CN103804738B - A kind of high-temperature stator elastomeric material and preparation method thereof - Google Patents
A kind of high-temperature stator elastomeric material and preparation method thereof Download PDFInfo
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- CN103804738B CN103804738B CN201410078632.XA CN201410078632A CN103804738B CN 103804738 B CN103804738 B CN 103804738B CN 201410078632 A CN201410078632 A CN 201410078632A CN 103804738 B CN103804738 B CN 103804738B
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Abstract
The invention discloses a kind of high-temperature stator elastomeric material and preparation method thereof, belong to elastomeric material and preparation method thereof field.This elastomeric material is made by the raw material of following parts by weight: hydrogenated nitrile-butadiene rubber 70-80 part; Carboxyl hydrogenated nitrile-butadiene rubber 20-30 part; Semi-reinforcing hydrocarbon black 70-80 part; Zinc oxide 5-10 part; Stearic acid 1-2 part; Softening agent 10-20 part; Anti-aging agent 3-5 part; Linking agent 2-3 part; Additional crosslinker 1.5-2 part.The present invention adopts hydrogenated nitrile-butadiene rubber and carboxyl hydrogenated nitrile-butadiene rubber and uses, make paracril and carboxyl hydrogenated nitrile-butadiene rubber covulcanization, resistant to elevated temperatures requirement can be reached, adopt the hydrogenated nitrile-butadiene rubber of sulfurless curing system sulfuration, its maximum operation (service) temperature can the high temperature of resistance to 180 DEG C, vulcanizate has good thermotolerance, chemical stability and bonding strength, and crosslinking material obtains excellent bonding strength.
Description
Technical field
The invention belongs to elastomeric material and preparation method thereof field, more particularly, relate to a kind of high-temperature stator elastomeric material and preparation method thereof.
Background technology
Along with the development of petroleum drilling and mining industry, the working conditions of rubber item is day by day harsh, has higher requirement to heat-resisting, a lot of customer requirement high temperature resistant 180 DEG C for a long time.Hydrogenated nitrile-butadiene rubber has outstanding oil resistant, media-resistant, and especially heat aging property is good.But the quality problems of block, delamination appear falling in conventional vulcanization hydrogenated nitrile-butadiene rubber in long term high temperature use procedure, to such an extent as to cisco unity malfunction.
" application of hydrogenated nitrile-butadiene rubber and present situation " (rubber science and technology market, 10th phase in 2008, author: Yan Jinjun, Beijing Research & Design Institute of Rubber Industry, 11st page), point out in the document, hydrogenated nitrile-butadiene rubber (HNBR) to paracril (NBR) main chain double bond selectively hydrogenation obtain.After German Bayer AG in 1977 announces the patent of HNBR manufacture method, Nippon Zeon Co., Ltd. utilized the technology of oneself also to start regular merchandized handling in 1984.Commercial HNBR generally classifies by its acrylonitrile content and hydrogenation ratio, has the kind of acrylonitrile content from 17% ~ 50%, and hydrogenation ratio from 80% to main polymer chain hardly double bond containing more than 99% kind.
Hydrogenation and carboxylation combine by nearest technical development, and existing people has applied for the patent of hydrogenated carboxylated nitrile rubber (HXNBR).Novel HXNBR has interesting over-all properties, and this polymkeric substance, after suitably coordinating, can be used for developing the sizing material of the rigors that can meet oil well probing and rubber roll industry, and oil well probing and rubber roll industry are high abrasion application scenarios.The double bond that these performance gains of HXNBR are residual in HXNBR, the control of the concentration forming the reactive hydroxy-acid group of cross-link bond and the metal oxide consumption determining the close C degree of ionic cross-linked bond network.HXNBR and low viscosity HNBR is blended, can reach physicals and dynamic performance balances, and improves its hot air, oil-proofness, chemical-resistant and wear resistance, demonstrates high leakproofness to 150 DEG C of automobile gasolines.
Notification number CN1597753B patent document discloses a kind of nitrile polymer mixer for magnetic seal application, it comprises the rubber compounding thing of at least one hydrogenated carboxylated nitrile rubber, at least one hydrogenated nitrile-butadiene rubber and at least one magnetic compound, comprise the curable rubber formulation of described rubber compounding thing and at least one vulcanizing agent, and comprise the magnetic moulded products of described rubber compounding thing.
Notification number 1583856 patent document discloses a kind of high-performance, low stain reproducible metal-complexing crosslinking acrylonitrile butadiene material, the invention discloses a kind of high-performance, low stain reproducible metal-complexing crosslinking acrylonitrile butadiene material, it is 18wt% ~ 50wt% primarily of acrylonitrile content, mooney viscosity is the paracril of 20 ~ 100, nitrile (HTBN), carboxyl butyronitrile, hydrogenated butyronitrile, powdered nitrile rubber, blend containing paracril is or/and containing the copolymerization of itrile group or the halogenide of grafts and transition metal or/and oxysalt obtains in 140 DEG C ~ 200 DEG C for crosslinked 5 ~ 60 minutes.Compared with existing nitrile rubber, its advantage is: in preparation process, avoid the raw material used human body and bad environmental, and resulting materials is when adding without carbon black, there is good mechanical property equally, its oil-proofness is more excellent simultaneously, and has good bond properties and recyclability with metallic substance.
Notification number CN1320047C patent document discloses superlow hardness high elastic non-treatment rubber pipe and production method, the invention discloses a kind of superlow hardness high elastic non-treatment rubber pipe and production method, with carboxyl-1,4,6 paracrils, hydrogenated nitrile-butadiene rubber, polyurethane elastomer are that main raw material is made, and hardness is 58 ± 3 Shao Er A.Production method comprise plasticate, mixing and freshening, filter glue, mixing, sizing material extrudes, aluminum tube surfaces carries out coarsen treatment, be coated with adhesive glue, sulfidizing after depoling, obtain product.This invention composition of raw materials is unique, and simple process, easy to operate, the sebific duct hardness of production is low, long service life, and result of use is good.
Working environment due to high-temperature stator is arranged in the complicated geological layer of underground 5000-7000 rice, drives the rotor turns in high-temperature stator to reach by input mud the object made hole.The difference of technical scheme disclosed in high-temperature stator and above-mentioned 3 parts of patents of invention is, high-temperature stator heatproof of the present invention need reach 180 DEG C, and far above the requirement of 150 DEG C in the middle of industry, above-mentioned disclosed technical scheme cannot meet this requirement.In addition, when making hole, high-temperature stator can touch the corrosive gasess such as hydrogen sulfide, and how mitigate corrosion gas is to the infringement of rubber, is also this area unsolved technical barrier always.
Summary of the invention
1. the technical problem that will solve
150 DEG C can only be reached for the rubber heatproof existed in prior art, drilling well is short for work-ing life, easily there is falling the problem such as block, delamination, the invention provides a kind of high-temperature stator elastomeric material and preparation method thereof, this elastomeric material heatproof can reach 180 DEG C, have longer work-ing life, and sizing material is injected, the technological operation such as to be extruded and stablize, and can meet the requirement that goods are high temperature resistant to elastomeric material, adhesiveproperties is excellent well.
2. technical scheme
Object of the present invention is achieved through the following technical solutions.
A kind of high-temperature stator elastomeric material, make by the raw material of following parts by weight:
A preparation method for high-temperature stator elastomeric material, the steps include:
(1) masterbatch mix
Hydrogenated butyronitrile and carboxyl hydrogenated butyronitrile are placed in Banbury mixer plasticate 60-80 second, then zinc oxide, stearic acid, anti-aging agent mixing 30-40 second is added, bolt 100-120 second is risen after adding semi-reinforcing hydrocarbon black and softening agent banburying 80-100 second, binder removal when melting temperature reaches 120-130 DEG C, the storage period of master batch is greater than 16 hours.Wherein, the parts by weight of each component are as follows:
(2) master batch two sections adds sulphur
Master batch after parking is placed on mill mixer roller, after master batch bag roller smooth surface is smooth, adds linking agent and additional crosslinker, operate on after being all mixed into master batch Deng Synergist S-421 95 and turn refining, sizing material is beaten 2-3 triangle bag and two rear slices of volume, wherein, each composition weight number is as follows:
Linking agent 2-3 part;
Additional crosslinker 1.5-2 part.
3. beneficial effect
Compared to prior art, the invention has the advantages that:
(1) component of high-temperature stator elastomeric material of the present invention, adopt hydrogenated nitrile-butadiene rubber and carboxyl hydrogenated nitrile-butadiene rubber and use, by adjustment vulcanization system, make paracril and carboxyl hydrogenated nitrile-butadiene rubber covulcanization, can reach resistant to elevated temperatures requirement, adopt the hydrogenated nitrile-butadiene rubber of sulfurless curing system sulfuration, its maximum operation (service) temperature can the high temperature of resistance to 180 DEG C, vulcanizate has good thermotolerance, chemical stability and bonding strength, and crosslinking material obtains excellent bonding strength;
(2) the present invention carrys out the infringement of mitigate corrosion gas to rubber by increasing cross-linking density in formulating of recipe;
(3) adopt the rubber item that method of the present invention is obtained, have longer work-ing life, and sizing material is injected, the technological operation such as to be extruded and stablize, and can meet the requirement that goods are high temperature resistant to elastomeric material, adhesiveproperties is excellent well.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Table 1
| Sequence number | Component | Consumption (mass fraction) |
| 1 | Bright Sheng hydrogenated butyronitrile 3904 | 70 |
| 2 | Bright Sheng carboxyl hydrogenated nitrile-butadiene rubber XT8889 | 30 |
| 3 | Cabot semi-reinforcing hydrocarbon black N550 | 70 |
| 4 | Zinc oxide | 5 |
| 5 | Stearic acid | 1 |
| 6 | Softening agent TP-95 | 10 |
| 7 | Antioxidant D | 2 |
| 8 | Antioxidant 4010 | 3 |
| 9 | Crosslink agent DCP | 2 |
| 10 | Crosslinking coagent TAIC | 2 |
Above-mentioned table 1 is each component of material of the present embodiment and the consumption situation of each component, wherein:
1, hydrogenated butyronitrile is 3904 hydrogenated butyronitriles that German Lanxess Corporation produces, and the acrylonitrile content of this hydrogenated nitrile-butadiene rubber is 39%, mooney viscosity 39, and residual double bonds content≤0.9 has better oil-proofness and lower mooney viscosity, is more suitable for Shooting Technique.
2, carboxyl hydrogenation fourth is fine is the XT8889 carboxyl hydrogenated butyronitrile that German Lanxess Corporation produces, acrylonitrile content is 33%, mooney viscosity 77, residual double bonds content 3.5%, there is better wear resisting property, with 3904 hydrogenated butyronitriles, there is synergy, substantially increase wear-resisting, the oil resistant of product, the performance such as heat-resisting.
3, zinc oxide is the indirect process zinc oxide that Zhenjiang plain boiled water Chemical Co., Ltd. produces.Stearic acid is that Malaysian southern grease company produces.Zinc oxide and stearic and with forming soluble salt, increases metal oxide to the activation capacity of promotor.
4, softening agent TP-95 is the polarity ester plasticizer that molecular weight is greater than 500.Because its molecular weight is large, is that volatility is lower being heated, and has good intermiscibility with hydrogenated butyronitrile and carboxyl hydrogenated butyronitrile, thus impart the better resistance toheat of sizing material.
5, antioxidant D and antioxidant 4010 use, anti-aging agent is secondary diarylamine class, and heat resistanceheat resistant, oxygen, flex crack and ozone-resistant ability all have remarkable increase.
6, have better resistance toheat with the rubber of crosslink agent DCP sulfuration compared with the rubber of sulfur cross-linking, and crosslinking coagent TAIC add the cross-linking density that improve rubber, substantially increase the erosion resistance of rubber.
The preparation method of above-mentioned materials, the steps include:
(1) masterbatch mix
Hydrogenated butyronitrile 3904 and carboxyl hydrogenated butyronitrile XT8889 are placed in Banbury mixer plasticate 60-80 second, then zinc oxide, stearic acid, antioxidant D, antioxidant 4010 mixing 30-40 second is added, bolt 100-120 second is risen after adding Cabot semi-reinforcing hydrocarbon black N550 and softening agent TP-95 banburying 80-100 second, binder removal when melting temperature reaches 120-130 DEG C, the storage period of master batch is greater than 16 hours.Wherein: each composition weight number is as follows:
(2) master batch two sections adds sulphur
Master batch after parking is placed on mill mixer roller, after master batch bag roller smooth surface is smooth, add crosslink agent DCP and additional crosslinker TAIC, operate on after waiting Synergist S-421 95 to be all mixed into master batch and turn refining, sizing material is beaten 2-3 triangle bag and two rear slices of volume, wherein: each constituent mass part is as follows:
Crosslink agent DCP 2;
Additional crosslinker 2.
Experimental data:
Hot air aging 180 DEG C of X168h performances: changes in hardness+5
Tensile strength velocity of variation-10%
Tensile yield velocity of variation-10%
Peel off-8% for 90 °.
Embodiment 2
Table 2
| Sequence number | Component | Consumption (mass parts) |
| 1 | Bright Sheng hydrogenated butyronitrile 3904 | 80 |
| 2 | Bright Sheng carboxyl hydrogenated nitrile-butadiene rubber XT8889 | 20 |
| 3 | Semi-reinforcing hydrocarbon black N550 | 80 |
| 4 | Zinc oxide | 10 |
| 5 | Stearic acid | 2 |
| 6 | Softening agent TP-95 | 10 |
| 7 | Anti-aging agent RD | 2 |
| 8 | Antioxidant 4010NA | 2 |
| 9 | Crosslink agent DCP | 3 |
| 10 | Crosslinking coagent TAIC | 1.5 |
Above-mentioned table 2 is each component of material of the present embodiment and the consumption situation of each component, wherein:
1, hydrogenated butyronitrile is 3904 hydrogenated butyronitriles that German Lanxess Corporation produces, and acrylonitrile content is 39%, mooney viscosity 39, residual double bonds content≤0.9, has better oil-proofness and lower mooney viscosity, is more suitable for Shooting Technique.
2, carboxyl hydrogenation fourth is fine is the XT8889 carboxyl hydrogenated butyronitrile that German Lanxess Corporation produces, and acrylonitrile content is 33%, mooney viscosity 77, residual double bonds content 3.5%, there is better wear resisting property, with 3904, there is synergy, substantially increase wear-resisting, the oil resistant of product, the performance such as heat-resisting.
3, zinc oxide is the indirect process zinc oxide that Zhenjiang plain boiled water Chemical Co., Ltd. produces.Stearic acid is that Malaysian southern grease company produces.Zinc oxide and stearic and with forming soluble salt, increases metal oxide to the activation capacity of promotor.
4, softening agent TP-95 is the polarity ester plasticizer that molecular weight is greater than 500.Because its molecular weight is large, is that volatility is lower being heated, and has good intermiscibility with hydrogenated butyronitrile and carboxyl hydrogenated butyronitrile, thus impart the better resistance toheat of sizing material.
5, anti-aging agent RD and antioxidant 4010NA use, anti-aging agent is secondary diarylamine class.The oxidation that energy rejection condition is harsher under dynamic property, thermal ageing and Weather.
6, have better resistance toheat with the rubber of crosslink agent DCP sulfuration compared with the rubber of sulfur cross-linking, and crosslinking coagent TAIC add the cross-linking density that improve rubber, substantially increase the erosion resistance of rubber.
The preparation method of above-mentioned materials, the steps include:
(1) masterbatch mix
Hydrogenated butyronitrile 3904 and carboxyl hydrogenated butyronitrile XT8889 are placed in Banbury mixer plasticate 60-80 second, then zinc oxide, stearic acid, anti-aging agent RD and antioxidant 4010NA mixing 30-40 second is added, bolt 100-120 second is risen after adding semi-reinforcing hydrocarbon black and softening agent TP-95 banburying 80-100 second, binder removal when melting temperature reaches 120-130 DEG C, the storage period of master batch is greater than 16 hours.Wherein: each constituent mass number is as follows:
(2) master batch two sections adds sulphur
Master batch after parking is placed on mill mixer roller, after master batch bag roller smooth surface is smooth, adds crosslink agent DCP and additional crosslinker TAIC, operate on after being all mixed into master batch Deng Synergist S-421 95 and turn refining, sizing material is beaten 2-3 triangle bag and two rear slices of volume, wherein, each constituent mass part is as follows:
Crosslink agent DCP 3;
Additional crosslinker 1.5.
Hot air aging 180 DEG C of X168h performances: changes in hardness+6
Tensile strength velocity of variation-20%
Tensile yield velocity of variation-15%
Peel off-10% for 90 °.
In embodiment 1-2, obtain excellent high temperature resistant, wear-resisting, not delamination to make material and do not fall the performance of block, have employed the warm and fine carboxyl hydrogenated butyronitrile of hydrogenation fourth is matrix and peroxide vulcanizing system.The soluble salt adopting zinc oxide and stearic acid to be formed improves activation capacity, antioxidant D (RD) and antioxidant 4010 (4010NA) and use, and the adding of crosslink agent DCP and crosslinking coagent TAIC, rubber against gas transmission is corroded, well heat-resisting, ageing-resistant performance is had under current intelligence, and meet the requirement of bonding strength, thus improve work-ing life.
Claims (7)
1. a high-temperature stator elastomeric material, make by the raw material of following parts by weight:
2. a kind of high-temperature stator elastomeric material according to claim 1, is characterized in that: the acrylonitrile content of described hydrogenated nitrile-butadiene rubber is 39%, mooney viscosity 39, residual double bonds content≤0.9.
3. according to a kind of high-temperature stator elastomeric material that claim 1 or 2 is stated, it is characterized in that: the acrylonitrile content of described carboxyl hydrogenated nitrile-butadiene rubber is 33%, mooney viscosity 77, residual double bonds content 3.5%.
4. a kind of high-temperature stator elastomeric material according to claim 3, is characterized in that: described softening agent is the polarity ester plasticizer that molecular weight is greater than 500.
5. a kind of high-temperature stator elastomeric material according to claim 4, is characterized in that: described anti-aging agent is secondary diarylamine class.
6. a kind of high-temperature stator elastomeric material according to claim 1, is characterized in that: described linking agent is organo-peroxide; Described additional crosslinker is isocyanuric acid ester class.
7. a preparation method for high-temperature stator elastomeric material, the steps include:
(1) masterbatch mix
Hydrogenated butyronitrile and carboxyl hydrogenated butyronitrile are placed in Banbury mixer plasticate 60-80 second, then zinc oxide, stearic acid, anti-aging agent mixing 30-40 second is added, bolt 100-120 second is risen after adding semi-reinforcing hydrocarbon black and softening agent banburying 80-100 second, binder removal when melting temperature reaches 120-130 DEG C, the storage period of master batch is greater than 16 hours, wherein, the parts by weight of each component are as follows:
(2) master batch two sections adds sulphur
Master batch after parking is placed on mill mixer roller, after master batch bag roller smooth surface is smooth, adds linking agent and additional crosslinker, operate on after being all mixed into master batch Deng Synergist S-421 95 and turn refining, sizing material is beaten 2-3 triangle bag and two rear slices of volume, wherein, each composition weight number is as follows:
Linking agent 2-3 part;
Additional crosslinker 1.5-2 part.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262728B (en) * | 2014-09-24 | 2016-06-29 | 湖北华强科技有限责任公司 | A kind of low Mooney high oil resistivity rubber, preparation method and the application on screw pump stator |
| CN104744748A (en) * | 2015-03-25 | 2015-07-01 | 江汉石油钻头股份有限公司 | Oil resistant stator rubber used for positive displacement motor drill with equal wall thickness |
| CN109384983A (en) * | 2018-10-29 | 2019-02-26 | 四川隆盛科发实业有限公司 | A kind of aviation oil resistant high-low temperature resistant rubber and preparation method thereof |
| CN110041584A (en) * | 2019-04-23 | 2019-07-23 | 无锡二橡胶股份有限公司 | A kind of high oil resistant, resistance to compression become the factory formula of spinning rubber-roller |
| CN112280133A (en) * | 2019-07-25 | 2021-01-29 | 赞南科技(上海)有限公司 | Low-temperature-resistant hydrogenated nitrile butadiene rubber composite material and preparation method thereof |
| CN110885482A (en) * | 2019-12-16 | 2020-03-17 | 江苏冠联新材料科技股份有限公司 | NBR (nitrile-butadiene rubber) material for high-strength super-wear-resistant rubber roll |
| CN112080052B (en) * | 2020-09-27 | 2022-11-15 | 烟台橡研材料科技有限公司 | Air suction noise reduction rubber and preparation method thereof |
| CN112980067A (en) * | 2021-03-01 | 2021-06-18 | 深圳市鑫华煦橡胶制品有限公司 | Temperature-resistant hydrogenated nitrile rubber |
| CN113736153B (en) * | 2021-09-30 | 2023-02-03 | 兰州瑞普科技实业有限责任公司 | Sealing gasket and preparation method and application thereof |
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| CN103435878A (en) * | 2013-08-26 | 2013-12-11 | 南京金三力橡塑有限公司 | High-hardness high-temperature-resistant rubber roller for aluminum foil/aluminum sheet production line and manufacturing method thereof |
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| CN101130679A (en) * | 2006-08-25 | 2008-02-27 | 比亚迪股份有限公司 | Adhesion agent and method of manufacturing the same |
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