CN107200794B - A kind of method of hydrotreating of NBR latex - Google Patents
A kind of method of hydrotreating of NBR latex Download PDFInfo
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- CN107200794B CN107200794B CN201610149598.XA CN201610149598A CN107200794B CN 107200794 B CN107200794 B CN 107200794B CN 201610149598 A CN201610149598 A CN 201610149598A CN 107200794 B CN107200794 B CN 107200794B
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Abstract
The present invention relates to hydrogenation of NBR latex fields, disclose a kind of method of hydrotreating of NBR latex, this method comprises the following steps: (1) mixing NBR latex, hydrogenation catalyst and ligand；(2) mixture that step (1) obtains successively is subjected to the first hydrogenation reaction and the second hydrogenation reaction in presence of hydrogen, the reaction temperature of first hydrogenation reaction is 0-30 DEG C, and the reaction temperature of second hydrogenation reaction is 50-180 DEG C；(3) solvent in the reaction product that removal step (2) obtains.NBR latex is carried out using method of the invention to add hydrogen, it can be improved the hydrogenation reaction activity of hydrogenation catalyst and the degree of hydrogenation of hydrogenation products, hydrogenation products increase compared with for the nitrile rubber added before hydrogen in NBR latex without obvious gel, and it is easy to operate, the reaction time is short, it is easy implement, be hydrogenated into it is low.
Description
Technical field
The present invention relates to hydrogenation of NBR latex fields, and in particular, to a kind of method of hydrotreating of NBR latex.
Background technique
In recent years, with the continuous hair of the industries such as automobile manufacture, machining, metallurgical seal, engineering construction, petroleum industry
Exhibition, is also constantly rising the demand of high-end polymer.Hydrogenated nitrile-butadiene rubber not only possesses good wear-resisting, low temperature resistant, resistance to
The performances such as oxidation, resistance to ozone, it is often more important that, hydrogenated nitrile-butadiene rubber have splendid thermal stability, these properties make it
One seat is occupied in high-end polymer, and dosage rises year by year.
But for hydrogenated nitrile-butadiene rubber, high price is serious to constrain its pushing away in China's various industries
Wide and application.The main reason for causing hydrogenated nitrile-butadiene rubber price to remain high for a long time has the following: (1) hydrogenation catalyst valence
Lattice are expensive；(2) existing synthesizing mean is mainly that solwution method adds hydrogen, complex technical process；(3) catalyst removal is difficult.For one
As for nitrile rubber, be mainly made by emulsion polymerisation process, as can directly carrying out latex hydrogenation, hydrogen will be greatly shortened
Change the technological process of production of nitrile rubber, reduces production cost.But for the lotion of nitrile rubber (i.e. NBR latex) plus hydrogen
For, existing latex hydrogenation method production cost is higher, and reaction temperature is high, and energy consumption is high, and hydrogenation catalyst reactivity is lower
And product gel content is higher, the degree of hydrogenation of hydrogenation products is also to be improved.
Summary of the invention
The purpose of the invention is to overcome, production cost is higher, is not easy reality during the hydrogenation of NBR latex of existing method
Apply that (reaction temperature high, energy consumption high), hydrogenation catalyst reactivity is lower, hydrogenation products degrees of hydrogenation are to be improved, product is solidifying
The higher defect of glue content, provide a kind of lower production costs, be easier to implement (reaction temperature is lower, easy to operate, low energy consumption),
The hydrogenation reaction activity height of hydrogenation catalyst, the degree of hydrogenation of hydrogenation products is improved significantly and hydrogenation products increase without obvious gel
The method of hydrotreating of long NBR latex.
The present inventor has been surprisingly found that under study for action, during hydrogenation of NBR latex, first by NBR latex, plus
Then mixture is successively carried out first plus the hydrogen that reaction temperature is 0-30 DEG C by hydrogen catalyst and ligand mixing in presence of hydrogen
The second hydrogenation reaction that reaction and reaction temperature are 50-180 DEG C uses low temperature hydrogenation reaction with high-temperature hydrogenation reaction bonded,
Reaction is set to be easier to implement (reaction temperature is lower, easy to operate, low energy consumption), can not only significantly improve hydrogenation catalyst adds hydrogen
Reactivity obtains faster reaction speed, shortens the reaction time, and can significantly improve the degree of hydrogenation of hydrogenation products, and
Hydrogenation products increase without obvious gel, simultaneously, additionally it is possible to the cost of hydrogenation of NBR latex be effectively reduced.
Therefore, to achieve the goals above, the present invention provides a kind of method of hydrotreating of NBR latex, this method includes such as
Lower step:
(1) NBR latex, hydrogenation catalyst and ligand are mixed；
(2) mixture that step (1) obtains successively is carried out the first hydrogenation reaction and second in presence of hydrogen adds hydrogen anti-
It answers, the reaction temperature of first hydrogenation reaction is 0-30 DEG C, and the reaction temperature of second hydrogenation reaction is 50-180 DEG C；
(3) solvent in the reaction product that removal step (2) obtains.
The method of hydrotreating of NBR latex of the invention can be improved the hydrogenation reaction activity of hydrogenation catalyst, obtain faster
Reaction speed, shorten the reaction time, can significantly improve the degree of hydrogenation of hydrogenation products, and hydrogenation products nitrile rubber relatively plus before hydrogen
Increase for nitrile rubber in cream without obvious gel.Meanwhile this method is with easy to operate, the reaction time is short, easy implementation is (anti-
Answer that temperature is lower, easy to operate, low energy consumption) the advantages that, can be effectively reduced NBR latex is hydrogenated into this.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of method of hydrotreating of NBR latex, and this method comprises the following steps:
(1) NBR latex, hydrogenation catalyst and ligand are mixed；
(2) mixture that step (1) obtains successively is carried out the first hydrogenation reaction and second in presence of hydrogen adds hydrogen anti-
It answers, the reaction temperature of first hydrogenation reaction is 0-30 DEG C, and the reaction temperature of second hydrogenation reaction is 50-180 DEG C；
(3) solvent in the reaction product that removal step (2) obtains.
It is not special for the method for mixing NBR latex, hydrogenation catalyst and ligand in the method for the present invention step (1)
Restriction, can be various methods commonly used in the art, if aforementioned substances are mixed, such as can for first anti-
It answers and NBR latex is added in kettle, fill and add hydrogenation catalyst and ligand after getting rid of gas, mixed.Those skilled in the art answer
It should be appreciated that fill get rid of gas occur before hydrogenation reaction, refer to by the air displacement in reaction kettle be inert gas or hydrogen,
Inert gas for example can be nitrogen.It gets rid of the method for gas for filling there is no particular limitation, can be commonly used in the art each
Kind method, this is known to those skilled in the art, and details are not described herein.
Hydrogenation reaction in order to improve hydrogenation catalyst is active and increases the degree of hydrogenation of hydrogenation products, under preferable case, fourth
The solid content of nitrile latex is 0.5%-5%.It will be understood by those skilled in the art that solid content (the Solid content of NBR latex
Content) refer to and dry acrylonitrile-butadiene rubber latex after, the quality of remaining solid substance accounts for the percentage of the quality of NBR latex.
For solid content is the NBR latex of 0.5%-5%, under normal circumstances, commercially available NBR latex is consolidated
Content is higher (mostly 40% or more), it is therefore desirable to the NBR latex prepared and obtain required solid content is re-started, for matching
There is no particular limitation for the specific method of system, can be various methods commonly used in the art, as long as obtained NBR latex is consolidated
Content is 0.5%-5%.Under preferable case, solid content is that the preparation method of the NBR latex of 0.5%-5% includes: to solid
Organic solvent is added in the NBR latex no more than 35% in content, is configured to the NBR latex that solid content is 0.5%-5%；Into one
Preferably, it is still more preferably 2%- that the solid content of NBR latex of the solid content no more than 35% is 2%-35% to step
15%；Alternatively,
Solid content is that the preparation method of the NBR latex of 0.5%-5% includes: the NBR latex for being greater than 35% to solid content
Middle addition water is configured to the NBR latex that solid content is not more than 35%, then adds in the NBR latex to solid content no more than 35%
Enter organic solvent, is configured to the NBR latex that solid content is 0.5%-5%；It is further preferred that the solid content is not more than
The solid content of 35% NBR latex is 2%-35%, is still more preferably 2%-15%.Those skilled in the art should manage
Solution can be obtained first carrying out filling getting rid of gas after NBR latex of the solid content no more than 35%, then be prepared again preparing
Solid content is the NBR latex of 0.5%-5%, adds hydrogenation catalyst and ligand, is mixed.
For organic solvent, there is no particular limitation, and can be can be miscible with NBR latex in this field, and can be molten
Solve hydrogenation catalyst and ligand (and auxiliary agent) various organic solvents, be added organic solvent after in order to make latex not to be demulsified,
It is layered and flocculates, under preferable case, organic solvent is aromatic hydrocarbons, aromatic hydrocarbons is replaced by alkyl or halogen derivative, halogenated alkane, ketone
With one of amide or a variety of；It is further preferred that organic solvent is benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, trichlorine
One of benzene, acetone, butanone and N,N-dimethylformamide are a variety of；It is further preferred that organic solvent is benzene, first
The mixed solvent that one of benzene, dimethylbenzene, chlorobenzene, dichloro-benzenes and trichloro-benzenes are formed with one of acetone and butanone, the former
The volume ratio of (i.e. in benzene,toluene,xylene, chlorobenzene, dichloro-benzenes and trichloro-benzenes any one) and the latter (acetone or butanone)
For 3:1-1:3.
For NBR latex, there is no particular limitation, can be the various binary NBR latexes in this field, preferable case
Under, NBR latex is the binary fourth that one of butadiene and isoprene are formed with one of acrylonitrile and methacrylonitrile
The binary NBR latex that nitrile latex, further preferably butadiene and acrylonitrile are formed.Specifically, for the synthesis of NBR latex
There is no particular limitation for method, can be various synthetic methods commonly used in the art, as long as in butadiene and isoprene
It is a kind of with one of acrylonitrile and methacrylonitrile are aggregated reacts formation, such as can be directly to be made through emulsion polymerization
The binary NBR latex obtained, or be formed by binary NBR latex after emulsifying using nitrile rubber, this is ability
Known to field technique personnel, details are not described herein.Aforementioned binary NBR latex can also be commercially available.With consolidating for NBR latex
On the basis of the weight of inclusion, the content of butadiene or isoprene can be 50-80 weight %, acrylonitrile or first in NBR latex
The content of base acrylonitrile can be 20-50 weight %.
In the method for the present invention step (1), for the hydrogenation catalyst of addition, there is no particular limitation, can be normal for this field
The various catalyst for chemigum hydrogenation, under preferable case, hydrogenation catalyst has following general formula: (RmA)zRhXn,
Wherein, the aralkyl of alkyl of each R independently selected from C1-C8, the naphthenic base 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.In order to
Further increase the hydrogenation reaction activity of hydrogenation catalyst and increase the degrees of hydrogenation of hydrogenation products, it is further preferred that plus hydrogen urge
Agent is (PPh3)3RhCl.Above-mentioned hydrogenation catalyst (the R of the present inventionmA)zRhXnIt can be commercially available.
Under preferable case, hydrogenation catalyst has following general formula: M1 aM2 bXmLn, wherein M1For rhodium, M2For ruthenium, X is chlorine, bromine
With one of hydrogen or a variety of, L is one in the organic compound of organic single phosphine, organic double phosphines, organic cerium and nitrogenous, sulphur or oxygen
Kind or a variety of, 1≤a≤6,1≤b≤3,3≤m≤7,6≤n≤21.In order to further increase the hydrogenation reaction of hydrogenation catalyst
Activity and the degree of hydrogenation for increasing hydrogenation products, it is further preferred that in hydrogenation catalyst, M1For rhodium, M2For ruthenium, X is chlorine, and L is to have
Machine list phosphine；It is further preferred that a:b:m:n is (1-3): 1:(3-5): (6-12), most preferably, L is triphenylphosphine, a:b:
M:n is 3:1:5:12.
Hydrogenation catalyst M1 aM2 bXmLnIt can prepare by the following method, method includes the following steps:
(1) reaction flask is added in L and solvent, under stiring reflux dissolution；
(2) by M1And M2Metal halide mixing after be dissolved in hot solvent, at a reflux temperature be added reaction flask reaction；
(3) solvent is removed, is crystallized or powdered hydrogenation catalyst.
Hydrogenation reaction in order to improve hydrogenation catalyst is active and increases the degree of hydrogenation of hydrogenation products, under preferable case, adds
The additional amount of hydrogen catalyst is the 0.01-5%, further preferably 0.05-1% of the quality of Solid content in NBR latex.
In the method for the present invention step (1), in order to increase the degree of hydrogenation of hydrogenation products, under preferable case, ligand is organic list
One of organic compound of phosphine, organic double phosphines, organic cerium and nitrogenous, sulphur or oxygen is a variety of；It is further preferred that ligand is
Organic list phosphine and/or organic double phosphines；Preferably, ligand is triphenylphosphine, bis- (diphenylphosphine) propane of 1,3- and Isosorbide-5-Nitrae-to a more step
At least one of bis- (diphenyl phosphine) butane；Still further preferably, ligand is triphenylphosphine.
For in hydrogenation catalyst and ligand organic single phosphine, organic double phosphines, organic cerium and nitrogenous, sulphur or oxygen organise
Closing object, there is no particular limitation, can for commonly used in the art various organic single phosphines, organic double phosphines, organic cerium and nitrogenous, sulphur or
The organic compound of oxygen, this is known to those skilled in the art, and details are not described herein.
In order to increase the degree of hydrogenation of hydrogenation products, under preferable case, the additional amount of ligand is the 1- of hydrogenation catalyst quality
20 times, further preferably 4-15 times.
In the method for the present invention step (1), in order to improve degree of hydrogenation and reduce gel content, under preferable case, in mixing
It is additionally added auxiliary agent, that is, step (1) is to mix NBR latex, hydrogenation catalyst, ligand and auxiliary agent.It is not special for auxiliary agent
Restriction, can be various auxiliary agents commonly used in the art, under preferable case, auxiliary agent is aliphatic tertiary amine and/or aromatic series three
Grade amine；Preferably, auxiliary agent is triethylamine (i.e. N, N- diethyl ethanamine) and/or diisopropyl ethyl amine (i.e. N, N- bis- to a more step
Wopropyl ethyl amine).
In order to further increase degree of hydrogenation and reduce gel content, under preferable case, the additional amount of auxiliary agent is hydrogenation catalyst
0.5-10 times of agent quality, it is further preferred that the additional amount of auxiliary agent is 1-5 times of hydrogenation catalyst quality.
In the method for the present invention step (2), add hydrogen to further increase the hydrogenation reaction activity of hydrogenation catalyst and increase
The degree of hydrogenation of product, under preferable case, the condition of first hydrogenation reaction includes: that reaction temperature is 0-30 DEG C, further excellent
It is selected as 10-25 DEG C；Hydrogen Vapor Pressure is 0.05-15Mpa, further preferably 1-5Mpa；Reaction time is 1-120 minutes, into one
Step preferably 20-40 minutes.
In the method for the present invention step (2), in order to further increase the degree of hydrogenation of hydrogenation products, under preferable case, second plus
The condition of hydrogen reaction includes: that reaction temperature is 50-180 DEG C, further preferably 80-150 DEG C；Hydrogen Vapor Pressure is 0.1-15Mpa,
Further preferably 4-12Mpa；Reaction time is 1-20 hours, further preferably 4-16 hours.
In the method for the present invention step (3), the method for the solvent in reaction product obtained for removal step (2) is without spy
Other restriction can be those skilled in the art's commonly various methods, such as can pass through ethyl alcohol cohesion, steam distillation
Then the most solvent in reaction product obtained Deng removal step (2) is dried so that hydrogenation products be precipitated to remove
The small part solvent for going hydrogenation products to contain.For removing the method for solvent that hydrogenation products contain, there is no particular limitation, can
Think those skilled in the art's commonly various methods, under preferable case, removes the method for solvent as vacuum drying, vacuum drying
Condition include: temperature be 50-100 DEG C, the time be 1-10 hours.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In following embodiment and comparative example, the measuring method of degree of hydrogenation is according to document (hydrogenated nitrile-butadiene rubber microstructure
And hydrogenation degree calculate nmr analysis method petrochemical industry, 2014,43,403) method tested.
The measuring method of gel content: weighing w1 grams of dry glue, and chlorobenzene is added, and is made into the solution of 1g/100mL, and dissolution 24 is small
Solution is poured into the strainer filtering of constant weight (w2 grams) by Shi Hou, then the strainer for filling insoluble matter is dry to constant weight, and weight is denoted as
W3 grams, then gel content are as follows: (w3-w2)/w1*106ppm。
Hydrogenation catalyst (PPh3)3RhCl is purchased from Acros company, is denoted as C1.
RhCl3.H2O、RuCl3.H2O is purchased from Kunming Boren Precious Metals Co., Ltd..
The NBR latex that solid content is 43.5% is purchased from the chemical inc Taiwan Nan Di, trade mark NANTEX-
640, on the basis of the weight of Solid content, the content of butadiene is 63%, and the content of acrylonitrile is 37%, and viscosity is 50 centipoises,
PH is 8.2, is denoted as S1；The gel content that nitrile rubber is measured after removal solvent is 397ppm.
Preparation example 1
This preparation example is for illustrating hydrogenation catalyst M1 aM2 bXmLn(C2) preparation method, wherein M1For rhodium, M2For ruthenium, X
For chlorine, L is triphenylphosphine, a:b:m:n 2:1:4:9.
By 4.5 grams of PPh3It is dissolved in 70 DEG C of hot ethanol solution under protection of argon gas, and dissolved solution is added to instead
It answers in bottle；Weigh 0.5 gram of RhCl3.H2O and 0.23 gram of RuCl3.H2O is dissolved in ethanol solution under protection of argon gas, is added at 78 DEG C
Heat reflux, by RhCl3.H2O and RuCl3.H2The ethanol solution of O, which is added dropwise in reaction flask, to react 2.5 hours, is cooled to 25 DEG C, takes out
Filter, is washed with ether, obtains the hydrogenation catalyst of powdered Rh:Ru=2:1, be denoted as C2.
Preparation example 2
This preparation example is for illustrating hydrogenation catalyst M1 aM2 bXmLn(C3) preparation method, wherein M1For rhodium, M2For ruthenium, X
For chlorine, L is triphenylphosphine, a:b:m:n 3:1:5:12.
By 6 grams of PPh3It is dissolved in 70 DEG C of hot ethanol solution under protection of argon gas, and dissolved solution is added to reaction
In bottle；Weigh 0.75 gram of RhCl3.H2O and 0.23 gram of RuCl3.H2O is dissolved in ethanol solution under protection of argon gas, is heated at 78 DEG C
Reflux, by RhCl3.H2O and RuCl3.H2The ethanol solution of O, which is added dropwise in reaction flask, to react 2.5 hours, is cooled to 25 DEG C, takes out
Filter, is washed with ether, obtains the hydrogenation catalyst of powdered Rh:Ru=3:1, be denoted as C3.
Preparation example 3
This preparation example is for illustrating hydrogenation catalyst M1 aM2 bXmLn(C4) preparation method, wherein M1For rhodium, M2For ruthenium, X
For chlorine, L is triphenylphosphine, a:b:m:n 1:1:3:6.
By 3 grams of PPh3It is dissolved in 70 DEG C of hot ethanol solution under protection of argon gas, and dissolved solution is added to reaction
In bottle；Weigh 0.25 gram of RhCl3.H2O and 0.23 gram of RuCl3.H2O is dissolved in ethanol solution under protection of argon gas, is heated at 78 DEG C
Reflux, by RhCl3.H2O and RuCl3.H2The ethanol solution of O, which is added dropwise in reaction flask, to react 2.5 hours, is cooled to 25 DEG C, takes out
Filter, is washed with ether, obtains the hydrogenation catalyst of powdered Rh:Ru=1:1, be denoted as C4.
Embodiment 1-13
The embodiment of the present invention 1-13 is used to illustrate the method for hydrotreating of NBR latex of the invention.
(1) deionized water is added into binary NBR latex S1, is configured to the NBR latex that solid content is p%, fills and get rid of
Gas；
(2) organic solvent is added into the NBR latex that solid content is p%, is configured to the NBR latex that solid content is q%,
Then the NBR latex that prepared solid content is q% is added into reaction kettle；
(3) hydrogenation catalyst, ligand and auxiliary agent, mixing are added in a kettle；
(4) it is filled with hydrogen, stirs, is reacted, the condition of reaction includes: that reaction temperature is b DEG C, Hydrogen Vapor Pressure a
MPa, reaction time are c minutes；
(5) be warming up to e DEG C, holding Hydrogen Vapor Pressure be d MPa, react f hours；
(6) hydrogenation products are agglomerated by ethyl alcohol and are precipitated, and are dried in vacuo 8 hours at 60 DEG C.
In embodiment 1-13, solid content p%, solid content q%, hydrogenation catalyst, ligand, auxiliary agent, catalyst/NBR latex
Middle Solid content (i.e. the mass ratio of Solid content in hydrogenation catalyst and NBR latex), ligand/catalyst (i.e. ligand and hydrogenation catalyst
The mass ratio of agent), auxiliary agent/catalyst (i.e. the mass ratio of auxiliary agent and hydrogenation catalyst), a-f and obtained hydrogenation products plus hydrogen
It spends, the measurement result of gel content is shown in Table 1.
Comparative example 1-6
Binary NBR latex, solid content p%, solid content q%, hydrogenation catalyst, ligand, auxiliary agent, catalysis in comparative example 1-4
Solid content (i.e. the mass ratio of hydrogenation catalyst and Solid content in NBR latex), ligand/catalyst (are matched in agent/NBR latex
The mass ratio of body and hydrogenation catalyst), auxiliary agent/catalyst (i.e. the mass ratio of auxiliary agent and hydrogenation catalyst) respectively with embodiment 1-
4 is identical, unlike, it is reacted in comparative example 1-4 method without low temperature hydrogenation.Comparative example 5 is compared with comparative example 1, the difference is that will
Reaction time f of comparative example 1 extends.Comparative example 6 compared with Example 1, adds the difference is that low temperature hydrogenation reaction is changed to high temperature
Hydrogen reaction.In comparative example 1-6, solid content p%, solid content q%, hydrogenation catalyst, ligand, auxiliary agent, in catalyst/NBR latex
Solid content (i.e. the mass ratio of Solid content in hydrogenation catalyst and NBR latex), ligand/catalyst (i.e. ligand and hydrogenation catalyst
Mass ratio), auxiliary agent/catalyst (i.e. the mass ratio of auxiliary agent and hydrogenation catalyst), a-f and obtained hydrogenation products plus hydrogen
It spends, the measurement result of gel content is shown in Table 2.
Comparative example 7
According to the method for embodiment 1, unlike, hydrogenation catalyst, ligand and auxiliary agent is added in (1) in a kettle, is mixed
It closes, fills and get rid of gas；(2) it is filled with hydrogen, stirs, is reacted, the condition of reaction includes: that reaction temperature is 20 DEG C, Hydrogen Vapor Pressure
For 3MPa, the reaction time is 30 minutes；(3) deionized water is added into S1, is configured to the NBR latex that solid content is 10.9%,
Then organic solvent is added in the NBR latex for being 10.9% to solid content, is configured to the NBR latex that solid content is 1.5%, and
The NBR latex that prepared solid content is 1.5% is added into reaction kettle, is mixed；(4) 90 DEG C are warming up to, keeps hydrogen pressure
Power is 6MPa, is reacted 8 hours；(5) hydrogenation products are agglomerated by ethyl alcohol and are precipitated, and are dried in vacuo 8 hours at 60 DEG C.Wherein, have
Solvent, hydrogenation catalyst, ligand, auxiliary agent, Solid content, ligand/catalyst, auxiliary agent/catalyst in catalyst/NBR latex
Condition is the same as embodiment 1.
After measured, the degree of hydrogenation of hydrogenation products is 87.2%, gel content 640ppm.
By embodiment 1 compared with embodiment 5-6, when the temperature of step (3) low temperature hydrogenation reaction is 10-25 DEG C, Neng Goujin
One step improves the degree of hydrogenation of hydrogenation products, further decreases the gel content of hydrogenation products.
By embodiment 1 compared with embodiment 7-8, when the temperature of step (4) high-temperature hydrogenation reaction is 80-150 DEG C, Neng Goujin
The degree of hydrogenation of one step raising hydrogenation products.
By embodiment 1 compared with embodiment 9-10, when organic solvent is benzene,toluene,xylene, chlorobenzene, dichloro-benzenes and three
When the mixed solvent that one of chlorobenzene is formed with one of acetone and butanone, can further increase hydrogenation products adds hydrogen
Degree, further decreases the gel content of hydrogenation products.
By embodiment 4 compared with embodiment 11-12, hydrogenation catalyst M1aM2bXmLn(M1 is rhodium, and M2 is ruthenium, and X is chlorine, and L is
Triphenylphosphine) in, when a:b:m:n is 3:1:5:12, the degree of hydrogenation of hydrogenation products can be further increased.
By embodiment 1 compared with embodiment 13, when ligand selects PPh3, when auxiliary agent selects triethylamine, can further increase
The degree of hydrogenation of big hydrogenation products, further decreases the gel content of hydrogenation products.
By embodiment 1-4 respectively compared with comparative example 1-4 it is found that increasing reaction temperature before high-temperature hydrogenation reacts is 0-30
DEG C low temperature hydrogenation reaction the step of, can effectively improve reaction rate, increase the degree of hydrogenation of hydrogenation products.
By embodiment 1 compared with comparative example 5, if the low temperature hydrogenation that reactionless temperature is 0-30 DEG C before high-temperature hydrogenation reacts
The step of reaction, can not still obtain similar degree of hydrogenation under the reaction condition that reaction time f is extended 2 hours, illustrate successively
The reaction rate of hydrogenation reaction can be significantly improved by carrying out low temperature hydrogenation reaction and high-temperature hydrogenation reaction, effectively improve hydrogenation products
Degree of hydrogenation, and the gel content of hydrogenation products can be further decreased.
By embodiment 1 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 the reaction speed of hydrogenation reaction can be significantly improved by successively carrying out low temperature hydrogenation reaction and high-temperature hydrogenation reaction
Rate effectively improves the degree of hydrogenation of hydrogenation products, and can further decrease the gel content of hydrogenation products.
By embodiment 1 compared with comparative example 7, changes the charging sequence of NBR latex and hydrogenation catalyst, will cause low temperature
Hydrogenation reaction with high-temperature hydrogenation reaction combines plus hydrogen effect decline, eliminate hydrogenation catalyst low temperature hydrogenation reaction in
Hydrogen reacts so that catalyst structure changes a possibility that changing so as to cause catalyst activity, while hydrogenation products
Middle gel content increases.
The method of hydrotreating of NBR latex of the invention can be improved the hydrogenation reaction activity of hydrogenation catalyst, obtain faster
Reaction speed, shorten the reaction time, can significantly improve the degree of hydrogenation of hydrogenation products, and hydrogenation products nitrile rubber relatively plus before hydrogen
Increase for nitrile rubber in cream without obvious gel.Meanwhile this method is with easy to operate, the reaction time is short, easy implementation is (anti-
Answer that temperature is lower, easy to operate, low energy consumption) the advantages that, can be effectively reduced NBR latex is hydrogenated into this.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (31)
1. a kind of method of hydrotreating of NBR latex, which is characterized in that this method comprises the following steps:
(1) NBR latex, hydrogenation catalyst and ligand are mixed；
(2) mixture that step (1) obtains successively is subjected to the first hydrogenation reaction and the second hydrogenation reaction, institute in presence of hydrogen
The reaction temperature for stating the first hydrogenation reaction is 0-30 DEG C, and the reaction temperature of second hydrogenation reaction is 50-150 DEG C；
(3) solvent in the reaction product that removal step (2) obtains；
The hydrogenation catalyst has following general formula: M1 aM2 bXmLn, wherein M1For rhodium, M2For ruthenium, X is one in chlorine, bromine and hydrogen
Kind or it is a variety of, L is one of organic compound of organic single phosphine, organic double phosphines, organic cerium and nitrogenous, sulphur or oxygen or a variety of, 1
≤ a≤6,1≤b≤3,3≤m≤7,6≤n≤21；Or
The hydrogenation catalyst has following general formula: (RmA)zRhXn, wherein alkyl of each R independently selected from C1-C8,
The aralkyl of the naphthenic base 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.
2. according to the method described in claim 1, wherein, the condition of first hydrogenation reaction includes: that reaction temperature is 0-30
℃；Hydrogen Vapor Pressure is 0.05-15Mpa；Reaction time is 1-120 minutes.
3. according to the method described in claim 2, wherein, the condition of first hydrogenation reaction includes: that reaction temperature is 10-25
℃；Hydrogen Vapor Pressure is 1-5Mpa；Reaction time is 20-40 minutes.
4. according to the method described in claim 1, wherein, the condition of second hydrogenation reaction includes: that reaction temperature is 50-
150℃；Hydrogen Vapor Pressure is 0.1-15Mpa；Reaction time is 1-20 hours.
5. according to the method described in claim 4, wherein, the condition of second hydrogenation reaction includes: that reaction temperature is 80-
150℃；Hydrogen Vapor Pressure is 4-12Mpa；Reaction time is 4-16 hours.
6. method described in any one of -5 according to claim 1, wherein in step (1), the solid content of the NBR latex
For 0.5%-5%.
7. according to the method described in claim 6, wherein, the preparation method of the NBR latex includes: to be not more than to solid content
Organic solvent is added in 35% NBR latex, is configured to the NBR latex that solid content is 0.5%-5%；Alternatively,
The preparation method of the NBR latex includes: that water is added into NBR latex of the solid content greater than 35%, is configured to solid content
NBR latex no more than 35%, then to solid content no more than 35% NBR latex in organic solvent is added, be configured to solid content
For the NBR latex of 0.5%-5%.
8. according to the method described in claim 7, wherein, the solid content of NBR latex of the solid content no more than 35% is 2%-
15%。
9. method according to claim 7 or 8, wherein the organic solvent is aromatic hydrocarbons, aromatic hydrocarbons is replaced by alkyl or halogen
One of derivative, halogenated alkane, ketone and amide or a variety of.
10. according to the method described in claim 9, wherein, the organic solvent be benzene,toluene,xylene, chlorobenzene, dichloro-benzenes,
One of trichloro-benzenes, acetone, butanone and N,N-dimethylformamide are a variety of.
11. according to the method described in claim 10, wherein, the organic solvent is benzene,toluene,xylene, chlorobenzene, dichloro-benzenes
With the mixed solvent of one of trichloro-benzenes and one of acetone and butanone composition, the volume ratio of the two is 3:1-1:3.
12. method described in any one of -5 according to claim 1, wherein the NBR latex is acrylonitrile and methyl-prop
The binary NBR latex that one of alkene nitrile is formed with butadiene.
13. according to the method for claim 12, wherein the NBR latex is the binary fourth that butadiene and acrylonitrile are formed
Nitrile latex.
14. method described in any one of -5 according to claim 1, wherein the hydrogenation catalyst is (PPh3)3RhCl。
15. method described in any one of -5 according to claim 1, wherein M1For rhodium, M2For ruthenium, X is chlorine, and L is organic list
Phosphine.
16. according to the method for claim 15, wherein a:b:m:n 1-3:1:3-5:6-12.
17. according to the method for claim 16, wherein L is triphenylphosphine, a:b:m:n 3:1:5:12.
18. method described in any one of -5 according to claim 1, wherein the additional amount of the hydrogenation catalyst is described
The 0.01-5% of the quality of Solid content in NBR latex.
19. according to the method for claim 18, wherein the additional amount of the hydrogenation catalyst is solid in the NBR latex
The 0.05-1% of the quality of inclusion.
20. method described in any one of -5 according to claim 1, wherein the ligand be organic single phosphine, organic double phosphines,
One of organic compound of organic cerium and nitrogenous, sulphur or oxygen is a variety of.
21. according to the method for claim 20, wherein the ligand is organic single phosphine and/or organic double phosphines.
22. according to the method for claim 21, wherein the ligand is triphenylphosphine, bis- (diphenylphosphine) propane of 1,3-
At least one of with bis- (diphenyl phosphine) butane of 1,4-.
23. according to the method for claim 22, wherein the ligand is triphenylphosphine.
24. method described in any one of -5 according to claim 1, wherein the additional amount of the ligand is that described plus hydrogen is urged
1-20 times of agent quality.
25. according to the method for claim 24, wherein the additional amount of the ligand is the 4- of the hydrogenation catalyst quality
15 times.
26. method described in any one of -5 according to claim 1, wherein in step (1), it is additionally added auxiliary agent in mixing,
The auxiliary agent is aliphatic tertiary amine and/or aromatic series tertiary amine.
27. according to the method for claim 26, wherein the auxiliary agent is triethylamine and/or diisopropyl ethyl amine.
28. according to the method for claim 26, wherein the additional amount of the auxiliary agent is the hydrogenation catalyst quality
0.5-10 times.
29. according to the method for claim 28, wherein the additional amount of the auxiliary agent is the 1- of the hydrogenation catalyst quality
5 times.
30. according to the method for claim 27, wherein the additional amount of the auxiliary agent is the hydrogenation catalyst quality
0.5-10 times.
31. according to the method for claim 30, wherein the additional amount of the auxiliary agent is the 1- of the hydrogenation catalyst quality
5 times.
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|---|---|---|---|---|
| CN1167774A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of acrylonitrile-butadiene rubber |
| CN1199051A (en) * | 1997-05-08 | 1998-11-18 | 南帝化学工业股份有限公司 | Unsaturated copolymer hydrogenating method and bimetal containing catalyst system therefor |
| CN104271607A (en) * | 2012-04-28 | 2015-01-07 | 朗盛德国有限责任公司 | Hydrogenation of nitrile rubber |
| CN105175581A (en) * | 2015-09-25 | 2015-12-23 | 北京化工大学 | Preparation method for hydrophilic aminated hydrogenated butadiene-acrylonitrile rubber and prepared product |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167774A (en) * | 1997-04-22 | 1997-12-17 | 中国石油化工总公司 | Process for hydrogenation of acrylonitrile-butadiene rubber |
| CN1199051A (en) * | 1997-05-08 | 1998-11-18 | 南帝化学工业股份有限公司 | Unsaturated copolymer hydrogenating method and bimetal containing catalyst system therefor |
| CN104271607A (en) * | 2012-04-28 | 2015-01-07 | 朗盛德国有限责任公司 | Hydrogenation of nitrile rubber |
| CN105175581A (en) * | 2015-09-25 | 2015-12-23 | 北京化工大学 | Preparation method for hydrophilic aminated hydrogenated butadiene-acrylonitrile rubber and prepared product |
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