CN102850615A - Production process of high-temperature-resistant HNBR (hydrogenated nitrile butadiene rubber) nanocomposite - Google Patents
Production process of high-temperature-resistant HNBR (hydrogenated nitrile butadiene rubber) nanocomposite Download PDFInfo
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- CN102850615A CN102850615A CN2012103482505A CN201210348250A CN102850615A CN 102850615 A CN102850615 A CN 102850615A CN 2012103482505 A CN2012103482505 A CN 2012103482505A CN 201210348250 A CN201210348250 A CN 201210348250A CN 102850615 A CN102850615 A CN 102850615A
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- hydrogenated nitrile
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Abstract
The invention relates to rubber and improved rubber production processes, in particular to a production process of a high-temperature-resistant HNBR (hydrogenated nitrile butadiene rubber) nanocomposite. According to the production process, hydrogenated nitrile butadiene rubber serves as matrix materials, nanosilicon dioxide and carbon nano tubes are jointly used as reinforcement materials, organic peroxides serve as crosslinkers, multifunctional groups of activated monomers serve as assistant crosslinkers, and an open mill and an internal mixer are used for processing the rubber composite, so that the problems of nanofiller dispersion and interface adhesion among rubber are solved. Compared with existing rubber in performance, the HNBR nanocomposite processed by the production process has excellent normal-temperature mechanical property, high high-temperature mechanical property retention rate and excellent ageing resistance.
Description
Technical field
The present invention relates to rubber, particularly the production technique of modified version rubber.
Background technology
Hydrogenated nitrile-butadiene rubber (HNBR) be thermotolerance, the weathering resistance of improving common paracril (NBR) be the new type rubber that purpose is produced.Hydrogenated nitrile-butadiene rubber is to make by the two keys on the hydrogenated nbr macromolecular main chain, compare with NBR, keeping preferably having improved thermotolerance, weathering resistance and chemical stability etc. on the basis of oil-proofness, simultaneously, its physical and mechanical properties has also obtained very large improvement.At present, hydrogenated nitrile-butadiene rubber can be used for the goods of Oil extraction such as screw pump rubber stator, used elastomeric material concentrates on common butyronitrile material substantially in the oil field at present, but owing to containing multiple corrosive medium in the crude oil, add that mining environment is more and more abominable, the goods before causing are difficult to satisfy present exploitation requirement.
Summary of the invention
The object of the invention is to propose a kind of production technique that is applicable to the high temperature resistant HNBR nano composite material of Petroleum Industry.
Processing step of the present invention is:
1) be that 50 ℃ and rotating speed are to add first hydrogenated nitrile-butadiene rubber under the condition of 30rpm at ultrasonic wave mixer melting temperature, and then add zinc oxide, magnesium oxide, stearic acid, N550, white carbon black, carbon nanotube CNT, anti-aging agent, softening agent, superoxide and additional crosslinker, carry out ultrasonic wave mixing;
2) in mill, play the triangle bag, and lower sheet
3) sulfuration.
The mass ratio that feeds intake of described hydrogenated nitrile-butadiene rubber, zinc oxide, magnesium oxide, stearic acid, white carbon black, carbon nanometer, anti-aging agent, softening agent, superoxide and additional crosslinker is 100 ︰, 5 ︰, 6 ︰, 1 ︰, 50 ︰, 15 ︰, 30 ︰, 4 ︰, 15 ︰, 7 ︰ 2.
Described mixing time is 20 minutes.
The temperature of described sulfuration is 175 ℃, curing time 90 ± 2min.
The present invention is take hydrogenated nitrile-butadiene rubber as organism material, with nano silicon and carbon nanotube and be used as supporting material, select organo-peroxide as linking agent, take the polyfunctional group reactive monomer as additional crosslinker, with mill and Banbury mixer rubber composite is processed.And by the research temperature on the impact of HNBR nano composite material structure and performance, developed carbon nanotube in the hydrogenated nitrile-butadiene rubber system in-situ modified-dispersion technology, the dispersion that has solved Nano filling reach and rubber between the interfacial adhesion problem.The present invention has fully adopted the synergy of white carbon black and Nano filling, and is perfect collaborative and prepare the technology of high temperature resistant, high pressure resistant oil production usefulness sealing material with, staple fibre and novel rubber processing aids by hydrogenated nitrile-butadiene rubber, white carbon black and Nano filling.The rubber unvulcanizate of processing has been realized the new type rubber matrix material of ionic polymer grafting carbochain main chain through original position phase Free Radicals polyreaction.Compare with the performance of existing rubber, the novel HNBR rubber composite of processing has the ambient temperature mechanical properties of excellence, higher mechanical behavior under high temperature conservation rate and excellent ageing resistance.
Description of drawings
Fig. 1 is the Electronic Speculum figure without the product of ultrasonication.
Fig. 2 is the Electronic Speculum figure of the product of employing ultrasonication.
Fig. 3 is without filling HNBR and the thermogravimetric curve figure of multi-wall carbon nano-tube composite material in nitrogen atmosphere.
Fig. 4 is the graph of a relation of multi-walled carbon nano-tubes consumption and hydrogenated butyronitrile/multi-wall carbon nano-tube composite material volume change Δ V%.
Fig. 5 is (150 ℃ * 168h) figure of the variations of tensile strength before and after the different sorts filler composite materials high-temperature oil resistance under the equal volume filling ratio.
Fig. 6 be under the equal volume filling ratio different sorts filler on (150 ℃ * 168h) figure of the impacts of stretching strength retentivity before and after the matrix material high-temperature oil resistance.
Embodiment
One, get the raw materials ready:
Hydrogenated nitrile-butadiene rubber (HNBR) 100kg, zinc oxide 5 kg, magnesium oxide 6 kg, stearic acid 1 kg, N550 50 kg, white carbon black 15 kg, carbon nanotube 30 kg, anti-aging agent 4 kg, softening agent 15 kg, superoxide Perkadox14-40BD 7 kg, additional crosslinker TAIC-70 2 kg.
Wherein, hydrogenated nitrile-butadiene rubber (HNBR) is bright Sheng chemical production, and model is Therban3407; Carbon nanotube is the multi-walled carbon nano-tubes Baytubes C150 P that Beyer Co., Ltd produces; Anti-aging agent is that Chemtura Corporation produces anti-aging agent Naugard445; Superoxide is produced by Lay mattress chemical company, model Perkadox14-40BD; Additional crosslinker is produced by Akzo Nobel N.V., model: TAIC-70.
Two, production stage:
1, be that 50 ℃ and rotating speed are under the condition of 30rpm at ultrasonic wave mixer melting temperature, add first hydrogenated nitrile-butadiene rubber (HNBR), and then add zinc oxide, magnesium oxide, stearic acid, N550, white carbon black, carbon nanometer, anti-aging agent, softening agent, superoxide and additional crosslinker, carry out the mixing 20min of ultrasonic wave.
2, the triangle bag played in the work piece after ultrasonic wave is mixing in mill.
3, compressing tablet: roll spacing is transferred to 1.1mm, and the lower sheet thickness of control is about 2.1mm, parks after 16 hours the product after the extruding for subsequent use in pressure roller.
4, sulfuration:
Temperature is 175 ℃, curing time 90 ± 2min.
Three, analyze:
1, the impact of ultrasonication:
Ultrasonic wave can be broken gathering of white carbon black and many carbon nanotubes CNT in the rubber base material, (frequency is 2Hz to Banbury mixer by being equipped with ultrasonic generator, be 2s pitch time) the HNBR nano composite material is carried out blend, thereby improve the dispersiveness of nano material in body material, the consistency of rubber unvulcanizate is provided, and white carbon black and carbon nanotube are having ultrasonic wave and without the contrast situation under the effect of ultrasonic wave aid dispersion as depicted in figs. 1 and 2 respectively in rubber base material.Compare through Fig. 1 and Fig. 2, the product uniformity coefficient that the employing ultrasonic wave is processed is apparently higher than the product that does not adopt ultrasonic wave to process.
2, the consumption of multi-walled carbon nano-tubes MWCNT is on the impact of matrix material vulcanization characteristics:
Annotate: Vc=1/(tc in the upper table
90-tc
10), cure conditions is 175 ℃.
As can be seen from the above table, behind the adding multi-walled carbon nano-tubes, the highest torque value (M of matrix material
H) and minimum torque value (M
L) all significantly improve; And increase the highest torque value (M of matrix material along with the multi-walled carbon nano-tubes consumption
H) and minimum torque value (M
L) difference increase.The analysis reason is thought, because after the increase of multi-walled carbon nano-tubes consumption, BRC bound rubber content increases, and the flowability reduction of sizing material, simultaneously, because the hydrokinetics strengthening action so that the viscosity of sizing material further increases, causes moment of torsion to increase.
From showing upper it can also be seen that, increase the time of scorch (tc of sizing material along with the multi-walled carbon nano-tubes consumption
10) shorten, sulfurizing time (tc
90) shorten, vulcanization rate Vc increases.The analysis reason thinks, on the one hand, the good heat conductivity of carbon nanotube after the increase of consumption, has increased the heat conductivility of material itself, has promoted the sulfidation of rubber.On the other hand, the total specific surface area of filler increases, and increases in conjunction with glue content, improves in conjunction with glue net structure density, hinders the motion of macromolecular chain, has shortened time of scorch and the curing time of sizing material.
3, the consumption of multi-walled carbon nano-tubes MWCNT is on the impact of hydrogenated butyronitrile/multi-wall carbon nano-tube composite material physical and mechanical properties:
Following table is the property indices of the product that adopts technique of the present invention and make:
As seen from the above table, indices of the present invention is better than HNBR.
4, carbon nanotube is on the impact of matrix material thermal stability:
As seen from Figure 3, the thermal degradation temperature of the matrix material behind the adding carbon nanotube all has the trend of rising, and the resistance toheat of the carbon nanotube that surfactivity is higher is better.Wherein, the most degradation speed of the matrix material of many walls MWCNT filling is 565 ℃ of appearance; The analysis reason is thought, this is because the active function groups of carbon nanotube with rubber molecular chain Chemical bond has occured in sulfidation, promoted cross-linking process, in conjunction with after carbon nanotube suppressed the high temperature degradation process of molecular chain, cause the degraded peak value of matrix material to move to the high temperature place.
4, the consumption of multi-walled carbon nano-tubes is on the impact of hydrogenated butyronitrile/multi-wall carbon nano-tube composite material oil resistance:
As can be seen from Figure 4, along with mass change and volume change before and after the multi-walled carbon nano-tubes consumption increase sizing material immersion oil all present the trend that reduces.The analysis reason thinks, in the few sizing material of content of carbon nanotubes, it is intermolecular that oil molecule more easily diffuses into sizing material when immersion oil, so that the mass change of sizing material and volume change increase.When content of carbon nanotubes increased, nano level filler had been filled the cross-link bond space between molecule segment, and the physical crosslinking density of sizing material increases, and oil molecule is difficult for diffusing between the sizing material molecule, causes the mass change of sizing material and volume change to reduce.
5, during the equal volume filling ratio different sorts filler on the impact of matrix material high-temperature oil resistance performance:
Can find out from 5, the stretching strength retentivity of carbon nanotube/hydrogenated butyronitrile matrix material is the highest, secondly is carbon black N990, N660, N330.As can be seen from Figure 6, under the equal volume filling ratio, all be that the tensile strength of carbon nanotube/hydrogenated butyronitrile matrix material is the highest before and after the oil resistant.Analyzing reason is that carbon nano tube surface is smooth on the one hand, and structure level is low, and the carbon black minimum than structure level to the adsorptive capacity of oil molecule is also little; On the other hand, nano level filler has been filled the cross-link bond space between molecule segment, and the physical crosslinking density of sizing material increases, so that oil molecule is difficult for diffusing between the sizing material molecule.That stretching strength retentivity is the highest in the carbon black series is N990, because its structure level is minimum, surperficial chain branch structure is undeveloped, and is close to sphere, less to the adsorptive capacity of oil molecule; The N330 carbon black that structure level is high and N660 carbon black so that oil molecule glue easily enters into matrix material, have caused the stretching strength retentivity reduction.
Conclusion: by the auxiliary finely dispersed HNBR nano composite material of nano material that obtains of ultrasonic wave, pass through carbon nanotubes application, improved oil-proofness and resistance to elevated temperatures, this material can be applied to high temperature high voltage resistant the oil field rubber item, such as stator rubber of screw drilling tools etc.
Claims (4)
1. the production technique of high temperature resistant HNBR nano composite material is characterized in that may further comprise the steps:
1) be that 50 ℃ and rotating speed are to add first hydrogenated nitrile-butadiene rubber under the condition of 30rpm at ultrasonic wave mixer melting temperature, and then add zinc oxide, magnesium oxide, stearic acid, N550, white carbon black, carbon nanotube CNT, anti-aging agent, softening agent, superoxide and additional crosslinker, carry out ultrasonic wave mixing;
2) in mill, play the triangle bag, and lower sheet
3) sulfuration.
2. the production technique of described high temperature resistant HNBR nano composite material according to claim 1, the mass ratio that feeds intake that it is characterized in that described hydrogenated nitrile-butadiene rubber, zinc oxide, magnesium oxide, stearic acid, white carbon black, carbon nanometer, anti-aging agent, softening agent, superoxide and additional crosslinker is 100 ︰, 5 ︰, 6 ︰, 1 ︰, 50 ︰, 15 ︰, 30 ︰, 4 ︰, 15 ︰, 7 ︰ 2.
3. the production technique of described high temperature resistant HNBR nano composite material according to claim 1 is characterized in that described mixing time is 20 minutes.
4. the production technique of described high temperature resistant HNBR nano composite material according to claim 1, the temperature that it is characterized in that described sulfuration is 175 ℃, curing time 90 ± 2min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009131A (en) * | 2016-06-14 | 2016-10-12 | 航天材料及工艺研究所 | Preparing method for antioxidant-modified carbon nano tube/hydrogenated butadiene-acrylonitrile rubber |
| CN106336544A (en) * | 2016-08-29 | 2017-01-18 | 宁波旭泰橡胶工业有限公司 | Seal ring with high performance |
| CN106633259A (en) * | 2016-12-10 | 2017-05-10 | 李晓光 | Pressure resistant sealing ring for ship body |
| CN111269477A (en) * | 2018-11-20 | 2020-06-12 | 中国石油化工股份有限公司 | Rubber composite material and preparation method thereof |
| CN112250926A (en) * | 2020-10-20 | 2021-01-22 | 广州万德福密封技术有限公司 | High-wear-resistance self-lubricating rubber-plastic composite sealing ring |
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| JP2004331929A (en) * | 2003-05-02 | 2004-11-25 | Masao Goto | Method of compounding a nanocarbon |
| CN1554693A (en) * | 2003-12-26 | 2004-12-15 | 江汉石油钻头股份有限公司 | Modified hydrogenated nitrile-butadiene rubber and its preparing method |
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| JP2004331929A (en) * | 2003-05-02 | 2004-11-25 | Masao Goto | Method of compounding a nanocarbon |
| CN1554693A (en) * | 2003-12-26 | 2004-12-15 | 江汉石油钻头股份有限公司 | Modified hydrogenated nitrile-butadiene rubber and its preparing method |
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| 《Journal of Applied Polymer Science》 20081231 D. Felho¨ s et al. Tribological Testing of Peroxide Cured HNBR with Different MWCNT and Silica Contents under Dry Sliding and Rolling Conditions Against Steel 第108卷, * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009131A (en) * | 2016-06-14 | 2016-10-12 | 航天材料及工艺研究所 | Preparing method for antioxidant-modified carbon nano tube/hydrogenated butadiene-acrylonitrile rubber |
| CN106009131B (en) * | 2016-06-14 | 2018-04-10 | 航天材料及工艺研究所 | A kind of antioxidant is carbon nano-tube modified/preparation method of hydrogenated nitrile-butadiene rubber |
| CN106336544A (en) * | 2016-08-29 | 2017-01-18 | 宁波旭泰橡胶工业有限公司 | Seal ring with high performance |
| CN106633259A (en) * | 2016-12-10 | 2017-05-10 | 李晓光 | Pressure resistant sealing ring for ship body |
| CN111269477A (en) * | 2018-11-20 | 2020-06-12 | 中国石油化工股份有限公司 | Rubber composite material and preparation method thereof |
| CN112250926A (en) * | 2020-10-20 | 2021-01-22 | 广州万德福密封技术有限公司 | High-wear-resistance self-lubricating rubber-plastic composite sealing ring |
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