CN105622783B - A kind of preparation method of copolymer - Google Patents
A kind of preparation method of copolymer Download PDFInfo
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- CN105622783B CN105622783B CN201410594179.8A CN201410594179A CN105622783B CN 105622783 B CN105622783 B CN 105622783B CN 201410594179 A CN201410594179 A CN 201410594179A CN 105622783 B CN105622783 B CN 105622783B
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Abstract
The invention discloses a kind of preparation method of copolymer, the method comprises the following steps：(1) unsaturated copolymer is dissolved in organic solvent, fills and get rid of gas；(2) catalyst for hydrogenation and part are added, the catalyst for hydrogenation has below general formula：(RmA)zRhXn；(3) hydrogen is filled with, is stirred, reacted, the condition of the reaction includes：Reaction temperature is 0 30 DEG C, and Hydrogen Vapor Pressure is 0.05 15Mpa, and the reaction time is 1 120 minutes；(4) 50 180 DEG C are warming up to, holding Hydrogen Vapor Pressure is 0.1 15Mpa, is reacted 1 20 hours；(5) organic solvent in the product that removal step (4) is obtained.Implementation is more easy to using method of the invention, it is possible to reduce the application cost of catalyst, reaction, the degrees of hydrogenation of the active high, hydrogenation products of hydrogenation reaction can be improved significantly, and growth of the product without obvious gel content.
Description
Technical field
The present invention relates to copolymer field, in particular it relates to a kind of preparation method of copolymer, more particularly to a kind of low
The preparation method of gel, highly saturated nitrile rubber.
Background technology
Hydrogenated nitrile-butadiene rubber (HNBR) has the performance such as good oil resistant, heat-resisting, high temperature resistant, high pressure resistant, anti-oxidant, while
Also there is very outstanding mechanical property, be widely used in the neck such as automobile making, machining, metallurgical seal, petroleum industry
In domain.
For many years, the preparation for hydrogenated nitrile-butadiene rubber is constantly subjected to the concern of chemist, and its focus is concentrated mainly on：
How the hydrogenated nitrile-butadiene rubber product of high saturation, low-gel content is prepared using new, cheap catalyst system；Such as
Where on existing catalyst system basis, by the constantly improve to method, more efficiently realize to carbon-carbon double bond (C=
C selective hydrogenation).At this stage, for the homogeneous phase solution hydrogenation method of hydrogenated nitrile-butadiene rubber, on the one hand, still mainly use rhodium
Metallo-organic complex catalyst, although rhodium metal organic complex catalyst has to the carbon-carbon double bond (C=C) in nitrile rubber
There is hydrogenation selectivity and reactivity very high, but abundance of the rhodium element in the earth is smaller, expensive, application cost
It is higher；On the other hand, existing homogeneous phase solution hydrogenation method all has reaction temperature high, complex operation, high energy consumption, hydrogenation always
The defect such as reactivity is low and hydrogenation products degrees of hydrogenation have much room for improvement.
The content of the invention
The invention aims to overcoming in art methods that catalyst application cost is high, being difficult to implement (reaction temperature
Degree height, complex operation, high energy consumption), the defect that has much room for improvement of hydrogenation reaction low and hydrogenation products the degree of hydrogenation of activity, there is provided one kind
Catalyst application cost is relatively low, be more easy to implementation (reaction temperature is relatively low, simple to operate, energy consumption is low), hydrogenation reaction activity is high, hydrogenation
The preparation method of the copolymer that the degree of hydrogenation of product is improved significantly and hydrogenation products increase without obvious gel.
The present inventor has been surprisingly found that under study for action, during copolymer is prepared, unsaturated copolymer is molten
In organic solvent, fill after getting rid of gas, add catalyst for hydrogenation (RmA)zRhXnAnd part, then first in low temperature (0-30
DEG C) under carry out hydrogenation reaction, then carry out hydrogenation reaction under high temperature (50-180 DEG C), low temperature hydrogenation is reacted anti-with high-temperature hydrogenation
Should be used in combination, make reaction be more easy to implement (reaction temperature is relatively low, simple to operate, energy consumption is low), catalysis can not only be significantly improved
The hydrogenation reaction activity of agent, obtains faster reaction speed, shortens the reaction time, and can significantly improve adding for hydrogenation products
Hydrogen degree, and hydrogenation products increase without obvious gel, while, additionally it is possible to effectively reduce the preparation cost of saturated copolymer high.
Therefore, to achieve these goals, the invention provides a kind of preparation method of copolymer, methods described include with
Lower step：
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, filled and get rid of gas；
(2) catalyst for hydrogenation and part are added, the catalyst for hydrogenation has below general formula：(RmA)zRhXn, its
In, aralkyl of each R independently selected from the alkyl of C1-C8, the cycloalkyl of C4-C8, the aryl of C6-C15 or C7-C15；A
Selected from phosphorus, arsenic, sulphur or sulfoxide radicals S=O；X is selected from hydrogen or anion；Z is 2,3 or 4；M is 2 or 3；N is 1,2 or 3；
(3) hydrogen is filled with, is stirred, reacted, the condition of the reaction includes：Reaction temperature is 0-30 DEG C, hydrogen pressure
Power is 0.05-15Mpa, and the reaction time is 1-120 minutes；
(4) 50-180 DEG C is warming up to, holding Hydrogen Vapor Pressure is 0.1-15Mpa, is reacted 1-20 hours；
(5) organic solvent in the product that removal step (4) is obtained.
The preparation method of copolymer of the invention, it is possible to increase the hydrogenation reaction activity of catalyst, obtains reaction faster
Speed, shortens the reaction time, can significantly improve the degree of hydrogenation of hydrogenation products, and hydrogenation products compared with nothing for unsaturated copolymer
Obvious gel increases.Meanwhile, the method has that the simple to operate, reaction time is short, easy implementation (reaction temperature is relatively low, simple to operate,
Energy consumption is low) the advantages of, can effectively reduce the preparation cost of saturated copolymer high.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of preparation method of copolymer, the method is comprised the following steps：
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, filled and get rid of gas；
(2) catalyst for hydrogenation and part are added, the catalyst for hydrogenation has below general formula：(RmA)zRhXn, its
In, aralkyl of each R independently selected from the alkyl of C1-C8, the cycloalkyl of C4-C8, the aryl of C6-C15 or C7-C15；A
Selected from phosphorus, arsenic, sulphur or sulfoxide radicals S=O；X is selected from hydrogen or anion；Z is 2,3 or 4；M is 2 or 3；N is 1,2 or 3；
(3) hydrogen is filled with, is stirred, reacted, the condition of the reaction includes：Reaction temperature is 0-30 DEG C, hydrogen pressure
Power is 0.05-15Mpa, and the reaction time is 1-120 minutes；
(4) 50-180 DEG C is warming up to, holding Hydrogen Vapor Pressure is 0.1-15Mpa, is reacted 1-20 hours；
(5) organic solvent in the product that removal step (4) is obtained.
In the inventive method step (1), for mass percentage concentration (the i.e. unsaturated copolymerization of unsaturated copolymer in glue
The quality of thing is divided by unsaturated copolymer and the quality sum of organic solvent) there is no particular limitation, can be commonly used in the art
Concentration, under preferable case, in glue the mass percentage concentration of unsaturated copolymer be 2-15%, more preferably 4-
12%.
In the inventive method step (1), for unsaturated copolymer, there is no particular limitation, can be to contain carbon-carbon double bond
(C=C) various unsaturated copolymers, under preferable case, unsaturated copolymer is bipolymer and/or terpolymer；
It is further preferred that bipolymer includes butadiene-acrylonitrile, butadiene-(methyl) acrylonitrile, 2- methyl isophthalic acids, 3- fourths two
Alkene-acrylonitrile, 2- methyl isophthalic acids, in 3- butadiene-(methyl) acrylonitrile and SBS
One or more, terpolymer includes butadiene-acrylonitrile-(methyl) acrylic acid, butadiene-(methyl) acrylonitrile-propylene
One or more in acid, butadiene-(methyl) acrylonitrile-(methyl) acrylic acid and butadiene-acrylonitrile-acrylic acid；More one
Preferably, unsaturated copolymer is butadiene-acrylonitrile and/or butadiene-(methyl) acrylonitrile to step.When unsaturated copolymer is
During the mixture of butadiene-acrylonitrile and butadiene-(methyl) acrylonitrile, for butadiene-acrylonitrile and butadiene-(methyl)
The ratio that acrylonitrile is added is not required, can be arbitrary proportion.
In the inventive method step (1), for organic solvent, there is no particular limitation, can be can to dissolve in this area
The various organic solvents of unsaturated copolymer, catalyst for hydrogenation and part, under preferable case, organic solvent is aromatic hydrocarbons, aromatic hydrocarbons
One or more in the derivative, halogenated alkane, ketone and the acid amides that are replaced by alkyl or halogen；It is further preferred that organic molten
Agent is the one kind or many in benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichloro-benzenes, acetone, butanone and N,N-dimethylformamide
Kind.
In the inventive method step (2), in order to improve the hydrogenation reaction activity of catalyst for hydrogenation and increase hydrogenation products
Degree of hydrogenation, under preferable case, the addition of catalyst for hydrogenation is the 0.01-5% of unsaturated copolymer quality, further excellent
Elect 0.05-1% as.
In the inventive method step (2), in order to increase the degree of hydrogenation of hydrogenation products, under preferable case, the addition of part
It is 1-20 times of catalyst for hydrogenation quality, more preferably 4-15 times.
In the inventive method step (2), in order to improve the hydrogenation reaction activity of catalyst for hydrogenation and increase hydrogenation products
Degree of hydrogenation, under preferable case, catalyst for hydrogenation be (PPh3)3RhCl.Catalyst for hydrogenation (RmA)zRhXnCan be by business
Available from.
In the inventive method step (2), in order to increase the degree of hydrogenation of hydrogenation products, under preferable case, part be organic phosphine,
One or more in the organic compound of the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen；It is further preferred that part is have
Machine phosphine；Preferably, part is triphenylphosphine to a more step.
For organising for the organic phosphine in catalyst for hydrogenation and part, organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen
There is no particular limitation for compound, can be various organic phosphines commonly used in the art, the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen
Organic compound.
In the inventive method step (3), the present inventor under study for action it has furthermore been found that low temperature hydrogenation reaction it is anti-
Overlong time is answered, the cyano group in hydrogenated nitrile-butadiene rubber can be caused to be reduced, so as to cause product structure and performance to change, because
This, under preferable case, the reaction time is 20-40 minutes.In order to the hydrogenation reaction for further improving catalyst for hydrogenation is active simultaneously
Increase the degree of hydrogenation of hydrogenation products, it is further preferred that the condition of reaction includes：Reaction temperature is 10-25 DEG C, and Hydrogen Vapor Pressure is
1-5Mpa, the reaction time is 20-40 minutes.
In the inventive method step (4), in order to further increase the degree of hydrogenation of hydrogenation products, under preferable case, it is warming up to
80-150 DEG C, holding Hydrogen Vapor Pressure is 4-12Mpa, is reacted 4-16 hours.
In the inventive method step (5), the method for the organic solvent in the product obtained for removal step (4) does not have
There is special restriction, the various methods that can be commonly used for those skilled in the art can for example be condensed, vapor steams by ethanol
The organic solvent in the product that the removal steps such as method (4) are obtained is evaporated, so as to obtain hydrogenation products, what then removing was obtained adds
Solvent on hydrogen product.For removing the method for solvent on hydrogenation products, there is no particular limitation, can be art technology
The various methods that personnel commonly use, under preferable case, it is vacuum drying to remove the method for solvent, and vacuum drying condition includes：Temperature
It is 50-100 DEG C to spend, and the time is 1-10 hours.
Embodiment
The present invention is further illustrated for following embodiment, but and is not so limited the present invention.
In following examples and comparative example, the assay method of degree of hydrogenation is bromine iodine method.
The assay method of gel content：W1 grams of dry glue is weighed, chlorobenzene is added, the solution of 1g/100mL is made into, dissolving 24 is small
Shi Hou, solution is poured into the 360 mesh filter screens filtering of constant weight (w2 grams), then will be filled 360 mesh filter screens of insoluble matter and dried constant weight,
Weight is designated as w3 grams, then gel content is：(w3-w2)/w1*106ppm。
Cyano reduction rate in hydrogenated nitrile-butadiene rubber is determined using nmr analysis method, specific method is：W4 grams is weighed to do
Glue, its cyano content is A mass % (known), is dissolved with deuterochloroform, and using styrene as internal standard, the addition of styrene is
M1 moles, it is M2 moles that the cyano content being reduced in dry glue is calculated according to internal standard integral area, then hydrogenated nitrile-butadiene rubber
In cyano reduction rate be (M2*26)/(w4*A%).
Catalyst for hydrogenation (PPh3)3RhCl is purchased from Acros companies.
Butadiene-propylene nitrile rubber is purchased from Lan Hua companies, and the trade mark is N21L, and cyano content is 41 mass %.
Embodiment 1-14
Embodiments of the invention 1-14 is used to illustrate the preparation method of copolymer of the invention：
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, be added in reactor, filled and get rid of gas；
(2) catalyst for hydrogenation and part are added；
(3) hydrogen is filled with, is stirred, reacted, the condition of reaction includes：Reaction temperature is b DEG C, and Hydrogen Vapor Pressure is a
MPa, the reaction time is c minutes；
(4) be warming up to e DEG C, holding Hydrogen Vapor Pressure be d MPa, react f hours；
(5) hydrogenation products are condensed by ethanol and separated out, and are vacuum dried 8 hours at 60 DEG C.
In embodiment 1-14, unsaturated copolymer is butadiene-propylene nitrile rubber, and butadiene-propylene nitrile rubber
Gel content is 304ppm, and the quality of glue is 540g, gelatin concentration (the quality percentage of unsaturated copolymer i.e. in glue
Concentration), catalyst/unsaturated copolymer (i.e. the mass ratio of catalyst for hydrogenation and unsaturated copolymer), part/catalyst
Degree of hydrogenation, gel content, the cyano reduction of (i.e. the mass ratio of part and catalyst for hydrogenation), a-f and the hydrogenation products for obtaining
The measurement result of situation is shown in Table 1.
Table 1
Comparative example 1-7
The condition of unsaturated copolymer, organic solvent, catalyst for hydrogenation and part, gelatin concentration be (i.e. in comparative example 1-4
The mass percentage concentration of unsaturated copolymer in glue), catalyst/unsaturated copolymer (i.e. catalyst for hydrogenation with it is unsaturated
The mass ratio of copolymer), part/catalyst (i.e. the mass ratio of part and catalyst for hydrogenation) respectively with embodiment 2,8,10 and
11 is identical, unlike, reacted without low temperature hydrogenation in comparative example 1-4 methods.Comparative example 5 is compared with comparative example 1, the difference is that inciting somebody to action
The reaction time f extensions of comparative example 1.Comparative example 6 adds compared with Example 2, the difference is that low temperature hydrogenation being reacted and being changed to high temperature
Hydrogen reacts.In comparative example 1-6, gelatin concentration (mass percentage concentration of unsaturated copolymer i.e. in glue), catalyst/unsaturation
Copolymer (i.e. the mass ratio of catalyst for hydrogenation and unsaturated copolymer), part/catalyst (i.e. part and catalyst for hydrogenation
Mass ratio), the degree of hydrogenation of a-f and the hydrogenation products for obtaining, gel content, the measurement result of cyano reduction situation be shown in Table 2.
Table 2
Comparative example 7
According to the method for embodiment 2, unlike, (1) adds catalyst for hydrogenation and part in a kettle., fills and gets rid of
Gas；(2) hydrogen is filled with, is stirred, reacted, the condition of reaction includes：Reaction temperature is 15 DEG C, and Hydrogen Vapor Pressure is 3.0MPa,
Reaction time is 30 minutes；(3) unsaturated copolymer is dissolved in organic solvent, obtains glue, be added in reactor；(4)
Be warming up to 130 DEG C, holding Hydrogen Vapor Pressure be 4.0MPa, react 8.0 hours；(5) hydrogenation products are condensed by ethanol and separated out, and 60
It is vacuum dried 8 hours at DEG C.Wherein, the same embodiment of the condition of unsaturated copolymer, organic solvent, catalyst for hydrogenation and part
2。
After measured, the degree of hydrogenation of hydrogenation products is 96.1%, and gel content is 753ppm.
By embodiment 2 compared with Example 5, when the temperature of step (3) low temperature hydrogenation reaction is 10-25 DEG C, one can be entered
Step improves the degree of hydrogenation of hydrogenation products.
By embodiment 2 compared with Example 9, when the time of step (3) low temperature hydrogenation reaction is 20-40 minutes, Neng Gouyou
Effect improves the degree of hydrogenation of hydrogenation products, while hydrogenation products increase without obvious gel；And prolong when by the time that low temperature hydrogenation reacts
When length was to 120 minutes, cyano group is reduced in causing hydrogenated nitrile-butadiene rubber, so as to cause product structure and performance to change.
By embodiment 2 compared with embodiment 12, when organic solvent uses chlorobenzene, can further increase hydrogenation products
Degree of hydrogenation.
By embodiment 2 compared with embodiment 13, when part uses PPh3When, can further increase the hydrogenation of hydrogenation products
Degree.
By embodiment 2 compared with embodiment 14, when organic solvent is using chlorobenzene and part uses PPh3When, can be further
Increase the degree of hydrogenation of hydrogenation products.
Embodiment 2 is compared with comparative example 1 respectively, embodiment 8 compares with comparative example 2, embodiment 10 compares with comparative example 3
Compare with comparative example 4 compared with, embodiment 11, it is known that, before high-temperature hydrogenation reaction increasing low temperature hydrogenation reacts (the condition bag of reaction
Include：Reaction temperature is 0-30 DEG C, and Hydrogen Vapor Pressure is 0.05-15Mpa, and the reaction time is 1-120 minutes) the step of, can be effective
Raising reaction rate, increase the degree of hydrogenation of hydrogenation products, and hydrogenation products increase without obvious gel.
By embodiment 2 compared with comparative example 5, if reacting (the condition bag of reaction without low temperature hydrogenation before high-temperature hydrogenation reaction
Include：Reaction temperature is 0-30 DEG C, and Hydrogen Vapor Pressure is 0.05-15Mpa, and the reaction time is 1-120 minutes) the step of, will react
Time f extends under the reaction condition of 2 hours, could obtain similar degree of hydrogenation, illustrates successively to carry out low temperature hydrogenation reaction and height
Warm hydrogenation reaction can significantly improve the reaction rate of hydrogenation reaction, effectively improve the degree of hydrogenation of hydrogenation products, while be hydrogenated with producing
Thing increases without obvious gel.
By embodiment 2 compared with comparative example 6, low temperature hydrogenation reaction is changed to high-temperature hydrogenation reaction, hydrogenation of net product degree has no
Improvement, illustrates that successively carrying out low temperature hydrogenation reaction and high-temperature hydrogenation reaction can significantly improve the reaction speed of hydrogenation reaction
Rate, effectively improves the degree of hydrogenation of hydrogenation products, while hydrogenation products increase without obvious gel.
By embodiment 2 compared with comparative example 7, change the charging sequence of glue and catalyst, low temperature hydrogenation can be caused to react
The decline of hydrogenation effect is combined with high-temperature hydrogenation reaction, while there is obvious gel to increase in hydrogenation products.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of preparation method of copolymer, it is characterised in that the method comprises the following steps：
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, filled and get rid of gas；
(2) catalyst for hydrogenation and part are added, the catalyst for hydrogenation has below general formula：(RmA)zRhXn, wherein, often
Aralkyl of one R independently selected from the alkyl of C1-C8, the cycloalkyl of C4-C8, the aryl of C6-C15 or C7-C15；A is selected from
Phosphorus, arsenic, sulphur or sulfoxide radicals S=O；X is selected from hydrogen or anion；Z is 2,3 or 4；M is 2 or 3；N is 1,2 or 3；
(3) hydrogen is filled with, is stirred, reacted, the condition of the reaction includes：Reaction temperature is 0-30 DEG C, and Hydrogen Vapor Pressure is
0.05-15MPa, the reaction time is 1-120 minutes；
(4) 50-180 DEG C is warming up to, holding Hydrogen Vapor Pressure is 0.1-15MPa, is reacted 1-20 hours；
(5) organic solvent in the product that removal step (4) is obtained.
2. preparation method according to claim 1, wherein, in step (3), the condition of the reaction includes：Reaction temperature
It it is 10-25 DEG C, Hydrogen Vapor Pressure is 1-5MPa, the reaction time is 20-40 minutes.
3. preparation method according to claim 1, wherein, in step (4), 80-150 DEG C is warming up to, keep Hydrogen Vapor Pressure
It is 4-12MPa, reacts 4-16 hours.
4. the preparation method according to any one in claim 1-3, wherein, it is unsaturated in the glue in step (1)
The mass percentage concentration of copolymer is 2-15%.
5. the preparation method according to any one in claim 1-3, wherein, the unsaturated copolymer is binary copolymerization
Thing and/or terpolymer.
6. preparation method according to claim 5, wherein, the bipolymer includes butadiene-acrylonitrile, fourth two
Alkene-(methyl) acrylonitrile, 2- methyl isophthalic acids, 3- butadiene-acrylonitriles, 2- methyl isophthalic acids, 3- butadiene-(methyl) acrylonitrile and benzene second
One or more in alkene-butadiene-styrene block copolymer, the terpolymer includes butadiene-acrylonitrile-(first
Base) acrylic acid, butadiene-(methyl) acrylonitrile-acrylic acid, butadiene-(methyl) acrylonitrile-(methyl) acrylic acid and fourth two
One or more in alkene-acrylonitrile-acrylic acid.
7. preparation method according to claim 6, wherein, the unsaturated copolymer is butadiene-acrylonitrile and/or fourth
Diene-(methyl) acrylonitrile.
8. the preparation method according to any one in claim 1-3, wherein, the organic solvent is aromatic hydrocarbons, aromatic hydrocarbons quilt
One or more in alkyl or the derivative of halogen substitution, halogenated alkane, ketone and acid amides.
9. preparation method according to claim 8, wherein, the organic solvent is benzene,toluene,xylene, chlorobenzene, dichloro
One or more in benzene, trichloro-benzenes, acetone, butanone and N,N-dimethylformamide.
10. the preparation method according to any one in claim 1-3, wherein, in step (2), the hydrogenation catalysis
The addition of agent is the 0.01-5% of the unsaturated copolymer quality.
11. preparation methods according to claim 10, wherein, in step (2), the addition of the catalyst for hydrogenation is
The 0.05-1% of the unsaturated copolymer quality.
12. preparation methods according to claim 10, wherein, the addition of the part is the catalyst for hydrogenation matter
1-20 times of amount.
13. preparation methods according to claim 12, wherein, the addition of the part is the catalyst for hydrogenation matter
4-15 times of amount.
14. preparation method according to any one in claim 1-3, wherein, the catalyst for hydrogenation is (PPh3)3RhCl。
15. preparation method according to any one in claim 1-3, wherein, the part is organic phosphine, You Jishuan
One or more in the organic compound of phosphine, organic cerium and nitrogenous, sulphur or oxygen.
16. preparation methods according to claim 15, wherein, the part is organic phosphine.
17. preparation methods according to claim 16, wherein, the part is triphenylphosphine.
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| EP0134023B1 (en) * | 1983-08-19 | 1987-05-06 | Bayer Ag | Preparation of hydrogenated nitrile rubbers |
| CN1167774A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of acrylonitrile-butadiene rubber |
| EP1219640A2 (en) * | 2000-12-28 | 2002-07-03 | Bayer Inc. | Hydrogenation of nitrile rubber |
| CN100999595A (en) * | 2002-12-05 | 2007-07-18 | 拜尔公司 | Preparation method of low molecular weight hydrogenated nitrile rubber |
| CN101081878A (en) * | 2006-06-01 | 2007-12-05 | 朗盛德国有限责任公司 | Process for preparing hydrogenated nitrile rubbers |
| CN103333290A (en) * | 2013-07-23 | 2013-10-02 | 蒲城瑞鹰新材料科技有限公司 | Continuous production technology for microchannel reactor of hydrogenated butadiene-acrylonitrile rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2533559B2 (en) * | 1987-08-14 | 1996-09-11 | 三菱化学株式会社 | Method for producing hydrogenated nitrile rubber |
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|---|---|---|---|---|
| EP0134023B1 (en) * | 1983-08-19 | 1987-05-06 | Bayer Ag | Preparation of hydrogenated nitrile rubbers |
| CN1167774A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of acrylonitrile-butadiene rubber |
| EP1219640A2 (en) * | 2000-12-28 | 2002-07-03 | Bayer Inc. | Hydrogenation of nitrile rubber |
| CN100999595A (en) * | 2002-12-05 | 2007-07-18 | 拜尔公司 | Preparation method of low molecular weight hydrogenated nitrile rubber |
| CN101081878A (en) * | 2006-06-01 | 2007-12-05 | 朗盛德国有限责任公司 | Process for preparing hydrogenated nitrile rubbers |
| CN101081878B (en) * | 2006-06-01 | 2011-10-05 | 朗盛德国有限责任公司 | Process for preparing hydrogenated nitrile rubbers |
| CN103333290A (en) * | 2013-07-23 | 2013-10-02 | 蒲城瑞鹰新材料科技有限公司 | Continuous production technology for microchannel reactor of hydrogenated butadiene-acrylonitrile rubber |
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