CN102134325B - Method for vulcanizing nitrile elastomer - Google Patents
Method for vulcanizing nitrile elastomer Download PDFInfo
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- CN102134325B CN102134325B CN 201110036253 CN201110036253A CN102134325B CN 102134325 B CN102134325 B CN 102134325B CN 201110036253 CN201110036253 CN 201110036253 CN 201110036253 A CN201110036253 A CN 201110036253A CN 102134325 B CN102134325 B CN 102134325B
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- nitrile rubber
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Abstract
The invention relates to a method for vulcanizing a nitrile elastomer. The method is characterized by comprising the following steps: adding 100 parts by mass of nitrile rubber resin and 5-55 parts by mass of vulcanized cross-linking agent, and mixing at 20-50 DEG C to obtain a composite sizing material; feeding the composite sizing material into reacting equipment at 130-200 DEG C for vulcanization reaction; and discharging after 5-6 minutes and cooling to obtain the nitrile elastomer, wherein the vulcanized cross-linking agent is tartaric acid, malic acid or lactic acid or mixed hydroxy carboxylic acid of two or three of the above hydroxy carboxylic acids mixed at any ratio; and the nitrile rubber resin is chemigum resin, butadiene rubber resin, powdered nitrile rubber, carboxy terminated nitrile rubber resin or liquid carboxy terminated nitrile rubber resin, or the mixed nitrile rubber resin of two or three nitrile resins mixed at any ratio. The method has the advantage of simple vulcanization system, and the cross-linking agent is non-toxic, thereby meeting the requirement of low-carbon and environment-friendly chemical industry development and having wide application prospects.
Description
Technical field
The present invention relates to a kind of elastomeric vulcanization process, particularly relate to the elastomeric vulcanization process of a kind of nitrile.
Background technology
Sulfuration is the crosslinked general designation of rubber macromolecule bridge formation, is the prerequisite that elastomerics has excellent use properties.After sulfuration, the linear macromolecule chain of rubber can be cross-linked into three-dimensional space net structure, can not be subjected to stress and produces the chain slippage, vulcanized rubber thereby just have good visco-elasticity.Press the character of the main body cross-link bond of three-dimensional space net structure, vulcanized rubber roughly can be divided into: five kinds of covalent cross-linking elastomerics, coordination bond cross-linking elastomerics, ionic crosslinking elastomerics, Van der Waals force cross-linked elastomer and hydrogen bond cross-linked elastomers.Wherein, the elastomeric comprehensive mechanical property of covalent cross-linking is optimum, and range of application is also the widest.
So far, known have two kinds of sulfurization technologies can obtain the covalent cross-linking elastomerics: (1) contains the sulphur vulcanization system, is comprised of vulcanizing agent (mainly being sulphur or organic sulfide), activator (generally using zinc oxide), promotor (comprising thiazoles, sulfenamide, thiurams, Thiourea, dithiocarbamate(s), aldehyde amines, guanidine class and xanthogenic acid salt etc.) three parts; (2) contain peroxide vulcanizing system, by superoxide (as, dicumyl peroxide, di-t-butyl peroxide and peroxidized t-butyl perbenzoate etc.) and cocuring agent (as, triallyl isocyanuric acid fat, triallyl cyanogen urea acid fat, N, N '-metaphenylene-bismaleimides etc.) two portions composition.Contain the sulphur sulfurization technology, be applicable to vulcanize unsaturated rubber, can make rubber obtain carbon-single sulphur-carbon bond and carbon-crosslinked reticulated structure of many sulphur-carbon bonds, and then make vulcanized rubber have good visco-elasticity, but, this technical formula is complicated, murder by poisoning organism consumption is large, exists the problem of serious environment pollution.Contain the peroxide cure technology, fill a prescription simpler, saturated or unsaturated rubber all are suitable for, can give the rubber C-C crosslinked reticulated structure, and then make vulcanized rubber have higher modulus and thermotolerance, still, the rubber visco-elasticity of this technology sulfuration is bad, and superoxide is generally all poisonous.Along with the increasingly deterioration of human ecological environment, low-carbon (LC), green chemical industry have been the main flow in epoch, and research and development are economical, nontoxic sulfuration new technology just becomes the task of top priority of rubber industry.
The covalent cross-linking nitrile rubber, comprise paracril, hydrogenated nitrile-butadiene rubber, Powdered acrylonitrile-butadiene rubber, carboxy nitrile rubber and liquid carboxy nitrile rubber etc., be proved to be oil resistant, anti-benzene, resistance toheat and good mechanical property with excellence, obtain important in fields such as petrochemical complex, aerospace, automobile, electric wire, printing and weavings and widely application.So far, obtain the sulfurization technology of covalent cross-linking nitrile rubber, only relate to and aforesaidly contain the sulphur vulcanization system and contain peroxide vulcanizing system.And about economical, the elastomeric technology of nontoxic sulfuration nitrile is still very rare.
Summary of the invention
The object of the invention provides a kind of economy, the elastomeric vulcanization process of nontoxic nitrile, to satisfy the industry requirement of the green sulfuration of rubber.
For realizing that the technical scheme that purpose of the present invention adopts is:
A) toward the disposable input 100 weight part nitrile rubber resins of processing units and 5 ~ 55 weight part vulcanization crosslinking agent, mixing even under 20 ℃ ~ 50 ℃, get compound sizing material;
B) compound sizing material being sent into temperature is 130 ~ 200 ℃ conversion unit, makes compound sizing material generation vulcanization reaction, discharging behind 5min ~ 60min, cooling, vulcanize the nitrile elastomerics.
Nitrile rubber resin of the present invention refers to nitrile rubber resin, hydrogenated nitrile-butadiene rubber resin, Powdered acrylonitrile-butadiene rubber resin, carboxy nitrile rubber resin or liquid carboxy nitrile rubber resin, or the mixing nitrile rubber resin that mixes of the arbitrary proportion of above-mentioned two or three nitrile rubber resin.
Vulcanization crosslinking agent of the present invention refers to the hydroxycarboxylic acid vulcanization crosslinking agent of one of tartrate, oxysuccinic acid or lactic acid, or the mixing hydroxycarboxylic acid vulcanization crosslinking agent that mixes of the arbitrary proportion of above-mentioned two or three hydroxycarboxylic acid.
Processing units of the present invention refers to Banbury mixer or mill.
Conversion unit of the present invention refers to vulcanizer.
The elastomeric method of a kind of sulfuration nitrile of the present invention, vulcanization system only is comprised of linking agent, and described linking agent is hydroxycarboxylic acid, has the features such as vulcanization system is simple, linking agent is nontoxic, meet low-carbon (LC), green chemical industry demand for development, have bright application prospect.
Description of drawings
Fig. 1 adopts vulcanization process of the present invention, vulcanizes graphic representation the typical case of 180 ℃ of compound sizing materials of lower NBR/ tartrate.
Among the figure: 180 ℃ of curing temperatures, NBR resin 100phr, tartrate 15phr.
Embodiment
Below by specific embodiment the present invention is described in more detail or describes, rather than limit the invention.
Embodiment 1
Toward 100 kilograms of nitrile rubber resin of the disposable input of mill and 55 kilograms of tartrate, mixing even under 45 ℃, get compound sizing material; The vulcanizing press of compound sizing material being sent into fast temperature again and be 180 ℃ vulcanizes, discharging behind 60 min, cooling, vulcanize the nitrile elastomerics.Test to get the vulcanization characteristics parameter by GB: sulfurizing time t
90=20.83min, minimal torque M
L=0.82dNm, peak torque M
H=9.60 dNm, moment of torsion increment △ M=8.78 dNm.
Embodiment 2
Toward 100 kilograms of nitrile rubber resin of the disposable input of Banbury mixer and 45 kilograms of oxysuccinic acid, mixing even under 20 ℃, get compound sizing material; The vulcanizing press of compound sizing material being sent into fast temperature again and be 200 ℃ vulcanizes, discharging behind the 30min, cooling, vulcanize the nitrile elastomerics.Test to get the vulcanization characteristics parameter by GB: sulfurizing time t
90=6.32min, minimal torque M
L=0.74dNm, peak torque M
H=9.32 dNm, moment of torsion increment △ M=8.58 dNm.
Embodiment 3
Be the tartrate of 4:1 and the mixing hydroxycarboxylic acid that oxysuccinic acid mixes toward 100 kilograms of nitrile rubber resin of the disposable input of Banbury mixer and 25 kilograms by weight part ratio, in 35 ℃ lower mixing evenly, get compound sizing material; The vulcanizing press of compound sizing material being sent into fast temperature again and be 135 ℃ vulcanizes, discharging behind the 60min, cooling, vulcanize the nitrile elastomerics.Test to get the vulcanization characteristics parameter by GB: sulfurizing time t
90=44.21min, minimal torque M
L=0.77dNm, peak torque M
H=8.68 dNm, moment of torsion increment △ M=7.91 dNm.
Be the mixing nitrile rubber resin that 2:3 nitrile rubber resin and hydrogenated nitrile-butadiene rubber mixed with resin form toward 100 kilograms of disposable inputs of mill by weight part ratio, 15 kilograms of tartrate, in 40 ℃ lower mixing evenly, get compound sizing material; The vulcanizing press of compound sizing material being sent into fast temperature again and be 150 ℃ vulcanizes, discharging behind 30 min, cooling, vulcanize the nitrile elastomerics.Test to get the vulcanization characteristics parameter by GB: sulfurizing time t
90=16.31min, minimal torque M
L=0.89dNm, peak torque M
H=8.32 dNm, moment of torsion increment △ M=7.43 dNm.
Embodiment 5
Be the mixing nitrile rubber resin that 8:1:1 nitrile rubber resin, hydrogenated nitrile-butadiene rubber resin and Powdered acrylonitrile-butadiene rubber mixed with resin form toward 100 kilograms of disposable inputs of Banbury mixer by weight part ratio, 5 kilograms is the mixing hydroxycarboxylic acid that tartrate, oxysuccinic acid and the lactic acid of 3:2:1 mixes by mass ratio, mixing even under 25 ℃, get compound sizing material; The vulcanizing press of compound sizing material being sent into fast temperature again and be 165 ℃ vulcanizes, discharging behind 45 min, cooling, vulcanize the nitrile elastomerics.Test to get the vulcanization characteristics parameter by GB: sulfurizing time t
90=14.03min, minimal torque M
L=0.70dNm, peak torque M
H=7.34 dNm, moment of torsion increment △ M=6.64 dNm.
Claims (1)
1. elastomeric vulcanization process of nitrile is characterized in that:
A) with weight part ratio be nitrile rubber resin and the vulcanization crosslinking agent of 100 ︰ 5 ~ 55, in 20 ℃ ~ 50 ℃ lower mixing even compound sizing materials that get;
B) compound sizing material is sent into conversion unit and under 130 ~ 200 ℃, carried out 5min ~ 60min vulcanization reaction, the nitrile elastomerics that must vulcanize after discharging, the cooling;
Described nitrile rubber resin refers to nitrile rubber resin, hydrogenated nitrile-butadiene rubber resin or carboxy nitrile rubber resin, or the mixing nitrile rubber resin that mixes of the arbitrary proportion of above-mentioned two or three nitrile rubber resin;
Described vulcanization crosslinking agent refers to the hydroxycarboxylic acid vulcanization crosslinking agent of one of tartrate, oxysuccinic acid or lactic acid, or the mixing hydroxycarboxylic acid vulcanization crosslinking agent that mixes of the arbitrary proportion of above-mentioned two or three hydroxycarboxylic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110036253 CN102134325B (en) | 2011-02-11 | 2011-02-11 | Method for vulcanizing nitrile elastomer |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110036253 CN102134325B (en) | 2011-02-11 | 2011-02-11 | Method for vulcanizing nitrile elastomer |
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| CN102134325A CN102134325A (en) | 2011-07-27 |
| CN102134325B true CN102134325B (en) | 2013-01-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102532623B (en) * | 2011-12-29 | 2014-09-03 | 福建师范大学 | Renewable bundled and crosslinked rubber material |
| CN105482280B (en) * | 2016-01-14 | 2017-11-24 | 武夷学院 | One kind is without sulphur without aldehyde plug and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313356A (en) * | 2001-04-04 | 2001-09-19 | 南开大学 | Modified nitrile rubber and its preparing process |
| JP2005141791A (en) * | 2003-11-04 | 2005-06-02 | Sony Corp | Casing for recording medium |
| CN1944508A (en) * | 2006-09-28 | 2007-04-11 | 上海交通大学 | Process for preparing hydrogenized nitrile-butadiene rubber vulcanized rubber |
| CN101186726A (en) * | 2007-11-20 | 2008-05-28 | 广州机械科学研究院 | Rubber-plastic composite material and application thereof |
| CN101475713A (en) * | 2008-12-11 | 2009-07-08 | 陈树望 | Rubber composition for crawler equipment |
| CN101735494A (en) * | 2008-11-07 | 2010-06-16 | 海堡(厦门)橡胶有限公司 | Synthetic rubber |
| CN101824172A (en) * | 2010-04-16 | 2010-09-08 | 青岛科技大学 | Preparation method of high temperature and high pressure resistant rubber sealing material |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313356A (en) * | 2001-04-04 | 2001-09-19 | 南开大学 | Modified nitrile rubber and its preparing process |
| JP2005141791A (en) * | 2003-11-04 | 2005-06-02 | Sony Corp | Casing for recording medium |
| CN1944508A (en) * | 2006-09-28 | 2007-04-11 | 上海交通大学 | Process for preparing hydrogenized nitrile-butadiene rubber vulcanized rubber |
| CN101186726A (en) * | 2007-11-20 | 2008-05-28 | 广州机械科学研究院 | Rubber-plastic composite material and application thereof |
| CN101735494A (en) * | 2008-11-07 | 2010-06-16 | 海堡(厦门)橡胶有限公司 | Synthetic rubber |
| CN101475713A (en) * | 2008-12-11 | 2009-07-08 | 陈树望 | Rubber composition for crawler equipment |
| CN101824172A (en) * | 2010-04-16 | 2010-09-08 | 青岛科技大学 | Preparation method of high temperature and high pressure resistant rubber sealing material |
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