CN101704909B - In-situ hydrogenation method of acrylonitrile-butadiene rubber latex - Google Patents
In-situ hydrogenation method of acrylonitrile-butadiene rubber latex Download PDFInfo
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- CN101704909B CN101704909B CN2009102363051A CN200910236305A CN101704909B CN 101704909 B CN101704909 B CN 101704909B CN 2009102363051 A CN2009102363051 A CN 2009102363051A CN 200910236305 A CN200910236305 A CN 200910236305A CN 101704909 B CN101704909 B CN 101704909B
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- nitrile rubber
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- butadiene rubber
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Abstract
The invention belongs to the field of hydrogenation of acrylonitrile-butadiene rubber latex. The hydrogenation of acrylonitrile-butadiene rubber latex is realized through the technical scheme as follows: the mixture of acrylonitrile-butadiene rubber latex and hydrazine hydrate is heated to 30 to 70 DEG C, and then constant temperature is kept for 2 to 8 h, and in the process with constant temperature, aqueous solution of sodium periodate is dripped into the mixture, the dripping rate is controlled, and the dripping is accomplished within 2 to 6 hours. The method has the advantages of simple process flow, low cost, less pollution, high hydrogenation rate, low cross linking level of the prepared hydrogenated acrylonitrile-butadiene rubber latex, and good processing property.
Description
Technical field
The invention belongs to the acrylonitrile-butadiene rubber latex field of hydrogenation, be specifically related to a kind of imide that utilizes hydrazine derivative and sodium periodate reaction to generate carries out the original position hydrogenation to nitrile rubber (NBR) method.
Background technology
The hydrogenation of paracril is that wherein divinyl segment is carried out selectable hydrogenation, and it is saturated that the two keys on most of divinyl segment are carried out hydrogenation, and the two keys that only stay a small amount of (1-5%) 1,4 divinyl are for crosslinked usefulness, and reservation CN base.
Hydrogenated nitrile-butadiene rubber has not only been inherited the oil resistant of common paracril, anti-solvent and antiwear characteristic, and high temperature resistant, ageing-resistant, resistant to chemical media burn into high tensile that has obtained that high saturated structures vouchsafes and the long-term less over-all properties of compression set, therefore the constantly service requirements of the harshness of proposition of oil-field development and automotive industry can be satisfied, expensive viton can be replaced in a lot of places.At present realized that the method for hydrogenation of industrialized paracril is to utilize the compound of Noble Metal Rhodium, ruthenium, palladium to be catalyzer mostly, unsaturated link(age) in hydrogen catalyzed and the paracril carries out selective reaction, this class methods catalytic activity height, product hydrogenation degree height, but noble metal catalyst is very expensive, cost is higher, and reclaims difficulty, and the hydrogenated products performance is had disadvantageous effect.
In recent years, by imide the method that carbon-carbon double bond carries out the cyclisation hydrogenation has more and more been caused researchist's concern.This method can be divided into original position emulsion hydrogenation and ex situ emulsion hydrogenation according to the difference of reaction unit, wherein original position emulsion hydrogenation is meant and utilizes some materials, as, in latex, directly add hydrazine hydrate and hydrogen peroxide, hydrazine hydrate and hydrogen peroxide carry out the redox reaction original position and generate the intermediate imide, carbon-carbon double bond generation addition reaction in imide and the latex realizes hydrogenation.Though this method can not used noble metal catalyst and high pressure hydrogen, cost reduces greatly, and hydrogen peroxide inevitably can produce free radical and cause product crosslinked in the reaction process.
In order to solve the crosslinked problem of above-mentioned product, people such as the Yue Dongmei of Beijing University of Chemical Technology improve at the device of above-mentioned reaction: hydrazine derivative will be housed be communicated with the hydrogenation container that nitrile rubber is housed with the decomposition reaction container of reductive agent, two reaction vessels are heated to temperature of reaction simultaneously, during the constant temperature, open the valve of coupling device, the imide that generates is imported in the hydrogenation container, and it is 72% hydrogenated nitrile-butadiene rubber that reaction finishes to obtain degree of hydrogenation.This method belongs to the ex situ hydrogenation, the imide that generates needs could realize hydrogenation earlier after the decomposition reaction container enters the hydrogenation container, this period two imide is very unstable, easy and other material generation side reaction, the imide concentration instability that causes entering the hydrogenation container.Though therefore this method has solved the crosslinked problem of product, degree of hydrogenation is on the low side.
Summary of the invention
The objective of the invention is to solve the deficiencies in the prior art, and provide a kind of product original position that generates by hydrazine hydrate and sodium periodate reaction nitrile rubber to be carried out the method for hydrogenation.The inventive method is realizing further improving hydrogenation speed and hydrogenation effect under the prerequisite that cost is low, pollution is low, easy and simple to handle, the hydrogenated products degree of crosslinking is low.
The add in-place hydrogen methods of nitrile rubber provided by the present invention may further comprise the steps:
With behind mixture heating up to 30～70 of nitrile rubber and hydrazine hydrate ℃, constant temperature 2～8h drips the aqueous solution of sodium periodate in mixture during the constant temperature, and the control drop rate, dropwises at 2～6 hours;
Wherein, the acrylonitrile content in the described nitrile rubber is 19～50%; Each material with magnitude relation be: the volume of hydrazine hydrate is 0.68～4 times of nitrile rubber volume; The amount of substance of sodium periodate is 0.385～4 times of carbon-carbon double bond mole number in the nitrile rubber.
As the preferred technical solution of the present invention, with behind mixture heating up to 40～50 of nitrile rubber and hydrazine hydrate ℃, constant temperature 4～7h drips the aqueous solution of sodium periodate in mixture during the constant temperature, and the control drop rate, dropwises at 4～6 hours;
Wherein, each material with magnitude relation is: the volume of hydrazine hydrate is 2～3.7 times of nitrile rubber volume; The amount of substance of sodium periodate is 1～3 times of carbon-carbon double bond mole number in the nitrile rubber.
Compare with the hydrogenation side of existing nitrile rubber, the present invention has following beneficial effect:
1) method provided by the present invention is an original position emulsion hydrogenation, can overcome the existing intermediate imide of ex situ emulsion method of hydrotreating instability, side reaction easily takes place, the problem that the final product hydrogenation degree is not high.
2) method hydrogenation speed height provided by the present invention just can reach higher hydrogenation effect in the short period of time, and the final product hydrogenation is effective.
3) adopt the prepared hydrogenation products of the inventive method solvable through breakdown of emulsion cohesion oven dry back, gel content is low, the good processability of product.
Embodiment
Employed nitrile rubber among the following embodiment (nitrile group content 26%) is purchased the neat imperial chemical industry company limited in Zibo, Shandong; Hydrazine hydrate solution (mass concentration 85%) is purchased in Xu Dong chemical plant, Beijing; Sodium periodate (purity 99%) is purchased rich Dihua worker company limited in Tianjin.
Embodiment 1
In reaction vessel, add 25mL nitrile rubber and 20mL hydrazine hydrate solution, and after being heated to 30 ℃, constant temperature 2h, constant temperature pick up counting and drip the aqueous solution (the 6g sodium periodate is dissolved in the 20mL deionized water) of sodium periodate in 2h.Product can be dissolved in the trichloromethane solvent after breakdown of emulsion, oven dry, and to record hydrogenation degree be 43.1%.
Embodiment 2
In reaction vessel, add 5mL nitrile rubber and 20mL hydrazine hydrate solution, and after being heated to 70 ℃, constant temperature 8h, constant temperature pick up counting and drip the aqueous solution (the 13g sodium periodate is dissolved in the 40mL deionized water) of sodium periodate in 6h.Product can be dissolved in the trichloromethane solvent after breakdown of emulsion, oven dry, and to record hydrogenation degree be 77.7%.
Embodiment 3
In reaction vessel, add 4.5mL nitrile rubber and 20mL hydrazine hydrate solution, and after being heated to 45 ℃, constant temperature 6h, constant temperature pick up counting and drip the aqueous solution (the 4g sodium periodate is dissolved in the 20mL deionized water) of sodium periodate in 6h.Product can be dissolved in the trichloromethane solvent after breakdown of emulsion, oven dry, and to record hydrogenation degree be 84.4%.
The infrared spectrum of the nitrile rubber among above-mentioned three embodiment before and after the hydrogenation is all at 2236cm
-1There is absorption peak in the place, and be the absorption peak of CN group herein, and secondary amine do not occur, the absorption peak of primary amine, what this illustrated that method of hydrotreating of the present invention can success carries out selective hydrogenation to NBR, does not influence the CN group, and the while can be avoided the generation of gel effectively.
Claims (2)
1. the add in-place hydrogen methods of a nitrile rubber, it is characterized in that, may further comprise the steps: nitrile rubber and hydrazine hydrate are mixed, and after being heated to 30～70 ℃, constant temperature 2～8h, in mixture, drip the aqueous solution of sodium periodate during the constant temperature, and the control drop rate, dropwised at 2～6 hours;
Wherein, the acrylonitrile content in the nitrile rubber is 19～50%; Each material with magnitude relation be: the volume of hydrazine hydrate is 0.68～4 times of nitrile rubber volume; The amount of substance of sodium periodate is 0.385～4 times of carbon-carbon double bond mole number in the nitrile rubber.
2. method according to claim 1 is characterized in that, with behind mixture heating up to 40～50 of nitrile rubber and hydrazine hydrate ℃, constant temperature 4～7h, in mixture, drip the aqueous solution of sodium periodate during the constant temperature, and the control drop rate, dropwised at 4～6 hours;
Wherein, each material with magnitude relation is: the volume of hydrazine hydrate is 2～3.7 times of nitrile rubber volume; The amount of substance of sodium periodate is 1～3 times of carbon-carbon double bond mole number in the nitrile rubber.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102363051A CN101704909B (en) | 2009-10-16 | 2009-10-16 | In-situ hydrogenation method of acrylonitrile-butadiene rubber latex |
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|---|---|---|---|
| CN2009102363051A CN101704909B (en) | 2009-10-16 | 2009-10-16 | In-situ hydrogenation method of acrylonitrile-butadiene rubber latex |
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| CN101704909A CN101704909A (en) | 2010-05-12 |
| CN101704909B true CN101704909B (en) | 2011-06-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104231118B (en) * | 2014-09-15 | 2016-01-06 | 北京化工大学 | Hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber and preparation method thereof |
| CN110527159B (en) * | 2019-08-30 | 2021-03-26 | 北京化工大学 | In-situ hydrogenated rubber graphene elastomer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472232A (en) * | 2002-07-31 | 2004-02-04 | 南帝化学工业股份有限公司 | Preparation of hydrogenated butyronitrile copolymer by hydrogenation of butadiene-acrylonitrile copolymer latex |
| CN101367887A (en) * | 2008-10-17 | 2009-02-18 | 北京化工大学 | Hydrogenation method of acryionitrile-butadiene-rubber latex |
| CN101486775A (en) * | 2009-02-27 | 2009-07-22 | 北京化工大学 | Hydrogenation method for NBR Latex |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472232A (en) * | 2002-07-31 | 2004-02-04 | 南帝化学工业股份有限公司 | Preparation of hydrogenated butyronitrile copolymer by hydrogenation of butadiene-acrylonitrile copolymer latex |
| CN101367887A (en) * | 2008-10-17 | 2009-02-18 | 北京化工大学 | Hydrogenation method of acryionitrile-butadiene-rubber latex |
| CN101486775A (en) * | 2009-02-27 | 2009-07-22 | 北京化工大学 | Hydrogenation method for NBR Latex |
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