CN1554693A - Modified hydrogenated nitrile-butadiene rubber and its preparing method - Google Patents
Modified hydrogenated nitrile-butadiene rubber and its preparing method Download PDFInfo
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- CN1554693A CN1554693A CNA2003101116609A CN200310111660A CN1554693A CN 1554693 A CN1554693 A CN 1554693A CN A2003101116609 A CNA2003101116609 A CN A2003101116609A CN 200310111660 A CN200310111660 A CN 200310111660A CN 1554693 A CN1554693 A CN 1554693A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2309/02—Copolymers with acrylonitrile
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Abstract
The present invention relates to the preparing technology of composite rubber material. Carbon nanotube via surface treatment and liquid rubber are ultrasonically mixed and added into partial hydrogenated nitrile-butadiene rubber to prepare mother rubber; the mother rubber is mixed with the rest hydrogenated nitrile-butadiene rubber, carbon black, zinc oxide and sulfurizing agent, and the mixture is mixed in a rolling mixer or a Banbury mixer and sulfurized to obtain the carbon nanotube modified hydrogenated nitrile-butadiene rubber. The present invention has the beneficial effects of raised heat performance, antiwear performance, mechanical strength, antiageing performance, etc. raised use performance and expanded application range.
Description
Technical field
The present invention relates to a kind of carbon nano-tube modification hydrogenated nitrile-butadiene rubber and preparation method thereof, belong to rubber polymer Composite Preparation technical field.
Background technology
Many equilibriums such as that hydrogenated nitrile-butadiene rubber owing to have both has is heat-resisting, oil resistant, wear-resisting and physical strength height and good performance, thereby be widely used in many industries such as automobile, machinery, oil bits.But it is, more and more higher to performance demands such as heat-resisting, wear-resisting as the rubber seal of functional accessory along with the raising of development of science and technology and equipment performance.The rubber parts that existing hydrogenated nitrile-butadiene rubber is made has been difficult to satisfy that some occasion is wear-resisting to it, the requirement of resistance toheat.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists at above-mentioned prior art and a kind of modified hydrogenated paracril and preparation method thereof is provided, and heat-resisting, the wear resisting property and the physical strength of this modified hydrogenated paracril can effectively be improved and improve.
The technical scheme of the modified hydrogenated paracril of the present invention is: include hydrogenated nitrile-butadiene rubber, carbon nanotube, vulcanizing agent, zinc oxide, carbon black and anti-friction composition, each component concentration is by weight:
100 parts of carbon nanotube 0.5-15 of hydrogenated nitrile-butadiene rubber part
Vulcanizing agent 2-10 part zinc oxide 2-8 part
Carbon black 40-80 part anti-friction composition 0-25 part.
Press such scheme, described hydrogenated butyronitrile rubber can be adopted a kind of trade mark hydrogenated nitrile-butadiene rubber, or the blend hydrogenated nitrile-butadiene rubber of two kinds and the two or more trades mark; Carbon nanotube is the multi-walled carbon nano-tubes of 20-40nm caliber, and carbon nanotube is through surface treatment, and surface treatment comprises hydrochloric acid, nitric acid treatment, promoting agent processing or ultrasonication.Described zinc oxide is nano zine oxide or active zinc flower; Described vulcanizing agent is a sulfuric peroxide thing vulcanizing agent, can be oxidation diisopropylbenzene(DIPB) (DCP); Described anti-friction composition is one or more in graphite, mica, the molybdenumdisulphide; Can add protective agent 0.5-5 part in the above-mentioned component by weight.
Preparation method's of the present invention technical scheme is: earlier carbon nanotube is carried out surface treatment, carbon nanotube after the surface treatment and a kind of fluid rubber are mixed by ultrasonic wave, add then in the partial hydrogenation paracril (rubber) and make master batch, in master batch, add remaining hydrogenated nitrile-butadiene rubber (rubber), carbon black, zinc oxide, vulcanizing agent, with mill or Banbury mixer said mixture is processed, obtain hydrogenated nitrile-butadiene rubber rubber unvulcanizate with carbon nano-tube modification, by sulfuration processing, can obtain modified hydrogenated paracril of the present invention.In modified hydrogenated paracril, add anti-friction composition, can reduce the rubber friction coefficient.
Fluid rubber described in the above-mentioned preparation method is liquid acrylonitrile butadiene rubber or liquid carboxy nitrile rubber or hydrogenated liquid paracril; The blending ratio of carbon nanotube and fluid rubber is 1: 10～10: 10 by weight when making master batch.The carbon nanotube and the mixture of fluid rubber and the blending ratio of hydrogenated nitrile-butadiene rubber (rubber) are 6～9: 10 by weight when making master batch.
Principal feature of the present invention is the employing of carbon nano-tube material, and carbon nanotube strengthens tensile strength and the tensile elongation that can obviously improve hydrogenated nitrile-butadiene rubber by nano effect and carbon nanotube microfibers.Carbon nanotube itself because the carbon nanotube good heat-conducting can be conducted amount of localized heat in the rubber evenly rapidly, be avoided localized hyperthermia's damage after belonging in a kind of high temperature material adding rubber, improves the resistant to elevated temperatures effect of rubber thereby play.
Beneficial effect of the present invention is the heat-resisting abrasion resistance, physical strength of hydrogenated nitrile-butadiene rubber and over-all properties such as anti-aging are significantly improved and improve by infiltrate nano material in sizing material, thereby improve the use properties of hydrogenated nitrile-butadiene rubber, enlarge the use range of hydrogenated nitrile-butadiene rubber.Particularly in rubber seal products, this composite material rubber all has obvious superiority at aspects such as work-ing life, sealing property, suitable operating modes.Experimental results show that, content of carbon nanotubes is 4～8% o'clock in rubber, obtain the best net effect that improves, the tensile strength of this matrix material surpasses 27Mpa, tensile elongation surpasses 300%, compare with unmodified hydrogenated nitrile-butadiene rubber, over-all propertieies such as tensile strength, tensile elongation, wear resistance improve 15%, and the temperature classification temperature improves 10～15 ℃.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1:
Produce carbon nano-tube modification hydrogenated nitrile-butadiene rubber sizing material.Selecting caliber for use is the carbon nanotube of 20-40nm, carry out dispersion treatment with tensio-active agent (as sodium laurylsulfonate), in container, add 50 parts of fluid rubbers, 40 parts of carbon nanotubes then successively, on ultrasonic instrument, carry out ultrasonic skin dispersion treatment, then this mixture and the hydrogenated nitrile-butadiene rubber part by weight by 9: 10 is mixed in mill, make the master batch that adds carbon nanotube.The hydrogenated butyronitrile of selecting Therban 3850 trades mark for use is as the prescription rubber.
Take by weighing 38 parts of master batchs, 80 parts of rubbers, 3.8 portions of oxidation diisopropylbenzene(DIPB)s (DCP), 5 parts of nano zine oxides, 55 parts of carbon blacks, 17 parts of graphite successively, 1.5 part protective agent RD (2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer) mixing even in mill.Overnight the parking of sizing material that refining is good, sulfuration is 5 minutes under 180 ℃ of conditions, carries out 3 hours post vulcanization then under 150 ℃.Hydrogenated nitrile-butadiene rubber can be obtained, the low-friction coefficient sealing-ring can be made with this hydrogenated nitrile-butadiene rubber, the Akron abrasion value≤0.1cm of sealing circle sizing material with carbon nano-tube modification
3/ 1.61km, temperature classification 〉=165 ℃, tensile strength at yield 〉=27Mpa, tensile yield 〉=280%, frictional coefficient descends 20%, and the material over-all properties improves more than 20% on unmodified rubber basis.
Embodiment 2:
Produce carbon nano-tube modification hydrogenated nitrile-butadiene rubber sizing material.Selecting caliber for use is the carbon nanotube of 20-40nm, carry out dispersion treatment with tensio-active agent (as sodium laurylsulfonate), in container, add 50 parts of fluid rubbers, 30 parts of carbon nanotubes then successively, carrying out ultrasonic dispersing on ultrasonic instrument handles, then this mixture and the hydrogenated nitrile-butadiene rubber part by weight by 8: 10 is mixed in mill, make the master batch that adds carbon nanotube.The hydrogenated butyronitrile of selecting Therban 3850 trades mark for use is as the prescription rubber.
Take by weighing 36 parts of master batchs, 80 parts of rubbers, 3.5 portions of oxidation diisopropylbenzene(DIPB)s (DCP), 5 parts of nano zine oxides, 72 parts of carbon blacks successively, in mill mixing evenly.Overnight the parking of sizing material that refining is good, sulfuration is 5 minutes under 180 ℃ of conditions, carries out 3 hours post vulcanization then under 150 ℃.Can obtain hydrogenated nitrile-butadiene rubber with carbon nano-tube modification, can make the snappiness sealing-ring with this hydrogenated nitrile-butadiene rubber, temperature classification 〉=165 of sealing circle sizing material ℃, tensile strength at yield 〉=27Mpa, tensile yield 〉=300%, rebound degree 〉=20%, material over-all properties improve more than 20% on unmodified rubber basis.
Claims (11)
1, a kind of modified hydrogenated paracril is characterized in that including hydrogenated nitrile-butadiene rubber, carbon nanotube, vulcanizing agent, zinc oxide, carbon black and anti-friction composition, and each component concentration is by weight:
100 parts of carbon nanotube 0.5-15 of hydrogenated nitrile-butadiene rubber part
Vulcanizing agent 2-10 part zinc oxide 2-8 part
Carbon black 40-80 part anti-friction composition 0-25 part.
2, by the described modified hydrogenated paracril of claim 1, it is characterized in that described hydrogenated butyronitrile rubber can adopt a kind of trade mark hydrogenated nitrile-butadiene rubber, or the blend hydrogenated nitrile-butadiene rubber of two kinds and the two or more trades mark.
3, by claim 1 or 2 described modified hydrogenated paracrils, it is characterized in that carbon nanotube is the multi-walled carbon nano-tubes of 20-40nm caliber.
4, by the described modified hydrogenated paracril of claim 3, it is characterized in that carbon nanotube through surface treatment, surface treatment comprises hydrochloric acid, nitric acid treatment, promoting agent processing or ultrasonication.
5, by claim 1 or 2 described modified hydrogenated paracrils, it is characterized in that described zinc oxide is nano zine oxide or active zinc flower.
6, by claim 1 or 2 described modified hydrogenated paracrils, it is characterized in that adding by weight in the above-mentioned component protective agent 0.5-5 part.
7, by claim 1 or 2 described modified hydrogenated paracrils, it is characterized in that described anti-friction composition is one or more in graphite, mica, the molybdenumdisulphide.
8, a kind of preparation method of modified hydrogenated paracril, it is characterized in that earlier carbon nanotube being carried out surface treatment, carbon nanotube after the surface treatment and a kind of fluid rubber are mixed by ultrasonic wave, add then in the partial hydrogenation paracril and make master batch, in master batch, add remaining hydrogenated nitrile-butadiene rubber, carbon black, zinc oxide, vulcanizing agent, with mill or Banbury mixer said mixture is processed, obtain hydrogenated nitrile-butadiene rubber rubber unvulcanizate with carbon nano-tube modification, by sulfuration processing, can obtain modified hydrogenated paracril of the present invention; The content of described hydrogenated nitrile-butadiene rubber, carbon nanotube, vulcanizing agent, zinc oxide, carbon black is by weight:
100 parts of carbon nanotube 0.5-15 of hydrogenated nitrile-butadiene rubber part
Vulcanizing agent 2-10 part zinc oxide 2-8 part
Carbon black 40-80 part.
9, by the preparation method of the described modified hydrogenated paracril of claim 8, it is characterized in that described fluid rubber is liquid acrylonitrile butadiene rubber or liquid carboxy nitrile rubber or hydrogenated liquid paracril.
10,, it is characterized in that the blending ratio of carbon nanotube and fluid rubber is 1: 10～10: 10 by weight when making master batch by the preparation method of claim 8 or 9 described modified hydrogenated paracrils.
11,, it is characterized in that carbon nanotube and the mixture of fluid rubber and the blending ratio of hydrogenated nitrile-butadiene rubber are 6～9: 10 by weight when making master batch by the preparation method of claim 8 or 9 described modified hydrogenated paracrils.
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| CN 200310111660 CN1250633C (en) | 2003-12-26 | 2003-12-26 | Modified hydrogenated nitrile-butadiene rubber and its preparing method |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312206C (en) * | 2005-03-29 | 2007-04-25 | 清华大学 | Carbon nanotube modified powder natural rubber and method for preparing same |
| EP1749853A3 (en) * | 2005-06-30 | 2009-04-01 | Nissin Kogyo Co., Ltd | Composite material |
| WO2009155728A1 (en) * | 2008-06-23 | 2009-12-30 | Lanxess Deutschland Gmbh | Carbon nanotube containing rubber compositions |
| CN102190820A (en) * | 2011-03-23 | 2011-09-21 | 天津市金岭科技有限公司 | Preparation of seal assistant for leak stoppage through carbon nano tube modification |
| CN102604178A (en) * | 2011-11-29 | 2012-07-25 | 上海大学 | Wear-resistant modified HNBR (hydrogenated nitrile butadiene rubber), NBR (nitrile butadiene rubber) and NBR/PVC (polyvinyl chloride) dynamic sealing material adopting molybdenum disulfide solid lubricant and preparation method for same |
| CN102702591A (en) * | 2012-06-25 | 2012-10-03 | 青岛科技大学 | Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof |
| CN102825673A (en) * | 2011-06-16 | 2012-12-19 | 上海天普汽车零部件有限公司 | Preparation method of rubber material for preparing high-/low-temperature resistant automobile pipeline rubber products |
| CN102850615A (en) * | 2012-09-19 | 2013-01-02 | 扬州东星橡胶股份有限公司 | Production process of high-temperature-resistant HNBR (hydrogenated nitrile butadiene rubber) nanocomposite |
| CN102975303A (en) * | 2011-09-07 | 2013-03-20 | 上海天普汽车零部件有限公司 | Preparation method of rubber material for preparing temperature-resistant and oil-resistant rubber products for vehicle pipelines |
| CN101613495B (en) * | 2008-06-23 | 2013-03-27 | 朗盛德国有限责任公司 | Rubber composition containing carbon nano-tube |
| CN103980578A (en) * | 2014-05-06 | 2014-08-13 | 徐州工业职业技术学院 | Regenerated vulcanized hydrogenated nitrile-butadiene rubber and preparation method thereof |
| JP2014189578A (en) * | 2013-03-26 | 2014-10-06 | Nissin Kogyo Co Ltd | Carbon fiber composite material and method for producing the same |
| CN106279831A (en) * | 2016-08-25 | 2017-01-04 | 昆明云垦橡胶有限公司 | A kind of nanometer height heat conductive rubber and preparation method thereof |
| 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 |
| CN106366370A (en) * | 2016-08-29 | 2017-02-01 | 宁波旭泰橡胶工业有限公司 | Sealing ring |
| CN106519363A (en) * | 2016-10-19 | 2017-03-22 | 中国石油化工股份有限公司 | Hydrogenated nitrile-butadiene rubber composition |
| CN106661280A (en) * | 2014-07-25 | 2017-05-10 | 日本瑞翁株式会社 | Cross-linkable rubber composition and cross-linked rubber |
| CN109021342A (en) * | 2017-06-08 | 2018-12-18 | 浙江赞昇新材料有限公司 | A kind of high performance hydrogenated butyronitrile base rubber composite and preparation method thereof |
| CN110396230A (en) * | 2019-08-23 | 2019-11-01 | 陕西特种橡胶制品有限公司 | A kind of preparation method of nuclear power circulating pump bearing shell hard wear rubber product |
| 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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2003
- 2003-12-26 CN CN 200310111660 patent/CN1250633C/en not_active Expired - Fee Related
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312206C (en) * | 2005-03-29 | 2007-04-25 | 清华大学 | Carbon nanotube modified powder natural rubber and method for preparing same |
| EP1749853A3 (en) * | 2005-06-30 | 2009-04-01 | Nissin Kogyo Co., Ltd | Composite material |
| CN101613495B (en) * | 2008-06-23 | 2013-03-27 | 朗盛德国有限责任公司 | Rubber composition containing carbon nano-tube |
| WO2009155728A1 (en) * | 2008-06-23 | 2009-12-30 | Lanxess Deutschland Gmbh | Carbon nanotube containing rubber compositions |
| EP2138535A1 (en) | 2008-06-23 | 2009-12-30 | Lanxess Deutschland GmbH | Carbon nanotube containing rubber compositions |
| US8895671B2 (en) | 2008-06-23 | 2014-11-25 | Lanxess Deutschland Gmbh | Carbon nanotube containing rubber compositions |
| CN102190820A (en) * | 2011-03-23 | 2011-09-21 | 天津市金岭科技有限公司 | Preparation of seal assistant for leak stoppage through carbon nano tube modification |
| CN102825673B (en) * | 2011-06-16 | 2014-11-12 | 上海天普汽车零部件有限公司 | Preparation method of rubber material for preparing high-/low-temperature resistant automobile pipeline rubber products |
| CN102825673A (en) * | 2011-06-16 | 2012-12-19 | 上海天普汽车零部件有限公司 | Preparation method of rubber material for preparing high-/low-temperature resistant automobile pipeline rubber products |
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| CN102975303A (en) * | 2011-09-07 | 2013-03-20 | 上海天普汽车零部件有限公司 | Preparation method of rubber material for preparing temperature-resistant and oil-resistant rubber products for vehicle pipelines |
| CN102604178A (en) * | 2011-11-29 | 2012-07-25 | 上海大学 | Wear-resistant modified HNBR (hydrogenated nitrile butadiene rubber), NBR (nitrile butadiene rubber) and NBR/PVC (polyvinyl chloride) dynamic sealing material adopting molybdenum disulfide solid lubricant and preparation method for same |
| CN102702591B (en) * | 2012-06-25 | 2013-11-27 | 青岛科技大学 | Hydrogenated nitrile rubber/carbon nanotube composite material and preparation method thereof |
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| CN102850615A (en) * | 2012-09-19 | 2013-01-02 | 扬州东星橡胶股份有限公司 | Production process of high-temperature-resistant HNBR (hydrogenated nitrile butadiene rubber) nanocomposite |
| JP2014189578A (en) * | 2013-03-26 | 2014-10-06 | Nissin Kogyo Co Ltd | Carbon fiber composite material and method for producing the same |
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| CN106661280B (en) * | 2014-07-25 | 2019-10-18 | 日本瑞翁株式会社 | Bridging property rubber composition and rubber cross object |
| US10538641B2 (en) | 2014-07-25 | 2020-01-21 | Zeon Corporation | Crosslinkable rubber composition and crosslinked rubber |
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| CN106366370B (en) * | 2016-08-29 | 2018-09-07 | 宁波旭泰橡胶工业有限公司 | A kind of sealing ring |
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| CN106519363A (en) * | 2016-10-19 | 2017-03-22 | 中国石油化工股份有限公司 | Hydrogenated nitrile-butadiene rubber composition |
| CN106519363B (en) * | 2016-10-19 | 2020-06-26 | 中国石油化工股份有限公司 | Hydrogenated nitrile rubber composition |
| CN109021342A (en) * | 2017-06-08 | 2018-12-18 | 浙江赞昇新材料有限公司 | A kind of high performance hydrogenated butyronitrile base rubber composite and preparation method thereof |
| 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 |
| CN110396230A (en) * | 2019-08-23 | 2019-11-01 | 陕西特种橡胶制品有限公司 | A kind of preparation method of nuclear power circulating pump bearing shell hard wear rubber product |
| 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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