CN115819859A - Hydrogenated nitrile rubber/polyvinyl chloride composition and application thereof, vulcanized rubber and preparation method and application thereof - Google Patents
Hydrogenated nitrile rubber/polyvinyl chloride composition and application thereof, vulcanized rubber and preparation method and application thereof Download PDFInfo
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- CN115819859A CN115819859A CN202111091348.2A CN202111091348A CN115819859A CN 115819859 A CN115819859 A CN 115819859A CN 202111091348 A CN202111091348 A CN 202111091348A CN 115819859 A CN115819859 A CN 115819859A
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- polyvinyl chloride
- hydrogenated nitrile
- nitrile rubber
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- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 48
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 48
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 45
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 229920001971 elastomer Polymers 0.000 claims abstract description 34
- 239000005060 rubber Substances 0.000 claims abstract description 34
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 32
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 28
- 239000006229 carbon black Substances 0.000 claims abstract description 28
- 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
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 13
- 239000012744 reinforcing agent 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
- 239000003566 sealing material Substances 0.000 claims abstract description 10
- 239000012936 vulcanization activator Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 45
- 238000004073 vulcanization Methods 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 2
- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical compound [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 claims description 2
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 claims description 2
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 claims description 2
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 2
- 238000007906 compression Methods 0.000 abstract description 10
- 230000006835 compression Effects 0.000 abstract description 10
- 239000012190 activator Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 230000032683 aging Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 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 5
- 238000012545 processing Methods 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 group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical group OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 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
- 239000000565 sealant Substances 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
- 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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000000758 substrate Substances 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 rubber/polyvinyl chloride composition and application thereof, vulcanized rubber and a preparation method and application thereof. The composition comprises 100 parts by weight of hydrogenated nitrile rubber, 5-15 parts by weight of polyvinyl chloride, a reinforcing agent, 1-9 parts by weight of a vulcanizing agent, 1-8 parts by weight of a co-vulcanizing agent, a vulcanizing activator, 0.5-5 parts by weight of an anti-aging agent and 0-16 parts by weight of a plasticizer; the reinforcing agent comprises 30-60 parts by weight of carbon black, 5-18 parts by weight of white carbon black, 5-12 parts by weight of acrylic acid metal salt and 8-18 parts by weight of calcium sulfate whisker; 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 obviously improve the processability and the dimensional stability of vulcanized rubber on the premise of excellent mechanical property, heat resistance, oil resistance and compression set, and can be further used for sealing materials for oil fields.
Description
Technical Field
The invention relates to the field of rubber, and in particular relates to a hydrogenated nitrile rubber/polyvinyl chloride 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 inherits excellent performances of the nitrile rubber such as good oil resistance, high strength and the like, and is further endowed with special performances such as high temperature resistance, chemical corrosion resistance and the like, so that 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 rubbers, 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, and provide more rigorous service conditions for sealing materials, and the sealing materials are collectively expressed as high strength, high temperature resistance, oil resistance, corrosion resistance and the like.
In addition to various application properties, processability is also a focus of attention in the production process of rubber products, particularly for molded products such as sealing materials, the flowability of rubber (i.e. the Mooney viscosity of rubber compound) and the dimensional stability of vulcanized rubber are processing property indexes which are extremely concerned by production enterprises, and the processing property indexes are directly related to stable production of products and high and low defective rate.
The research hotspots in the rubber industry field are formed by selecting a proper base material, optimizing a formula and a processing technology to cooperatively improve various processing properties and application performance indexes of the sealing material for the oil field.
Disclosure of Invention
The invention aims to overcome the problems of low processability and low dimensional stability of a hydrogenated nitrile rubber composition in the prior art, and provides a hydrogenated nitrile rubber/polyvinyl chloride composition and application thereof, a vulcanized rubber and a preparation method and application thereof.
In order to achieve the above object, the present invention provides in a first aspect a hydrogenated nitrile rubber/polyvinyl chloride composition, characterized in that the composition comprises a hydrogenated nitrile rubber, polyvinyl chloride, a reinforcing agent, a vulcanizing agent, a co-vulcanizing agent, a vulcanization activator, an anti-aging agent and a plasticizer; the reinforcing agent comprises carbon black, white carbon black, acrylic acid metal salt and calcium sulfate whisker; the vulcanization activator comprises zinc oxide, magnesium oxide, and stearic acid;
relative to 100 parts by weight of hydrogenated nitrile rubber, the polyvinyl chloride content is 5-15 parts by weight, the carbon black content is 30-60 parts by weight, the white carbon black content is 5-18 parts by weight, the acrylic acid metal salt content is 5-15 parts by weight, the calcium sulfate whisker content is 8-18 parts by weight, the zinc oxide content is 2-7 parts by weight, the magnesium oxide content is 3-10 parts by weight, the stearic acid content is 1-5 parts by weight, the vulcanizing agent content is 1-9 parts by weight, the co-vulcanizing agent content is 1-8 parts by weight, the anti-aging agent content is 0.5-5 parts by weight, and the plasticizer content is 0-16 parts by weight.
A second aspect of the present invention provides a method for producing a vulcanized rubber, characterized in that the method comprises: and (2) mixing the components in the hydrogenated nitrile rubber/polyvinyl chloride composition to obtain a mixed rubber, and vulcanizing the mixed rubber to obtain the vulcanized rubber.
The third aspect of the present invention provides a vulcanized rubber produced by the above production method.
In a fourth aspect the present invention provides the use of a hydrogenated nitrile rubber/polyvinyl chloride composition or a vulcanised rubber as described above in an oilfield sealant.
Through the technical scheme, the hydrogenated nitrile rubber/polyvinyl chloride composition, the application thereof, the vulcanized rubber, the preparation method and the application thereof provided by the invention have the following beneficial effects:
the hydrogenated nitrile rubber/polyvinyl chloride composition provided by the invention contains hydrogenated nitrile rubber and polyvinyl chloride, can be matched with a reinforcing agent containing carbon black, white carbon black, acrylic acid metal salt and calcium sulfate whisker, a vulcanization activator containing zinc oxide, magnesium oxide and stearic acid and other components in a specific proportion, can obviously improve the processability of the composition and the dimensional stability of vulcanized rubber on the premise that the prepared vulcanized rubber has excellent mechanical property, heat resistance, oil resistance and compression permanent deformation, and can be used as a sealing material for oil fields.
Further, the rubber composition provided by the invention is subjected to mixing, in particular, each component in the composition is subjected to sectional mixing and then vulcanized, so that the processability of the composition can be further improved, and the dimensional stability of vulcanized rubber can be further improved.
Furthermore, by controlling the conditions such as the mixing temperature of each stage and the vulcanization conditions, the dimensional stability of the vulcanized rubber obtained is remarkably improved on the premise that the vulcanized rubber has excellent mechanical properties, heat resistance, oil resistance and compression set, so that the vulcanized rubber can be used as a sealing material for oil fields.
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.
The invention provides a hydrogenated nitrile rubber/polyvinyl chloride composition, which is characterized by comprising hydrogenated nitrile rubber, polyvinyl chloride, a reinforcing agent, a vulcanizing agent, a co-vulcanizing agent, a vulcanizing activator, an anti-aging agent and a plasticizer; the reinforcing agent comprises carbon black, white carbon black, acrylic acid metal salt and calcium sulfate whisker; the vulcanization activator comprises zinc oxide, magnesium oxide, and stearic acid;
relative to 100 parts by weight of hydrogenated nitrile rubber, the polyvinyl chloride content is 5-15 parts by weight, the carbon black content is 30-60 parts by weight, the white carbon black content is 5-18 parts by weight, the acrylic acid metal salt content is 5-15 parts by weight, the calcium sulfate whisker content is 8-18 parts by weight, the zinc oxide content is 2-7 parts by weight, the magnesium oxide content is 3-10 parts by weight, the stearic acid content is 1-5 parts by weight, the vulcanizing agent content is 1-9 parts by weight, the co-vulcanizing agent content is 1-8 parts by weight, the anti-aging agent content is 0.5-5 parts by weight, and the plasticizer content is 0-16 parts by weight.
According to the invention, the hydrogenated nitrile rubber/polyvinyl chloride composition contains hydrogenated nitrile rubber and polyvinyl chloride, and can be matched with a reinforcing agent containing carbon black, white carbon black, acrylic acid metal salt and calcium sulfate whisker, a vulcanization activator containing zinc oxide, magnesium oxide and stearic acid and other components in a specific proportion, so that the processability of the composition and the dimensional stability of the vulcanized rubber are remarkably improved on the premise that the prepared vulcanized rubber has excellent mechanical properties, heat resistance, oil resistance and compression set, and the composition and the vulcanized rubber can be used as sealing materials for oil fields.
Further, when the content of the polyvinyl chloride is 8-12 parts by weight, the content of the carbon black is 30-50 parts by weight, the content of the white carbon black is 8-15 parts by weight, the content of the acrylic acid metal salt is 8-12 parts by weight, the content of the calcium sulfate whisker is 10-15 parts by weight, the content of the zinc oxide is 3-6 parts by weight, the content of the magnesium oxide is 4-8 parts by weight, the content of the stearic acid is 1-3 parts by weight, the content of the vulcanizing agent is 2-6 parts by weight, the content of the co-vulcanizing agent is 2-5 parts by weight, the content of the anti-aging agent is 1-4 parts by weight, and the content of the plasticizer is 2-10 parts by weight, relative to 100 parts by weight of the hydrogenated nitrile rubber, the processability of the composition and the dimensional stability of the vulcanized rubber prepared from the composition are further improved.
According to the invention, the content of bound acrylonitrile structural units of the hydrogenated nitrile rubber is 15-50 wt%, the degree of hydrogenation is not less than 95%, and the Mooney viscosity ML (1+4) is 60-150 at 100 ℃;
furthermore, the content of the bonded acrylonitrile structural unit of the hydrogenated nitrile rubber is 20-40 wt%, the hydrogenation degree is not less than 99%, and the Mooney viscosity ML (1+4) is 70-120 at 100 ℃.
According to the invention, the melt index of the polyvinyl chloride is 900 to 1300g/10min at 190 ℃ and a load of 2.16 kg.
Further, the melt index of the polyvinyl chloride is 1000-1200g/10min under the condition of 190 ℃ and the load of 2.16 kg.
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。
In the present invention, the acrylic metal may be an acrylic metal salt or a methacrylic metal salt which is conventional in the art, and specifically, when the acrylic metal salt is at least one selected from a zinc acrylate salt, a magnesium acrylate salt, a zinc methacrylate salt and a magnesium methacrylate salt, the processability of the composition and the dimensional stability of the vulcanized rubber can be more excellent. Preferably, the acrylic acid-based metal salt is zinc methacrylate.
According to the invention, the length-diameter ratio of the calcium sulfate whiskers is 15-200, and the average diameter of the calcium sulfate whiskers is 1-6 μm.
In the present invention, the vulcanizing agent may be a vulcanizing agent of the kind conventional in the art, preferably a peroxide vulcanizing agent. Specifically, the vulcanizing agent is selected from DCP and/or Bidawu.
In the present invention, in order to improve the crosslinking efficiency and vulcanization rate of the composition, a co-vulcanizing agent, which may be of a type conventional in the art, is added to the composition. Preferably, the co-vulcanizing agent is selected from TAIC and/or HVA-2.
In the invention, the anti-aging agent can be an anti-aging agent of a conventional kind in the field, specifically, the anti-aging agent is at least one selected from quinoline anti-aging agents, diphenylamine anti-aging agents, naphthylamine anti-aging agents and imidazole anti-aging agents, preferably, the anti-aging agent is a combination of diphenylamine anti-aging agents and imidazole anti-aging agents, and more preferably, the using amount ratio of the diphenylamine anti-aging agents to the imidazole anti-aging agents is 1:2-1:1.
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: mixing the components in the hydrogenated nitrile rubber/polyvinyl chloride composition to obtain a mixed rubber, and vulcanizing the mixed rubber.
In order to further improve the processability of the hydrogenated nitrile rubber/polyvinyl chloride composition according to the invention and the dimensional stability of the vulcanizates prepared from the rubber composition, the components of the rubber composition are preferably compounded according to the following steps:
(1) Carrying out first mixing on a component A containing hydrogenated nitrile rubber, polyvinyl chloride, 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.
In the invention, the Mooney viscosity ML (1+4) of the rubber compound is 80-110 at 100 ℃.
The raw materials for preparing the vulcanized rubber in the second aspect of the invention are the composition described in the first aspect of the invention, and the component A and the component B in the second aspect together form the rubber composition described in the first aspect of the invention, so that the types of the raw materials in the second aspect of the invention are all the same as the types described in the first aspect of the invention, and in order to avoid repetition, the description of the invention in the second aspect is omitted, and the person skilled in the art should not be construed as limiting the invention.
In the invention, the rubber composition provided by the invention is mixed, and particularly, each component in the composition is vulcanized after being mixed in sections, so that the processability of the composition can be further improved, and the dimensional stability of vulcanized rubber can be further improved.
According to the invention, the conditions of the first mixing include: the mixing temperature is 80-100 ℃, and the mixing time is 3-8min.
Further, the conditions of the first mixing include: the mixing temperature is 80-90 ℃, and the mixing time is 4-6min.
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 40-55 ℃, and the mixing time is 3-5min.
In the present invention, the first mixing and the second mixing may be carried out in a mixing apparatus, and for example, may be carried out in an open mill or an internal mixer, and preferably, both the first mixing and the second mixing are carried out in an internal mixer. Preferably, said first mixing is carried out in an internal mixer at a speed of 50 to 90rpm, more preferably 60 to 80rpm. Preferably, the second mixing is carried out in an internal mixer at a speed of 30 to 80rpm, more 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; the vulcanizing time is 2-30min.
Further, the conditions of the vulcanization treatment include: the vulcanization temperature is 170-190 ℃; the vulcanization pressure is 10-15MPa; the vulcanizing time is 5-20min.
In the present invention, the discharged rubber may be tabletted, for example, in an open mill, before it is vulcanized. Preferably, the open mill conditions include: the open milling temperature is 30-70 ℃. And the discharged glue after tabletting can be placed for 4 to 48 hours, for example.
Unless otherwise specified, all pressures described herein are expressed as gauge pressure.
The third aspect of the present invention provides a vulcanized rubber obtained by the above-mentioned production method.
In the invention, the shrinkage rate of the vulcanized rubber is less than or equal to 3 percent, preferably less than or equal to 2 percent; the tensile strength of the vulcanized rubber is more than or equal to 26MPa, preferably more than or equal to 28MPa; the elongation at break of the vulcanized rubber is 300-420%, preferably 360-410%; the compression set of the vulcanized rubber is less than or equal to 23 percent, preferably less than or equal to 20 percent, and more preferably less than or equal to 16 percent; under the conditions of 150 ℃ and 70h of thermo-oxidative aging, the strength change rate of the vulcanized rubber is less than or equal to +/-10 percent, preferably less than or equal to +/-8 percent, and more preferably less than or equal to +/-4 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 +/-8.5 percent, preferably less than or equal to +/-8 percent, and more preferably less than or equal to +/-5 percent; the volume change rate of the vulcanized rubber is less than or equal to +/-8.5 percent, preferably less than or equal to +/-8 percent, and preferably less than or equal to +/-5 percent.
In a fourth aspect, the present invention provides the use of the hydrogenated nitrile rubber/polyvinyl chloride composition or the vulcanizate in an oilfield sealant.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
Hydrogenated nitrile rubber: manufactured by Nippon Ruiyang company, the number 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 ℃; no. 2010H, acrylonitrile content 36 wt%, degree of hydrogenation 95%, mooney viscosity ML (1+4) 140 at 100 ℃; 4300, acrylonitrile content of 18 wt%, hydrogenation degree not less than 99%, mooney viscosity (1+4) of 75 at 100 ℃; no. 2020, acrylonitrile content 36 wt.%, degree of hydrogenation 90%, mooney viscosity ML (1+4) 100 ℃ 85.
Polyvinyl chloride: the trade mark S1000, produced by Chinese petrochemical Qilu division, the melt index of polyvinyl chloride is 1000-1100g/10min under the conditions of 190 ℃ and 2.16kg of load;
polyvinyl chloride: the trade mark S700 is produced by China petrochemical Qilu division, and the melt index of the polyvinyl chloride is 650-700g/10min under the conditions of 190 ℃ and 2.16kg of load;
carbon black: number N330 (specific surface area 73-85 m) 2 G) and N234 (specific surface area 109-125 m) 2 (g), available from Shanghai Kabo chemical Co., ltd.);
white carbon black: number 165MP (specific surface area of 150-180 m) 2 (g) from underwriters laboratories, inc.;
zinc methacrylate (ZDMA): industrial grade products, available from maireil chemical technologies, inc;
calcium sulfate whisker: purchased from Jiangsu Xinyuan mining mailbox company, the particle size is 1-6 μm, and the length-diameter ratio is 30/1-80/1;
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 Saint Olympic chemical science and technology Limited of Jiangsu;
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 | Model number | Manufacturer of the product | Use of |
| 1 | Internal mixer | BR1600 | Rall of American Farad | 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 |
| 6 | Mooney viscometer | SMV-300 | Taiwan area high speed railway | Mooney viscosity test |
Example 1
The composition formulation of this example is 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 rotating speed to be 70rpm, adding a rubber substrate, polyvinyl chloride, a reinforcing agent, a vulcanization activator, an anti-aging agent and a plasticizer into the internal mixer to carry out first mixing, wherein the first mixing time is 6min, the first mixing temperature is 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 compound obtained in the above manner was passed once through an open mill having a roll nip of 0.5mm and a roll temperature of 50. + -.5 ℃ and then the roll nip was adjusted to 5mm and then passed twice, and the resulting rubber compound was left to stand for 24 hours (in the following examples, the operating conditions in the open mill and the standing time of the rubber compound 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)
Table 2 (continuation watch)
Test example
Test examples are provided to illustrate the testing of properties of the vulcanizates.
(1) Mooney viscosity of the compounded rubber: the Mooney viscosity of the compounded rubber was measured by a Mooney viscometer in accordance with the method specified in GB/T1232.1-2016, at a measuring temperature of 100 ℃, for a preheating time of 1min and for a measuring time of 4min, and the results are expressed by ML (1+4) at 100 ℃ and shown in Table 4.
(2) Shrinkage S of vulcanized rubber: and (3) standing the vulcanized sample for 24 hours, measuring the thickness, recording the thickness as D, and recording the thickness of the vulcanization mold as D, wherein S = (D/D-1) × 100%.
(3) Tensile strength of vulcanized rubber: the tensile strength and elongation at break were 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 active 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.
(4) Compression set of vulcanized rubber: the compression set was tested according to the method specified in GB/T7759.1-2015, using A-property sample, compression ratio 25%, test temperature 150 ℃ and test time 70h. For each set of samples, 3 replicates were tested and the results were averaged, and the results are shown in table 3.
(5) Thermal-oxidative aging resistance: the thermo-oxidative ageing test was carried out according to the method specified in GB/T3512, the samples were tested for tensile strength under the following conditions: 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%.
(6) Oil resistance of vulcanized rubber: and respectively soaking the vulcanized rubber sample 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 sample 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 hydrogenated nitrile rubber/polyvinyl chloride composition provided by the present invention has a suitable mooney viscosity, indicating that the composition has excellent processability, and the vulcanized rubber prepared from the composition has excellent mechanical properties, heat resistance, oil resistance and compression set, the shrinkage of the vulcanized rubber is significantly reduced, indicating that the dimensional stability of the vulcanized rubber is significantly improved.
In particular, the rubber compound prepared by the mixing process of the invention and the vulcanized rubber prepared by the rubber compound by the vulcanization process of the invention can further improve and promote the processability of the composition, and the mechanical performance, heat resistance, oil resistance, compression set and dimensional stability 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 (11)
1. A hydrogenated nitrile rubber/polyvinyl chloride composition is characterized by comprising hydrogenated nitrile rubber, polyvinyl chloride, a reinforcing agent, a vulcanizing agent, an auxiliary vulcanizing agent, a vulcanization activating agent, an anti-aging agent and a plasticizer; the reinforcing agent comprises carbon black, white carbon black, acrylic acid metal salt and calcium sulfate whisker; the vulcanization activator comprises zinc oxide, magnesium oxide, and stearic acid;
relative to 100 parts by weight of hydrogenated nitrile rubber, the polyvinyl chloride content is 5-15 parts by weight, the carbon black content is 30-60 parts by weight, the white carbon black content is 5-18 parts by weight, the acrylic acid metal salt content is 5-15 parts by weight, the calcium sulfate whisker content is 8-18 parts by weight, the zinc oxide content is 2-7 parts by weight, the magnesium oxide content is 3-10 parts by weight, the stearic acid content is 1-5 parts by weight, the vulcanizing agent content is 1-9 parts by weight, the co-vulcanizing agent content is 1-8 parts by weight, the anti-aging agent content is 0.5-5 parts by weight, and the plasticizer content is 0-16 parts by weight.
2. The hydrogenated nitrile rubber/polyvinyl chloride composition according to claim 1, wherein the polyvinyl chloride is contained in an amount of 8 to 12 parts by weight, the carbon black is contained in an amount of 30 to 50 parts by weight, the white carbon black is contained in an amount of 8 to 15 parts by weight, the acrylic acid metal salt is contained in an amount of 8 to 12 parts by weight, the calcium sulfate whiskers are contained in an amount of 10 to 15 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 10 parts by weight, based on 100 parts by weight of the hydrogenated nitrile rubber.
3. The hydrogenated nitrile rubber/polyvinyl chloride composition according to claim 1 or 2, wherein said hydrogenated nitrile rubber has a bound acrylonitrile structural unit content of 15 to 50% by weight, a degree of hydrogenation of 95% or more, a Mooney viscosity ML (1+4) of 60 to 150 at 100 ℃;
preferably, the hydrogenated nitrile rubber has a bound acrylonitrile structural unit content of 20 to 40% by weight, a degree of hydrogenation of not less than 99%, and a Mooney viscosity ML (1+4) of 70 to 120 at 100 ℃.
4. A hydrogenated nitrile rubber/polyvinyl chloride composition according to any of claims 1 to 3, wherein the polyvinyl chloride has a melt index of 900 to 1300g/10min at 190 ℃ and a load of 2.16 kg.
5. A hydrogenated nitrile rubber/polyvinyl chloride composition according to any of claims 1 to 4, wherein the carbon black has a specific surface area of from 70 to 130m 2 /g；
Preferably, the specific surface area of the white carbon black is 70-250m 2 /g；
Preferably, the acrylic acid metal salt is at least one selected from the group consisting of acrylic acid zinc salt, acrylic acid magnesium salt, methacrylic acid zinc salt and methacrylic acid magnesium salt;
preferably, the aspect ratio of the calcium sulfate whiskers is 15-200, and the average diameter of the calcium sulfate whiskers is 1-6 μm.
6. A method of preparing a vulcanizate, the method comprising: mixing the components of the hydrogenated nitrile rubber/polyvinyl chloride composition according to any of claims 1 to 5 to obtain a mix, and vulcanizing the mix to obtain the vulcanized rubber.
7. The process according to claim 6, wherein the components of the hydrogenated nitrile rubber/polyvinyl chloride composition are compounded according to the following steps:
(1) Performing first mixing on a component A containing hydrogenated nitrile rubber, polyvinyl chloride, a reinforcing agent, a vulcanization activator, an anti-aging agent and optionally a 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 a mixed rubber.
8. The production method according to claim 7, wherein the conditions of the first mixing include: 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.
9. The production method according to any one of claims 6 to 8, wherein the conditions of the vulcanization treatment include: the vulcanization temperature is 160-200 ℃; the vulcanization pressure is 3-20MPa; the vulcanizing time is 2-30min;
preferably, the conditions of the vulcanization treatment include: the vulcanization temperature is 170-190 ℃; the vulcanization pressure is 10-15MPa; the vulcanizing time is 5-20min.
10. A vulcanized rubber obtained by the production method according to any one of claims 6 to 9.
11. Use of a hydrogenated nitrile rubber/polyvinyl chloride composition according to any of claims 1 to 5 or of a vulcanized rubber according to claim 10 in oilfield sealing materials.
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