CN101486775A - Hydrogenation method for NBR Latex - Google Patents
Hydrogenation method for NBR Latex Download PDFInfo
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- CN101486775A CN101486775A CNA2009100785699A CN200910078569A CN101486775A CN 101486775 A CN101486775 A CN 101486775A CN A2009100785699 A CNA2009100785699 A CN A2009100785699A CN 200910078569 A CN200910078569 A CN 200910078569A CN 101486775 A CN101486775 A CN 101486775A
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- hydrazine hydrate
- butadiene
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Abstract
The invention relates to a butadiene-acrylonitrile latex hydrogenation method, belonging to the butadiene-acrylonitrile rubber latex hydrogenation field. The existing butadiene-acrylonitrile latex hydrogenation method has the disadvantages of high cost, cross-linking in the product of hydrogenation, and the like. The invention achieves hydrogenation of butadiene-acrylonitrile latex by adopting the following technical proposal: firstly, hydrazine hydrate and butadiene-acrylonitrile rubber latex are respectively added into two communicated reaction vessels; secondly, the reaction vessel containing the butadiene-acrylonitrile latex is heated, when the temperature of the butadiene-acrylonitrile latex reaches 50 to 70 DEG C, the constant temperature is maintained for 6 to 48h; thirdly, during the constant temperature, a mixture of boric acid and hydrogen peroxide is dropwise added into the hydrazine hydrate, wherein, the total amount of the added hydrazine hydrate is 1 to 3 times of the mole number of the carbon-carbon double bond in the butadiene-acrylonitrile latex, the mole number of the added hydrogen peroxide is 0.6 to 1.4 times of the mole number of the adopted hydrazine hydrate, and the mass of the added boric acid is 0.01 to 0.1 time of the mass of the adopted hydrazine hydrate. The method has the advantages of low cost, less pollution, low degree of cross-linking in the prepared hydrogenated butadiene-acrylonitrile latex, good processing performance, and the like.
Description
Technical field
The invention belongs to the acrylonitrile-butadiene rubber latex field of hydrogenation, be specifically related to a kind of hydrazine hydrate and hydroperoxidation of utilizing, nitrile rubber (NBR) is carried out the method for hydrogenation.
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 been inherited the oil resistant of common paracril, anti-solvent and antiwear characteristic, and what obtained that high saturated structures vouchsafes is high temperature resistant, ageing-resistant, the resistant to chemical media corrosion, high tensile and the long-term less over-all properties of compression set, thereby can satisfy the constantly service requirements of the new harshness of proposition of oil-field development and automotive industry, can replace expensive viton in a lot of places, therefore be widely used in the automobile fuel flexible pipe, gasket, cog belt and industrial roller, oil production occupies very consequence with fields such as rubber components in oil-proofness rubber.
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, the unsaturated link(age) in hydrogen catalyzed and the paracril carries out selective reaction.Patent US6084033 discloses a kind of solution hydrogenation method that adopts rhodium-ruthenium bimetal System Catalyst to NBR, is catalyzer with Rh-Ru (mol ratio is 3:2), 145 ℃ of temperature, and hydrogenation pressure 1.4Mpa reacted 4 hours, and degree of hydrogenation reaches more than 98%.The characteristics of this type of noble metal catalyst are the hydrogenation activity height, and degree of hydrogenation can reach more than 98%, and selectivity is good, and itrile group does not change, and hydrogenated products does not have gel.But this class methods cost is very high, and needs a large amount of solvents and high pressure hydrogen, causes severe contamination and explosion hazard easily.
Hydrazine derivative original position emulsion hydrogenation is meant and utilizes as hydrazine hydrate, p-toluene sulfonyl hydrazide etc., original position produces the cis imide, the cis imide has selective reduction, can reduce symmetric unsaturated link(age) (N=N, O=O, C=C etc.), act on faint to polarity unsaturated link(age) (C ≡ N, C=O etc.).The present most of people of its reaction mechanism think that cis imide and olefinic double bonds form cyclic intermediate, realize hydrogenation then.
People such as Parker adopt similar method that NBR is carried out emulsion hydrogenation (Parker D K, RobertsF R.A new process for the preparation of highly saturated nitrilerubber in latex form[J] .Rubb Chem Technol, 1992,65:245-257), raw material is (mass ratio): NBR latex 100, CuSO
45H
2O 0.008, sodium lauryl sulphate 0.15, hydrazine hydrate 15.68, H
2O
216.66, defoamer; In reactor, add NBR latex, CuSO
4.5H
2O, tensio-active agent add hydrazine hydrate when being heated to 40-50 ℃, add H in 7 hours afterwards then
2O
2, and adding defoamer, stirring reaction under constant temperature is further improved degree of hydrogenation.And carry out aftertreatment with ozone, eliminate the crosslinked of hydrogenated products, promptly make the two key chain ruptures of multipolymer, molecular weight and molecular weight with ozone.Wet product (undried) after breakdown of emulsion, the cohesion dissolves in chloroform, but in drying process, the terminal aldehyde group that chain rupture place forms, end carboxyl take place crosslinked once more, makes the product can't processing and utilization.
Patent WO2004/009655 discloses a kind of method of utilizing aftertreatment inhibition emulsion to add hydroxide gel, this method is pointed out, the group that causes gel in the HNBR emulsion hydrogenation products can react with certain amine substance, mix with this amine substance after the hydrogenation products drying, high-temperature fusion is mediated reaction in twin screw extruder then, and think that this amine substance can influence the mechanical property of the finished product, so add the Tetra hydro Phthalic anhydride that to remove this amine substance, finally obtain the HNBR that can refine.This method has reached the pilot scale level of 2000L at present.But this method gained mechanical property of vulcanized rubber is compared with traditional solution hydrogenation cross-linked rubber, and still there is a big difference, and its reason may be to have destroyed the molecular chain of HNBR in the high-temperature fusion process, has caused the decline of mechanical property.
Summary of the invention
The objective of the invention is to solve the deficiencies in the prior art, and provide a kind of reactant that nitrile rubber is carried out method of hydrotreating by hydrazine hydrate and hydrogen peroxide.The present invention is realizing that cost is low, it is low to pollute, under the prerequisite that nitrile rubber degree of crosslinking after the operational safety, hydrogenation is low, is further improving the hydrogenation effect.
Technical scheme of the present invention is to realize in two reaction units that are interconnected, as shown in Figure 1, reaction unit of the present invention includes decomposition reaction container, hydrogenation container, conduit, reflux condensate device, whipping appts, Dropping feeder, valve, wherein, the A end of conduit extend in the decomposition reaction container, the B end of conduit extend in the hydrogenation container, and the decomposition reaction container is communicated with Dropping feeder, and the hydrogenation container is connected with reflux condensate device and whipping appts.
The method of hydrotreating of nitrile rubber provided by the present invention may further comprise the steps:
1) in the hydrogenation container, adds nitrile rubber, the B of conduit end is extend in the hydrogenation container, and insert below the liquid level of nitrile rubber;
2) add hydrazine hydrate in the decomposition reaction container, the add-on of hydrazine hydrate is 1～3 times of institute's carbon-carbon double bonds mole number in the nitrile rubber in the hydrogenation container, the A end of conduit is extend in the decomposition reaction container, and place more than the liquid level;
3) under the state of valve-off, in Dropping feeder, add the mixture of hydrogen peroxide and boric acid, add hydrogen peroxide mole number be 0.6～1.4 times of hydrazine hydrate mole number in the decomposition reaction container; Add boric acid quality be 0.01～0.1 times of hydrazine hydrate quality in the decomposition reaction container;
4) heating hydrogenation container, the hydrogenation container is heated to 50～70 ℃ after, constant temperature 6～48h, constant temperature pick up counting and open the valve of Dropping feeder, and the rate of addition of control hydrogen peroxide and mebor, and it is dripped off in 2～24h;
Wherein, the acrylonitrile content in the nitrile rubber described in the step 1) is 19～50%.
As the preferred technical solution of the present invention, the mole number that adds the hydrogen peroxide in the Dropping feeder in step 3) is 0.8 times of hydrazine hydrate mole number in the decomposition reaction container; The quality of boric acid is 0.06 times of hydrazine hydrate quality in the decomposition reaction container.
The Heating temperature of hydrogenation container is preferred 60 ℃ in the step 4); Preferred 16～the 24h of constant temperature time; Preferred 7～the 12h of dropping time of hydrogen peroxide.
Compare with the hydrogenation side of existing nitrile rubber, the present invention has following beneficial effect:
1) avoids using noble metal catalyst, reduced production cost.
2) need not with an organic solvent, reduced pollution environment.
3) temperature of reaction is low, does not use hydrogen, the danger of having avoided High Temperature High Pressure to bring in the reaction process.
4) reactant by hydrazine hydrate and hydrogen peroxide carries out hydrogenation to nitrile rubber, does not need to avoid high temperature to be unfavorable for the stability of imide to the heating of decomposition reaction container, and hydrogenation is effective.
5) decomposition reaction and the nitrile rubber of hydrazine hydrate and hydrogen peroxide are isolated, avoid producing the nitrile rubber adverse influence in the reaction process, avoid a large amount of generations of gel effectively, improve the processing characteristics of hydrogenated products.
Description of drawings
Fig. 1, hydrogenated butyronitrile latex device synoptic diagram, wherein, 1 is the decomposition reaction container, and 2 is the hydrogenation container, and 3 is conduit, and 4 is reflux condensate device, and 5 is whipping appts, and 6 is Dropping feeder, and 7 is valve.
Below in conjunction with the drawings and specific embodiments invention is described further.
Embodiment
Adopt the Dropping feeder 6 among constant pressure funnel replacement Fig. 1 among the following embodiment; The there-necked flask of two 150ml replaces decomposition reaction container 1 and the hydrogenation container 2 among Fig. 1, there-necked flask 2 is equipped with reflux condensate device 4 and whipping appts 5, and connect with conduit 3 between there-necked flask 1 and 2, the A end of conduit 3 extend in the there-necked flask 1, and place more than the liquid level, the B of conduit 3 holds below the liquid level that extend in the there-necked flask 2.There-necked flask 2 adopts the water bath with thermostatic control heating.
The model of infrared spectrometer is NiCOLET 60SXB FTIR
Boric acid (analytical pure) is purchased in Beijing chemical reagents corporation
Hydrazine hydrate (mass concentration 80%) is purchased in Beijing chemical reagents corporation
Hydrogen peroxide (mass concentration 30%) is purchased in Beijing chemical reagents corporation
Nitrile rubber, solid content are 46%, and acrylonitrile content is 26%, purchase Yu Lanhua company
Embodiment 1
1) the 11.5ml hydrazine hydrate is added in the there-necked flask 1, the A end of conduit 3 is extend in the there-necked flask 1, and place more than the liquid level;
2) the 25mL nitrile rubber is added in the there-necked flask 2, and add the tetrafluoro rotor, the B end of conduit 3 is stretched into below the nitrile rubber liquid level;
3) valve-off 7, add the mixture of 12.5ml hydrogen peroxide and 0.12g boric acid in constant pressure funnel;
4) heating there-necked flask 2, open reflux condensate device 4 and whipping appts 5 simultaneously, treat that there-necked flask 2 is heated to 50 ℃, isothermal reaction 6h during the constant temperature, opens the valve of constant pressure funnel, in there-necked flask 1, drip the mixture of hydrogen peroxide and boric acid, and control its rate of addition, and it is dripped in 2h, obtain product hydrogenated butyronitrile latex at last.
Product can be dissolved in the trichloromethane solvent after breakdown of emulsion, oven dry, and to record hydrogenation degree be 43.1%.
1) the 11.5ml hydrazine hydrate is added in the there-necked flask 1, the A end of conduit 3 is extend in the there-necked flask 1, and place more than the liquid level;
2) the 25mL nitrile rubber is added in the there-necked flask 2, and add the tetrafluoro rotor, the B end of conduit 3 is stretched into below the nitrile rubber liquid level;
3) valve-off 7, add the mixture of 29.1ml hydrogen peroxide and 1.1g boric acid in constant pressure funnel;
4) heating there-necked flask 2, open reflux condensate device 4 and whipping appts 5 simultaneously, treat that there-necked flask 2 is heated to 70 ℃, isothermal reaction 48h during the constant temperature, opens the valve of constant pressure funnel, in there-necked flask 1, drip the mixture of hydrogen peroxide and boric acid, and control its rate of addition, and it is dripped in 24h, obtain product hydrogenated butyronitrile latex at last.
Product can be dissolved in the trichloromethane solvent after breakdown of emulsion, oven dry, and to record hydrogenation degree be 58%.
1) the 23ml hydrazine hydrate is added in the there-necked flask 1, the A end of conduit 3 is extend in the there-necked flask 1, and place more than the liquid level;
2) the 25mL nitrile rubber is added in the there-necked flask 2, and add the tetrafluoro rotor, the B end of conduit 3 is stretched into below the nitrile rubber liquid level;
3) valve-off 7, add the mixture of 33.4ml hydrogen peroxide and 13g boric acid in constant pressure funnel;
4) heating there-necked flask 2, open reflux condensate device 4 and whipping appts 5 simultaneously, treat that there-necked flask 2 is heated to 60 ℃, isothermal reaction 16h during the constant temperature, opens the valve of constant pressure funnel, in there-necked flask 1, drip the mixture of hydrogen peroxide and boric acid, and control its rate of addition, and it is dripped in 7h, obtain product hydrogenated butyronitrile latex at last.
Product can be dissolved in the trichloromethane solvent after breakdown of emulsion, oven dry, and to record hydrogenation degree be 73%.
1) the 11.5ml hydrazine hydrate is added in the there-necked flask 1, the A end of conduit 3 is extend in the there-necked flask 1, and place more than the liquid level;
2) the 25mL nitrile rubber is added in the there-necked flask 2, and add the tetrafluoro rotor, the B end of conduit 3 is stretched into below the nitrile rubber liquid level;
3) valve-off 7, add the mixture of 11.6ml hydrogen peroxide and 11g boric acid in constant pressure funnel;
4) heating there-necked flask 2, open reflux condensate device 4 and whipping appts 5 simultaneously, treat that there-necked flask 2 is heated to 60 ℃, isothermal reaction 24h during the constant temperature, opens the valve of constant pressure funnel, in there-necked flask 1, drip the mixture of hydrogen peroxide and boric acid, and control its rate of addition, and it is dripped in 12h, obtain product hydrogenated butyronitrile latex at last.
Product can be dissolved in the trichloromethane solvent after breakdown of emulsion, oven dry, and to record hydrogenation degree be 68.1%.
The infrared spectrum of the nitrile rubber among above-mentioned four 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 (5)
1, a kind of method of hydrotreating of nitrile rubber is characterized in that, may further comprise the steps:
1) in hydrogenation container (2), adds nitrile rubber, the B end of conduit (3) is extend in the hydrogenation container (2), and insert below the liquid level of nitrile rubber;
2) in decomposition reaction container (1), add hydrazine hydrate, the add-on of hydrazine hydrate is 1～3 times of institute's carbon-carbon double bonds mole number in the nitrile rubber in the hydrogenation container (2), the A end of conduit (3) is extend in the decomposition reaction container (1), and place more than the liquid level;
3) under the state of valve-off (7), the mixture that in Dropping feeder (6), adds hydrogen peroxide and boric acid, add hydrogen peroxide mole number be 0.6～1.4 times of hydrazine hydrate mole number in the decomposition reaction container (1), the quality that institute adds boric acid is 0.01～0.1 times of the middle hydrazine hydrate quality of decomposition reaction container (1);
4) heating hydrogenation container (2), after hydrogenation container (2) is heated to 50～70 ℃, the valve (7) that constant temperature 6～48h, constant temperature pick up counting and open Dropping feeder (6), the rate of addition of control hydrogen peroxide and mebor drips off it in 2～24h.
2, method according to claim 1 is characterized in that, the acrylonitrile content in the nitrile rubber described in the step 1) is 19～50%.
3, method according to claim 1 is characterized in that, the mole number that adds the hydrogen peroxide in the Dropping feeder (6) in the step 3) is 0.8 times of the middle hydrazine hydrate mole number of decomposition reaction container (1).
4, method according to claim 1 is characterized in that, the quality that adds the boric acid in the Dropping feeder (6) in the step 3) is 0.06 times of the middle hydrazine hydrate quality of decomposition reaction container (1).
5, method according to claim 1 is characterized in that, the Heating temperature of hydrogenation container (2) is 60 ℃ in the step 4); Constant temperature time is 16～24h; The dropping time of hydrogen peroxide is 7～12h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100785699A CN101486775B (en) | 2009-02-27 | 2009-02-27 | Hydrogenation method for NBR Latex |
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| CN2009100785699A CN101486775B (en) | 2009-02-27 | 2009-02-27 | Hydrogenation method for NBR Latex |
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| CN101486775B CN101486775B (en) | 2012-03-21 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787087A (en) * | 2010-03-12 | 2010-07-28 | 北京化工大学 | Hydrogenation method of hydroxyl terminated butyl nitrile (HTBN) |
| CN101704909B (en) * | 2009-10-16 | 2011-06-01 | 北京化工大学 | In-situ hydrogenation method of acrylonitrile-butadiene rubber latex |
| CN102336843A (en) * | 2011-06-30 | 2012-02-01 | 北京化工大学 | Process for hydrogenating liquid acrylonitrile butadiene containing terminal hydroxyl group |
| CN102617901A (en) * | 2012-03-22 | 2012-08-01 | 北京化工大学 | Application of hydrogenated nitrile latex |
| CN102827309A (en) * | 2012-09-08 | 2012-12-19 | 北京化工大学 | Hydrogenation method for organic catalyst normal-pressure catalytic butyronitrile rubber latex |
| CN104231118A (en) * | 2014-09-15 | 2014-12-24 | 北京化工大学 | Hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber and preparation method thereof |
| CN111234052A (en) * | 2020-01-20 | 2020-06-05 | 青岛科技大学 | Method for preparing polymer materials with different saturation degrees by emulsion reaction |
| CN114478839A (en) * | 2022-02-14 | 2022-05-13 | 北京化工大学 | Hydrogenated nitrile latex prepared by self-hydrogen production hydrogenation method |
-
2009
- 2009-02-27 CN CN2009100785699A patent/CN101486775B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704909B (en) * | 2009-10-16 | 2011-06-01 | 北京化工大学 | In-situ hydrogenation method of acrylonitrile-butadiene rubber latex |
| CN101787087A (en) * | 2010-03-12 | 2010-07-28 | 北京化工大学 | Hydrogenation method of hydroxyl terminated butyl nitrile (HTBN) |
| CN101787087B (en) * | 2010-03-12 | 2012-01-04 | 北京化工大学 | Hydrogenation method of hydroxyl terminated butyl nitrile (HTBN) |
| CN102336843A (en) * | 2011-06-30 | 2012-02-01 | 北京化工大学 | Process for hydrogenating liquid acrylonitrile butadiene containing terminal hydroxyl group |
| CN102617901A (en) * | 2012-03-22 | 2012-08-01 | 北京化工大学 | Application of hydrogenated nitrile latex |
| CN102617901B (en) * | 2012-03-22 | 2013-10-30 | 北京化工大学 | Application of hydrogenated nitrile latex |
| CN102827309A (en) * | 2012-09-08 | 2012-12-19 | 北京化工大学 | Hydrogenation method for organic catalyst normal-pressure catalytic butyronitrile rubber latex |
| CN104231118A (en) * | 2014-09-15 | 2014-12-24 | 北京化工大学 | Hydrogenated hydroxyl-terminated liquid nitrile-butadiene rubber and preparation method thereof |
| 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 |
| CN111234052A (en) * | 2020-01-20 | 2020-06-05 | 青岛科技大学 | Method for preparing polymer materials with different saturation degrees by emulsion reaction |
| CN111234052B (en) * | 2020-01-20 | 2022-06-07 | 青岛科技大学 | Method for preparing polymer materials with different saturation degrees by emulsion reaction |
| CN114478839A (en) * | 2022-02-14 | 2022-05-13 | 北京化工大学 | Hydrogenated nitrile latex prepared by self-hydrogen production hydrogenation method |
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