High-temperature-resistant permanent compression deformation-resistant nitrile rubber composition and preparation method thereof

Abstract

The invention discloses a nitrile rubber composition with high temperature resistance and compression set resistance and a preparation method thereof, and relates to the technical field of rubber compositions, and the nitrile rubber composition is prepared from the following components in parts by weight: nitrile rubber, zinc oxide, sodium stearate, an enhanced supplementary additive, nano cerium oxide, carbon black, methyl phenyl silicone oil, resin, an anti-aging agent, sulfur and an accelerant. The nitrile rubber composition prepared by the invention is rich in elasticity and rebound resilience; the sealing material has excellent mechanical strength including expansion strength, elongation, tear strength and the like, has the characteristics of good air tightness, high temperature resistance and excellent compression set resistance, and can be suitable for most sealing occasions.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber compositions, in particular to a high temperature resistant and compression permanent deformation resistant nitrile rubber composition and a preparation method thereof. Background Art

[0002] The sealing ring is a kind of sealing part. Usually, the sealing ring is used in some structures that need to be sealed. Therefore, the performance of the sealing ring will directly affect the normal use of equipment and pipelines.

[0003] Since rubber materials have relatively complete functions, sealing rings are mostly made of rubber materials.

[0004] Nitrile rubber (NBR) is a copolymer of butadiene and acrylonitrile. Because nitrile rubber has excellent oil resistance, wear resistance and air tightness, and its oil resistance is second only to polysulfide rubber and fluororubber, and its cost is lower than that of polysulfide rubber and fluororubber, it is better suitable for the application of sealing rings.

[0005] The prior art discloses a nitrile recycled rubber sealing ring material with application publication number CN102731864A, which specifically discloses "the present invention discloses a nitrile recycled rubber sealing ring material, which is made of nitrile rubber 3345, nitrile recycled rubber, antioxidant SP, antioxidant MB, sodium stearate, sulfur powder, palm wax, zinc oxide, processing aid WB16, carbon black N550, carbon black N330, sodium pentachlorostearate methyl ester, accelerator TETD, accelerator TETD, accelerator BZ, nano calcium carbonate, modified acrylate, alkylresorcinol formaldehyde resin, maleic anhydride, plasticizer, etc. The present invention utilizes recycled nitrile rubber as raw material, optimizes the formula raw materials, and prepares a nitrile recycled rubber sealing ring material with excellent performance, good high temperature resistance, high hardness, and saves money." However, the high temperature resistance of the sealing ring material prepared by it is relatively general, and it does not have good resistance to permanent compression deformation, which limits its application in many fields, and the permanent compression deformation of rubber can intuitively measure its sealing and product performance.

[0006] Based on this, a high temperature resistant and compression permanent deformation resistant nitrile rubber composition and a preparation method thereof are provided to solve the existing technical problems. Summary of the invention

[0007] The purpose of the present invention is to provide a high temperature resistant and compression permanent deformation resistant nitrile rubber composition and a preparation method thereof, so as to solve the deficiencies in the prior art.

[0008] The technical solution adopted by the present invention is as follows:

[0009] A high temperature resistant and compression permanent deformation resistant nitrile rubber composition comprises the following components in parts by weight:

[0010] 100 parts of nitrile rubber, 5-8 parts of zinc oxide, 1-2 parts of sodium stearate, 1.5-3 parts of reinforcing supplementary additives, 0.02-0.03 parts of nano cerium oxide, 40-55 parts of carbon black, 2-5 parts of methylphenyl silicone oil, 6-10 parts of resin, 3-6 parts of antioxidant, 0.4-0.8 parts of sulfur, and 1-4 parts of accelerator.

[0011] As a further technical solution: the carbon black is N550 carbon black;

[0012] The antioxidants include antioxidant DNP, antioxidant ODA, and antioxidant MB;

[0013] The mixing mass ratio of the antioxidant DNP, antioxidant ODA and antioxidant MB is 1:2:1;

[0014] The accelerators include: accelerator BZ, accelerator TETD;

[0015] The mixing mass ratio of the accelerator BZ to the accelerator TETD is 5:1.

[0016] As a further technical solution: the preparation method of the enhanced supplementary auxiliary agent is:

[0017] First, diethylene glycol diglycidyl ether, propylene glycol n-propyl ether, and allyl glycidyl ether are sequentially added to an organic solvent, and then stirred and mixed to obtain a mixed solution;

[0018] The mixed solution prepared above is added into the reactor, an inert gas is introduced into the reactor, and the air in the reactor is exhausted;

[0019] Add the catalyst solution into the reactor, stir and mix for 10-15 minutes at room temperature, then drop the epichlorohydrin solution while stirring, after the dropwise addition is completed, continue to stir and react for 15-20 minutes, add methanol to the reaction solution to terminate the reaction, then add n-hexane for precipitation, filter, wash with water, and dry to obtain the enhanced supplementary auxiliary agent.

[0020] As a further technical solution: the concentration of diethylene glycol diglycidyl ether in the mixed solution is 1-1.5 mol / L;

[0021] The concentration of propylene glycol n-propyl ether is 0.5-1 mol / L;

[0022] The concentration of allyl glycidyl ether is 1-1.5 mol / L;

[0023] The concentration of the epichlorohydrin solution is 2-3 mol / L.

[0024] As a further technical solution: the organic solvent is toluene.

[0025] As a further technical solution: the inert gas is nitrogen or neon.

[0026] As a further technical solution: the catalyst solution preparation method is:

[0027] First, 1,8-diazabicycloundec-7-ene and calcium hydride are stirred at a mass ratio of 1:1 for 10-12 hours, then vacuum distilled and subjected to freeze degassing treatment twice, and then mixed with toluene and stirred evenly to obtain a 1,8-diazabicycloundec-7-ene solution;

[0028] Among them, the concentration of 1,8-diazabicycloundec-7-ene solution is 0.3 mol / L;

[0029] Under the protection of nitrogen atmosphere, phosphoric acid is added to ether, and the mixture is stirred to be uniform, so as to obtain a phosphoric acid solution;

[0030] Wherein, the concentration of phosphoric acid solution is 0.85mol / L;

[0031] Under the protection of nitrogen atmosphere, triisobutylaluminum is added to toluene, and the mixture is stirred and mixed to obtain a triisobutylaluminum solution;

[0032] Wherein, the concentration of triisobutylaluminum solution is 0.8 mol / L;

[0033] The 1,8-diazabicycloundec-7-ene solution, the phosphoric acid solution and the triisobutylaluminum solution were uniformly mixed in a volume ratio of 1:2:1 to obtain a catalyst solution.

[0034] As a further technical solution: the mixed solution, catalyst solution, and epichlorohydrin solution have a mixed volume ratio of 5-6:0.2-0.4:8-10;

[0035] The amount of methanol added was 5% of the reaction solution volume;

[0036] The amount of n-hexane added was 60% of the volume of the reaction solution.

[0037] A method for preparing a high temperature resistant and compression set resistant nitrile rubber composition, comprising:

[0038] 1) First, add the nitrile rubber into an internal mixer for internal mixing to obtain a rubber compound;

[0039] 2) mixing the rubber obtained in step (1) with zinc oxide, sodium stearate, enhanced supplementary additives and methylphenyl silicone oil and performing a first mixing process;

[0040] 3) After the first mixing, N550 carbon black and nano cerium oxide are added for the second mixing to obtain a mixed rubber;

[0041] 4) Add sulfur, accelerator, and accelerator to the obtained rubber mixture in sequence for vulcanization treatment and thin pass treatment, and thin pass twice;

[0042] In step (1), the mixture is mixed to 125-135° C. and then discharged, and then left to stand for 18-20 hours.

[0043] The first mixing parameters are: mixing temperature is 120-125°C, mixing time is 4-5min;

[0044] The second mixing parameters are: mixing temperature is 112-115°C, mixing time is 3-4min;

[0045] The vulcanization treatment parameters are: the vulcanization temperature is 150-155°C, and the vulcanization time is 30-40 minutes.

[0046] The nitrile rubber composition prepared by the method of the present invention is applied to a sealing ring.

[0047] Beneficial effects:

[0048] The nitrile rubber composition prepared by the invention is rich in elasticity and resilience; has excellent mechanical strength, including expansion strength, elongation and tearing strength, etc., good air tightness, high temperature resistance and excellent resistance to compression permanent deformation, and can be applied to most sealing occasions.

[0049] The performance of the nitrile rubber composition prepared by the present invention is greatly improved compared with conventional nitrile rubber available on the market.

[0050] The present invention introduces sodium stearate and an enhanced supplementary auxiliary agent, and the two cooperate to promote the cross-linking effect between nitrile rubber molecules in the nitrile rubber composition, thereby effectively improving the ductility and flexibility of the nitrile rubber. The improvement of the ductility and flexibility can make the prepared nitrile rubber mixture easier to process and shape during the process of processing into a rubber sealing ring, thereby effectively improving the performance of the rubber sealing ring;

[0051] Through the combined action of carbon black, reinforcing supplementary additives and sodium stearate, the high temperature resistance of the nitrile rubber composition can be greatly improved. This is mainly because the groups on the surfaces of carbon black, reinforcing supplementary additives and sodium stearate are combined with the groups on the main chain of the nitrile rubber, making it difficult for the thermal movement of the main chain of the nitrile rubber and oxygen to diffuse in the nitrile rubber network. In this way, at high temperatures, the free radicals generated by the rubber will react and be consumed in time, thereby greatly improving the high temperature resistance of the nitrile rubber composition.

[0052] Since the vulcanization efficiency of acrylonitrile-butadiene rubber is relatively slow, the present invention can play a role of a crosslinking accelerator by introducing a certain amount of zinc oxide, and the introduction of zinc oxide also has a certain degree of reinforcement. In the initial stage of acrylonitrile-butadiene rubber vulcanization, the introduction of zinc oxide can accelerate the progress of the vulcanization reaction and delay the vulcanization reaction in the later stage of vulcanization, which helps to improve the minimum torque and the maximum torque of the acrylonitrile-butadiene rubber composition, and by improving the vulcanization efficiency, the hardness of the vulcanized rubber formed by the acrylonitrile-butadiene rubber will also be increased accordingly, and the mechanical properties of the acrylonitrile-butadiene rubber composition can also be improved simultaneously.

[0053] The introduction of carbon black can improve the wear resistance of the nitrile rubber composition, mainly by increasing the hardness of the nitrile rubber and reducing the friction coefficient. By combining with reinforcing supplementary additives, it can also effectively improve the resistance of the nitrile rubber composition to permanent compression deformation, thereby broadening its application range. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 The figure is a bar graph of the compression permanent deformation rate of the rubber sealing rings made from the examples and comparative examples. DETAILED DESCRIPTION

[0055] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0056] Example 1

[0057] A high temperature resistant and compression permanent deformation resistant nitrile rubber composition, the dosage of each component is:

[0058] 100kg of nitrile rubber, 5kg of zinc oxide, 1kg of sodium stearate, 1.5kg of enhanced supplementary additive, 0.02kg of nano-cerium oxide, 40kg of carbon black, 2kg of methylphenyl silicone oil, 6kg of resin, 3kg of antioxidant, 0.4kg of sulfur, and 1kg of accelerator. The nitrile rubber used is: nitrile rubber 1845;

[0059] The antioxidants include antioxidant DNP, antioxidant ODA and antioxidant MB in a mass ratio of 1:2:1;

[0060] The accelerator includes: accelerator BZ and accelerator TETD in a mass ratio of 5:1;

[0061] The preparation method of the enhanced supplementary auxiliary agent is as follows:

[0062] First, diethylene glycol diglycidyl ether, propylene glycol n-propyl ether, and allyl glycidyl ether are added to toluene in sequence, and then stirred and mixed to obtain a mixed solution; the concentration of diethylene glycol diglycidyl ether in the mixed solution is 1 mol / L; the concentration of propylene glycol n-propyl ether is 0.5 mol / L; and the concentration of allyl glycidyl ether is 1 mol / L;

[0063] The mixed solution prepared above was added into the reactor, nitrogen was introduced into the reactor, and the air in the reactor was exhausted;

[0064] Add the catalyst solution into the reactor, stir and mix for 10 minutes at room temperature, then dropwise add epichlorohydrin solution, the concentration of epichlorohydrin solution is 2 mol / L, stir while dropping, after the dropwise addition is completed, continue to stir and react for 15 minutes, add methanol to the reaction solution to terminate the reaction, then add n-hexane for precipitation, filter, wash with water, and dry to obtain the enhanced supplementary auxiliary agent.

[0065] The catalyst solution preparation method is:

[0066] First, 1,8-diazabicycloundec-7-ene and calcium hydride were stirred at a mass ratio of 1:1 for 10 hours, and then vacuum distilled and subjected to freeze degassing treatment twice, and then mixed with toluene and stirred to obtain a 1,8-diazabicycloundec-7-ene solution;

[0067] Among them, the concentration of 1,8-diazabicycloundec-7-ene solution is 0.3 mol / L;

[0068] Under the protection of nitrogen atmosphere, phosphoric acid is added to ether, and the mixture is stirred to be uniform, so as to obtain a phosphoric acid solution;

[0069] Wherein, the concentration of phosphoric acid solution is 0.85mol / L;

[0070] Under the protection of nitrogen atmosphere, triisobutylaluminum is added to toluene, and the mixture is stirred and mixed to obtain a triisobutylaluminum solution;

[0071] Wherein, the concentration of triisobutylaluminum solution is 0.8 mol / L;

[0072] The 1,8-diazabicycloundec-7-ene solution, the phosphoric acid solution and the triisobutylaluminum solution were uniformly mixed in a volume ratio of 1:2:1 to obtain a catalyst solution.

[0073] The mixed solution, catalyst solution, and epichlorohydrin solution have a mixed volume ratio of 5:0.2:8;

[0074] The amount of methanol added was 5% of the reaction solution volume;

[0075] The amount of n-hexane added was 60% of the volume of the reaction solution.

[0076] A method for preparing a high temperature resistant and compression set resistant nitrile rubber composition, comprising:

[0077] 1) First, add nitrile rubber to an internal mixer for internal mixing to obtain a rubber compound; in step (1), the rubber compound is discharged after internal mixing at 125° C. and then left for 18 hours after discharge;

[0078] 2) Mixing the rubber obtained in step (1) with zinc oxide, sodium stearate, enhanced supplementary additives and methylphenyl silicone oil for the first mixing; the first mixing parameters are: mixing temperature of 120° C., mixing time of 4 min;

[0079] 3) After the first mixing, N550 carbon black and nano cerium oxide are added for the second mixing to obtain a mixed rubber;

[0080] The second mixing parameters are: mixing temperature is 112°C, mixing time is 3 min;

[0081] 4) Add sulfur, accelerator and accelerator to the above-obtained rubber mixture in turn for vulcanization treatment and thin pass treatment, thin pass 2 times; adjust the roller distance of the open mill to 1mm for thin pass treatment, the temperature is 90°C, and the time is 2min; the vulcanization treatment parameters are: the vulcanization temperature is 150°C, and the vulcanization time is 30min.

[0082] Example 2

[0083] A high temperature resistant and compression permanent deformation resistant nitrile rubber composition, the dosage of each component is:

[0084] 100kg of nitrile rubber, 6kg of zinc oxide, 1.5kg of sodium stearate, 1.8kg of enhanced supplementary additives, 0.025kg of nano-cerium oxide, 44kg of carbon black, 3kg of methylphenyl silicone oil, 8kg of resin, 4kg of antioxidant, 0.5kg of sulfur, and 2kg of accelerator; the resin is phenolic resin. The nitrile rubber is: nitrile rubber 1845;

[0085] The antioxidants include antioxidant DNP, antioxidant ODA and antioxidant MB in a mass ratio of 1:2:1;

[0086] The accelerator includes: accelerator BZ and accelerator TETD in a mass ratio of 5:1;

[0087] The preparation method of the enhanced supplementary auxiliary agent is as follows:

[0088] First, diethylene glycol diglycidyl ether, propylene glycol n-propyl ether, and allyl glycidyl ether are added to toluene in sequence, and then stirred and mixed to obtain a mixed solution; the concentration of diethylene glycol diglycidyl ether in the mixed solution is 1.2 mol / L; the concentration of propylene glycol n-propyl ether is 0.8 mol / L; and the concentration of allyl glycidyl ether is 1.2 mol / L;

[0089] The mixed solution prepared above was added into the reactor, nitrogen was introduced into the reactor, and the air in the reactor was exhausted;

[0090] Add the catalyst solution into the reactor, stir and mix for 12 minutes at room temperature, then dropwise add epichlorohydrin solution, the concentration of epichlorohydrin solution is 2.5 mol / L, stir while dropping, after the dropwise addition is completed, continue to stir and react for 18 minutes, add methanol to the reaction solution to terminate the reaction, then add n-hexane for precipitation, filter, wash with water, and dry to obtain the enhanced supplementary auxiliary agent.

[0091] The catalyst solution preparation method is:

[0092] First, 1,8-diazabicycloundec-7-ene and calcium hydride were stirred at a mass ratio of 1:1 for 10 hours, and then vacuum distilled and subjected to freeze degassing treatment twice, and then mixed with toluene and stirred to obtain a 1,8-diazabicycloundec-7-ene solution;

[0093] Among them, the concentration of 1,8-diazabicycloundec-7-ene solution is 0.3 mol / L;

[0094] Under the protection of nitrogen atmosphere, phosphoric acid is added to ether, and the mixture is stirred to be uniform, so as to obtain a phosphoric acid solution;

[0095] Wherein, the concentration of phosphoric acid solution is 0.85mol / L;

[0096] Under the protection of nitrogen atmosphere, triisobutylaluminum is added to toluene, and the mixture is stirred and mixed to obtain a triisobutylaluminum solution;

[0097] Wherein, the concentration of triisobutylaluminum solution is 0.8 mol / L;

[0098] The 1,8-diazabicycloundec-7-ene solution, the phosphoric acid solution and the triisobutylaluminum solution were uniformly mixed in a volume ratio of 1:2:1 to obtain a catalyst solution.

[0099] The mixed solution, catalyst solution, and epichlorohydrin solution have a mixed volume ratio of 5.5:0.3:9;

[0100] The amount of methanol added was 5% of the reaction solution volume;

[0101] The amount of n-hexane added was 60% of the volume of the reaction solution.

[0102] A method for preparing a high temperature resistant and compression set resistant nitrile rubber composition, comprising:

[0103] 1) First, add nitrile rubber to an internal mixer for internal mixing to obtain a rubber compound; in step (1), the rubber compound is discharged after internal mixing at 128° C. and then left for 19 hours after discharge;

[0104] 2) Mixing the rubber obtained in step (1) with zinc oxide, sodium stearate, enhanced supplementary additives and methylphenyl silicone oil for the first mixing; the first mixing parameters are: mixing temperature of 122° C., mixing time of 4.5 min;

[0105] 3) After the first mixing, N550 carbon black and nano cerium oxide are added for the second mixing to obtain a mixed rubber;

[0106] The second mixing parameters are: mixing temperature is 113°C, mixing time is 3 min;

[0107] 4) Add sulfur, accelerator and accelerator to the above-obtained rubber mixture in turn for vulcanization treatment and thin pass treatment, thin pass 2 times; adjust the roller distance of the open mill to 1mm for thin pass treatment, the temperature is 95°C, and the time is 2min; the vulcanization treatment parameters are: the vulcanization temperature is 152°C, and the vulcanization time is 35min.

[0108] Example 3

[0109] A high temperature resistant and compression permanent deformation resistant nitrile rubber composition, the dosage of each component is:

[0110] 100kg of nitrile rubber, 6kg of zinc oxide, 1.5kg of sodium stearate, 2kg of enhanced supplementary additives, 0.025kg of nano-cerium oxide, 48kg of carbon black, 3kg of methylphenyl silicone oil, 8kg of resin, 5kg of antioxidant, 0.6kg of sulfur, and 2kg of accelerator; the resin is phenolic resin. The nitrile rubber is: nitrile rubber 1845;

[0111] The antioxidants include antioxidant DNP, antioxidant ODA and antioxidant MB in a mass ratio of 1:2:1;

[0112] The accelerator includes: accelerator BZ and accelerator TETD in a mass ratio of 5:1;

[0113] The preparation method of the enhanced supplementary auxiliary agent is as follows:

[0114] First, diethylene glycol diglycidyl ether, propylene glycol n-propyl ether, and allyl glycidyl ether are added to toluene in sequence, and then stirred and mixed to obtain a mixed solution; the concentration of diethylene glycol diglycidyl ether in the mixed solution is 1.5 mol / L; the concentration of propylene glycol n-propyl ether is 0.5 mol / L; and the concentration of allyl glycidyl ether is 1.5 mol / L;

[0115] The mixed solution prepared above was added into the reactor, nitrogen was introduced into the reactor, and the air in the reactor was exhausted;

[0116] Add the catalyst solution into the reactor, stir and mix for 10 minutes at room temperature, then dropwise add epichlorohydrin solution, the concentration of epichlorohydrin solution is 3 mol / L, stir while dropping, after the dropwise addition is completed, continue to stir and react for 15 minutes, add methanol to the reaction solution to terminate the reaction, then add n-hexane for precipitation, filter, wash with water, and dry to obtain the enhanced supplementary auxiliary agent.

[0117] The catalyst solution preparation method is:

[0118] First, 1,8-diazabicycloundec-7-ene and calcium hydride are stirred at a mass ratio of 1:1 for 12 hours, and then vacuum distilled and subjected to freeze degassing treatment twice, and then mixed with toluene and stirred to obtain a 1,8-diazabicycloundec-7-ene solution;

[0119] Among them, the concentration of 1,8-diazabicycloundec-7-ene solution is 0.3 mol / L;

[0120] Under the protection of nitrogen atmosphere, phosphoric acid is added to ether, and the mixture is stirred to be uniform, so as to obtain a phosphoric acid solution;

[0121] Wherein, the concentration of phosphoric acid solution is 0.85mol / L;

[0122] Under the protection of nitrogen atmosphere, triisobutylaluminum is added to toluene, and the mixture is stirred and mixed to obtain a triisobutylaluminum solution;

[0123] Wherein, the concentration of triisobutylaluminum solution is 0.8 mol / L;

[0124] The 1,8-diazabicycloundec-7-ene solution, the phosphoric acid solution and the triisobutylaluminum solution were uniformly mixed in a volume ratio of 1:2:1 to obtain a catalyst solution.

[0125] The mixed solution, catalyst solution, and epichlorohydrin solution have a mixed volume ratio of 5:0.3:9;

[0126] The amount of methanol added was 5% of the reaction solution volume;

[0127] The amount of n-hexane added was 60% of the volume of the reaction solution.

[0128] A method for preparing a high temperature resistant and compression set resistant nitrile rubber composition, comprising:

[0129] 1) First, add nitrile rubber to an internal mixer for internal mixing to obtain a rubber compound; in step (1), the rubber compound is discharged after internal mixing at 130° C. and then left to stand for 20 hours;

[0130] 2) Mixing the rubber obtained in step (1) with zinc oxide, sodium stearate, enhanced supplementary additives and methylphenyl silicone oil for the first mixing; the first mixing parameters are: mixing temperature of 124° C., mixing time of 5 min;

[0131] 3) After the first mixing, N550 carbon black and nano cerium oxide are added for the second mixing to obtain a mixed rubber;

[0132] The second mixing parameters are: mixing temperature is 114°C, mixing time is 3 min;

[0133] 4) Add sulfur, accelerator and accelerator to the above-obtained rubber mixture in turn for vulcanization treatment and thin pass treatment, thin pass 2 times; adjust the roller distance of the open mill to 1mm for thin pass treatment, the temperature is 96°C, and the time is 2min; the vulcanization treatment parameters are: the vulcanization temperature is 152°C, and the vulcanization time is 35min.

[0134] Example 4

[0135] A high temperature resistant and compression permanent deformation resistant nitrile rubber composition, the dosage of each component is:

[0136] 100kg of nitrile rubber, 6kg of zinc oxide, 1.5kg of sodium stearate, 2kg of enhanced supplementary additives, 0.08kg of nano-cerium oxide, 50kg of carbon black, 4kg of methylphenyl silicone oil, 7kg of resin, 5kg of antioxidant, 0.6kg of sulfur, and 3kg of accelerator; the resin is phenolic resin. The nitrile rubber is: nitrile rubber 1845;

[0137] The antioxidants include antioxidant DNP, antioxidant ODA and antioxidant MB in a mass ratio of 1:2:1;

[0138] The accelerator includes: accelerator BZ and accelerator TETD in a mass ratio of 5:1;

[0139] The preparation method of the enhanced supplementary auxiliary agent is as follows:

[0140] First, diethylene glycol diglycidyl ether, propylene glycol n-propyl ether, and allyl glycidyl ether are added to toluene in sequence, and then stirred and mixed to obtain a mixed solution; the concentration of diethylene glycol diglycidyl ether in the mixed solution is 1.2 mol / L; the concentration of propylene glycol n-propyl ether is 0.8 mol / L; and the concentration of allyl glycidyl ether is 1.2 mol / L;

[0141] The mixed solution prepared above was added into the reactor, nitrogen was introduced into the reactor, and the air in the reactor was exhausted;

[0142] Add the catalyst solution into the reactor, stir and mix for 15 minutes at room temperature, then dropwise add epichlorohydrin solution, the concentration of epichlorohydrin solution is 3 mol / L, stir while dropping, after the dropwise addition is completed, continue to stir and react for 15 minutes, add methanol to the reaction solution to terminate the reaction, then add n-hexane for precipitation, filter, wash with water, and dry to obtain the enhanced supplementary auxiliary agent.

[0143] The catalyst solution preparation method is:

[0144] First, 1,8-diazabicycloundec-7-ene and calcium hydride are stirred at a mass ratio of 1:1 for 12 hours, and then vacuum distilled and subjected to freeze degassing treatment twice, and then mixed with toluene and stirred to obtain a 1,8-diazabicycloundec-7-ene solution;

[0145] Among them, the concentration of 1,8-diazabicycloundec-7-ene solution is 0.3 mol / L;

[0146] Under the protection of nitrogen atmosphere, phosphoric acid is added to ether, and the mixture is stirred to be uniform, so as to obtain a phosphoric acid solution;

[0147] Wherein, the concentration of phosphoric acid solution is 0.85mol / L;

[0148] Under the protection of nitrogen atmosphere, triisobutylaluminum is added to toluene, and the mixture is stirred and mixed to obtain a triisobutylaluminum solution;

[0149] Wherein, the concentration of triisobutylaluminum solution is 0.8 mol / L;

[0150] The 1,8-diazabicycloundec-7-ene solution, the phosphoric acid solution and the triisobutylaluminum solution were uniformly mixed in a volume ratio of 1:2:1 to obtain a catalyst solution.

[0151] The mixed solution, catalyst solution, and epichlorohydrin solution have a mixed volume ratio of 5.5:0.3:9;

[0152] The amount of methanol added was 5% of the reaction solution volume;

[0153] The amount of n-hexane added was 60% of the volume of the reaction solution.

[0154] A method for preparing a high temperature resistant and compression set resistant nitrile rubber composition, comprising:

[0155] 1) First, add nitrile rubber to an internal mixer for internal mixing to obtain a rubber compound; in step (1), the rubber compound is discharged after internal mixing at 132° C. and then left for 18 hours after discharge;

[0156] 2) Mixing the rubber obtained in step (1) with zinc oxide, sodium stearate, enhanced supplementary additives and methylphenyl silicone oil for the first mixing; the first mixing parameters are: mixing temperature of 123° C., mixing time of 4 min;

[0157] 3) After the first mixing, N550 carbon black and nano cerium oxide are added for the second mixing to obtain a mixed rubber;

[0158] The second mixing parameters were: mixing temperature was 114°C, mixing time was 4 min;

[0159] 4) Add sulfur, accelerator and accelerator to the above-obtained rubber mixture in turn for vulcanization treatment and thin pass treatment, thin pass 2 times; adjust the roller distance of the open mill to 1mm for thin pass treatment, the temperature is 98°C, and the time is 3min; the vulcanization treatment parameters are: the vulcanization temperature is 152°C, and the vulcanization time is 35min.

[0160] Example 5

[0161] A high temperature resistant and compression permanent deformation resistant nitrile rubber composition, the dosage of each component is:

[0162] 100kg of nitrile rubber, 8kg of zinc oxide, 2kg of sodium stearate, 3kg of enhanced supplementary additives, 0.03kg of nano-cerium oxide, 55kg of carbon black, 5kg of methylphenyl silicone oil, 10kg of resin, 6kg of antioxidant, 0.8kg of sulfur, and 4kg of accelerator; the resin is phenolic resin. The nitrile rubber is: nitrile rubber 1845;

[0163] The antioxidants include antioxidant DNP, antioxidant ODA and antioxidant MB in a mass ratio of 1:2:1;

[0164] The accelerator includes: accelerator BZ and accelerator TETD in a mass ratio of 5:1;

[0165] The preparation method of the enhanced supplementary auxiliary agent is as follows:

[0166] First, diethylene glycol diglycidyl ether, propylene glycol n-propyl ether, and allyl glycidyl ether are added to toluene in sequence, and then stirred and mixed to obtain a mixed solution; the concentration of diethylene glycol diglycidyl ether in the mixed solution is 1.5 mol / L; the concentration of propylene glycol n-propyl ether is 1 mol / L; and the concentration of allyl glycidyl ether is 1.5 mol / L;

[0167] The mixed solution prepared above was added into the reactor, nitrogen was introduced into the reactor, and the air in the reactor was exhausted;

[0168] Add the catalyst solution into the reactor, stir and mix for 15 minutes at room temperature, then dropwise add epichlorohydrin solution, the concentration of epichlorohydrin solution is 3 mol / L, stir while dropping, after the dropwise addition is completed, continue to stir and react for 20 minutes, add methanol to the reaction solution to terminate the reaction, then add n-hexane for precipitation, filter, wash with water, and dry to obtain the enhanced supplementary auxiliary agent.

[0169] The catalyst solution preparation method is:

[0170] First, 1,8-diazabicycloundec-7-ene and calcium hydride are stirred at a mass ratio of 1:1 for 12 hours, and then vacuum distilled and subjected to freeze degassing treatment twice, and then mixed with toluene and stirred to obtain a 1,8-diazabicycloundec-7-ene solution;

[0171] Among them, the concentration of 1,8-diazabicycloundec-7-ene solution is 0.3 mol / L;

[0172] Under the protection of nitrogen atmosphere, phosphoric acid is added to ether, and the mixture is stirred to be uniform, so as to obtain a phosphoric acid solution;

[0173] Wherein, the concentration of phosphoric acid solution is 0.85mol / L;

[0174] Under the protection of nitrogen atmosphere, triisobutylaluminum is added to toluene, and the mixture is stirred and mixed to obtain a triisobutylaluminum solution;

[0175] Wherein, the concentration of triisobutylaluminum solution is 0.8 mol / L;

[0176] The 1,8-diazabicycloundec-7-ene solution, the phosphoric acid solution and the triisobutylaluminum solution were uniformly mixed in a volume ratio of 1:2:1 to obtain a catalyst solution.

[0177] The mixed solution, catalyst solution, and epichlorohydrin solution have a mixed volume ratio of 6:0.4:10;

[0178] The amount of methanol added was 5% of the reaction solution volume;

[0179] The amount of n-hexane added was 60% of the volume of the reaction solution.

[0180] A method for preparing a high temperature resistant and compression set resistant nitrile rubber composition, comprising:

[0181] 1) First, add nitrile rubber to an internal mixer for internal mixing to obtain a rubber compound; in step (1), the rubber compound is discharged after internal mixing at 135° C. and then left to stand for 20 hours;

[0182] 2) Mix the rubber obtained in step (1) with zinc oxide, sodium stearate, enhanced supplementary additives and methylphenyl silicone oil and then perform the first mixing; the first mixing parameters are: mixing temperature is 125° C., and mixing time is 5 min;

[0183] 3) After the first mixing, N550 carbon black and nano cerium oxide are added for the second mixing to obtain a mixed rubber;

[0184] The second mixing parameters are: mixing temperature is 115°C, mixing time is 4 min;

[0185] 4) Add sulfur, accelerator and accelerator to the above-obtained rubber mixture in turn for vulcanization treatment and thin pass treatment, thin pass 2 times; adjust the roller distance of the open mill to 1mm for thin pass treatment, the temperature is 100°C, and the time is 3min; the vulcanization treatment parameters are: the vulcanization temperature is 155°C, and the vulcanization time is 40min.

[0186] Comparative Example 1:

[0187] On the basis of Example 1, the enhanced supplementary auxiliary agent used in Example 1 is not added.

[0188] test:

[0189] The rubber sealing rings of the same specifications prepared in the embodiment and the comparative example were subjected to hardness test according to the relevant test standard of GB / T531.12008;

[0190] Table 1

[0191] hardness Example 1 73 Example 2 73 Example 3 74 Example 4 74 Example 5 75

[0192] It can be seen from Table 2 that the rubber sealing ring prepared by the material of the present invention has a relatively suitable hardness and can be used in most occasions and environments.

[0193] The rubber sealing rings of the same specifications made from the examples and comparative samples were subjected to high temperature resistance tests, referring to TB / T1681;

[0194] Table 2

[0195]

[0196]

[0197] It can be seen from Table 2 that the nitrile rubber composition material prepared in the present invention has excellent high temperature resistance.

[0198] The rubber sealing rings of the same specifications prepared from the materials of the examples and comparative examples were kept at -60°C for 72 hours and tested for their compression permanent deformation % at a compression rate of 25%;

[0199] Table 3

[0200] Compression set % Example 1 17.0 Example 2 16.8 Example 3 16.5 Example 4 16.2 Example 5 16.1 Comparative Example 1 23.1

[0201] It can be seen from Table 3 that the nitrile rubber composition prepared in the present invention has excellent resistance to compression set.

[0202] The above description is only a preferred embodiment of the present invention, but the present invention is not limited to the scope of implementation shown. Any changes made in accordance with the concept of the present invention, or modifications to equivalent embodiments with equivalent changes, which still do not exceed the spirit covered by the specification, should be within the protection scope of the present invention.

Claims

1. A high temperature resistant and compression set resistant nitrile rubber composition, characterized in that: The following ingredients are included by weight: 100 parts of nitrile rubber, 5-8 parts of zinc oxide, 1-2 parts of sodium stearate, 1.5-3 parts of reinforcing supplementary additives, 0.02-0.03 parts of nano cerium oxide, 40-55 parts of carbon black, 2-5 parts of methylphenyl silicone oil, 6-10 parts of resin, 3-6 parts of antioxidant, 0.4-0.8 parts of sulfur, and 1-4 parts of accelerator.

2. The high temperature resistant and compression set resistant nitrile rubber composition according to claim 1, characterized in that: The carbon black is N550 carbon black; The antioxidants include antioxidant DNP, antioxidant ODA, and antioxidant MB; The mixing mass ratio of the antioxidant DNP, antioxidant ODA and antioxidant MB is 1:2:1; The accelerators include: accelerator BZ, accelerator TETD; The mixing mass ratio of the accelerator BZ to the accelerator TETD is 5:

1.

3. The high temperature resistant and compression set resistant nitrile rubber composition according to claim 2, characterized in that: The preparation method of the enhanced supplementary auxiliary agent is: First, diethylene glycol diglycidyl ether, propylene glycol n-propyl ether, and allyl glycidyl ether are sequentially added to an organic solvent, and then stirred and mixed to obtain a mixed solution; The mixed solution prepared above is added into the reactor, an inert gas is introduced into the reactor, and the air in the reactor is exhausted; Add the catalyst solution into the reactor, stir and mix for 10-15 minutes at room temperature, then drop the epichlorohydrin solution while stirring, after the dropwise addition is completed, continue to stir and react for 15-20 minutes, add methanol to the reaction solution to terminate the reaction, then add n-hexane for precipitation, filter, wash with water, and dry to obtain the enhanced supplementary auxiliary agent.

4. The high temperature resistant and compression set resistant nitrile rubber composition according to claim 3, characterized in that: The concentration of diethylene glycol diglycidyl ether in the mixed solution is 1-1.5 mol / L; The concentration of propylene glycol n-propyl ether is 0.5-1 mol / L; The concentration of allyl glycidyl ether is 1-1.5 mol / L; The concentration of the epichlorohydrin solution is 2-3 mol / L.

5. The high temperature resistant and compression set resistant nitrile rubber composition according to claim 3, characterized in that: The organic solvent is toluene.

6. The high temperature resistant and compression set resistant nitrile rubber composition according to claim 3, characterized in that: The inert gas is nitrogen or neon.

7. The high temperature resistant and compression set resistant nitrile rubber composition according to claim 2, characterized in that: The catalyst solution preparation method is: First, 1,8-diazabicycloundec-7-ene and calcium hydride are stirred at a mass ratio of 1:1 for 10-12 hours, then vacuum distilled and subjected to freeze degassing treatment twice, and then mixed with toluene and stirred evenly to obtain a 1,8-diazabicycloundec-7-ene solution; Among them, the concentration of 1,8-diazabicycloundec-7-ene solution is 0.3 mol / L; Under the protection of nitrogen atmosphere, phosphoric acid is added to ether, and the mixture is stirred to be uniform, so as to obtain a phosphoric acid solution; Wherein, the concentration of phosphoric acid solution is 0.85 mol / L; Under the protection of nitrogen atmosphere, triisobutylaluminum is added to toluene, and the mixture is stirred and mixed to obtain a triisobutylaluminum solution; Among them, the concentration of triisobutylaluminum solution is 0.8 mol / L; The 1,8-diazabicycloundec-7-ene solution, the phosphoric acid solution and the triisobutylaluminum solution were uniformly mixed in a volume ratio of 1:2:1 to obtain a catalyst solution.

8. The high temperature resistant and compression set resistant nitrile rubber composition according to claim 7, characterized in that: The mixed solution, catalyst solution, and epichlorohydrin solution have a mixed volume ratio of 5-6:0.2-0.4:8-10; The amount of methanol added was 5% of the reaction solution volume; The amount of n-hexane added was 60% of the volume of the reaction solution.

9. The method for preparing a high temperature resistant and compression set resistant nitrile rubber composition according to claim 1, characterized in that: include: 1) First, add the nitrile rubber into an internal mixer for internal mixing to obtain a rubber compound; 2) mixing the rubber obtained in step (1) with zinc oxide, sodium stearate, enhanced supplementary additives and methylphenyl silicone oil and performing a first mixing process; 3) After the first mixing, N550 carbon black and nano cerium oxide are added for the second mixing to obtain a mixed rubber; 4) Add sulfur, accelerator, and accelerator to the obtained rubber mixture in sequence for vulcanization treatment and thin pass treatment, and thin pass twice; In step (1), the mixture is mixed to 125-135° C. and then discharged, and then left to stand for 18-20 hours. The first mixing parameters are: mixing temperature is 120-125°C, mixing time is 4-5min; The second mixing parameters are: mixing temperature is 112-115°C, mixing time is 3-4min; The vulcanization treatment parameters are: the vulcanization temperature is 150-155°C, and the vulcanization time is 30-40 minutes.

10. A nitrile rubber composition prepared by the method as claimed in claim 9, used in a sealing ring.

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