CN102140189B - Hydrogenated nitrile rubber composition capable of resisting hydrothion corrosion - Google Patents
Hydrogenated nitrile rubber composition capable of resisting hydrothion corrosion Download PDFInfo
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- CN102140189B CN102140189B CN2011100735517A CN201110073551A CN102140189B CN 102140189 B CN102140189 B CN 102140189B CN 2011100735517 A CN2011100735517 A CN 2011100735517A CN 201110073551 A CN201110073551 A CN 201110073551A CN 102140189 B CN102140189 B CN 102140189B
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- hydrogenated nitrile
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- butadiene rubber
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Abstract
The invention provides a hydrogenated nitrile rubber composition capable of resisting hydrothion corrosion. The composition provided by the invention is characterized in that hydrogenated nitrile is used as a main material, organic peroxide is used as a cross-liking agent, hard carbon black is used as a reinforced filling material, resin is used as a flowing modifier, and metal oxide is used a pore-blocking agent; and the composition is good in hydrothion corrosion resisting property at the hydrothion environment with the temperature of 100 DEG C and the pressure of 6.9 MPa.
Description
Technical field
The present invention relates to the macromolecular material preparation, specifically, relate to a kind of hydrogenated nitrile rubber composition that can be used under the hydrogen sulfide existence condition, this kind compsn can be used for being prepared in the rubber hydrogenated butyronitrile goods that use in the hydrogen-sulfide environmental.
Background technology
In recent decades, the fld of sulfide hydrogen corrosive medium occurs in succession, and etching problem more and more causes people's attention.Corrosion causes enormous economic loss not only for the exploitation of fld, production, has also caused environmental pollution simultaneously, and has threatened personnel safety.Phase early 1980s, the sulfide hydrogen Sweet natural gas that China is verified accounts for 1/4 of national gas-bearing formation reserves.In China's investigation and prospecting, constantly find high sulfur-bearing fld in recent years.The appearance of high sulfur-bearing fld in the petroleum industry not only to steel, has also proposed anti-H to rubber item
2The performance requriements of S.In the high sulfur-bearing fld production process, HTHP H
2S/CO
2Operating mode can cause strong erosion to rubber packing material, especially H
2The S severe corrosive causes seal failure more easily, causes containing H
2The serious accident of S natural gas leaking.H
2A large amount of existence of S have become one of technical bottleneck of the effective exploitation of the high sulfur-bearing hydrocarbon-bearing pool of restriction.
A kind of oil resistant high-temperature resistant rubber material that hydrogenated nitrile-butadiene rubber is commonly used; Usually under the condition that high temperature, high pressure, nonpolar alkyl oil exist, being used widely, is sealing material commonly used in the exploitation of oil-gas field process, but with the appearance of hydrogen sulfide in the fld open procedure; Hydrogenated nitrile-butadiene rubber rubber a large amount of problems occurs in use; Like hardening or deliquescing, volumetric expansion, tensile strength and elongation at break instability etc.These issues limit the use of hydrogenated nitrile-butadiene rubber, hindered the exploitation of sulfur-bearing fld.The domestic research of anti-sulfur materials is less, and existing abroad related prods, domestic used anti-sulfur materials is all trusted import, therefore demands carrying out the exploitation of anti-sulfur materials urgently.CN101143931A discloses the rubber combination that is used to make high temperature-resistant compression type packer tubling, and said composition can be used for temperature up in 150 ℃ the oil and gas environments.But its service condition under the sulfur-bearing condition is not described really.(oil field is with the anti-H of rubber for Zhang Ruyi
2The research of S performance, starting material, 1994; (2), 1-3) studied the ageing of performance of hydrogenated nitrile-butadiene rubber in the low pressure hydrogen-sulfide environmental, found that the elongation at break decline degree of hydrogenation fourth hydrogen rubber is very big in traditional cooperation system; This is owing in weathering process, can produce hole in the rubber matrix, makes the infiltrating more easily in the rubber matrix of hydrogen sulfide, quickens rubber aging in hydrogen-sulfide environmental; Therefore the present invention is through adding the metal peroxides that can react with hydrogen sulfide, reaction product volumetric expansion, but the hole that generates in the shutoff weathering process; Thereby delay the weathering process of rubber, improve the aging back of hydrogen sulfide rubber colloidality ability.
Summary of the invention
The present invention relates to a kind of hydrogenated nitrile rubber composition, specifically, relate to the hydrogenated nitrile-butadiene rubber constituent of making a kind of hydrogen sulfide corrosion-resistant, can be used for the sulfide hydrogen environment.
The present invention aims to provide a kind of rubber combination of specific cooperation, utilizes said composition, can obtain having the hydrogenated nitrile-butadiene rubber of anti-preferably hydrogen sulfide performance and being used for the sulfide hydrogen environment.
The present invention is characterized in that said composition is a material of main part with the hydrogenated butyronitrile, is linking agent with the organo-peroxide; With the carbon black is reinforcing filler, is additional crosslinker with the polyfunctional group reactive monomer, is flow ability modifying agent with the resin; Its composition is 100 weight parts in hydrogenated nitrile-butadiene rubber, comprising:
The cyanic acid content of use therein hydrogenated nitrile-butadiene rubber is 36～44%; Mooney viscosity is at 60-85; Residual double bonds is 0.5-6%, this kind hydrogenated nitrile-butadiene rubber have preferably oil-proofness and processing characteristics better, the hydrogenated nitrile-butadiene rubber 2010,2020 and 1010 of specific product such as Nippon Zeon Co., Ltd..Double bond content is less on the molecular chain of this type rubber, should not adopt the sulfur cross-linking system, generally adopts peroxide vulcanizing system, and the C-C cross-link bond bond energy of formation is higher, has good heat-resisting and anti-hydrogen sulfide performance.
Described organo-peroxide is Di Cumyl Peroxide 99 (DCP), dual-tert-butyl Di Cumyl Peroxide 99 (BIBP) and Lucidol (BPO); Consumption is 100 weight parts in hydrogenated nitrile-butadiene rubber, is preferably the 2-6 weight part, and consumption is too much; Form excessively crosslinked; All can the performance of the finished product be had a negative impact, and the resistates of peroxide breakdown can influence the anti-hydrogen sulfide performance of hydrogenated nitrile-butadiene rubber, so superoxide has consumption to be difficult for too much.Additional crosslinker adopts iso-cyanuric acid triallyl ester (TAIC) or TAC (TAC) usually, improves the number of rubber cross point, improves anti-hydrogen sulfide performance.
The present invention adopts hard(carbon)black N220, N330 and N550 as strongthener, all has hydrogen sulfide corrosion-resistant performance preferably, in order to regulate the hardness of product, goes back the consumption of adjustable carbon black, to meet the different needs.
In order to solve the problem that rubber mobility that carbon black loading too much causes can descend, the present invention has added flow modifier, for a kind of of coumarone indene resin, phthalic ester or and usefulness, improve the flowability of rubber unvulcanizate.Be acvator with zinc oxide and/or Natural manganese dioxide among the present invention
The present invention adopts except that acvator ZnO and/or MgO; Also added a kind of oxide compound hole-blocking agent; Like nickel oxide or chromic oxide, it can generate sulfide with the hydrogen sulfide reaction, and sulfide has lower density; Can block owing to the hole that produces after the hydrogen sulfide corrosion, improve the ability of the hydrogen sulfide corrosion-resistant of rubber.The optimum amount of hole-blocking agent is 2-10 part, if consumption is low excessively, the shutoff hole number is less, anti-sulphur DeGrain; The excessive original performance that then influences cross-linked rubber of consumption has limited the range of application of cross-linked rubber.
Embodiment
Below in conjunction with embodiment 1-7 and comparative example 1-2 the present invention is further specified, but the present invention never is confined to these embodiment.
Embodiment 1-7 and comparative example 1-2
The hydrogenated nitrile-butadiene rubber (2010,1010) that adopts Japanese auspicious father-in-law is a material of main part; In it is 100 weight parts; Meeting being linking agent, being strongthener, being the rubber combination of softening agent with the coumarone indene resin with hard(carbon)black N220, N330, N550 with Di Cumyl Peroxide 99 (DCP) of requirement of the present invention according to preparing shown in the table 1, is that hole-blocking agent is embodiment 1-7 with NiO.Adopt similar cooperation, use carbon black to be comparative example 1, adopt similar combination, do not use hole-blocking agent to be comparative example 2 as N990.
Carry out the hydrogen sulfide corrosion-resistant performance test through the sulfuration test piece, the result after corrosion sees table 2.Can find out that from table 2 the present invention can obtain the hydrogenated nitrile-butadiene rubber that uses at hydrogen-sulfide environmental.
Table 1 hydrogenated nitrile-butadiene rubber is implemented prescription
Aging front and back performance in the table 2 hydrogenated nitrile-butadiene rubber hydrogen-sulfide environmental
*Etching condition is: 100 ℃ of temperature, stagnation pressure 6.9MPa, gas composition H
2S:20 ± 2%, CO
2: 5 ± 1%, CH
4: 75 ± 3%, liquid phase is tested into the n-hexane: 25 ± 1%, the n-octane: 20 ± 1%, the n-decane: 50 ± 1%, n-toluene: 5 ± 0.5%, 100 ± 2 hours time, other conditions are with reference to NACE TM0187-2003.
Claims (5)
1. be used for the hydrogenated nitrile rubber composition of hydrogen-sulfide environmental, it is characterized in that, said composition is material of main part with the hydrogenated nitrile-butadiene rubber; With the organo-peroxide is linking agent; With the hard(carbon)black is reinforcing filler, is flow ability modifying agent with the resin, is hole-blocking agent with the MOX; In hydrogenated nitrile-butadiene rubber is 100 weight parts, comprising:
Described hole-blocking agent be in nickel oxide and the chromic oxide one or more and use.
2. rubber combination according to claim 1 is characterized in that, the cyanic acid content of said hydrogenated nitrile-butadiene rubber is 36～44%, mooney viscosity ML
1+4100 ℃ is 60-85kgcm, and residual double bonds is 0.5-6mol%.
3. rubber combination according to claim 1 is characterized in that, described reinforcing filler is 25-80 part hard(carbon)black N220, N330 and/or N550.
4. rubber combination according to claim 1 is characterized in that, described organo-peroxide be in Di Cumyl Peroxide 99, dual-tert-butyl peroxo-diisopropyl benzene and the Lucidol one or more and use.
5. rubber combination according to claim 1 is characterized in that, described flow ability modifying agent be in coumarone and the phthalate properties-correcting agent one or more and use.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100735517A CN102140189B (en) | 2011-03-25 | 2011-03-25 | Hydrogenated nitrile rubber composition capable of resisting hydrothion corrosion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100735517A CN102140189B (en) | 2011-03-25 | 2011-03-25 | Hydrogenated nitrile rubber composition capable of resisting hydrothion corrosion |
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| Publication Number | Publication Date |
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| CN102140189A CN102140189A (en) | 2011-08-03 |
| CN102140189B true CN102140189B (en) | 2012-06-13 |
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| CN2011100735517A Expired - Fee Related CN102140189B (en) | 2011-03-25 | 2011-03-25 | Hydrogenated nitrile rubber composition capable of resisting hydrothion corrosion |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504374B (en) * | 2011-10-18 | 2013-05-08 | 山东省自主创新促进中心 | Stereo garage |
| CN102391554B (en) * | 2011-10-18 | 2013-05-01 | 山东省自主创新促进中心 | Rubber plate for stereoscopic garage |
| CN102504375B (en) * | 2011-10-18 | 2013-05-08 | 山东省自主创新促进中心 | Flame-retardant cushion formula for stereo garage |
| CN103613812A (en) * | 2013-11-22 | 2014-03-05 | 无锡市威海达机械制造有限公司 | Sealing material |
| CN104194108B (en) * | 2014-08-11 | 2017-04-26 | 广州加士特密封技术有限公司 | Hydrogenated butadiene-acrylonitrile rubber vulcanized rubber with high strength, high pressure resistance and hydrogen sulfide corrosion resistance |
| CN105545543A (en) * | 2015-12-07 | 2016-05-04 | 青岛讯达捷电子科技有限公司 | Sulfur tolerant inlet manifold branch |
| CN105464860A (en) * | 2015-12-10 | 2016-04-06 | 青岛玻莱莫斯新材料技术有限公司 | Sulfur-resisting intake manifold resonant cavity |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186726A (en) * | 2007-11-20 | 2008-05-28 | 广州机械科学研究院 | Rubber-plastic composite material and application thereof |
| CN101624456A (en) * | 2009-08-03 | 2010-01-13 | 哈尔滨工业大学 | Screw pump rubber stator material and preparation method thereof |
| CN101649078A (en) * | 2009-09-15 | 2010-02-17 | 哈尔滨工业大学 | Hydrogenated nitrile-butadiene rubber modified by rectorite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1781243C (en) * | 1989-09-29 | 1992-12-15 | Всесоюзный научно-исследовательский и конструкторско-технологический институт резиновой промышленности | Rubber stock based on butadiene-nitrile rubber |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186726A (en) * | 2007-11-20 | 2008-05-28 | 广州机械科学研究院 | Rubber-plastic composite material and application thereof |
| CN101624456A (en) * | 2009-08-03 | 2010-01-13 | 哈尔滨工业大学 | Screw pump rubber stator material and preparation method thereof |
| CN101649078A (en) * | 2009-09-15 | 2010-02-17 | 哈尔滨工业大学 | Hydrogenated nitrile-butadiene rubber modified by rectorite and preparation method thereof |
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