Hydrogenated nitrile rubber material with low methane permeability and preparation method and application thereof

Abstract

The invention belongs to the technical field of mining, gathering and transportation, and discloses a hydrogenated nitrile rubber material with low methane permeability and a preparation method and application thereof. The composition comprises hydrogenated butadiene-acrylonitrile rubber, activated zinc oxide, an anti-aging agent, stearic acid (SA), reinforcing carbon black, two-dimensional nanoparticles, a cross-linking agent and a vulcanizing aid. The hydrogenated butadiene-acrylonitrile rubber material is prepared by banburying and mixing the raw material components. Wherein the two-dimensional nanoparticles need to be calendered for multiple times, so that the two-dimensional nanoparticles achieve a better orientation effect in a rubber matrix. The permeability coefficient of methane gas in rubber can be greatly reduced, the gathering effect of methane in a closed place is greatly delayed, and the operation safety is improved.

Description

Technical Field

[0001] The present invention belongs to the field of mining and gathering technology, and the present invention relates to a hydrogenated nitrile rubber material with low methane permeability, a preparation method and application thereof, and a high-temperature sealing material that can be widely used in the field of high-pressure or ultra-high-pressure natural gas mining and gathering. Background Art

[0002] In recent years, in order to improve my country's natural gas production, supply, storage and sales system, and enhance the gas storage peak regulation and emergency guarantee capabilities of the natural gas pipeline network, my country has accelerated the construction of supporting gas storage facilities, and the gas storage capacity has been greatly improved. The design pressure of gas storage facilities is generally high, up to 30MPa or more; at the same time, methane is highly flammable and explosive. Once it leaks or is improperly stored, it will bring huge safety hazards. Therefore, during the operation of gas storage facilities, the sealing performance requirements of pipelines, valves, containers and other parts are relatively high. The suspension of production and work due to sealing failure and leakage will seriously affect the stable operation of the gas storage facility.

[0003] Pipeline and valve seals are mostly made of rubber materials, and methane gas has a high permeability in rubber materials. Conventional material reinforcement methods and production processes (such as those disclosed in patents CN106519363A and CN109021342A_) usually use one-dimensional nanofillers, such as carbon nanotubes, carbon fibers, aramid and other materials to reinforce the mechanical properties of materials, which greatly improves the heat and pressure resistance of products, but less involves improving the gas barrier properties of rubber. For high-pressure or ultra-high-pressure pipelines, even if the sealing part looks good, methane gas can still slowly penetrate through the sealing part and accumulate on the outside. If the pipelines and equipment are in a closed place, the concentration of methane gas will gradually increase over time, posing a high safety risk. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the present invention provides a hydrogenated nitrile rubber material with low methane permeability and a preparation method and application thereof, which can greatly reduce the permeability coefficient of methane gas in rubber, significantly delay the accumulation effect of methane in closed places, and improve operational safety.

[0005] The above object of the present invention is achieved through the following technical solutions:

[0006] A hydrogenated nitrile rubber material with low methane permeability comprises hydrogenated nitrile rubber, active zinc oxide, an antioxidant, stearic acid (SA), reinforcing carbon black, two-dimensional nanoparticles, a crosslinking agent and a vulcanization aid.

[0007] Furthermore, the hydrogenated nitrile rubber is a product with a medium to high acrylonitrile content (≥36%), preferably any one of Zetpol HNBR 1010, Zetpol HNBR 0020, Therban 3907 and Therban 4309.

[0008] Furthermore, the antioxidant is any one of antioxidant 445, antioxidant MBZ, antioxidant RD, or a combination of two or more thereof.

[0009] Furthermore, the carbon black is a small particle size, high reinforcement carbon black, preferably any one of N220, N234, N330, and N356.

[0010] Furthermore, the two-dimensional nanoparticles are inorganic particles with a two-dimensional lamellar structure, preferably any one of graphite, kaolin, talc, montmorillonite and hydrotalcite.

[0011] Further, the crosslinking agent is any one of diisopropylbenzene peroxide (DCP), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DCP), 2,4-di-tert-butylperoxide isopropylbenzene (BIBP), or a combination of two or more thereof. The crosslinking aid is preferably triallyl isocyanurate (TAIC).

[0012] Furthermore, the components of the above hydrogenated nitrile rubber material are calculated in parts by weight, specifically: 90-110 parts of hydrogenated nitrile rubber, 4-6 parts of active zinc oxide, 1-4 parts of antioxidant, 1-2 parts of stearic acid (SA), 20-70 parts of reinforcing carbon black, 5-20 parts of two-dimensional nanoparticles, 1-5 parts of crosslinking agent, and 1-5 parts of vulcanization aid.

[0013] The present invention also requests protection for a method for preparing the above-mentioned hydrogenated nitrile rubber material, wherein the raw material components are kneaded and mixed to obtain the hydrogenated nitrile rubber material; wherein the two-dimensional nanoparticles need to be subjected to "multiple calendering" to achieve a better orientation effect in the rubber matrix.

[0014] Furthermore, the preparation method of hydrogenated nitrile rubber material is specifically as follows: each raw material component is subjected to banburying and mixing to obtain hydrogenated nitrile rubber mixture; the rubber mixture is calendered several times in a calender with a roller distance of 0.5-2mm, the calendering times are not less than 10 times, the rubber sheet is not wrapped with a roller or a pack during the calendering process, and the calendering process is continued after the rubber sheet is folded in half. The orientation behavior of the two-dimensional nanofiller in the rubber matrix is ​​ensured by calendering several times.

[0015] The present invention also seeks to protect the use of the hydrogenated nitrile rubber material prepared by the above preparation method as a high-temperature sealing material used in the field of high-pressure or ultra-high-pressure natural gas exploitation and gathering and transportation.

[0016] The beneficial effects of the present invention compared with the prior art are:

[0017] The present invention provides a hydrogenated nitrile rubber material with low methane permeability, a preparation method and an application thereof. In the material provided by the present invention, hydrogenated nitrile rubber is used as the main material, and the natural gas (CH 4 The solubility parameters and permeability coefficient of natural gas in rubber are calculated. At the same time, by introducing two-dimensional nanomaterials and inducing their orientation, the permeability coefficient of natural gas is further reduced. This material is used in the sealing parts of natural gas gathering and transportation pipelines, especially high-pressure pipelines, which greatly reduces the risk of methane gas accumulation due to penetration in a closed environment. DETAILED DESCRIPTION

[0018] The present invention is described in detail below by specific examples, but the protection scope of the present invention is not limited. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and the experimental equipment, materials, reagents, etc. used can be obtained from commercial channels.

[0019] A hydrogenated nitrile rubber material with low methane permeability comprises hydrogenated nitrile rubber, active zinc oxide, an antioxidant, stearic acid (SA), reinforcing carbon black, two-dimensional nanoparticles, a crosslinking agent and a vulcanization aid.

[0020] The hydrogenated nitrile rubber is a product with a medium to high acrylonitrile content (≥36%), preferably any one of Zetpol HNBR1010, Zetpol HNBR 0020, Therban 3907 and Therban 4309.

[0021] The antioxidant is any one of antioxidant 445, antioxidant MBZ, and antioxidant RD, or a combination of two or more thereof.

[0022] The carbon black is a small particle size, high reinforcement carbon black, preferably any one of N220, N234, N330, and N356.

[0023] The two-dimensional nanoparticles are inorganic particles with a two-dimensional lamellar structure, preferably any one of graphite, kaolin, talc, montmorillonite and hydrotalcite.

[0024] The crosslinking agent is any one of diisopropylbenzene peroxide (DCP), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DCP), 2,4-di-tert-butylperoxide isopropylbenzene (BIBP), or a combination of two or more thereof. The crosslinking aid is preferably triallyl isocyanurate (TAIC).

[0025] The preparation method of hydrogenated nitrile rubber material comprises the following steps: mixing and kneading the raw material components uniformly to obtain hydrogenated nitrile rubber mixture; calendering the rubber mixture multiple times in a calender with a roller distance of 0.5-2 mm, the calendering times being not less than 10 times, the rubber sheet is not wrapped with rollers or packages during the calendering process, and the calendering process is continued after the rubber sheet is folded in half. The orientation behavior of the two-dimensional nanofiller in the rubber matrix is ​​ensured by multiple calendering.

[0026] The following is further described in detail in conjunction with Examples 1-4 and Comparative Examples 1-3, but the present invention is not limited to the following examples.

[0027] Example 1

[0028] The main material is hydrogenated nitrile rubber produced by Japan Zeon Co., Ltd., 100 parts (by weight), zinc oxide 5 parts, stearic acid 1 part, antioxidant MBZ, 445 combination, 1 part, 1.5 parts respectively; carbon black N330 60 parts; nano filler talcum powder 5 parts; vulcanization system DCP / TAIC, the amount is 2.5 parts / 4 parts respectively. The specific formula is shown in Table 1.

[0029] The preparation process is as follows: weigh the materials, use a double-roller open mill to plasticize the raw rubber for 3 minutes, add processing aids, antioxidants, reinforcing systems, cross-linking agents, etc. in sequence, mix evenly, make thin and smooth, make triangle packages 5 to 6 times, adjust the roller distance to 3mm for sheeting. After the mixed rubber is left to stand for 16 hours, it is calendered for no less than 10 times in a calender with a roller distance of 0.5-2mm. During the calendering process, the rubber sheet is not wrapped with rollers or packages. After one calendering, the film is folded in half and continued.

[0030] Example 2

[0031] The main material is hydrogenated nitrile rubber produced by Japan Zeon Co., Ltd., 100 parts (by weight), zinc oxide 5 parts, stearic acid 1 part, antioxidant MBZ, 445 combination, respectively 1 part, 1.5 parts; carbon black N330 60 parts; nano filler talcum powder 10 parts; vulcanization system DCP / TAIC, the amount is 2.5 parts / 4 parts. The specific formula is shown in Table 1.

[0032] The preparation process is as follows: weigh the materials, use a double-roller open mill to plasticize the raw rubber for 3 minutes, add processing aids, antioxidants, reinforcing systems, cross-linking agents, etc. in sequence, mix evenly, make thin and smooth, make triangle packages 5 to 6 times, adjust the roller distance to 3mm for sheeting. After the mixed rubber is left to stand for 16 hours, it is calendered for no less than 10 times in a calender with a roller distance of 0.5-2mm. During the calendering process, the rubber sheet is not wrapped with rollers or packages. After one calendering, the film is folded in half and continued.

[0033] Example 3

[0034] The main material is hydrogenated nitrile rubber produced by Japan Zeon Co., Ltd., 100 parts (by weight), zinc oxide 5 parts, stearic acid 1 part, antioxidant MBZ, 445 combination, respectively 1 part, 1.5 parts; carbon black N330 60 parts; nano filler talcum powder 15 parts; vulcanization system DCP / TAIC, the amount is 2.5 parts / 4 parts. The specific formula is shown in Table 1.

[0035] The preparation process is as follows: weigh the materials, use a double-roller open mill to plasticize the raw rubber for 3 minutes, add processing aids, antioxidants, reinforcing systems, cross-linking agents, etc. in sequence, mix evenly, make thin and smooth, make triangle packages 5 to 6 times, adjust the roller distance to 3mm for sheeting. After the mixed rubber is left to stand for 16 hours, it is calendered for no less than 10 times in a calender with a roller distance of 0.5-2mm. During the calendering process, the rubber sheet is not wrapped with rollers or packages. After one calendering, the film is folded in half and continued.

[0036] Example 4

[0037] The main material is hydrogenated nitrile rubber produced by Japan Zeon Co., Ltd., 100 parts (by weight), zinc oxide 5 parts, stearic acid 1 part, antioxidant MBZ, 445 combination, 1 part, 1.5 parts respectively; carbon black N330 60 parts; nano filler talcum powder 20 parts; vulcanization system DCP / TAIC, the amount is 2.5 parts / 4 parts respectively. The specific formula is shown in Table 1.

[0038] The preparation process is as follows: weigh the materials, use a double-roller open mill to plasticize the raw rubber for 3 minutes, add processing aids, antioxidants, reinforcing systems, cross-linking agents, etc. in sequence, mix evenly, make thin and smooth, make triangle packages 5 to 6 times, adjust the roller distance to 3mm for sheeting. After the mixed rubber is left to stand for 16 hours, it is calendered for no less than 10 times in a calender with a roller distance of 0.5-2mm. During the calendering process, the rubber sheet is not wrapped with rollers or packages. After one calendering, the film is folded in half and continued.

[0039] Comparative Example 1

[0040] Hydrogenated nitrile rubber (Zetpol HNBR 4310) produced by Zeon Co., Ltd. of Japan is used as the main material, 100 parts (by weight), zinc oxide 5 parts, stearic acid 1 part, antioxidant MBZ, 445 combination, respectively 1 part, 1.5 parts; carbon black N330 60 parts; vulcanization system DCP / TAIC, the amount is 2.5 parts / 4 parts. The specific formula is shown in Table 1.

[0041] The preparation process is as follows: weigh the materials, use a double-roller open mill to plasticize the raw rubber for 3 minutes, add processing aids, antioxidants, reinforcing systems, cross-linking agents, etc. in sequence, mix evenly, make thin passes, make triangle packages 5 to 6 times, and cut into sheets. The mixed rubber is vulcanized on a flat vulcanizer.

[0042] Comparative Example 2

[0043] The main material is hydrogenated nitrile rubber produced by Japan Zeon Co., Ltd., 100 parts (by weight), zinc oxide 5 parts, stearic acid 1 part, antioxidant MBZ, 445 combination, 1 part, 1.5 parts respectively; carbon black N330 60 parts; nano filler talcum powder 5 parts; vulcanization system DCP / TAIC, the amount is 2.5 parts / 4 parts respectively. The specific formula is shown in Table 1.

[0044] The preparation process is as follows: weigh the materials, use a double-roller open mill to plasticize the raw rubber for 3 minutes, add processing aids, antioxidants, reinforcing systems, cross-linking agents, etc. in sequence, mix evenly, make thin passes, make triangle packages 5 to 6 times, and cut into sheets. The mixed rubber is vulcanized on a flat vulcanizer.

[0045] Comparative Example 3

[0046] Hydrogenated nitrile rubber (Zetpol HNBR 1010) produced by Zeon Co., Ltd. of Japan is used as the main material, 100 parts (by weight), zinc oxide 5 parts, stearic acid 1 part, antioxidant MBZ, 445 combination, respectively 1 part, 1.5 parts; carbon black N330 60 parts; vulcanization system DCP / TAIC, the amount is 2.5 parts / 4 parts. The specific formula is shown in Table 1.

[0047] The preparation process is as follows: weigh the materials, use a double-roller open mill to plasticize the raw rubber for 3 minutes, add processing aids, antioxidants, reinforcing systems, cross-linking agents, etc. in sequence, mix evenly, make thin passes, make triangle packages 5 to 6 times, and cut into sheets. The mixed rubber is vulcanized on a flat vulcanizer.

[0048] Table 1 Formula table of embodiments and comparative examples

[0049]

[0050]

[0051] The materials prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were used to prepare Φ70×3 mm circular sheets, and the gas permeation rates of methane gas in different vulcanized samples were tested according to the standard "ISO 2782-1 Determination of gas permeability of vulcanized or thermoplastic rubber", and the test conditions are shown in Table 2. At the same time, the standard test pieces were vulcanized to test the mechanical properties of the materials.

[0052] Table 2 Permeability coefficient test conditions

[0053] Test medium Test temperature Test pressure <![CDATA[100%CH 4 ]]> 50℃ 15.0MPa

[0054] The methane permeability coefficients of the circular thin sheet samples of Examples 1 to 4 and Comparative Examples 1 to 3 are as follows:

[0055] Table 3 Sample performance table

[0056]

[0057]

[0058] Comparing Comparative Example 1 and Comparative Example 3, it can be seen that the Zetpol HNBR 1010 material with high acrylonitrile content has higher strength and hardness, which is more conducive to achieving high-temperature and high-pressure oil and gas sealing. More importantly, the methane gas permeability coefficient of the Zetpol HNBR 4310 material with low acrylonitrile content (Comparative Example 1) is reduced by about half, which is very beneficial in the case of high-pressure gas sealing rings.

[0059] Compared with Comparative Examples 2 and 3, the addition of two-dimensional nanofillers slightly increases the hardness and strength of the material, and reduces the material permeability coefficient, which is helpful to achieve high-pressure gas sealing. At the same time, it should be noted that this improvement has not achieved obvious results.

[0060] Comparing Comparative Example 2 with Example 1, multiple calendering processes can significantly reduce the methane gas permeability coefficient, while improving the material strength and elongation at break. This is because the calendering process used in the example greatly improves the orientation of the nanofiller in the rubber matrix, and has a barrier effect on the diffusion of gas in the rubber matrix. Comparing Comparative Example 2 with Examples 1-4, the methane permeability coefficient of the material is the lowest when 10 and 15 parts of nanofiller are added, and the effect is not good when 20 parts are added, which should be related to the excessive content of nanofiller and poor dispersion. Comparing Example 4 with Comparative Example 3, by introducing nanofillers and adopting multiple calendering processes, the gas permeability coefficient of the material is reduced by more than 8 times. This means that under the same service environment, using the rubber material of the present invention, the time for gas to gather to the explosion limit can be extended by more than 8 times, greatly improving operational safety.

[0061] The above-described embodiments are only preferred embodiments of the present invention, but not all feasible embodiments of the present invention. For those skilled in the art, any obvious changes made thereto without departing from the principles and spirit of the present invention should be considered to be included in the scope of protection of the claims of the present invention.

Claims

1. A hydrogenated nitrile rubber material with low methane permeability, characterized in that: The raw material components include hydrogenated nitrile rubber, active zinc oxide, antioxidant, stearic acid, reinforcing carbon black, two-dimensional nanoparticles, crosslinking agent, and vulcanization accelerator; The components are calculated by weight, including 90-110 parts of hydrogenated nitrile rubber, 4-6 parts of active zinc oxide, 1-4 parts of antioxidant, 1-2 parts of stearic acid, 20-70 parts of reinforcing carbon black, 5-20 parts of two-dimensional nanoparticles, 1-5 parts of crosslinking agent and 1-5 parts of vulcanization aid.

2. A hydrogenated nitrile rubber material with low methane permeability as claimed in claim 1, characterized in that: The two-dimensional nanoparticles are inorganic particles with a two-dimensional layer structure.

3. A hydrogenated nitrile rubber material with low methane permeability as claimed in claim 1, characterized in that: The crosslinking agent is any one of dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (bis(2,5-dimethyl)hexane), and 2,4-di-tert-butylperoxide isopropylbenzene, or a combination of two or more thereof.

4. A hydrogenated nitrile rubber material with low methane permeability as claimed in claim 1, characterized in that: The two-dimensional nanoparticles are any one of graphite, kaolin, talc, montmorillonite and hydrotalcite.

5. A method for preparing a hydrogenated nitrile rubber material with low methane permeability as claimed in any one of claims 1 to 4, characterized in that: The raw material components are kneaded and mixed to obtain hydrogenated nitrile rubber material; the two-dimensional nanoparticles need to be oriented in the rubber matrix through multiple calendering.

6. A method for preparing a hydrogenated nitrile rubber material with low methane permeability as claimed in claim 5, characterized in that: The raw material components are mixed and kneaded uniformly to obtain a hydrogenated nitrile rubber mixture; the rubber mixture is calendered several times in a calender with a roller spacing.

7. A method for preparing a hydrogenated nitrile rubber material with low methane permeability as claimed in claim 6, characterized in that: The roller distance of the calender is 0.5-2mm.

8. A method for preparing a hydrogenated nitrile rubber material with low methane permeability as claimed in claim 6, characterized in that: The calendering times shall not be less than 10 times.

9. A method for preparing a hydrogenated nitrile rubber material with low methane permeability as claimed in claim 6, characterized in that: During the calendering process, the film is not rolled or packaged, and the process continues after the film is folded in half.

10. Use of the hydrogenated nitrile rubber material prepared by the preparation method according to any one of claims 6 to 9 as a high-temperature sealing material for high-pressure or ultra-high-pressure natural gas exploitation and gathering and transportation.

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