rubber (HNBR) hose is directly related to the operating reliability and safety of the entire system.

[0003] With the increasing frequency of extreme environment operations such as aerospace, deep-sea exploration, and polar scientific research, ultra-low temperature environments have posed new challenges to existing hydrogenated nitrile rubber materials. Hose materials with poor low-temperature resistance will harden and become brittle at low temperatures, causing the hose to lose elasticity and flexibility, leading to serious problems such as seal failure, media leakage, and even pipeline rupture.

[0004] For example, the Chinese invention patent with application number 201810141972.0 discloses a high-temperature resistant hydrogenated nitrile rubber material for a cooling system and a preparation method thereof. The high-temperature resistant hydrogenated nitrile rubber material disclosed in the invention patent has excellent high-temperature resistance, but the low-temperature resistance can only reach -33 to (-34) °C. In an ultra-low temperature environment, especially when the temperature is below -40 °C or even lower, the hydrogenated nitrile rubber material provided by the invention cannot guarantee the long-term and stable use of the hose.

[0005] At the same time, whether it is the fuel transportation of aircraft in high-altitude low-temperature areas, the hydraulic oil transmission of polar vehicles, or the pipeline distribution of low-temperature coolant in deep-sea equipment, it is urgently necessary to develop hydrogenated nitrile hose rubber compounds that can withstand ultra-low temperature (<-40°C) working conditions. Therefore, it is necessary to further improve the existing hydrogenated nitrile rubber materials to improve their low-temperature resistance. Summary of the invention

[0006] The object of the present invention is to provide an ultra-low temperature resistant hydrogenated nitrile hose rubber material and a preparation method thereof, so as to improve the low temperature resistance of the hydrogenated nitrile hose rubber material.

[0007] The purpose of the present invention can be achieved through the following technical solutions: A super-low temperature resistant hydrogenated nitrile hose rubber material, comprising the following raw materials in parts by weight: 100 parts of hydrogenated nitrile rubber; 65-80 parts of carbon black; 2-5 parts of zinc oxide; 1-2 parts of stearic acid; 8-12 parts of low temperature resistant plasticizer; 1 to 3 parts of vulcanizing agent; 1-2 parts of accelerator; 2-5 parts of antioxidant; The low plasticizer resistant agent is prepared by the following steps: Adipic acid and 2-propylheptanol are mixed, and then tetrabutyl titanate is added thereto. The mixture is stirred and heated to 180°C. The mixture is stirred at a constant temperature until reflux occurs. Water in the reflux liquid is collected, and then a sample is taken to determine the acid value. The acid value is determined in terms of KOH. When the acid value is ≤0.2 mg / g, the reaction is determined to be complete, and heating is stopped. When the material in the reactor is cooled to 90°C, it is neutralized, washed with water, and allowed to stand for stratification. After the aqueous phase is separated, the crude ester is collected, and then decolorized by vacuum distillation, steam stripping to remove water, and activated carbon filtration to obtain a low-resistance plasticizer.

[0008] Furthermore, the molar ratio of adipic acid to 2-propylheptanol is 1:2.5-3.0.

[0009] Furthermore, the amount of tetrabutyl titanate used is 0.2% to 0.3% of the total mass of adipic acid and 2-propylheptanol.

[0010] Furthermore, the mass fraction of acrylonitrile in the hydrogenated nitrile rubber is 43%.

[0011] Furthermore, the carbon black is one of carbon black N330, carbon black N550 and carbon black N772.

[0012] Furthermore, the vulcanizing agent is 1,4-di-tert-butylperoxyisopropylbenzene.

[0013] Furthermore, the accelerator is one of accelerator TBBS, accelerator DZ and accelerator DPTT.

[0014] Furthermore, the antioxidant is one of antioxidant TMQ and antioxidant 6PPD.

[0015] Furthermore, a method for preparing a super-low temperature resistant hydrogenated nitrile hose rubber material comprises the following steps: S1. Weigh the raw materials according to the above mass parts, heat the internal mixer to 50-55°C, set the speed to 50-60r / min, add hydrogenated nitrile rubber, plasticize for 90s, then add carbon black, zinc oxide, stearic acid and low-temperature resistant plasticizer in sequence, and continue mixing for 4-5min to obtain a rubber compound; S2, transferring the rubber material to an open mixing mill, adding a vulcanizing agent, an accelerator and an antioxidant, and after the rubber material is completely consumed, cutting the rubber material, thinning the rubber material, and then making a triangular package 3 to 5 times, and then unrolling the sheet to obtain a mixed rubber; S3, vulcanizing the mixed rubber, taking out the rubber material after the vulcanization is completed, and naturally cooling it to room temperature to obtain the ultra-low temperature resistant hydrogenated nitrile hose rubber material.

[0016] Furthermore, the vulcanization temperature in S3 is 170-172° C., the vulcanization time is 3 min, and the vulcanization pressure is 10 MPa.

[0017] Beneficial effects of the present invention: The present invention provides a hydrogenated nitrile hose rubber material resistant to ultra-low temperature and a preparation method thereof. After testing, the hydrogenated nitrile hose rubber material prepared by the present invention has excellent ultra-low temperature resistance. The specific principle is as follows: First, the low-temperature resistant plasticizer prepared by the present invention is prepared by dehydration condensation of adipic acid and 2-propyl heptanol, wherein adipic acid provides the acidic part in the plasticizer molecule, and 2-propyl heptanol is a long-chain alcohol (containing 7 carbon atoms). The long-chain structure helps to increase the flexibility of the molecule, which is beneficial to improve the low-temperature resistance of the rubber compound. The long carbon chain of 2-propyl heptanol provides steric hindrance at low temperatures, reduces the close stacking between polymer chains, thereby reducing the glass transition temperature of the rubber compound, so that the rubber hose can still maintain excellent flexibility at low temperatures. At the same time, in the preparation method, the present invention strictly controls the reaction conditions so that the reaction is determined to be complete when the acid value (in terms of KOH) is ≤0.2 mg / g, which can ensure the purity of the plasticizer and reduce the interference of impurities on the low-temperature resistance. In summary, the present invention has reasonable raw material ratios, effective reaction control and strict post-treatment. After testing, the prepared low-temperature resistant plasticizer can significantly improve the low-temperature resistance of the hydrogenated nitrile hose rubber compound. It enables the hose to maintain good flexibility at lower temperatures and reduces the phenomenon of the hose becoming hard and brittle in low temperature environments, thereby extending the service life of the hose and broadening its application range in low temperature environments.

[0018] Then, the present invention selects hydrogenated nitrile rubber with a mass fraction of 43% of acrylonitrile as a matrix. The hydrogenated nitrile rubber itself has good oil resistance, chemical medium resistance and other properties. The control of acrylonitrile content can balance the polarity and flexibility of the rubber. A higher acrylonitrile content makes the rubber have better oil resistance, but reduces its flexibility. In this formula, the hydrogenated nitrile rubber with a mass fraction of 43% not only ensures chemical resistance, but also can work in synergy with other components to provide a basis for ultra-low temperature resistance.

[0019] Finally, the preparation process provided by the present invention optimizes the ultra-low temperature resistance. Specifically, in the vulcanization process of the present invention, the vulcanization conditions are 170-172°C, 3min, and 10MPa. During this vulcanization process, the three-dimensional network structure of the rubber is formed. Strict control of the vulcanization conditions can make the cross-linking density of the rubber reach the optimal state, ensuring that the rubber has good elasticity and toughness at ultra-low temperatures. If the vulcanization temperature is too high or the time is too long, excessive cross-linking may occur, and the rubber may become hard and brittle; if the vulcanization temperature is too low or the time is too short, insufficient cross-linking will occur, and the strength and stability of the rubber at ultra-low temperatures will be affected. After vulcanization, natural cooling in a well-ventilated and uniformly heated environment avoids stress concentration inside the rubber due to sudden cooling or uneven local cooling, thereby improving the performance stability of the rubber in an ultra-low temperature environment.

[0020] In summary, the ultra-low temperature resistant hydrogenated nitrile hose rubber material provided by the present invention has outstanding progress in ultra-low temperature resistance through a special plasticizer structure, a reasonable rubber formula synergy and a precise preparation process, and can maintain good flexibility, strength and stability in an ultra-low temperature environment. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Example 1

[0022] Preparation of low plasticizer resistance: Adipic acid (purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and 2-propylheptanol (98%; purchased from Sinopharm Chemical Reagent Co., Ltd.) were added to the reactor in a molar ratio of 1:2.5, and then tetrabutyl titanate (industrial grade; purchased from Sinopec Catalyst Co., Ltd. Changling Branch) was added thereto in an amount of 0.2% of the total mass of the acid and the alcohol. Stirring was started, the temperature was raised to 180°C, and constant temperature stirring was performed until reflux occurred. Water in the reflux liquid was collected, and then the material in the reactor was sampled to determine the acid value. The acid value was determined in terms of KOH. When the acid value was ≤0.2 mg / g, the reaction was determined to be complete, and heating was stopped. When the material in the reactor was cooled to 90°C, the material in the reactor was neutralized and washed with a sodium hydroxide solution having a mass fraction of 10%, and then the crude ester was collected after standing and stratification, and the aqueous phase was separated. The crude ester was then subjected to reduced pressure distillation to remove excess 2-propylheptanol, and then water was removed by steam stripping, and then decolorized by activated carbon filtration to obtain a low-resistance plasticizer. Example 2

[0023] Preparation of low plasticizer resistance: Adipic acid (purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and 2-propylheptanol (98%; purchased from Sinopharm Chemical Reagent Co., Ltd.) were added to the reactor in a molar ratio of 1:2.8, and then tetrabutyl titanate (industrial grade; purchased from Sinopec Catalyst Co., Ltd. Changling Branch) was added thereto in an amount of 0.3% of the total mass of the acid and the alcohol. Stirring was started, the temperature was raised to 180°C, and constant temperature stirring was performed until reflux occurred. Water in the reflux liquid was collected, and then the material in the reactor was sampled to determine the acid value. The acid value was determined in terms of KOH. When the acid value was ≤0.2 mg / g, the reaction was determined to be complete, and heating was stopped. When the material in the reactor was cooled to 90°C, the material in the reactor was neutralized and washed with a sodium hydroxide solution having a mass fraction of 10%, and then the crude ester was collected after standing and stratification, and the aqueous phase was separated. The crude ester was then subjected to reduced pressure distillation to remove excess 2-propylheptanol, and then water was removed by steam stripping, and then decolorized by activated carbon filtration to obtain a low-resistance plasticizer. Example 3

[0024] Preparation of low plasticizer resistance: Adipic acid (purchased from Shanghai MacLean Biochemical Technology Co., Ltd.) and 2-propylheptanol (98%; purchased from Sinopharm Chemical Reagent Co., Ltd.) were added to the reactor at a molar ratio of 1:3.0, and then tetrabutyl titanate (industrial grade; purchased from Sinopec Catalyst Co., Ltd. Changling Branch) was added thereto at 0.3% of the total mass of the acid and the alcohol, stirring was started, the temperature was raised to 180°C, and constant temperature stirring was performed until reflux occurred, and water in the reflux liquid was collected, and then the material in the reactor was sampled to determine the acid value, and the acid value was determined in terms of KOH. When the acid value was ≤0.2 mg / g, the reaction was determined to be complete, and heating was stopped. When the material in the reactor was cooled to 90°C, the material in the reactor was neutralized and washed with sodium hydroxide solution with a mass fraction of 10%, and then the crude ester was collected after standing and stratification, and the aqueous phase was separated. The crude ester was then subjected to reduced pressure distillation to remove excess 2-propylheptanol, and then water was removed by steam stripping, and then decolorized by activated carbon filtration to obtain a low-resistance plasticizer. Example 4

[0025] Preparation of ultra-low temperature resistant hydrogenated nitrile hose compound: First, the ultra-low temperature resistant hydrogenated nitrile hose rubber material includes the following raw materials by weight: 100 parts of hydrogenated nitrile rubber; 65 parts of carbon black; 2 parts of zinc oxide; 1 part of stearic acid; 8 parts of the low temperature resistant plasticizer prepared in Example 1; 1 part of vulcanizing agent; 1 part of accelerator; 2 parts of antioxidant.

[0026] Then, the preparation method of the ultra-low temperature resistant hydrogenated nitrile hose rubber material comprises the following steps: S1. Before starting mixing, ensure that the internal mixer and the open mixer are in good operating condition, and conduct strict quality inspection on all kinds of raw materials to ensure that they meet the test requirements; S2. Weigh each raw material according to the above mass parts and officially start the mixing process. First, accurately set the initial temperature of the mixing chamber of the internal mixer to 50°C, and stably control the rotor speed at 50r / min. Then, add hydrogenated nitrile rubber (Therban4367; acrylonitrile mass fraction of 43%; Mooney viscosity 61; purchased from LANXESS Chemical Co., Ltd., Germany). The hydrogenated nitrile rubber is plasticized in the internal mixer for 90s. During this process, always pay attention to the plasticization state of the hydrogenated nitrile rubber and check the hydrogenated nitrile rubber through the observation window on the internal mixer. After the plasticization is completed, carbon black (carbon black N330; iodine absorption value 82g / kg; purchased from Hebei Jingxian Xinyuan Rubber Chemical Co., Ltd.), zinc oxide (analytical grade; purchased from Shanghai MacLean Biochemical Technology Co., Ltd.), stearic acid (analytical grade; purchased from Sinopharm Chemical Reagent Co., Ltd.) and the low-temperature resistant plasticizer prepared in Example 1 are added in sequence. The addition should be slow and uniform to avoid agglomeration of materials due to a large amount of one-time addition, which affects the mixing effect. Then, the mixing is continued for 4 minutes to ensure that the components of the rubber are fully mixed; S3. After the rubber compound in the internal mixer is evenly mixed, the rubber compound is quickly transferred to the open mixer. On the open mixer, the vulcanizer (1,4-di-tert-butyl peroxyisopropylbenzene; purchased from Luxing Rubber Additive Co., Ltd. in Aksu), the accelerator (accelerator TBBS; purchased from Sinopharm Chemical Reagent Co., Ltd.) and the antioxidant (anti-aging agent TMQ; purchased from Ningbo Aikemu New Materials Co., Ltd.) are carefully added. The addition process should be slow to prevent the flying of materials from causing waste and pollution. After the rubber compound is completely consumed, the operator holds a cutting knife and performs standardized rubber tapping operations on both sides of the rubber compound three times to facilitate the discharge of internal gas in the rubber compound. Then, the roller spacing is finely adjusted to 0.48mm, and a thin pass operation is performed. During the thin pass, attention should be paid to the passing of the rubber compound to avoid jamming. Then, the triangular package is continuously made three times to further remove the air in the rubber compound and refine the dispersion of the rubber compound. S4. After completing the above steps, adjust the roller distance of the mixing mill to 2 mm, so that the rubber material can be rolled and exhausted smoothly between the rollers. During the process, pay attention to the compactness and flatness of the rubber roll to ensure that the gas is fully discharged, and finally unroll the sheet to obtain the mixed rubber; S5. After the rubber mix is ​​prepared, it is immediately placed in the vulcanization equipment for vulcanization. The vulcanization conditions are strictly controlled at 170°C, the vulcanization time is controlled at 3 minutes, and the vulcanization pressure is maintained at 10MPa. During the vulcanization process, the temperature and pressure parameters of the vulcanization equipment must be monitored in real time to ensure that the vulcanization process is stable. After the vulcanization is completed, the rubber is quickly taken out and placed in a well-ventilated and temperature-uniform environment to cool naturally to room temperature to avoid damage to the rubber performance due to sudden cooling or uneven local cooling. Finally, a hydrogenated nitrile hose rubber with excellent ultra-low temperature resistance is obtained. Example 5

[0027] Preparation of ultra-low temperature resistant hydrogenated nitrile hose compound: First, the ultra-low temperature resistant hydrogenated nitrile hose rubber material includes the following raw materials by weight: 100 parts of hydrogenated nitrile rubber; Carbon black 70 parts; 4 parts of zinc oxide; 1 part of stearic acid; 10 parts of the low temperature resistant plasticizer prepared in Example 2; 1 part of vulcanizing agent; 1 part of accelerator; 4 parts of antioxidant.

[0028] Then, the preparation method of the ultra-low temperature resistant hydrogenated nitrile hose rubber material comprises the following steps: S1. Before starting mixing, ensure that the internal mixer and the open mixer are in good operating condition, and conduct strict quality inspection on all kinds of raw materials to ensure that they meet the test requirements; S2. Weigh each raw material according to the above mass parts and officially start the mixing process. First, accurately set the initial temperature of the mixing chamber of the internal mixer to 55°C, and stably control the rotor speed at 60r / min. Then, add hydrogenated nitrile rubber (Therban 4367; acrylonitrile mass fraction of 43%; Mooney viscosity 61; purchased from LANXESS Chemical Co., Ltd., Germany). The hydrogenated nitrile rubber is plasticized in the internal mixer for 90s. During this process, always pay attention to the plasticization state of the hydrogenated nitrile rubber and check the hydrogenated nitrile rubber through the observation window on the internal mixer. After the plasticization is completed, carbon black (carbon black N550; iodine absorption value 43g / kg; purchased from Hebei Jingxian Xinyuan Rubber Chemical Co., Ltd.), zinc oxide (analytical grade; purchased from Shanghai MacLean Biochemical Technology Co., Ltd.), stearic acid (analytical grade; purchased from Sinopharm Chemical Reagent Co., Ltd.) and the low-temperature resistant plasticizer prepared in Example 2 are added in sequence. The addition should be slow and uniform to avoid agglomeration of materials due to a large amount of one-time addition, which affects the mixing effect. Then continue mixing for 5 minutes to ensure that the components of the rubber are fully mixed; S3. After the rubber compound in the internal mixer is evenly mixed, quickly transfer the rubber compound to the open mixer. Carefully add the vulcanizer (1,4-di-tert-butyl peroxyisopropylbenzene; purchased from Luxing Rubber Additive Co., Ltd., Aksu), accelerator (accelerator DZ; purchased from Sinopharm Chemical Reagent Co., Ltd.) and antioxidant (antioxidant 6PPD; purchased from Ningbo Aikemu New Materials Co., Ltd.) to the open mixer. The addition process should be slow to prevent the material from flying and causing waste and pollution. After the rubber compound is completely eaten, the operator holds a cutting knife and performs standardized rubber tapping operations on both sides of the rubber compound three times to facilitate the discharge of gas inside the rubber compound. Then, finely adjust the roller distance to 0.5mm and perform thin-pass operation. During thin-pass operation, pay attention to the passing of the rubber compound to avoid jamming. Then, make triangle packages five times in a row to further remove the air in the rubber compound and refine the dispersion of the rubber compound. S4. After completing the above steps, adjust the roller distance of the mixing mill to 2 mm, so that the rubber material can be rolled and exhausted smoothly between the rollers. During the process, pay attention to the compactness and flatness of the rubber roll to ensure that the gas is fully discharged, and finally unroll the sheet to obtain the mixed rubber; S5. After the rubber mix is ​​prepared, it is immediately placed in the vulcanization equipment for vulcanization. The vulcanization conditions are strictly controlled at 172°C, the vulcanization time is controlled at 3 minutes, and the vulcanization pressure is maintained at 10MPa. During the vulcanization process, the temperature and pressure parameters of the vulcanization equipment must be monitored in real time to ensure that the vulcanization process is stable. After the vulcanization is completed, the rubber is quickly taken out and placed in a well-ventilated and temperature-uniform environment to cool naturally to room temperature to avoid damage to the rubber performance due to sudden cooling or uneven local cooling. Finally, a hydrogenated nitrile hose rubber with excellent ultra-low temperature resistance is obtained. Example 6

[0029] Preparation of ultra-low temperature resistant hydrogenated nitrile hose compound: First, the ultra-low temperature resistant hydrogenated nitrile hose rubber material includes the following raw materials by weight: 100 parts of hydrogenated nitrile rubber; 80 parts of carbon black; Zinc oxide 5 parts; 2 parts of stearic acid; 12 parts of the low temperature resistant plasticizer prepared in Example 3; 3 parts of vulcanizing agent; 2 parts of accelerator; 5 parts of antioxidant.

[0030] Then, the preparation method of the ultra-low temperature resistant hydrogenated nitrile hose rubber material comprises the following steps: S1. Before starting mixing, ensure that the internal mixer and the open mixer are in good operating condition, and conduct strict quality inspection on all kinds of raw materials to ensure that they meet the test requirements; S2. Weigh each raw material according to the above mass parts and officially start the mixing process. First, accurately set the initial temperature of the mixing chamber of the internal mixer to 55°C, and stably control the rotor speed at 60r / min. Then, add hydrogenated nitrile rubber (Therban 4367; acrylonitrile mass fraction of 43%; Mooney viscosity 61; purchased from LANXESS Chemical Co., Ltd., Germany). The hydrogenated nitrile rubber is plasticized in the internal mixer for 90s. During this process, always pay attention to the plasticization state of the hydrogenated nitrile rubber and check the hydrogenated nitrile rubber through the observation window on the internal mixer. After the plasticization is completed, carbon black (carbon black N772; iodine absorption value 32g / kg; purchased from Hebei Jingxian Xinyuan Rubber Chemical Co., Ltd.), zinc oxide (analytical grade; purchased from Shanghai MacLean Biochemical Technology Co., Ltd.), stearic acid (analytical grade; purchased from Sinopharm Chemical Reagent Co., Ltd.) and the low-temperature resistant plasticizer prepared in Example 3 are added in sequence. The addition should be slow and uniform to avoid agglomeration of materials due to a large amount of one-time addition, which affects the mixing effect. Then continue mixing for 5 minutes to ensure that the components of the rubber are fully mixed; S3. After the rubber compound in the internal mixer is evenly mixed, the rubber compound is quickly transferred to the open mixer. On the open mixer, the vulcanizer (1,4-di-tert-butyl peroxyisopropylbenzene; purchased from Luxing Rubber Additive Co., Ltd. in Aksu), the accelerator (accelerator DPTT; purchased from Sinopharm Chemical Reagent Co., Ltd.) and the antioxidant (antioxidant 6PPD; purchased from Ningbo Aikemu New Materials Co., Ltd.) are carefully added. The addition process should be slow to prevent the material from flying and causing waste and pollution. After the rubber compound is completely consumed, the operator holds a cutting knife and performs standardized rubber tapping operations 3 times on both sides of the rubber compound to facilitate the discharge of internal gas in the rubber compound. Then, the roller spacing is finely adjusted to 0.5mm, and a thin pass operation is performed. During the thin pass, attention should be paid to the passing of the rubber compound to avoid jamming. Then, the triangular package is continuously made 5 times to further remove the air in the rubber compound and refine the dispersion degree of the rubber compound. S4. After completing the above steps, adjust the roller distance of the mixing mill to 2 mm, so that the rubber material can be rolled and exhausted smoothly between the rollers. During the process, pay attention to the compactness and flatness of the rubber roll to ensure that the gas is fully discharged, and finally unroll the sheet to obtain the mixed rubber; S5. After the rubber mix is ​​prepared, it is immediately placed in the vulcanization equipment for vulcanization. The vulcanization conditions are strictly controlled at 172°C, the vulcanization time is controlled at 3 minutes, and the vulcanization pressure is maintained at 10MPa. During the vulcanization process, the temperature and pressure parameters of the vulcanization equipment must be monitored in real time to ensure that the vulcanization process is stable. After the vulcanization is completed, the rubber is quickly taken out and placed in a well-ventilated and temperature-uniform environment to cool naturally to room temperature to avoid damage to the rubber performance due to sudden cooling or uneven local cooling. Finally, a hydrogenated nitrile hose rubber with excellent ultra-low temperature resistance is obtained.

[0031] Comparative Example 1 Comparative Example 1 is the control group of Example 5, in which the low-resistance plasticizer prepared in Raw Material Example 2 in Example 5 is replaced with dioctyl phthalate, and the other raw materials, raw material amounts and preparation methods remain unchanged, and finally a hydrogenated nitrile hose rubber compound is obtained.

[0032] Comparative Example 2 Comparative Example 1 is the control group of Example 5, in which the low-resistance plasticizer prepared in Raw Material Example 2 in Example 5 is replaced with dibutyl phthalate, and the other raw materials, raw material amounts and preparation methods remain unchanged, and finally a hydrogenated nitrile hose rubber compound is obtained.

[0033] Test Example 1 The performance test of the hydrogenated nitrile hose rubber materials prepared in Examples 4 to 6 and Comparative Examples 1 to 2 was carried out, and the test standards and test results are shown in Table 1 below: Table 1 Test standards and test results ; It can be seen from Table 1 that the hydrogenated nitrile hose rubber materials prepared in Examples 4 to 6 of the present invention have excellent mechanical properties, aging resistance and low temperature resistance, wherein the low temperature brittle temperature reaches -57 to (-58) °C.

[0034] It should be noted that, in this article, terms such as "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or equipment that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or equipment.

Claims

1. A super low temperature resistant hydrogenated nitrile hose rubber material, characterized in that: Including the following raw materials by weight: 100 parts of hydrogenated nitrile rubber; 65-80 parts of carbon black; 2-5 parts of zinc oxide; 1-2 parts of stearic acid; 8-12 parts of low temperature resistant plasticizer; 1 to 3 parts of vulcanizing agent; 1-2 parts of accelerator; 2-5 parts of antioxidant; The low plasticizer resistant agent is prepared by the following steps: Adipic acid and 2-propylheptanol are mixed, and then tetrabutyl titanate is added thereto. The mixture is stirred and heated to 180°C. The mixture is stirred at a constant temperature until reflux occurs. Water in the reflux liquid is collected, and then a sample is taken to determine the acid value. The acid value is determined in terms of KOH. When the acid value is ≤0.2 mg / g, the reaction is determined to be complete, and heating is stopped. When the material in the reactor is cooled to 90°C, it is neutralized, washed with water, and allowed to stand for stratification. After the aqueous phase is separated, the crude ester is collected, and then decolorized by vacuum distillation, steam stripping to remove water, and activated carbon filtration to obtain a low-resistance plasticizer.

2. The ultra-low temperature resistant hydrogenated nitrile hose rubber material according to claim 1, characterized in that: The molar ratio of the adipic acid to the 2-propylheptanol is 1:2.5-3.

0.

3. The ultra-low temperature resistant hydrogenated nitrile hose rubber material according to claim 1, characterized in that: The amount of tetrabutyl titanate used is 0.2% to 0.3% of the total mass of adipic acid and 2-propylheptanol.

4. The ultra-low temperature resistant hydrogenated nitrile hose rubber material according to claim 1, characterized in that: The mass fraction of acrylonitrile in the hydrogenated nitrile rubber is 43%.

5. The ultra-low temperature resistant hydrogenated nitrile hose rubber material according to claim 1, characterized in that: The carbon black is one of carbon black N330, carbon black N550 and carbon black N772.

6. The ultra-low temperature resistant hydrogenated nitrile hose rubber material according to claim 1, characterized in that: The vulcanizing agent is 1,4-di-tert-butylperoxyisopropylbenzene.

7. The ultra-low temperature resistant hydrogenated nitrile hose rubber material according to claim 1, characterized in that: The accelerator is one of accelerator TBBS, accelerator DZ and accelerator DPTT.

8. The ultra-low temperature resistant hydrogenated nitrile hose rubber material according to claim 1, characterized in that: The antioxidant is one of antioxidant TMQ and antioxidant 6PPD.

9. A method for preparing a super low temperature resistant hydrogenated nitrile hose rubber compound according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Weigh each raw material according to the above mass parts, heat the internal mixer to 50-55°C, set the speed to 50-60r / min, add hydrogenated nitrile rubber, plasticize for 90s, then add carbon black, zinc oxide, stearic acid and low-temperature resistant plasticizer in sequence, and continue mixing for 4-5min to obtain a rubber compound; S2, transferring the rubber material to an open mixing mill, adding a vulcanizing agent, an accelerator and an antioxidant, and after the rubber material is completely consumed, cutting the rubber material, thinning the rubber material, and then making a triangular package 3 to 5 times, and then unrolling the sheet to obtain a mixed rubber; S3, vulcanizing the mixed rubber, taking out the rubber material after the vulcanization is completed, and naturally cooling it to room temperature to obtain the ultra-low temperature resistant hydrogenated nitrile hose rubber material.

10. The method for preparing a super low temperature resistant hydrogenated nitrile hose rubber material according to claim 9, characterized in that: The vulcanization temperature in S3 is 170-172° C., the vulcanization time is 3 min, and the vulcanization pressure is 10 MPa.