CN115819861A - 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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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 40
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920001971 elastomer Polymers 0.000 claims abstract description 60
- 239000005060 rubber Substances 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 239000006229 carbon black Substances 0.000 claims abstract description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004014 plasticizer Substances 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000012936 vulcanization activator Substances 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 12
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008117 stearic acid Substances 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 43
- 238000004073 vulcanization Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims 1
- 238000005486 sulfidation Methods 0.000 claims 1
- 238000007906 compression Methods 0.000 abstract description 13
- 230000006835 compression Effects 0.000 abstract description 13
- 239000003566 sealing material Substances 0.000 abstract description 10
- 239000003921 oil Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 12
- 230000032683 aging Effects 0.000 description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical group 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 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-butadiene rubber composition and application thereof, and vulcanized rubber and a preparation method and application thereof, wherein the composition comprises 100 parts by weight of matrix rubber hydrogenated nitrile-butadiene rubber, a reinforcing agent, 1-9 parts by weight of a vulcanizing agent, 1-8 parts by weight of an auxiliary vulcanizing agent, a vulcanization activator, 0.5-5 parts by weight of an anti-aging agent and 0-20 parts by weight of a plasticizer, the reinforcing agent contains 30-70 parts by weight of carbon black, 5-20 parts by weight of white carbon black and 5-15 parts by weight of acrylic acid metal salt, and the vulcanization activator contains 2-7 parts by weight of zinc oxide, 3-10 parts by weight of magnesium oxide and 1-5 parts by weight of stearic acid. The composition can ensure that vulcanized rubber prepared from the composition has the advantages of high mechanical strength, good heat resistance, excellent oil resistance, low compression set and the like, and further can meet the application requirements in the field of oilfield sealing materials.
Description
Technical Field
The invention relates to the field of rubber, and in particular relates to a hydrogenated nitrile-butadiene rubber composition and application thereof, and vulcanized rubber and a preparation method and application thereof.
Background
The hydrogenated nitrile rubber is a special synthetic rubber product prepared from nitrile rubber through catalytic hydrogenation, and due to the fact that molecular chains have high saturability, the material is endowed with special properties such as high temperature resistance and chemical corrosion resistance on the basis of inheriting excellent properties such as good oil resistance and high strength of the nitrile rubber, and the hydrogenated nitrile rubber is widely applied to the fields of key strategic cores of aerospace, oil fields, high-speed rails, automobiles and the like, high-end equipment manufacturing and the like.
Crude oil extraction is one of the most important fields of application of hydrogenated nitrile rubber, the main application component being sealing materials. In recent years, domestic oil fields gradually develop towards deep wells, ultra-deep wells and thermal production wells, enter secondary oil production and tertiary oil production stages, provide more rigorous service condition requirements for sealing materials, and collectively show that the materials are required to have the properties of high strength, high temperature resistance, oil resistance, corrosion resistance and the like. By selecting a proper base material, optimizing a formula and a processing technology, the research hotspot in the rubber industry field is formed by synergistically improving various performance indexes of the sealing material for the oil field.
Disclosure of Invention
The invention aims to solve the problems of low rubber strength, poor heat resistance, poor oil resistance and poor corrosion resistance in the prior art, and provides a hydrogenated nitrile rubber composition and application thereof, vulcanized rubber and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a hydrogenated nitrile rubber composition, which comprises a rubber matrix, a reinforcing agent, a vulcanizing agent, a co-vulcanizing agent, a vulcanization activator, an anti-aging agent and a plasticizer, wherein the rubber matrix is hydrogenated nitrile rubber, the reinforcing agent contains carbon black, white carbon black and an acrylic acid metal salt, and the vulcanization activator contains zinc oxide, magnesium oxide and stearic acid;
the rubber composition comprises, by weight, 30-70 parts of carbon black, 5-20 parts of white carbon black, 5-15 parts of acrylic acid metal salt, 2-7 parts of zinc oxide, 3-10 parts of magnesium oxide, 1-5 parts of stearic acid, 1-9 parts of a vulcanizing agent, 1-8 parts of an auxiliary vulcanizing agent, 0.5-5 parts of an anti-aging agent and 0-20 parts of a plasticizer, wherein the carbon black is contained in 100 parts of a rubber matrix.
The second aspect of the present invention provides a method for producing a vulcanized rubber, characterized in that the method comprises: the rubber composition is prepared by mixing the components to obtain a mixed rubber, and then vulcanizing the mixed rubber.
The third aspect of the present invention provides a vulcanized rubber obtained by the above-mentioned production method.
The fourth aspect of the present invention provides the use of the above rubber composition or vulcanized rubber in oilfield sealing materials.
Through the technical scheme, the hydrogenated nitrile rubber composition and the application thereof, the vulcanized rubber and the preparation method and the application thereof provided by the invention have the following beneficial effects:
the hydrogenated nitrile rubber composition provided by the invention comprises hydrogenated nitrile rubber, a reinforcing agent containing carbon black, white carbon black and acrylic acid metal salt, and a vulcanization activator containing zinc oxide, magnesium oxide and stearic acid, and the reinforcing agent and the vulcanization activator are matched with other specific components in a specific proportion, so that the vulcanized rubber prepared from the composition has the advantages of high mechanical strength, good heat resistance, excellent oil resistance, low compression set and the like, and further can meet the application requirements in the field of oilfield sealing materials.
Further, the rubber composition provided by the invention is subjected to mixing, particularly, each component in the composition is subjected to segmented mixing and then vulcanized, so that the obtained vulcanized rubber has the advantages of high mechanical strength, good heat resistance, excellent oil resistance, low compression set and the like, and further can meet the application requirements in the field of oilfield sealing materials.
Further, by controlling the conditions such as the kneading temperature and the vulcanization conditions in each stage, the mechanical properties, heat resistance, oil resistance and compression set of the vulcanized rubber obtained are further improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In order to achieve the above object, a first aspect of the present invention provides a hydrogenated nitrile rubber composition, which comprises a rubber matrix, a reinforcing agent, a vulcanizing agent, a co-vulcanizing agent, a vulcanization activator, an anti-aging agent and a plasticizer, wherein the rubber matrix is hydrogenated nitrile rubber, the reinforcing agent contains carbon black, white carbon black and an acrylic acid metal salt, and the vulcanization activator contains zinc oxide, magnesium oxide and stearic acid;
the rubber composition comprises, by weight, 30-70 parts of carbon black, 5-20 parts of white carbon black, 5-15 parts of acrylic acid metal salt, 2-7 parts of zinc oxide, 3-10 parts of magnesium oxide, 1-5 parts of stearic acid, 1-9 parts of a vulcanizing agent, 1-8 parts of an auxiliary vulcanizing agent, 0.5-5 parts of an anti-aging agent and 0-20 parts of a plasticizer, wherein the carbon black is contained in 100 parts of a rubber matrix.
According to the invention, the hydrogenated nitrile rubber composition comprises hydrogenated nitrile rubber, a reinforcing agent containing carbon black, white carbon black and acrylic acid metal salt and a vulcanization activator containing zinc oxide, magnesium oxide and stearic acid, and the hydrogenated nitrile rubber composition is matched with other specific components in a specific proportion, so that the vulcanized rubber prepared from the composition has the advantages of high mechanical strength, good heat resistance, excellent oil resistance, low compression set and the like, and further can meet the application requirements in the field of oilfield sealing materials.
Further, when the content of the carbon black is 40 to 60 parts by weight, the content of the white carbon black is 8 to 15 parts by weight, the content of the acrylic metal salt is 5 to 10 parts by weight, the content of the zinc oxide is 3 to 6 parts by weight, the content of the magnesium oxide is 4 to 8 parts by weight, the content of the stearic acid is 1 to 3 parts by weight, the content of the vulcanizing agent is 2 to 6 parts by weight, the content of the co-vulcanizing agent is 2 to 5 parts by weight, the content of the anti-aging agent is 1 to 4 parts by weight, and the content of the plasticizer is 2 to 12 parts by weight, relative to 100 parts by weight of the rubber matrix, the overall performance of the vulcanized rubber prepared from the rubber composition is further improved.
According to the invention, the content of the hydrogenated nitrile rubber combined acrylonitrile structural unit is 15-50 wt%, the hydrogenation degree is more than or equal to 95%, and the Mooney viscosity ML (1 + 4) is 60-150 at 100 ℃.
Furthermore, the content of the hydrogenated nitrile rubber combined acrylonitrile structural unit is 20-40 wt%, the hydrogenation degree is more than or equal to 99%, and the Mooney viscosity ML (1 + 4) is 70-120 at 100 ℃.
According to the invention, the carbon black has a specific surface area of 70 to 130m 2 /g。
According to the invention, the specific surface area of the white carbon black is 70-250m 2 A/g, preferably of 115 to 200m 2 /g。
According to the invention, the acrylic acid-like metal salt is an acrylic acid-like zinc salt, preferably zinc methacrylate.
In the invention, the vulcanizing agent is a peroxide vulcanizing agent. In particular, the peroxide curative may be selected from DCP and/or bis-di-penta.
In the present invention, the co-curing agent may be a co-curing agent conventional in the art, and preferably, in order to increase the crosslinking efficiency and the curing rate, the co-curing agent is selected from TAIC and/or HVA-2.
In the present invention, the antioxidant may be an antioxidant of a kind conventional in the art, specifically, the antioxidant is at least one selected from quinoline antioxidants, diphenylamine antioxidants, naphthylamine antioxidants and imidazole antioxidants, preferably, the antioxidant is a combination of diphenylamine antioxidants and imidazole antioxidants, and more preferably, the amounts of diphenylamine antioxidants and imidazole antioxidants are 1-2.
In the present invention, the plasticizer may be an agent which is conventional in the art and can improve the mixing efficiency of the rubber composition and the processability of the rubber composition, preferably, the plasticizer is at least one selected from the group consisting of a coal tar-based plasticizer, a fatty oil-based plasticizer, and a synthetic plasticizer, and more preferably, the plasticizer is a high-boiling point synthetic plasticizer.
The second aspect of the present invention provides a method for producing a vulcanized rubber, characterized in that the method comprises: the rubber composition is prepared by mixing the components to obtain a mixed rubber, and then vulcanizing the mixed rubber.
In order to enable the rubber compound prepared from the rubber composition of the invention to have better processability, and further enable the vulcanized rubber obtained by the rubber compound to have high mechanical strength, good heat resistance, excellent oil resistance and low compression set, the rubber composition is prepared by mixing the components according to the following steps:
(1) Carrying out first mixing on a component A containing a rubber matrix, a reinforcing agent, a vulcanization activator, an anti-aging agent and an optional plasticizer to obtain a master batch;
(2) And carrying out second mixing on the master batch and a component B containing a vulcanizing agent and an auxiliary vulcanizing agent to obtain the rubber compound.
The raw materials for preparing the vulcanized rubber in the second aspect of the invention adopt the composition described in the first aspect of the invention, and the component A and the component B related in the second aspect together form the rubber composition described in the first aspect of the invention, so the types of the raw materials in the second aspect of the invention are completely the same as the types described in the first aspect of the invention, the invention is not described in detail in the second aspect in order to avoid repetition, and the person skilled in the art should not be understood as limiting the invention.
In the invention, the rubber composition is obtained by mixing the components in the rubber composition to obtain a rubber compound, and particularly, the components in the composition are vulcanized after being mixed in sections, so that the vulcanized rubber obtained by the method has the advantages of high mechanical strength, good heat resistance, excellent oil resistance, low compression set and the like, and further can meet the application requirements in the field of oil field sealing materials.
According to the invention, the conditions of the first mixing include: the mixing temperature is 80-100 ℃, and the mixing time is 3-8min.
According to the invention, the conditions of the second mixing comprise: the mixing temperature is 30-60 ℃, and the mixing time is 3-6min.
Further, the conditions of the second mixing include: the mixing temperature is 35-55 ℃, and the mixing time is 4-5min.
In the present invention, the mixing may be carried out in mixing equipment conventional in the art, such as an open mill and/or an internal mixer, preferably, the mixing is carried out in an internal mixer.
According to the invention, said first mixing is carried out in an internal mixer at a speed of 50 to 90rpm, preferably 60 to 80rpm.
According to the invention, said second mixing is carried out in an internal mixer at a speed of 30 to 80rpm, preferably 40 to 60rpm.
According to the invention, the conditions of the vulcanization treatment include: the vulcanization temperature is 160-200 ℃, the vulcanization pressure is 3-20MPa, and the vulcanization time is 2-30min.
Further, the conditions of the vulcanization treatment include: the vulcanization temperature is 170-190 ℃, the vulcanization pressure is 10-15MPa, and the vulcanization time is 5-20min.
In the present invention, the rubber composition may be tabletted, for example, in an open mill, before the rubber composition is vulcanized. Preferably, the open mill conditions include: the open milling temperature is 30-70 ℃. Preferably, the tabletted rubber compound is left for 4-48h.
The third aspect of the present invention provides a vulcanized rubber obtained by the above-mentioned production method.
In the invention, the tensile strength of the vulcanized rubber is more than or equal to 19MPa, preferably more than or equal to 27MPa, and more preferably 28-31MPa; the elongation at break of the vulcanized rubber is 280-410%, preferably 280-400%, more preferably 350-400%; the compression set of the vulcanized rubber is less than or equal to 31 percent, preferably less than or equal to 20 percent, and more preferably less than or equal to 15 percent; under the conditions of 150 ℃ and 70h of thermal oxidation aging, the strength change rate of the vulcanized rubber is less than or equal to +/-18 percent, preferably less than or equal to +/-5 percent, and more preferably less than or equal to +/-3 percent; under the oil-resistant condition of 150 ℃ and 70h, the tensile strength change rate of the vulcanized rubber is less than or equal to +/-15%, preferably less than or equal to +/-5%, and more preferably less than or equal to +/-4%; the volume change rate of the vulcanized rubber is less than or equal to +/-10%, preferably less than or equal to +/-6%, and more preferably less than or equal to +/-4%.
In a fourth aspect, the present invention provides the use of the above hydrogenated nitrile rubber composition or vulcanized rubber in oilfield sealing materials.
Unless otherwise specified, all pressures described herein are expressed as gauge pressure.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used were commercially available unless otherwise specified.
Hydrogenated nitrile rubber: manufactured by Nippon Ruizhong company, the mark is 1000L, the content of acrylonitrile is 44 weight percent, the hydrogenation degree is more than or equal to 99 percent, and the Mooney viscosity ML (1 + 4) is 65 ℃ at 100 ℃; 2010H, acrylonitrile content of 36 wt%, hydrogenation degree of 95%, mooney viscosity ML (1 + 4) at 100 ℃ of 140; the trade mark 4300, the acrylonitrile content is 18 weight percent, the hydrogenation degree is more than or equal to 99 percent, and the Mooney viscosity ML (1 + 4) is 75 at 100 ℃; designation 2020, acrylonitrile content of 36% by weight, hydrogenation degree of 90%, mooney viscosity ML (1 + 4) at 100 ℃ of 85; zangnan company, trademark 35053, acrylonitrile content 36 wt%, hydrogenation degree not less than 99%, mooney viscosity ML (1 + 4) 100 deg.C 35.
Carbon black: number N330 (specific surface area 73-85 m) 2 Per gram) and N234 (specific surface area 109-125 m) 2 (g) from Zideli chemical technology, inc. of Dongguan city;
white carbon black: number 165MP (specific surface area 150-180 m) 2 (g) from underwriters laboratories, inc.;
zinc methacrylate (ZDMA): industrial grade products, available from maireil chemical technologies, inc;
vulcanizing agent: dicumyl peroxide (DCP), 2, 5-dimethyl-2, 5-DI (t-butylperoxy) hexane (bis-penta), national pharmaceutical group Chemicals, inc.;
auxiliary vulcanizing agent: triallyl isocyanurate (TAIC), N, N' -m-phenylene bismaleimide (HVA-2), shanghai Aladdin Biotech Ltd;
vulcanization activating agent: zinc oxide, magnesium oxide and stearic acid purchased from Weifang Hengfeng chemical Limited;
an anti-aging agent: anti-aging agent 445, anti-aging agent ODA, anti-aging agent MBZ, purchased from Jiangsu saint ao chemical technology Co., ltd;
plasticizer: plasticizer TP-95, plasticizer TOTM, available from Jinan Henry chemical Co., ltd.
The rubber processing and testing equipment conditions in the following examples are shown in table 1:
TABLE 1
| Serial number | Device name | Type number | Manufacturer of the product | Use of |
| 1 | Internal mixer | BR1600 | Farrel America Ltd | Mixing the raw materials |
| 2 | Open mill | XK-160 | Qingdao Xincheng Yiming mechanical Co Ltd | Tabletting/milling |
| 3 | Flat vulcanizing machine | XLB-D400*400*2 | Shanghai first rubber machinery plant | Vulcanization |
| 4 | Universal tensile machine | SHIMADZU,AG-20KNG | Shimadzu Japan Ltd | Mechanical testing |
| 5 | Aging tester | GT-7017-EL1 | Taiwan area high speed railway | Aging resistance test |
The amounts of the components in the following examples are parts by weight (or parts by weight).
The composition formulations of the present example and comparative example are shown in table 2.
The preparation method of the vulcanized rubber comprises the following steps:
first mixing:
setting the initial temperature of an internal mixer to be 90 ℃, setting the rotation speed to be 70rpm, adding a rubber matrix, a reinforcing agent, an activator, an anti-aging agent and an optional plasticizer into the internal mixer to perform first mixing for 6min, setting the first mixing temperature to be 90 ℃, discharging rubber, and standing for 4h to obtain master batch.
And (3) second mixing:
setting the initial temperature of the internal mixer to be 40 ℃, setting the rotation speed to be 60rpm, putting the master batch, the vulcanizing agent and the co-vulcanizing agent into the internal mixer, carrying out second mixing for 4.5min, and discharging rubber at the second mixing temperature of 40 ℃ to obtain the rubber compound.
The mixed rubber obtained by the method is passed through an open mill with the roller spacing of 0.5mm and the roller temperature of 50 +/-5 ℃ for one time, then the roller spacing is adjusted to 5mm, and the mixed rubber is passed through the open mill for two times and is parked for 24 hours. In the following examples, the operating conditions and the standing time of the compound in the open mill were all the same as in the present example, unless otherwise specified.
And vulcanizing the rubber compound on a flat vulcanizing machine to obtain vulcanized rubber which is marked as S1. The remaining examples and comparative examples were carried out by the same procedure as in example 1, unless otherwise specified, and the formulations and specific process conditions of the respective examples are shown in Table 2.
TABLE 2
Table 2 (continuation watch)
Table 2 (continuation watch)
Example 8
A vulcanized rubber was prepared in the same manner as in example 1, except that,
the preparation process of the vulcanized rubber is different from that of the embodiment 1, specifically, the first mixing temperature is 60 ℃, the time is 10min, and the rotating speed is 45rpm;
the second mixing temperature is 65 ℃, the time is 2.5min, and the rotating speed is 85rpm;
the vulcanization conditions include: the vulcanization temperature is 155 ℃, the vulcanization time is 50min, and the vulcanization pressure is 22MPa.
A vulcanizate was obtained, denoted S8. The properties of the prepared vulcanizates were analyzed and determined, and the formulations and specific process conditions of the examples are shown in Table 2, and the results of the tests are shown in Table 3.
Test example
Test examples are provided to illustrate the testing of the properties of the vulcanizates.
(1) Tensile strength of vulcanized rubber: the tensile strength was tested by means of a universal tensile machine according to the method specified in GB/T528-2009, where the tensile rate was 500mm/min, the test temperature was 23 ℃, the effective part length of the test specimen was 25mm, and the width was 6mm. For each set of samples, at least 3 replicates were run and the results were median and are shown in table 3.
(2) Compression set of vulcanized rubber: the compression set was tested according to the method specified in GB/T7759.1-2015, using a sample of property A, compression 25%, test temperature 150 ℃ and test time 70h. For each set of samples, 3 replicates were tested and the results were median and are shown in table 3.
(3) Thermal oxygen aging resistance: the thermo-oxidative ageing test was carried out according to the method specified in GB/T3512, the samples were the same as the tensile strength test, and the ageing conditions were as follows: the tensile strength of the sample is tested after a thermal oxidation aging test at 150 ℃ for 70h. Percent change in strength after thermo-oxidative aging = (tensile strength after aging-tensile strength before aging)/tensile strength before aging × 100%.
(4) Oil resistance of vulcanized rubber: and respectively soaking the vulcanized rubber samples in 903# standard test oil under the soaking condition of 150 ℃ for 70h, and testing the volume change and the tensile property change of the samples according to the method specified in GB/T1690-2010. Tensile strength change% = (tensile strength after immersion-tensile strength before immersion)/tensile strength before immersion × 100%. Volume change% = (volume after soaking-volume before soaking)/volume before aging × 100%.
TABLE 3
From the results in Table 3, it can be seen that the vulcanized rubber obtained from the hydrogenated nitrile rubber composition provided by the present invention has excellent mechanical properties, heat resistance, oil resistance, and low compression set.
Particularly, the vulcanized rubber prepared from the hydrogenated nitrile rubber composition by adopting the mixing process and the vulcanization process can further improve and promote the mechanical system performance, heat resistance, oil resistance and compression set of the vulcanized rubber.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The hydrogenated nitrile rubber composition is characterized by comprising a rubber matrix, a reinforcing agent, a vulcanizing agent, an auxiliary vulcanizing agent, a vulcanization activator, an anti-aging agent and a plasticizer, wherein the rubber matrix is hydrogenated nitrile rubber, the reinforcing agent contains carbon black, white carbon black and acrylic acid metal salt, and the vulcanization activator contains zinc oxide, magnesium oxide and stearic acid;
the rubber composition comprises, by weight, 30-70 parts of carbon black, 5-20 parts of white carbon black, 5-15 parts of acrylic acid metal salt, 2-7 parts of zinc oxide, 3-10 parts of magnesium oxide, 1-5 parts of stearic acid, 1-9 parts of a vulcanizing agent, 1-8 parts of an auxiliary vulcanizing agent, 0.5-5 parts of an anti-aging agent and 0-20 parts of a plasticizer, wherein the carbon black is contained in 100 parts of a rubber matrix.
2. The rubber composition according to claim 1, wherein the carbon black is contained in an amount of 40 to 60 parts by weight, the white carbon black is contained in an amount of 8 to 15 parts by weight, the acrylic metal salt is contained in an amount of 5 to 10 parts by weight, the zinc oxide is contained in an amount of 3 to 6 parts by weight, the magnesium oxide is contained in an amount of 4 to 8 parts by weight, the stearic acid is contained in an amount of 1 to 3 parts by weight, the vulcanizing agent is contained in an amount of 2 to 6 parts by weight, the co-vulcanizing agent is contained in an amount of 2 to 5 parts by weight, the anti-aging agent is contained in an amount of 1 to 4 parts by weight, and the plasticizer is contained in an amount of 2 to 12 parts by weight, based on 100 parts by weight of the rubber matrix.
3. The rubber composition according to claim 1 or 2, wherein the content of the hydrogenated nitrile rubber in combination with acrylonitrile structural units is 15 to 50% by weight, the degree of hydrogenation is not less than 95%, and the Mooney viscosity ML (1 + 4) is 60 to 150 at 100 ℃;
preferably, the content of the hydrogenated nitrile rubber combined acrylonitrile structural unit is 20-40 wt%, the hydrogenation degree is more than or equal to 99%, and the Mooney viscosity ML (1 + 4) is 70-120 at 100 ℃.
4. The rubber composition according to any one of claims 1 to 3, wherein the carbon black has a specific surface area of 70 to 130m 2 /g；
Preferably, the specific surface area of the white carbon black is 70-250m 2 /g；
Preferably, the acrylic acid-based metal salt is an acrylic acid-based zinc salt.
5. A method of preparing a vulcanized rubber, the method comprising: a rubber composition according to any one of claims 1 to 4, wherein the respective components are compounded to obtain a compounded rubber, and the compounded rubber is subjected to a vulcanization treatment.
6. The method of claim 5, wherein the components of the rubber composition are compounded by:
(1) Carrying out first mixing on a component A containing a rubber matrix, a reinforcing agent, a vulcanization activator, an anti-aging agent and an optional plasticizer to obtain a master batch;
(2) And carrying out second mixing on the master batch and a component B containing a vulcanizing agent and an auxiliary vulcanizing agent to obtain the rubber compound.
7. The method of claim 6, wherein the conditions of the first mixing comprise: the mixing temperature is 80-100 ℃, and the mixing time is 3-8min;
preferably, the conditions of the second mixing include: the mixing temperature is 30-60 ℃, and the mixing time is 3-6min;
preferably, the first mixing is carried out in an internal mixer, the rotating speed of the internal mixer is 50-90rpm;
preferably, the second mixing is carried out in an internal mixer at a speed of 30 to 80rpm.
8. The method of any one of claims 5-7, wherein the conditions of the sulfidation treatment comprise: the vulcanization temperature is 160-200 ℃, the vulcanization pressure is 3-20MPa, and the vulcanization time is 2-30min;
preferably, the conditions of the vulcanization treatment include: the vulcanization temperature is 170-190 ℃, the vulcanization pressure is 10-15MPa, and the vulcanization time is 5-20min.
9. A vulcanized rubber produced by the production method according to any one of claims 5 to 8.
10. Use of a hydrogenated nitrile rubber composition according to any of claims 1 to 3 or of a vulcanizate according to claim 9 in oilfield sealants.
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| CN105694162A (en) * | 2016-03-04 | 2016-06-22 | 中国石油集团渤海钻探工程有限公司 | High-temperature-resistant rubber core for rotating control head and preparing method thereof |
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| CN107964144A (en) * | 2016-10-18 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of rubber composition and vulcanization rubber and sebific duct |
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