CN105542037A - Unsaturated copolymer hydrogenation method - Google Patents
Unsaturated copolymer hydrogenation method Download PDFInfo
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- CN105542037A CN105542037A CN201410594157.1A CN201410594157A CN105542037A CN 105542037 A CN105542037 A CN 105542037A CN 201410594157 A CN201410594157 A CN 201410594157A CN 105542037 A CN105542037 A CN 105542037A
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Abstract
The present invention discloses an unsaturated copolymer hydrogenation method, which comprises: (1) dissolving a unsaturated copolymer in an organic solvent, and carrying out inflation discharge deaeration; (2) adding a hydrogenation catalyst and a ligand, wherein the hydrogenation catalyst has the following general formula: M1aM2bXmLn; (3) introducing hydrogen, stirring, and carrying out a reaction, wherein the reaction conditions comprise that the reaction temperature is 0-30 DEG C, the hydrogen pressure is 0.05-15 Mpa, and the reaction time is 1-120 min; (4) heating to a temperature of 50-180 DEG C, maintaining the hydrogen pressure at 0.1-15 Mpa, and carrying out a reaction for 1-20 h; and (5) removing the organic solvent in the reaction product obtained in the step (4). With the method of the present invention, the catalyst application cost can be reduced, the reaction is easy to perform, the hydrogenation reaction activity is high, the hydrogenation degree of the hydrogenated product can be significantly improved, and the product does not have the significantly-increased gel content.
Description
Technical field
The present invention relates to unsaturated copolymer field, particularly, relate to a kind of method of hydrotreating of unsaturated copolymer, particularly relate to the preparation method of a kind of low gel, highly saturated nitrile rubber.
Background technology
Hydrogenated nitrile-butadiene rubber (HNBR) has good oil resistant, the performance such as heat-resisting, high temperature resistant, high pressure resistant, anti-oxidant, also there is very outstanding mechanical property simultaneously, be widely used in the fields such as automobile making, mechanical workout, metallurgical seal, petroleum industry.
For many years, the preparation for hydrogenated nitrile-butadiene rubber receives the concern of chemist always, and its focus mainly concentrates on: how to use novel, cheap catalyst system to prepare the hydrogenated nitrile-butadiene rubber product of high saturation, low-gel content; How on existing catalyst system basis, constantly perfect by method, realizes the selective hydrogenation to carbon-carbon double bond (C=C) more efficiently.Present stage, for the homogeneous phase solution hydrogenation method of hydrogenated nitrile-butadiene rubber, on the one hand, still mainly use rhodium metal organic complex catalyzer, although rhodium metal organic complex catalyzer has very high hydrogenation selectivity and reactive behavior to the carbon-carbon double bond (C=C) in paracril, but the abundance of rhodium element in the earth is less, expensive, and application cost is higher; On the other hand, existing homogeneous phase solution hydrogenation method all also exists the defects such as temperature of reaction is high, complicated operation, energy consumption are high, the active degree of hydrogenation that is low and hydrogenation products of hydrogenation reaction has much room for improvement always.
Summary of the invention
The object of the invention is in order to overcome catalyst application cost in art methods high, not easily implement (temperature of reaction is high, complicated operation, energy consumption are high), defect that the active degree of hydrogenation that is low and hydrogenation products of hydrogenation reaction has much room for improvement, provide a kind of catalyst application cost lower, more easily implement (temperature of reaction is lower, simple to operate, energy consumption is low), hydrogenation reaction activity degree of hydrogenation that is high, hydrogenation products is improved significantly and the method for hydrotreating of unsaturated copolymer that increases without obvious gel of hydrogenation products.
The present inventor surprisingly finds under study for action, is being carried out by unsaturated copolymer, in the process of hydrogenation, being dissolved in by unsaturated copolymer in organic solvent, filling after getting rid of gas, then add catalyst for hydrogenation M
1 am
2 bx
ml
nand part, then first under low temperature (0-30 DEG C), hydrogenation reaction is carried out, hydrogenation reaction is carried out again under high temperature (50-180 DEG C), low temperature hydrogenation reaction is used with high temperature hydrogenation reaction bonded, reaction is more easily implemented (temperature of reaction is lower, simple to operate, energy consumption is low), the hydrogenation reaction that can not only significantly improve catalyzer is active, obtain speed of response faster, Reaction time shorten, and the degree of hydrogenation of hydrogenation products can be significantly improved, and hydrogenation products increases without obvious gel, meanwhile, production cost can also be effectively reduced.
Therefore, to achieve these goals, the invention provides a kind of method of hydrotreating of unsaturated copolymer, said method comprising the steps of:
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, fill and get rid of gas;
(2) add catalyst for hydrogenation and part, described catalyst for hydrogenation has following general formula: M
1 am
2 bx
ml
n, wherein, M
1for rhodium, M
2for ruthenium, X is one or more in chlorine, bromine and hydrogen, and L is one or more in the organic compound of organic phosphine, the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen, 1≤a≤6,1≤b≤3,3≤m≤7,6≤n≤21;
(3) be filled with hydrogen, stir, react, the condition of described reaction comprises: temperature of reaction is 0-30 DEG C, and hydrogen pressure is 0.05-15Mpa, and the reaction times is 1-120 minute;
(4) be warming up to 50-180 DEG C, maintenance hydrogen pressure is 0.1-15Mpa, reaction 1-20 hour;
(5) organic solvent in the reaction product that obtains of removal step (4).
The method of hydrotreating of unsaturated copolymer of the present invention, the hydrogenation reaction that can improve catalyzer is active, obtains speed of response faster, Reaction time shorten, the degree of hydrogenation of hydrogenation products can be significantly improved, and hydrogenation products comparatively unsaturated copolymer increase without obvious gel.Meanwhile, the method has simple to operate, the advantage such as the reaction times is short, easy enforcement (temperature of reaction is lower, simple to operate, energy consumption is low), greatly reduces the production cost of unsaturated copolymer.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of method of hydrotreating of unsaturated copolymer, the method comprises the following steps:
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, fill and get rid of gas;
(2) add catalyst for hydrogenation and part, described catalyst for hydrogenation has following general formula: M
1 am
2 bx
ml
n, wherein, M
1for rhodium, M
2for ruthenium, X is one or more in chlorine, bromine and hydrogen, and L is one or more in the organic compound of organic phosphine, the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen, 1≤a≤6,1≤b≤3,3≤m≤7,6≤n≤21;
(3) be filled with hydrogen, stir, react, the condition of described reaction comprises: temperature of reaction is 0-30 DEG C, and hydrogen pressure is 0.05-15Mpa, and the reaction times is 1-120 minute;
(4) be warming up to 50-180 DEG C, maintenance hydrogen pressure is 0.1-15Mpa, reaction 1-20 hour;
(5) organic solvent in the reaction product that obtains of removal step (4).
In the inventive method step (1), for the mass percentage concentration (namely the quality of unsaturated copolymer is divided by the quality sum of unsaturated copolymer and organic solvent) of unsaturated copolymer in glue, there is no particular limitation, the concentration can commonly used for this area, under preferable case, in glue, the mass percentage concentration of unsaturated copolymer is 2-15%, more preferably 4-12%.
In the inventive method step (1), for unsaturated copolymer, there is no particular limitation, can for the various unsaturated copolymers containing carbon-carbon double bond (C=C), under preferable case, unsaturated copolymer is copolymer and/or terpolymer; Further preferably, copolymer comprises butadiene-acrylonitrile, divinyl-(methyl) vinyl cyanide, 2-methyl isophthalic acid, 3-butadiene-acrylonitrile, 2-methyl isophthalic acid, one or more in 3-divinyl-(methyl) vinyl cyanide and styrene-butadiene-styrene block copolymer, terpolymer comprise in butadiene-acrylonitrile-(methyl) vinylformic acid, divinyl-(methyl) acrylonitrile-acrylic acid, divinyl-(methyl) vinyl cyanide-(methyl) vinylformic acid and butadiene-acrylonitrile-vinylformic acid one or more; More a step preferably, and unsaturated copolymer is butadiene-acrylonitrile and/or divinyl-(methyl) vinyl cyanide.When unsaturated copolymer is the mixture of butadiene-acrylonitrile and divinyl-(methyl) vinyl cyanide, for the ratio not requirement that butadiene-acrylonitrile and divinyl-(methyl) vinyl cyanide add, can be arbitrary proportion.
In the inventive method step (1), for organic solvent, there is no particular limitation, can for the various organic solvents of unsaturated copolymer, catalyst for hydrogenation and part can be dissolved in this area, under preferable case, organic solvent is that aromatic hydrocarbons, aromatic hydrocarbons are by one or more in the derivative of alkyl or halogen substiuted, halogenated alkane, ketone and acid amides; Further preferably, organic solvent is one or more in benzene,toluene,xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, acetone, butanone and DMF.
In the inventive method step (2), in order to the hydrogenation reaction improving catalyst for hydrogenation is active and increase the degree of hydrogenation of hydrogenation products, under preferable case, the add-on of catalyst for hydrogenation is the 0.01-5% of unsaturated copolymer quality, more preferably 0.05-1%.
In the inventive method step (2), in order to increase the degree of hydrogenation of hydrogenation products, under preferable case, the add-on of part is 1-20 times of catalyst for hydrogenation quality, and more preferably 4-15 doubly.
In the inventive method step (2), in order to the hydrogenation reaction improving catalyst for hydrogenation is active and increase the degree of hydrogenation of hydrogenation products, under preferable case, in catalyst for hydrogenation, M
1for rhodium, M
2for ruthenium, X is chlorine, and L is organic phosphine; Further preferably, a:b is 1-3:1, and more a step preferably, and L is triphenylphosphine, and a:b is 2:1.
Catalyst for hydrogenation M
1 am
2 bx
ml
ncan prepare by the following method, the method comprises the following steps:
(1) L and solvent are added reaction flask, under agitation reflux dissolving;
(2) by M
1and M
2metal halide mixing after be dissolved in hot solvent, add at a reflux temperature reaction flask reaction;
(3) except desolventizing, crystallization or Powdered catalyst for hydrogenation is obtained.
In the inventive method step (2), in order to increase the degree of hydrogenation of hydrogenation products, under preferable case, part is one or more in the organic compound of organic phosphine, the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen; Further preferably, part is organic phosphine; More a step preferably, and part is triphenylphosphine.
For the organic compound of the organic phosphine in catalyst for hydrogenation and part, the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen, there is no particular limitation, the organic compound of the various organic phosphines can commonly used for this area, the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen.
In the inventive method step (3), the present inventor finds under study for action further, the reaction times of low temperature hydrogenation reaction is long, the cyano group in hydrogenated nitrile-butadiene rubber can be caused to be reduced, thus cause product structure and performance to change, therefore, under preferable case, the reaction times is 20-40 minute.In order to the hydrogenation reaction improving catalyst for hydrogenation is further active and increase the degree of hydrogenation of hydrogenation products, further preferably, the condition of reaction comprises: temperature of reaction is 10-25 DEG C, and hydrogen pressure is 1-5Mpa, and the reaction times is 20-40 minute.
In the inventive method step (4), in order to increase the degree of hydrogenation of hydrogenation products further, under preferable case, be warming up to 80-150 DEG C, maintenance hydrogen pressure is 3-12Mpa, reaction 4-16 hour.
In the inventive method step (5), for the method for the organic solvent in the reaction product that removal step (4) obtains, there is no particular limitation, the various methods can commonly used for those skilled in the art, such as can be condensed by ethanol, organic solvent in reaction product that the removal step (4) such as steam distillation obtains, thus obtain hydrogenation products, then remove the solvent on the hydrogenation products that obtains.For the method for solvent on removing hydrogenation products, there is no particular limitation, the various methods can commonly used for those skilled in the art, under preferable case, the method except desolventizing is vacuum-drying, vacuum drying condition comprises: temperature is 50-100 DEG C, and the time is 1-10 hour.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In following examples and comparative example, the measuring method of degree of hydrogenation is bromine iodine method.
The measuring method of gel content: take w1 gram of dry glue, add chlorobenzene, be made into the solution of 1g/100mL, dissolve after 24 hours, 360 mesh filter screens solution being poured into constant weight (w2 gram) filter, the dry constant weight of 360 mesh filter screens will filling insolubles again, weight is designated as w3 gram, then gel content is: (w3-w2)/w1*10
6ppm.
Adopt the cyano reduction rate in nmr analysis method mensuration hydrogenated nitrile-butadiene rubber, concrete grammar is: take w4 gram of dry glue, its cyano content is A quality % (known), dissolve with deuterochloroform, using vinylbenzene as interior mark, cinnamic add-on is M1 mole, is M2 mole according to the cyano content that interior scalar product divides areal calculation to obtain being reduced in dry glue, then the cyano reduction rate in hydrogenated nitrile-butadiene rubber is (M2*26)/(w4*A%).
Butadiene-propylene nitrile rubber is purchased from Lan Hua company, and the trade mark is N21L, and cyano content is 41 quality %.
RhCl
3.H
2o, RuCl
3.H
2o is all purchased from Kunming Boren Precious Metals Co., Ltd..
Preparation example 1
This preparation example is for illustration of catalyst for hydrogenation M
1 am
2 bx
ml
n(P1) preparation method, wherein, M
1for rhodium, M
2for ruthenium, X is chlorine, and L is triphenylphosphine, and a:b is 2:1.
By 4.5 grams of PPh
3be dissolved under argon shield in 70 DEG C of hot ethanol solution, and the solution after dissolving is joined in reaction flask; Take 0.5 gram of RhCl
3.H
2o and 0.23 gram RuCl
3.H
2o is dissolved in ethanolic soln under argon shield, and reflux at 78 DEG C, by RhCl
3.H
2o and RuCl
3.H
2the ethanolic soln of O is added dropwise in reaction flask and reacts 2.5 hours, is cooled to 25 DEG C, suction filtration, with washed with diethylether, obtains the catalyst for hydrogenation of pulverous Rh:Ru=2:1.
Preparation example 2
This preparation example is for illustration of catalyst for hydrogenation M
1 am
2 bx
ml
n(P2) preparation method, wherein, M
1for rhodium, M
2for ruthenium, X is chlorine, and L is triphenylphosphine, and a:b is 3:1.
By 6 grams of PPh
3be dissolved under argon shield in 70 DEG C of hot ethanol solution, and the solution after dissolving is joined in reaction flask; Take 0.75 gram of RhCl
3.H
2o and 0.23 gram RuCl
3.H
2o is dissolved in ethanolic soln under argon shield, and reflux at 78 DEG C, by RhCl
3.H
2o and RuCl
3.H
2the ethanolic soln of O is added dropwise in reaction flask and reacts 2.5 hours, is cooled to 25 DEG C, suction filtration, with washed with diethylether, obtains the catalyst for hydrogenation of pulverous Rh:Ru=3:1.
Preparation example 3
This preparation example is for illustration of catalyst for hydrogenation M
1 am
2 bx
ml
n(P3) preparation method, wherein, M
1for rhodium, M
2for ruthenium, X is chlorine, and L is triphenylphosphine, and a:b is 1:1.
By 3 grams of PPh
3be dissolved under argon shield in 70 DEG C of hot ethanol solution, and the solution after dissolving is joined in reaction flask; Take 0.25 gram of RhCl
3.H
2o and 0.23 gram RuCl
3.H
2o is dissolved in ethanolic soln under argon shield, and reflux at 78 DEG C, by RhCl
3.H
2o and RuCl
3.H
2the ethanolic soln of O is added dropwise in reaction flask and reacts 2.5 hours, is cooled to 25 DEG C, suction filtration, with washed with diethylether, obtains the catalyst for hydrogenation of pulverous Rh:Ru=1:1.
Embodiment 1-15
Embodiments of the invention 1-15 is for illustration of the method for hydrotreating of unsaturated copolymer of the present invention:
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, join in reactor, fill and get rid of gas;
(2) catalyst for hydrogenation and part is added;
(3) be filled with hydrogen, stir, react, the condition of reaction comprises: temperature of reaction is b DEG C, and hydrogen pressure is aMPa, and the reaction times is c minute;
(4) be warming up to e DEG C, maintenance hydrogen pressure is dMPa, reaction f hour;
(5) hydrogenation products is condensed by ethanol and separates out, and vacuum-drying 8 hours at 60 DEG C.
In embodiment 1-15, unsaturated copolymer be Ding bis-Xi ?acrylic-nitrile rubber, and Ding bis-Xi ?the gel content of acrylic-nitrile rubber be 304ppm, the quality of glue is 540g, and the measurement result of the degree of hydrogenation of the gelatin concentration mass percentage concentration of unsaturated copolymer (namely in glue), catalyzer/unsaturated copolymer (i.e. the mass ratio of catalyst for hydrogenation and unsaturated copolymer), part/catalyzer (i.e. the mass ratio of part and catalyst for hydrogenation), a-f and the hydrogenation products that obtains, gel content, cyano reduction situation is in table 1.
Table 1
Comparative example 1-7
The condition of unsaturated copolymer in comparative example 1-4, organic solvent, catalyst for hydrogenation and part, the gelatin concentration mass percentage concentration of unsaturated copolymer (namely in glue), catalyzer/unsaturated copolymer (i.e. the mass ratio of catalyst for hydrogenation and unsaturated copolymer), part/catalyzer (i.e. the mass ratio of part and catalyst for hydrogenation) respectively with embodiment 2,3,11,12 identical, unlike, react without low temperature hydrogenation in comparative example 1-4 method.Comparative example 5, compared with comparative example 1, extends unlike by the reaction times f of comparative example 1.Comparative example 6, compared with embodiment 2, changes high temperature hydrogenation reaction into unlike by low temperature hydrogenation reaction.In comparative example 1-6, the measurement result of the degree of hydrogenation of the gelatin concentration mass percentage concentration of unsaturated copolymer (namely in glue), catalyzer/unsaturated copolymer (i.e. the mass ratio of catalyst for hydrogenation and unsaturated copolymer), part/catalyzer (i.e. the mass ratio of part and catalyst for hydrogenation), a-f and the hydrogenation products that obtains, gel content, cyano reduction situation is in table 2.
Table 2
Comparative example 7
According to the method for embodiment 2, unlike, (1) adds the obtained catalyst for hydrogenation (Rh:Ru=2:1) of preparation example 1 and part in a kettle., fills and gets rid of gas; (2) be filled with hydrogen, stir, react, the condition of reaction comprises: temperature of reaction is 25 DEG C, and hydrogen pressure is 3.0MPa, and the reaction times is 30 minutes; (3) unsaturated copolymer is dissolved in organic solvent, obtains glue, join in reactor; (4) be warming up to 130 DEG C, maintenance hydrogen pressure is 4.0MPa, react 8.0 hours; (5) hydrogenation products is condensed by ethanol and separates out, and vacuum-drying 8 hours at 60 DEG C.Wherein, the condition of unsaturated copolymer, organic solvent, catalyst for hydrogenation and part is with embodiment 2.
After measured, the degree of hydrogenation of hydrogenation products is 96.9%, and gel content is 841ppm.
By embodiment 2 compared with embodiment 4, when the time of step (3) low temperature hydrogenation reaction is 20-40 minute, effectively can improve the degree of hydrogenation of hydrogenation products, hydrogenation products increases without obvious gel simultaneously; And when the time lengthening to 120 minute of being reacted by low temperature hydrogenation, cyano group in hydrogenated nitrile-butadiene rubber can be caused to be reduced, thus product structure and performance is caused to change.
By embodiment 2 compared with embodiment 7, when the temperature of step (3) low temperature hydrogenation reaction is 10-25 DEG C, the degree of hydrogenation of hydrogenation products can be improved further.
By embodiment 2 compared with embodiment 11-12, in catalyst for hydrogenation, when a:b is 2:1, the degree of hydrogenation of hydrogenation products can be increased further.
By embodiment 2 compared with embodiment 13, when organic solvent adopts chlorobenzene, the degree of hydrogenation of hydrogenation products can be increased further.
By embodiment 2 compared with embodiment 14, when part adopts PPh
3time, the degree of hydrogenation of hydrogenation products can be increased further.
By embodiment 2 compared with embodiment 15, when organic solvent adopts chlorobenzene and part employing PPh
3time, the degree of hydrogenation of hydrogenation products can be increased further.
Respectively embodiment 2 is compared with comparative example 1, embodiment 3 compares with comparative example 2, embodiment 11 compares with comparative example 3, embodiment 12 compares with comparative example 4, known, before high temperature hydrogenation reaction, increasing low temperature hydrogenation reaction, (condition of reaction comprises: temperature of reaction is 0-30 DEG C, hydrogen pressure is 0.05-15Mpa, reaction times is 1-120 minute) step, effectively can improve speed of reaction, increase the degree of hydrogenation of hydrogenation products, and hydrogenation products increase without obvious gel.
By embodiment 2 compared with comparative example 5, if without low temperature hydrogenation reaction, (condition of reaction comprises: temperature of reaction is 0-30 DEG C before high temperature hydrogenation reaction, hydrogen pressure is 0.05-15Mpa, reaction times is 1-120 minute) step, under the reaction conditions that reaction times f is extended 2 hours, similar degree of hydrogenation could be obtained, illustrate that priority carries out low temperature hydrogenation reaction and high temperature hydrogenation reacts the speed of reaction that can significantly improve hydrogenation reaction, the degree of hydrogenation of effective raising hydrogenation products, and hydrogenation products increases without obvious gel.
By embodiment 2 compared with comparative example 6, change low temperature hydrogenation reaction into high temperature hydrogenation reaction, hydrogenation of net product degree there is no and improves effect, illustrate that priority carries out low temperature hydrogenation reaction and high temperature hydrogenation reacts the speed of reaction that can significantly improve hydrogenation reaction, the degree of hydrogenation of effective raising hydrogenation products, and hydrogenation products increases without obvious gel.
By embodiment 2 compared with comparative example 7, change the order of addition(of ingredients) of glue and catalyzer, low temperature hydrogenation can be caused to react and the decline of high temperature hydrogenation reacting phase in conjunction with hydrogenation effect, have obvious gel to increase in hydrogenation products simultaneously.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a method of hydrotreating for unsaturated copolymer, is characterized in that, the method comprises the steps:
(1) unsaturated copolymer is dissolved in organic solvent, obtains glue, fill and get rid of gas;
(2) add catalyst for hydrogenation and part, described catalyst for hydrogenation has following general formula: M
1 am
2 bx
ml
n, wherein, M
1for rhodium, M
2for ruthenium, X is one or more in chlorine, bromine and hydrogen, and L is one or more in the organic compound of organic phosphine, the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen, 1≤a≤6,1≤b≤3,3≤m≤7,6≤n≤21;
(3) be filled with hydrogen, stir, react, the condition of described reaction comprises: temperature of reaction is 0-30 DEG C, and hydrogen pressure is 0.05-15Mpa, and the reaction times is 1-120 minute;
(4) be warming up to 50-180 DEG C, maintenance hydrogen pressure is 0.1-15Mpa, reaction 1-20 hour;
(5) organic solvent in the reaction product that obtains of removal step (4).
2. preparation method according to claim 1, wherein, in step (3), the condition of described reaction comprises: temperature of reaction is 10-25 DEG C, and hydrogen pressure is 1-5Mpa, and the reaction times is 20-40 minute.
3. preparation method according to claim 1, wherein, in step (4), be warming up to 80-150 DEG C, maintenance hydrogen pressure is 3-12Mpa, reaction 4-16 hour.
4., according to the preparation method in claim 1-3 described in any one, wherein, in step (1), in described glue, the mass percentage concentration of unsaturated copolymer is 2-15%.
5. according to the preparation method in claim 1-3 described in any one, wherein, described unsaturated copolymer is copolymer and/or terpolymer; Preferably, described copolymer comprises butadiene-acrylonitrile, divinyl-(methyl) vinyl cyanide, 2-methyl isophthalic acid, 3-butadiene-acrylonitrile, 2-methyl isophthalic acid, one or more in 3-divinyl-(methyl) vinyl cyanide and styrene-butadiene-styrene block copolymer, described terpolymer comprise in butadiene-acrylonitrile-(methyl) vinylformic acid, divinyl-(methyl) acrylonitrile-acrylic acid, divinyl-(methyl) vinyl cyanide-(methyl) vinylformic acid and butadiene-acrylonitrile-vinylformic acid one or more; Further preferably, described unsaturated copolymer is butadiene-acrylonitrile and/or divinyl-(methyl) vinyl cyanide.
6. according to the preparation method in claim 1-3 described in any one, wherein, described organic solvent is that aromatic hydrocarbons, aromatic hydrocarbons are by one or more in the derivative of alkyl or halogen substiuted, halogenated alkane, ketone and acid amides; Preferably, described organic solvent is one or more in benzene,toluene,xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, acetone, butanone and DMF.
7. according to the preparation method in claim 1-3 described in any one, wherein, in step (2), the add-on of described catalyst for hydrogenation is the 0.01-5% of described unsaturated copolymer quality, is preferably 0.05-1%.
8. preparation method according to claim 7, wherein, the add-on of described part is 1-20 times of described catalyst for hydrogenation quality, is preferably 4-15 doubly.
9. according to the preparation method in claim 1-3 described in any one, wherein, M
1for rhodium, M
2for ruthenium, X is chlorine, and L is organic phosphine; Preferably, a:b is 1-3:1, and further preferably, L is triphenylphosphine, and a:b is 2:1.
10. according to the preparation method in claim 1-3 described in any one, wherein, described part is one or more in the organic compound of organic phosphine, the organic pair of phosphine, organic cerium and nitrogenous, sulphur or oxygen; Preferably, described part is organic phosphine; Further preferably, described part is triphenylphosphine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107200795A (en) * | 2016-03-16 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of method of hydrotreating of the polymer containing polar group |
| CN116041621A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Hydrogenated nitrile rubber and preparation method thereof |
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| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107200795A (en) * | 2016-03-16 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of method of hydrotreating of the polymer containing polar group |
| CN116041621A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Hydrogenated nitrile rubber and preparation method thereof |
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