Synthetic rubber material, method for producing the same, and use thereof

Abstract

The application discloses a synthetic rubber material and a preparation method and application thereof, and relates to the technical field of rubber materials.The synthetic rubber material comprises the following components in parts by weight: 100 parts of hydrogenated nitrile rubber, 2-3 parts of anti-aging agent, 50-100 parts of reinforcing filler, 5-15 parts of plasticizer, 3-5 parts of vulcanizing agent, and 2-3 parts of vulcanization aid; the reinforcing filler is a mixture of carbon material, fumed silica and calcium silicate, and the carbon material is at least one of carbon black and carbon nanotube.The hydrogenated nitrile rubber material prepared from the above synthetic rubber material has good corrosion resistance, the hydrogenated nitrile rubber material with a metal skeleton prepared from the above synthetic rubber material has a relatively high service life, and the adhesion strength retention between the metal skeleton and the hydrogenated nitrile rubber material is relatively high.

Description

Technical Field

[0001] This invention relates to the field of synthetic rubber materials technology, and in particular to a synthetic rubber material, its preparation method, and its application. Background Technology

[0002] Petroleum is a mineral resource stored in the upper layers of the Earth's crust, located in areas with high pressure and harsh environments. During oil extraction, hydrogenated nitrile butadiene rubber (NBR) sealants or NBR sealants with a metal skeleton are needed to prevent oil leaks and maintain pressure stability. NBR has good oil / fuel resistance, excellent mechanical properties, chemical resistance, and outstanding abrasion resistance, making it widely used in oil sealing. In some extreme cases, the sealant may come into contact with acidic gases, including hydrochloric acid, which can corrode the rubber sealant. Offshore oil extraction also exposes the sealant to seawater, primarily brine, which can also corrode the rubber sealant. Furthermore, existing NBR sealants with a skeleton, under high pressure and high temperature, are difficult to maintain the rubber-metal bond strength above 50% for extended periods when exposed to hydrochloric acid and brine, posing a risk of seal leakage and reducing product lifespan. Currently, commonly used synthetic rubber materials cannot be used to prepare hydrogenated nitrile butadiene rubber sealing materials with good resistance to acids and salt water. Furthermore, the adhesion between the metal skeleton and the hydrogenated nitrile butadiene rubber in the prepared hydrogenated nitrile butadiene rubber materials is poor, resulting in a short service life. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a synthetic rubber material, its preparation method and application. The hydrogenated nitrile butadiene rubber material and the hydrogenated nitrile butadiene rubber material with metal skeleton prepared from the synthetic rubber material have good mechanical properties, corrosion resistance and long service life.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A synthetic rubber material comprising the following components in parts by weight: 100 parts hydrogenated nitrile rubber, 2-3 parts antioxidant, 50-100 parts reinforcing filler, 5-15 parts plasticizer, 3-5 parts vulcanizing agent, and 2-3 parts co-vulcanizing agent; wherein the reinforcing filler is a mixture of carbon material, fumed silica, and calcium silicate, and the carbon material is at least one of carbon black and carbon nanotubes.

[0006] Through experiments, this invention has found that when the reinforcing filler is a compound of three fillers: carbon materials, fumed silica, and calcium silicate, the hydrogenated nitrile butadiene rubber material prepared from the synthetic rubber and the hydrogenated nitrile butadiene rubber material with a metal skeleton have better corrosion resistance and can still maintain good hydrochloric acid and salt water resistance under high temperature and high pressure.

[0007] Preferably, the mass ratio of carbon material, fumed silica, and calcium silicate in the reinforcing filler is (5-20):(30-50):(40-60).

[0008] Carbon materials and fumed silica help improve the strength of the material, while calcium silicate has a needle-like structure that can withstand greater pressure. By optimizing the ratio of the three materials as described above, the prepared product can be guaranteed to have better mechanical properties and resistance to high temperature and high pressure.

[0009] Preferably, the carbon material is a blend of carbon black with a particle size of 20-25 nm and carbon black with a particle size of 40-80 nm, and the mass ratio of the carbon black with a particle size of 20-25 nm to the carbon black with a particle size of 40-80 nm is 1:(1-3). When the synthetic rubber is made by blending carbon black with two different particle sizes, the prepared hydrogenated nitrile butadiene rubber material exhibits significantly better corrosion resistance in extreme environments; the prepared hydrogenated nitrile butadiene rubber material with a metal skeleton also shows higher bonding strength between the metal and the hydrogenated nitrile butadiene rubber.

[0010] Preferably, the synthetic rubber material further contains 1-3 parts of an internal release agent, which helps to reduce the adhesion between the product and the mold cavity wall.

[0011] Preferably, the vulcanizing agent is bis-tert-butylperoxyisopropylbenzene (BIPB), and the vulcanizing co-agent is N,N'-m-phenylenebismaleimide (HVA-2).

[0012] Preferably, the plasticizer is a compound of trioctyl trimellitate (TOTM) and dioctyl sebacate (DOS), and the mass ratio of trioctyl trimellitate to dioctyl sebacate is (2-4):(1-2). This invention, by selecting the type of plasticizer and the proportion of different types, can improve the toughness of rubber with a relatively small amount added, while not significantly affecting its high-pressure resistance.

[0013] Meanwhile, the present invention also discloses a method for preparing the synthetic rubber material, the method comprising the following steps:

[0014] (1) First, pass the hydrogenated nitrile rubber through a thin pass 2-3 times, then add the internal release agent and antioxidant according to the proportion, disperse evenly, then add the reinforcing filler and plasticizer, and mix.

[0015] (2) After the mixing in step (1) is completed, vulcanizing agent and vulcanizing agent are added and mixed to obtain the synthetic rubber material.

[0016] Preferably, in steps (1) to (2), the mixing temperature is 30-60℃.

[0017] Meanwhile, this invention also discloses the application of the synthetic rubber in the preparation of hydrogenated nitrile butadiene rubber materials, the preparation method of which includes the following steps:

[0018] (1) After the synthetic rubber material is placed for 12-20 hours, it is vulcanized once. The vulcanization pressure is 17-19 MPa, the vulcanization temperature is 165-185℃, and the vulcanization time is 600-900 seconds.

[0019] (2) After the first vulcanization is completed, a second vulcanization treatment is carried out. The second vulcanization temperature is 150-160℃ and the vulcanization time is 4-6h.

[0020] Furthermore, this invention also discloses a method for preparing a hydrogenated nitrile butadiene rubber material with a metal skeleton, the preparation method comprising the following steps:

[0021] (1) Pre-treatment of metal frame: clean, sandblast, clean again, dry, apply glue, and dry again to complete the pre-treatment;

[0022] (2) The synthetic rubber material and the pretreated metal skeleton are vulcanized at 165-185℃ for 600-1200s.

[0023] (3) After the first vulcanization is completed, a second vulcanization is carried out at 150-160℃ for 2-6 hours.

[0024] Preferably, in step (3), a gradient heating method is used for vulcanization, specifically as follows: the temperature is increased from room temperature to 90-110℃ for 80-90 minutes, and held for 10-20 minutes; then increased by 10-20℃ for 20-30 minutes, and held for 10-20 minutes; then increased by 10-20℃ for 20-30 minutes, and held for 10-20 minutes; finally, increased by 10-20℃ for 10-20 minutes, and held for 2-6 hours. Using a gradient heating method can prevent cracking at the contact points between the hydrogenated nitrile rubber and the metal skeleton.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] This invention, through screening the components of synthetic rubber materials, enables the hydrogenated nitrile butadiene rubber material prepared from the synthetic rubber materials to have good corrosion resistance, good resistance to salt water and hydrochloric acid under high temperature and high pressure, and good adhesion between the hydrogenated nitrile butadiene rubber and the metal skeleton in the hydrogenated nitrile butadiene rubber material with metal skeleton made from the synthetic rubber materials. Detailed Implementation

[0027] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0028] The materials used in the embodiments and comparative examples are shown below:

[0029] Hydrogenated nitrile butadiene rubber: Zeon Corporation, Japan;

[0030] Antioxidant: Antioxidant 445, commercially available;

[0031] Internal mold release agent: Internal mold release agent 935P, commercially available;

[0032] Carbon black 1: Particle size is 20nm;

[0033] Carbon black 2: Particle size is 25nm;

[0034] Carbon black 3: Particle size is 40nm;

[0035] Carbon black 4: Particle size is 80nm;

[0036] Carbon black 5: Particle size is 30nm;

[0037] Plasticizers: TOTM, DOS, commercially available;

[0038] Vulcanizing agent: BIPB, commercially available;

[0039] Vulcanizing aid: HVA-2, commercially available;

[0040] Fumed silica: average particle size 12nm, commercially available;

[0041] Calcium silicate: average particle size 0.02μm, commercially available;

[0042] Carbon nanotubes: average particle size 2-20nm, commercially available;

[0043] Base coat adhesive: Think Bond 12, commercially available;

[0044] Topcoat adhesive: Think Bond 80, commercially available;

[0045] The hydrogenated nitrile rubber, antioxidant, internal release agent, carbon black, plasticizer, vulcanizing agent, co-vulcanizing agent, fumed silica, calcium silicate, carbon nanotubes, primer adhesive, and topcoat adhesive used in the examples and comparative examples are all the same substance.

[0046] Examples 1-14

[0047] The formulations of Examples 1 to 14 of the synthetic rubber material described in this invention are shown in Table 1, and the preparation methods are as follows:

[0048] (1) Weigh each raw material according to the proportions;

[0049] (2) The hydrogenated nitrile rubber is passed through a two-roll mill twice, and after adjusting the roller gap, an internal release agent and an antioxidant are added. After being dispersed evenly, reinforcing filler and plasticizer are added and mixed. Then, vulcanizing agent BIPB and vulcanizing agent HVA-2 are added and mixed again. The synthetic rubber is obtained after mixing. The temperature of the two-roll mill is 40°C.

[0050] Table 1

[0051]

[0052]

[0053] The synthetic rubber materials described in Examples 1-14 were respectively prepared into hydrogenated nitrile butadiene rubber materials, named hydrogenated nitrile butadiene rubber 1-14, and the preparation methods are as follows:

[0054] (1) After the synthetic rubber material is left to stand for 16 hours, it is vulcanized once. The vulcanization is carried out for 600 seconds at a vulcanization temperature of 175℃ and a vulcanization pressure of 10MPa.

[0055] (2) After the first vulcanization is completed, a second vulcanization treatment is carried out. The second vulcanization temperature is 150℃ and the vulcanization time is 4h.

[0056] The synthetic rubber materials described in Examples 1-14 were respectively prepared into hydrogenated nitrile butadiene rubber materials with a metal skeleton, and named hydrogenated nitrile butadiene rubber with a metal skeleton 1-14, respectively. The preparation methods are as follows:

[0057] (1) Pre-treatment of metal skeleton: First, clean the metal skeleton with ethanol. After cleaning, dry the metal skeleton. After drying, sandblasting is performed. Then, clean with industrial alcohol (99 vol.%), dry again, and then apply base coat adhesive. After the base coat adhesive dries, apply top coat adhesive. After applying the adhesive, dry the skeleton.

[0058] (2) After the prepared synthetic rubber is left to stand for 16 hours, it is vulcanized with the pretreated metal skeleton at a vulcanization temperature of 175℃ and a vulcanization pressure of 10MPa for 900 seconds to form a first vulcanization.

[0059] (3) After the first vulcanization is completed, the product is trimmed and then subjected to a second vulcanization treatment. The second vulcanization method is as follows: First, the temperature is raised from room temperature to 100℃ for 90 minutes and held for 15 minutes; then the temperature is raised from 100℃ to 120℃ for 30 minutes and held for 15 minutes; then the temperature is raised from 120℃ to 140℃ for 30 minutes and held for 15 minutes; finally, the temperature is raised from 140℃ to 150℃ for 15 minutes and held for 4 hours to obtain hydrogenated nitrile rubber material with metal skeleton.

[0060] Performance tests were conducted on hydrogenated nitrile butadiene rubber 1-14 and hydrogenated nitrile butadiene rubber 1-14 with metal skeleton. The test results are shown in Tables 2-5.

[0061] Table 2

[0062]

[0063] Table 3 shows the resistance to 5% saline solution at 100℃ for 168 hours at 27.6 MPa.

[0064]

[0065] Table 4. Resistance to 10% HCl at 100℃ for 7 hours at 27.6 MPa

[0066]

[0067]

[0068] Table 5

[0069]

[0070]

[0071] As shown in Table 2-5, the reinforcing fillers in Examples 1-3 are compounded with carbon materials, fumed silica, and calcium silicate, which makes the hydrogenated nitrile butadiene rubber material prepared by synthetic rubber and the hydrogenated nitrile butadiene rubber material with metal skeleton have better corrosion resistance and can still maintain good hydrochloric acid and salt water resistance under high temperature and high pressure.

[0072] In Example 4, carbon black 1 with a particle size of 20 nm and carbon black 3 with a particle size of 40 nm were compounded, which further improved the corrosion resistance of the prepared hydrogenated nitrile butadiene rubber material under extreme environments. In addition, it also helped to improve the adhesion strength between the metal and the hydrogenated nitrile butadiene rubber in the hydrogenated nitrile butadiene rubber material with metal skeleton.

[0073] In Example 5, carbon black 3 with a particle size of 40 nm and carbon black 5 with a particle size of 30 nm were blended. The particle size of carbon black 3 is not in the range of 20-25 nm, and the particle size of carbon black 5 is not in the range of 40-80 nm. The performance of the hydrogenated nitrile butadiene rubber material and the hydrogenated nitrile butadiene rubber material with metal skeleton prepared in Example 5 is not as good as that in Example 4. This indicates that in this invention, only by using carbon black with a particle size of 20-25 nm and carbon black with a particle size of 40-80 nm blended can the hydrogenated nitrile butadiene rubber material have better corrosion resistance, while the hydrogenated nitrile butadiene rubber and the metal skeleton in the hydrogenated nitrile butadiene rubber material with metal skeleton have good bonding performance.

[0074] In Example 6, carbon black 2 with a particle size of 25 nm and carbon black 4 with a particle size of 80 nm were compounded. The particle sizes of carbon black 2 and carbon black 4 are both within the range protected by this invention. The hydrogenated nitrile butadiene rubber material and the hydrogenated nitrile butadiene rubber material with metal skeleton have good corrosion resistance. Furthermore, the hydrogenated nitrile butadiene rubber material with metal skeleton has good adhesion strength between the metal and the hydrogenated nitrile butadiene rubber.

[0075] In Example 7, the carbon material used was a combination of carbon black 1 with a particle size of 20 nm and carbon nanotubes. The types of carbon materials were not within the scope of protection of this invention. The corrosion resistance of the hydrogenated nitrile rubber material and the hydrogenated nitrile rubber material with metal skeleton was not as good as that of Example 4.

[0076] In Example 8, the amount of carbon material used was outside the scope protected by this invention. The corrosion resistance of both the hydrogenated nitrile butadiene rubber material and the hydrogenated nitrile butadiene rubber material with a metal skeleton was not as good as that in Example 1. This indicates that the mass ratio of carbon material, fumed silica, and calcium silicate in the reinforcing filler must be within the range of (5-20):(30-50):(40-60) to ensure that the prepared hydrogenated nitrile butadiene rubber material and the hydrogenated nitrile butadiene rubber material with a metal skeleton have better corrosion resistance and higher mechanical properties.

[0077] The difference between Examples 9-12 and Example 4 lies in the ratio of the two components in the plasticizer. In Examples 9-10, the plasticizer is a blend of trioctyl trimellitate and dioctyl sebacate, with a mass ratio of trioctyl trimellitate to dioctyl sebacate within the range of (2-4):(1-2). The corrosion resistance of the hydrogenated nitrile butadiene rubber material and the hydrogenated nitrile butadiene rubber material with a metal skeleton is similar to that of Example 4. However, in Examples 11-12, the mass ratio of trioctyl trimellitate to dioctyl sebacate is outside the range protected by this invention, and the hydrogenated nitrile butadiene rubber material... The corrosion resistance of the rubber material and the hydrogenated nitrile butadiene rubber material with metal skeleton is not as good as that of Example 4, indicating that the mass ratio of trioctyl trimellitate and dioctyl sebacate cannot achieve the effect of the present invention by using any ratio. In this application, only when the plasticizer is compounded with trioctyl trimellitate and dioctyl sebacate in a mass ratio of (2-4):(1-2) can the hydrogenated nitrile butadiene rubber material have better corrosion resistance and good adhesion between the hydrogenated nitrile butadiene rubber and the metal skeleton in the hydrogenated nitrile butadiene rubber material with metal skeleton have good adhesion.

[0078] Examples 13-14 contain only one type of plasticizer, and their performance is not as good as that of Example 4. This indicates that only by using a combination of trioctyl trimellitate and dioctyl sebacate as plasticizer can hydrogenated nitrile butadiene rubber materials and hydrogenated nitrile butadiene rubber materials with metal skeletons have good corrosion resistance.

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A synthetic rubber material, characterized in that, It contains the following components in parts by weight: 100 parts hydrogenated nitrile rubber, 2-3 parts antioxidant, 50-100 parts reinforcing filler, 5-15 parts plasticizer, 3-5 parts vulcanizing agent, and 2-3 parts co-vulcanizing agent; the reinforcing filler is a mixture of carbon material, fumed silica, and calcium silicate. The mass ratio of carbon material, fumed silica, and calcium silicate in the reinforcing filler is (5-20):(30-50):(40-60). The carbon material is a mixture of carbon black with a particle size of 20 nm and carbon black with a particle size of 40 nm, and the mass ratio of the carbon black with a particle size of 20 nm to the carbon black with a particle size of 40 nm is 1:1.

25. The plasticizer is a compound of trioctyl trimellitate and dioctyl sebacate, and the mass ratio of trioctyl trimellitate to dioctyl sebacate is (2-4):(1-2).

2. The synthetic rubber material as described in claim 1, characterized in that, The synthetic rubber material also contains 1-3 parts of an internal release agent.

3. The synthetic rubber material as described in claim 1, characterized in that, The vulcanizing agent is bis-tert-butylperoxyisopropylbenzene, and the co-vulcanizing agent is N,N'-m-phenylenebismaleimide.

4. A method for preparing the synthetic rubber material as described in claim 2, characterized in that, Includes the following steps: (1) First, pass the hydrogenated nitrile rubber through a thin pass 2-3 times, then add the internal release agent and antioxidant according to the ratio, disperse evenly, then add the reinforcing filler and plasticizer, and mix. (2) After the mixing in step (1) is completed, vulcanizing agent and vulcanizing agent are added and mixed to obtain the synthetic rubber material.

5. The preparation method according to claim 4, characterized in that, In steps (1) to (2), the mixing temperature is 30-60℃.

6. A method for preparing a hydrogenated nitrile butadiene rubber material, characterized in that, Includes the following steps: (1) After placing the synthetic rubber material for 12-20 hours, vulcanize it once. The vulcanization pressure is 17-19 MPa, the vulcanization temperature is 165-185℃, and the vulcanization time is 600-900 s. (2) After the first vulcanization is completed, a second vulcanization treatment is carried out. The second vulcanization temperature is 150-160℃ and the vulcanization time is 4-6h. The synthetic rubber material is the synthetic rubber material as described in any one of claims 1 to 3.

7. A method for preparing a hydrogenated nitrile butadiene rubber material with a metal skeleton, characterized in that, The preparation method includes the following steps: (1) Pre-treatment of metal frame: clean, sandblast, clean again, dry, apply glue, and dry again to complete the pre-treatment; (2) The synthetic rubber material and the pretreated metal skeleton are vulcanized at 165-185℃ for 600-1200s. (3) After the first vulcanization is completed, a second vulcanization is carried out at 150-160℃ for 2-6 hours; The synthetic rubber material is the synthetic rubber material as described in any one of claims 1 to 3.

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