CN116023725A - Hydrogenated nitrile rubber composition and application thereof, vulcanized rubber and preparation method and application thereof - Google Patents
Hydrogenated nitrile rubber composition and application thereof, vulcanized rubber and preparation method and application thereof Download PDFInfo
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- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 60
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 75
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 54
- 239000006229 carbon black Substances 0.000 claims abstract description 53
- 229920001971 elastomer Polymers 0.000 claims abstract description 34
- 239000005060 rubber Substances 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 25
- 239000004014 plasticizer Substances 0.000 claims abstract description 21
- 230000003213 activating effect Effects 0.000 claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical group 0.000 claims description 4
- 150000002978 peroxides Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005498 phthalate group Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000000306 component Substances 0.000 description 11
- 238000011056 performance test Methods 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LLZHXQRNOOAOFF-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2NC(S)=NC2=C1 LLZHXQRNOOAOFF-UHFFFAOYSA-N 0.000 description 1
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- -1 application thereof Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The invention relates to the field of rubber, and discloses a hydrogenated nitrile rubber composition and application thereof, vulcanized rubber and a preparation method and application thereof. The composition comprises hydrogenated nitrile rubber, a reinforcing agent, an activating agent, a plasticizer, an anti-aging agent, a vulcanizing agent and a crosslinking aid; the hydrogenated nitrile rubber comprises 100 parts of hydrogenated nitrile rubber, 30-95 parts of reinforcing agent, 4-15 parts of activating agent, 2-18 parts of plasticizer, 1-8 parts of anti-aging agent, 1-12 parts of vulcanizing agent and 5-25 parts of auxiliary crosslinking agent; the reinforcing agent comprises 15-60 parts of carbon black,15-30 parts of white carbon black and 2-5 parts of calcium sulfate whisker; the auxiliary crosslinking agent has a structure shown in a formula I;
Description
Technical Field
The invention relates to the field of rubber, in particular to a hydrogenated nitrile rubber composition, a preparation method of vulcanized rubber, the vulcanized rubber prepared by the method, and application of the hydrogenated nitrile rubber composition or the vulcanized rubber in an oilfield packer end cylinder.
Background
With the continuous deep development of oil and gas fields, more and more wells are required to be constructed by adopting the processes of layered injection and production, layered fracturing and staged water shutoff. The packer is one of key tools for petroleum well completion operation, and bears the heavy duty of sealing an oil-separating sleeve annulus and guaranteeing the safety of a well shaft. The rubber cylinder is a core component of the packer and is a direct executor of sealing effect, generally the packer rubber cylinder is formed by combining three rubber cylinders, the middle rubber cylinder mainly plays a role in sealing, and the end cylinders at the two ends play a role in bearing pressure, so that the end cylinders are required to have high hardness and equivalent strength, but the processability of high-hardness rubber is generally poor.
Therefore, how to maintain the performance of the packer packing material while improving the processability is one of the important research directions.
Disclosure of Invention
The invention aims to solve the problem of poor processability of packer rubber barrels for oil fields in the prior art, and provides a hydrogenated nitrile rubber composition, application thereof, vulcanized rubber, a preparation method thereof and application thereof.
In order to achieve the above object, the first aspect of the present invention provides a hydrogenated nitrile rubber composition, characterized in that the rubber composition comprises a hydrogenated nitrile rubber, a reinforcing agent, an activator, a plasticizer, an anti-aging agent, a vulcanizing agent and a secondary crosslinking agent;
the hydrogenated nitrile rubber comprises, by mass, 100 parts of hydrogenated nitrile rubber, 30-95 parts of reinforcing agent, 4-15 parts of activating agent, 2-18 parts of plasticizer, 1-8 parts of anti-aging agent, 1-12 parts of vulcanizing agent and 5-25 parts of auxiliary crosslinking agent;
the reinforcing agent comprises 15-60 parts by mass of carbon black, 15-30 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
the auxiliary crosslinking agent has a structure shown in a formula I;
wherein R is H, methyl or ethyl; r' is a C1-C5 alkylene group.
The second aspect of the present invention provides a method for producing a vulcanized rubber, characterized by comprising the steps of:
(1) First mixing a component A containing hydrogenated nitrile rubber, a reinforcing agent, an activating agent, an anti-aging agent and a plasticizer to obtain a master batch;
(2) Carrying out secondary mixing on the mixed rubber and a component B containing a vulcanizing agent and a secondary crosslinking agent to obtain final rubber;
(3) Vulcanizing the final rubber mixture to obtain vulcanized rubber;
wherein the content of the hydrogenated nitrile rubber is 100 parts by mass, the content of the reinforcing agent is 30-95 parts by mass, the content of the activating agent is 4-15 parts by mass, the content of the plasticizer is 2-18 parts by mass, the content of the anti-aging agent is 1-8 parts by mass, the content of the vulcanizing agent is 1-12 parts by mass, and the content of the auxiliary crosslinking agent is 5-25 parts by mass;
the reinforcing agent comprises 15-60 parts by mass of carbon black, 15-30 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
the auxiliary crosslinking agent has a structure shown in a formula I;
wherein R is H, methyl or ethyl; r' is a C1-C5 alkylene group.
In a third aspect, the present invention provides a vulcanized rubber produced by the above-described production method.
In a fourth aspect, the present invention provides the use of the hydrogenated nitrile rubber composition or vulcanized rubber described above in an oilfield packer end casing.
Through the technical scheme, the hydrogenated nitrile rubber composition and the application thereof, the vulcanized rubber and the preparation method and application thereof provided by the invention have the following beneficial effects:
the hydrogenated nitrile rubber composition provided by the invention adopts carbon black, white carbon black and calcium sulfate whiskers as reinforcing agents to be added into the hydrogenated nitrile rubber, and the reinforcing agents and the special auxiliary vulcanizing agents are combined to act together, so that the obtained rubber composition can obviously improve the processability of the hydrogenated nitrile rubber composition on the premise that the prepared vulcanized rubber has high strength and hardness, and the vulcanized rubber which has high strength and hardness and is easy to process and can meet the application requirements of a packer rubber cylinder can be obtained.
Furthermore, in the invention, the specific carbon black, the white carbon black and the calcium sulfate whisker are matched with the specific hydrogenated nitrile rubber, so that the strength, the hardness and the processing performance of the prepared vulcanized rubber can be further improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a hydrogenated nitrile rubber composition, characterized in that the rubber composition comprises a hydrogenated nitrile rubber, a reinforcing agent, an activator, a plasticizer, an anti-aging agent, a vulcanizing agent and a co-crosslinking agent;
the hydrogenated nitrile rubber comprises, by mass, 100 parts of hydrogenated nitrile rubber, 30-95 parts of reinforcing agent, 4-15 parts of activating agent, 2-18 parts of plasticizer, 1-8 parts of anti-aging agent, 1-12 parts of vulcanizing agent and 5-25 parts of auxiliary crosslinking agent;
the reinforcing agent comprises 15-60 parts by mass of carbon black, 15-30 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
the auxiliary crosslinking agent has a structure shown in a formula I;
wherein R is H, methyl or ethyl; r' is a C1-C5 alkylene group.
In the invention, the inventor researches and discovers that carbon black, white carbon black and calcium sulfate whisker are used as a reinforcing agent to be added into hydrogenated nitrile rubber to interact with other components, particularly a vulcanization system, and the obtained rubber composition can obviously improve the processability of the hydrogenated nitrile rubber composition on the premise that the prepared vulcanized rubber has high strength and hardness, so that the vulcanized rubber which has high strength and hardness and is easy to process and can meet the application requirements of a packer rubber cylinder can be obtained.
Further, the content of the hydrogenated nitrile rubber is 100 parts by mass, the content of the reinforcing agent is 45-85 parts by mass, the content of the activating agent is 5-13 parts by mass, the content of the plasticizer is 2-10 parts by mass, the content of the anti-aging agent is 2-6 parts by mass, the content of the vulcanizing agent is 3-8 parts by mass, and the content of the auxiliary crosslinking agent is 10-20 parts by mass;
the reinforcing agent comprises 25-52 parts by mass of carbon black, 18-28 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
in the formula I, R is H or methyl; r' is a C1-C3 alkylene group.
According to the invention, the Mooney viscosity ML of the hydrogenated nitrile rubber 1+4 100℃ More than or equal to 55 percent, the saturation is more than or equal to 90 percent, and the acrylonitrile content is more than or equal to 34 weight percent.
Further, the Mooney viscosity ML of the hydrogenated nitrile rubber 1+4 100℃ Is more than or equal to 65, the saturation is more than or equal to 95 percent, and the acrylonitrile content is more than or equal to 36 weight percent.
According to the invention, the carbon black has an iodine absorption value of 80-160g/kg and a DBP absorption value of (90-130). Times.10 -5 m 3 /kg。
According to the invention, the nitrogen adsorption specific surface area of the white carbon black is 100-220m 2 /g。
According to the invention, the diameter of the calcium sulfate whisker is 1-6 mu m, and the length-diameter ratio is (30-80): 1.
in the invention, the specific carbon black, the white carbon black and the calcium sulfate whisker are matched with the specific hydrogenated nitrile rubber, so that the strength, the hardness and the processability of the prepared vulcanized rubber can be further improved.
Further, the iodine absorption value of the carbon black is 120-160g/kg, and the DBP absorption value of the carbon black is (110-130) x 10 -5 m 3 /kg。
Further, the nitrogen adsorption specific surface area of the white carbon black is 150-220m 2 /g。
Further, the diameter of the calcium sulfate whisker is 1-3 mu m, and the length-diameter ratio is (30-50): 1.
according to the present invention, the antioxidant is at least one selected from the group consisting of amine antioxidants, phenol antioxidants, quinoline antioxidants and benzimidazole antioxidants.
According to the present invention, the plasticizer is selected from at least one of phthalates, fatty dibasic acid esters, partial benzene esters, ether esters and polyesters.
According to the invention, the activator is selected from the group consisting of metal oxides and fatty acids. Further, the metal oxide is selected from zinc oxide and/or magnesium oxide; the fatty acid is selected from stearic acid.
According to the invention, the vulcanizing agent is a peroxide vulcanizing agent.
Further, the vulcanizing agent is at least one selected from the group consisting of dicumyl peroxide, di-t-butyldicumyl peroxide and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
According to the invention, the co-crosslinking agent is selected from trimethylolpropane triacrylate (in formula I, R is H, R 'is methylene) and/or trimethylolpropane trimethacrylate (in formula I, R is methyl, R' is methylene).
The second aspect of the present invention provides a method for producing a vulcanized rubber, characterized by comprising the steps of:
(1) First mixing a component A containing hydrogenated nitrile rubber, a reinforcing agent, an activating agent, an anti-aging agent and a plasticizer to obtain a master batch;
(2) Carrying out secondary mixing on the mixed rubber and a component B containing a vulcanizing agent and a secondary crosslinking agent to obtain final rubber;
(3) Vulcanizing the final rubber mixture to obtain vulcanized rubber;
wherein the content of the hydrogenated nitrile rubber is 100 parts by mass, the content of the reinforcing agent is 30-95 parts by mass, the content of the activating agent is 4-15 parts by mass, the content of the plasticizer is 2-18 parts by mass, the content of the anti-aging agent is 1-8 parts by mass, the content of the vulcanizing agent is 1-12 parts by mass, and the content of the auxiliary crosslinking agent is 5-25 parts by mass;
the reinforcing agent comprises 15-60 parts by mass of carbon black, 15-30 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
the auxiliary crosslinking agent has a structure shown in a formula I;
wherein R is H, methyl or ethyl; r' is a C1-C5 alkylene group.
The raw materials for preparing the vulcanized rubber in the second aspect of the present invention adopt the composition described in the foregoing first aspect of the present invention, and the component a and the component B referred to in the second aspect together form the rubber composition described in the first aspect of the present invention, and thus, the kinds of raw material compositions in the second aspect of the present invention are all exactly the same as those described in the first aspect of the present invention, and the present invention is not repeated in the second aspect, and the person skilled in the art should not understand the limitation of the present invention.
According to the invention, the content of the hydrogenated nitrile rubber is 100 parts by mass, the content of the reinforcing agent is 45-85 parts by mass, the content of the activating agent is 5-13 parts by mass, the content of the plasticizer is 2-10 parts by mass, the content of the anti-aging agent is 2-6 parts by mass, the content of the vulcanizing agent is 3-8 parts by mass, and the content of the auxiliary crosslinking agent is 10-20 parts by mass;
the reinforcing agent comprises 25-52 parts by mass of carbon black, 18-28 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
the auxiliary crosslinking agent has a structure shown in a formula I;
wherein R is H or methyl; r' is a C1-C3 alkylene group.
In the present invention, the first mixing and the second mixing may be performed in mixing equipment conventional in the art, and preferably, the first mixing and the second mixing are performed in an internal mixer.
According to the invention, the process also comprises plasticating the hydrogenated nitrile rubber.
According to the invention, the conditions for plasticating the hydrogenated nitrile rubber include: plasticating temperature is 60-90 ℃; the plasticating time is 0.5-2min.
In the invention, an internal mixer is adopted to carry out internal mixing, and the rotating speed of the internal mixer is 60-80rpm during internal mixing.
According to the invention, the mixing temperature of the first mixing is 130-190 ℃, and the mixing time of the first mixing is 3-10min.
Further, the mixing temperature of the first mixing is 150-180 ℃; the mixing time of the first mixing is 5-8min.
In the invention, the rotating speed of the internal mixer is 60-80rpm during the first mixing.
In the invention, preferably, the method further comprises a step of plasticating a section of masterbatch, wherein the time for plasticating the masterbatch is 0.5-2min, and the temperature for plasticating the masterbatch is 40-60 ℃.
In the invention, the rotating speed of the internal mixer is 40-60rpm when the masterbatch is plasticated.
According to the invention, the mixing temperature of the second mixing is not more than 130 ℃, and the mixing time of the second mixing is 4-6min.
Further, the mixing temperature of the second mixing is 90-120 ℃; the mixing time of the second mixing is 4-5min.
In the invention, the rotating speed of the internal mixer is 40-60rpm during the second mixing.
According to the invention, the vulcanization conditions include: the vulcanizing time is 10-45min; the vulcanization temperature is 150-180 ℃; the vulcanizing pressure is 3.5-40MPa.
Further, the vulcanizing conditions include: the vulcanizing time is 15-35min; the vulcanization temperature is 165-180 ℃; the vulcanization pressure is 10-20MPa.
In the present invention, unless otherwise specified, the pressures used are gauge pressures.
In a third aspect, the present invention provides a vulcanized rubber produced by the above-described production method.
In a fourth aspect, the present invention provides the use of the above hydrogenated nitrile rubber composition or the above vulcanized rubber in an oilfield packer end cylinder.
The present invention will be described in detail by examples. In the following examples, various raw materials used below were all commercially available unless otherwise specified.
The equipment conditions for preparing vulcanized rubber in the following examples and comparative examples are shown in Table 1.
The test instruments and test conditions of the vulcanized rubbers obtained in examples and comparative examples are shown in Table 2 and Table 3.
The chemical reagents used in the examples and comparative examples are commercially available, and are specifically as follows:
hydrogenated nitrile rubber: 4309, ML 1+4 100℃ 100, 99% saturation, 43% acrylonitrile content, allangaceae product; 2010, ML 1+4 100℃ 85, 95% saturation, 36% acrylonitrile content, and a japanese rayleigh product; 3310, ML 1+4 100℃ 80, 95% saturation, 25% acrylonitrile content by weight, japanese rayleigh product;
carbon black N234 having an iodine absorption of 120g/kg and a DBP absorption of 115X 10 -5 m 3 Kg, dongguan Ji Deli chemical technology Co., ltd;
carbon black N774 with iodine absorption of 29g/kg and DBP absorption of 72×10 -5 m 3 Kg, cabot corporation;
white carbon 1165MP, BET 165m 2 G, qingdao Rodi white carbon Limited;
white carbon black 90GR, BET 90m 2 And/g, si Cheng chemical Co., ltd;
calcium sulfate whisker-1: the Jiangsu New Source mining Co., ltd., has an aspect ratio of 45:1 and an average diameter of 3 μm;
calcium sulfate whisker-2: jiangsu New Source mining Co., ltd., aspect ratio 15:1, average diameter 8 μm;
and (3) a plasticizer: trioctyl trimellitate (TOTM), shandong Langtai chemical Co., ltd;
an activating agent: zinc oxide, stearic acid, weifang Hengfeng chemical Co., ltd;
anti-aging agent: 4,4' -bis (α, α -dimethylbenzyl) diphenylamine (anti 445), shanghon Mei New Material technologies Co., ltd; 2-mercaptobenzimidazole zinc (MBZ-protected), a new chemical plant in the sea;
vulcanizing agent: dicumyl peroxide (DCP), shanghai Fang Rui, available from chemical company, inc;
auxiliary crosslinking agent: trimethylolpropane triacrylate (TMPTA), jiangsu Huaxing New Material technologies Co., ltd.
The amounts of the components in the following examples and comparative examples are parts by mass.
TABLE 1
| Sequence number | Device name | Model number | Manufacturing factories |
| 1 | Banbury mixer | BR1600 | America Rayleigh Corp |
| 2 | Open mill | XK-160 | Qingdao Xincheng Yi Ming mechanical Co Ltd |
| 3 | Flat vulcanizing machine | XLB-D400*400*2 | First rubber machinery plant of Shanghai |
TABLE 2
TABLE 3 Table 3
Example 1
The formula comprises the following components: hydrogenated nitrile rubber 4309 100; carbon black N234 38; white carbon 1165mp 23; calcium sulfate whisker-1 5; TOTM 6; zinc oxide 4; stearic acid 1; a vulcanizing agent 6; a secondary cross-linking agent 15; an anti-aging agent 445 2; an anti-aging agent MBZ 2.
Setting the rotating speed of the internal mixer to 80rpm, and plasticating raw rubber for 0.5min at the initial mixing temperature of 80 ℃; adding all materials except a vulcanizing agent and a crosslinking assistant for first mixing, wherein the first mixing temperature is 150-180 ℃, the first mixing time is 5min, discharging, and standing for 4h after discharging; setting the rotating speed of the internal mixer to be 60rpm, setting the initial plasticating temperature to be 40 ℃, plasticating the masterbatch in the previous step for 1min, adding a vulcanizing agent and a crosslinking assistant for secondary mixing, wherein the secondary mixing time is 4min, the secondary mixing temperature is 110-120 ℃, and discharging.
The mixed sample is subjected to plate vulcanization at 170 ℃ under the pressure of 15MPa for 20min, and the prepared sample is marked as S-1.
The test results of the performance test on sample S-1 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 2
The formula comprises the following components: hydrogenated nitrile rubber 2010 100; carbon black N234 52; white carbon 1165mp 28; calcium sulfate whisker-1 2; TOTM 10; zinc oxide 10; stearic acid 3; a vulcanizing agent 3; a co-crosslinking agent 10; an anti-aging agent 445 1; an anti-aging agent MBZ 1.
Setting the rotating speed of the internal mixer to 80rpm, and plasticating the raw rubber for 1min at the initial mixing temperature of 80 ℃; adding all other fillers except vulcanizing agent and auxiliary crosslinking agent for first mixing, wherein the first mixing temperature is 150-180 ℃, the first mixing time is 8min, discharging, and standing for 4h after discharging; setting the rotating speed of the internal mixer to be 60rpm, setting the initial plasticating temperature to be 40 ℃, plasticating the masterbatch in the previous step for 1min, adding a vulcanizing agent and a crosslinking assistant for secondary mixing, wherein the secondary mixing time is 4min, the secondary mixing temperature is 110-120 ℃, and discharging.
The mixed sample is subjected to plate vulcanization at 170 ℃ under the pressure of 15MPa for 20min, and the prepared sample is marked as S-2.
The test results of the performance test on sample S-2 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 3
The formula comprises the following components: hydrogenated nitrile rubber 4309 100; carbon black N234; white carbon 1165mp 18; calcium sulfate whisker-1 4; TOTM 2; zinc oxide 7; stearic acid 2; a vulcanizing agent 8; a co-crosslinking agent 20; an anti-aging agent 445 3; an anti-aging agent MBZ 3.
Setting the rotating speed of the internal mixer to 80rpm, and plasticating the raw rubber for 1min at the initial mixing temperature of 80 ℃; adding all other fillers except vulcanizing agent and auxiliary crosslinking agent for first mixing, wherein the first mixing temperature is 150-180 ℃, the first mixing time is 4min, discharging, and standing for 4h after discharging; setting the rotating speed of the internal mixer to be 60rpm, setting the initial plasticating temperature to be 40 ℃, plasticating the masterbatch in the previous step for 1min, adding a vulcanizing agent and a crosslinking assistant for secondary mixing, wherein the secondary mixing time is 4min, the secondary mixing temperature is 110-120 ℃, and discharging.
The mixed sample is subjected to plate vulcanization at 170 ℃ under 15MPa for 20min, and the prepared sample is marked as S-3.
The test results of the performance test on sample S-3 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 4
A vulcanized rubber sample was prepared as in example 1, except that: the dosage of the carbon black is 60, the white carbon black 1165MP is 30 parts, and the calcium sulfate whisker-1 is 5 parts.
The sample obtained is designated S-4.
The test results of the performance test on sample S-4 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 5
A sample of vulcanized rubber was prepared as in example 2, except that: TOTM was used in an amount of 18 parts.
The sample obtained was labeled S-5.
The test results of the performance test on sample S-5 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 6
A sample of vulcanized rubber was prepared as in example 3, except that: the DCP was used in an amount of 12 parts.
The sample obtained is designated S-6.
The test results of the performance test on sample S-6 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 7
A vulcanized rubber sample was prepared as in example 1, except that: the white carbon black is 90GR.
The sample obtained is designated S-7.
The test results of the performance test on sample S-7 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 8
A vulcanized rubber sample was prepared as in example 1, except that: and replacing the calcium sulfate whisker-1 with the calcium sulfate whisker-2.
The sample obtained is designated S-8.
The test results of the performance test on sample S-8 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 9
A vulcanized rubber sample was prepared as in example 1, except that: carbon black N234 was replaced with 20 parts of carbon black N234 and 18 parts of carbon black N774.
The sample obtained was designated S-9.
The test results of the performance test on sample S-9 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Example 10
A vulcanized rubber sample was prepared as in example 1, except that: hydrogenated nitrile rubber 3310 is used in place of hydrogenated nitrile rubber 4309.
The sample obtained is designated S-10.
The test results of the performance test on sample S-10 are shown in Table 4, according to the experimental methods shown in tables 2 and 3.
Comparative example 1
A vulcanized rubber sample was prepared as in example 1, except that: the amount of the auxiliary crosslinking agent was adjusted to 3 parts.
The sample obtained is designated D-1.
The performance of sample D-1 was tested according to the experimental methods shown in tables 2 and 3, and the results are shown in Table 4.
Comparative example 2
A sample of vulcanized rubber was prepared as in example 2, except that: the carbon black was replaced with an equal weight portion of calcium sulfate whiskers.
The sample obtained is designated D-2.
The performance of sample D-2 was tested according to the experimental methods shown in tables 2 and 3, and the results are shown in Table 4.
Comparative example 3
A sample of vulcanized rubber was prepared as in example 3, except that: the carbon black was replaced with an equal weight of white carbon black.
The sample obtained was labeled D-3.
The performance of sample D-3 was tested according to the experimental methods shown in tables 2 and 3, and the results are shown in Table 4.
Comparative example 4
A vulcanized rubber sample was prepared as in example 1, except that: the amount of carbon black used was 5.
The sample obtained is designated D-4.
The performance of sample D-4 was tested according to the experimental methods shown in tables 2 and 3, and the results are shown in Table 4.
TABLE 4 Table 4
| Sample numbering | Tensile Strength (MPa) | Shore A hardness/degree | Mooney viscosity of the rubber compound |
| S1 | 26.2 | 95 | 95 |
| S2 | 25.3 | 94 | 91 |
| S3 | 25.6 | 94 | 86 |
| S4 | 24.5 | 96 | 99 |
| S5 | 24.1 | 91 | 87 |
| S6 | 23.5 | 95 | 86 |
| S7 | 23.1 | 92 | 93 |
| S8 | 22.1 | 94 | 95 |
| S9 | 23.3 | 93 | 94 |
| S10 | 21.2 | 90 | 94 |
| D1 | 19.8 | 84 | 128 |
| D2 | 16.1 | 75 | 89 |
| D3 | 17.7 | 93 | 109 |
| D4 | 16.3 | 81 | 85 |
As can be seen from Table 4, the rubber composition of the present invention gives a vulcanized rubber having a high strength and a high hardness, and at the same time, the rubber composition of the present invention has a low rubber compound Mooney viscosity, indicating that the composition has excellent processability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. A hydrogenated nitrile rubber composition, characterized in that the rubber composition comprises a hydrogenated nitrile rubber, a reinforcing agent, an activator, a plasticizer, an anti-aging agent, a vulcanizing agent, and a secondary crosslinking agent;
the hydrogenated nitrile rubber comprises, by mass, 100 parts of hydrogenated nitrile rubber, 30-95 parts of reinforcing agent, 4-15 parts of activating agent, 2-18 parts of plasticizer, 1-8 parts of anti-aging agent, 1-12 parts of vulcanizing agent and 5-25 parts of auxiliary crosslinking agent;
the reinforcing agent comprises 15-60 parts by mass of carbon black, 15-30 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
the auxiliary crosslinking agent has a structure shown in a formula I;
wherein R is H, methyl or ethyl; r' is a C1-C5 alkylene group.
2. The hydrogenated nitrile rubber composition according to claim 1, wherein the content of the hydrogenated nitrile rubber is 100 parts by mass, the content of the reinforcing agent is 45 to 85 parts by mass, the content of the activating agent is 5 to 13 parts by mass, the content of the plasticizer is 2 to 10 parts by mass, the content of the anti-aging agent is 2 to 6 parts by mass, the content of the vulcanizing agent is 3 to 8 parts by mass, and the content of the auxiliary crosslinking agent is 10 to 20 parts by mass;
the reinforcing agent comprises 25-52 parts by mass of carbon black, 18-28 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
in the formula I, R is H or methyl; r' is a C1-C3 alkylene group.
3. The hydrogenated nitrile rubber composition according to claim 1 or 2, wherein the hydrogenated nitrile rubber has a mooney viscosity ML 1+4 100℃ More than or equal to 55 percent, the saturation is more than or equal to 90 percent, and the acrylonitrile content is more than or equal to 34 weight percent.
4. The hydrogenated nitrile rubber composition according to any one of claims 1 to 3, wherein said carbon black has an iodine absorption value of 80 to 160g/kg and a DBP absorption value of (90 to 130). Times.10 -5 m 3 /kg。
5. The hydrogenated nitrile rubber composition according to any one of claims 1 to 4, wherein the white carbon black has a nitrogen adsorption specific surface area of 100 to 220m 2 /g。
6. The hydrogenated nitrile rubber composition according to any one of claims 1 to 5, wherein said calcium sulfate whiskers have a diameter of 1 to 6 μm and an aspect ratio of (30 to 80): 1.
7. the hydrogenated nitrile rubber composition according to any one of claims 1 to 6, wherein the antioxidant is at least one selected from the group consisting of amine antioxidants, phenolic antioxidants, quinoline antioxidants and benzimidazole antioxidants;
preferably, the plasticizer is selected from at least one of phthalates, fatty dibasic acid esters, partial benzene esters, ether esters and polyesters;
preferably, the activator is selected from the group consisting of metal oxides and fatty acids;
preferably, the metal oxide is selected from zinc oxide and/or magnesium oxide;
preferably, the fatty acid is selected from stearic acid;
preferably, the vulcanizing agent is a peroxide vulcanizing agent, preferably at least one of dicumyl peroxide, di-t-butyldicumyl peroxide, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
8. A method for preparing vulcanized rubber, characterized in that the method comprises the following steps:
(1) First mixing a component A containing hydrogenated nitrile rubber, a reinforcing agent, an activating agent, an anti-aging agent and a plasticizer to obtain a master batch;
(2) Carrying out secondary mixing on the mixed rubber and a component B containing a vulcanizing agent and a secondary crosslinking agent to obtain final rubber;
(3) Vulcanizing the final rubber mixture to obtain vulcanized rubber;
wherein the content of the hydrogenated nitrile rubber is 100 parts by mass, the content of the reinforcing agent is 30-95 parts by mass, the content of the activating agent is 4-15 parts by mass, the content of the plasticizer is 2-18 parts by mass, the content of the anti-aging agent is 1-8 parts by mass, the content of the vulcanizing agent is 1-12 parts by mass, and the content of the auxiliary crosslinking agent is 5-25 parts by mass;
the reinforcing agent comprises 15-60 parts by mass of carbon black, 15-30 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker;
the auxiliary crosslinking agent has a structure shown in a formula I;
wherein R is H, methyl or ethyl; r' is a C1-C5 alkylene group.
9. The production method according to claim 8, wherein the hydrogenated nitrile rubber is contained in an amount of 100 parts by mass, the reinforcing agent is contained in an amount of 45 to 85 parts by mass, the activating agent is contained in an amount of 5 to 13 parts by mass, the plasticizer is contained in an amount of 2 to 10 parts by mass, the anti-aging agent is contained in an amount of 2 to 6 parts by mass, the vulcanizing agent is contained in an amount of 3 to 8 parts by mass, and the auxiliary crosslinking agent is contained in an amount of 10 to 20 parts by mass;
the reinforcing agent comprises 25-52 parts by mass of carbon black, 18-28 parts by mass of white carbon black and 2-5 parts by mass of calcium sulfate whisker.
10. The production process according to claim 8 or 9, wherein the process further comprises plasticating the hydrogenated nitrile rubber;
preferably, the plastication temperature is 60-90 ℃; the plasticating time is 0.5-2min.
11. The method of any one of claims 8-10, wherein the first mixing has a mixing temperature of 130-190 ℃, preferably 150-180 ℃; the mixing time of the first mixing is 3-10min, preferably 5-8min;
preferably, the mixing temperature of the second mixing is not more than 130 ℃, preferably 90-120 ℃; the mixing time of the second mixing is 4-6min, preferably 4-5min;
preferably, the vulcanization conditions include: the vulcanization time is 10-45min, preferably 15-35min; the vulcanization temperature is 150-180 ℃, preferably 165-180 ℃; the vulcanization pressure is 3.5-40MPa, preferably 10-20MPa.
12. A vulcanized rubber prepared by the preparation method of any one of claims 8 to 11.
13. Use of the hydrogenated nitrile rubber composition of any one of claims 1 to 7 or the vulcanized rubber of claim 12 in an oilfield packer end casing.
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