CN115703848A - Hydrogenated nitrile rubber and preparation method thereof - Google Patents
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Abstract
The invention discloses hydrogenated nitrile rubber and a preparation method thereof. Adding an organic solvent, a free radical initiator, a butadiene monomer and an acrylonitrile monomer into a polymerization kettle under anhydrous and anaerobic conditions, carrying out polymerization reaction to obtain solution polymerized nitrile-butadiene rubber glue solution, and carrying out hydrogenation reaction on the solution polymerized nitrile-butadiene rubber glue solution to obtain hydrogenated nitrile-butadiene rubber. The method can realize the controllable regulation of the acrylonitrile content and the molecular weight in the nitrile rubber by utilizing a solution polymerization technology, simultaneously adopts a metallocene catalytic hydrogenation technology, can realize high-selectivity and high-efficiency hydrogenation, has the characteristics of low catalyst cost, mild hydrogenation reaction conditions, controllable hydrogenation degree and the like, solves the technical problems of high cost and the like of the existing hydrogenated nitrile hydrogenation catalyst, can directly use the solution polymerized nitrile rubber for hydrogenation, and solves the problems of unstable nitrile rubber precursor product batch, complex nitrile rubber sol treatment process, large solvent treatment capacity and the like in hydrogenation.
Description
Technical Field
The invention relates to hydrogenated nitrile rubber and a preparation method thereof, in particular to hydrogenated nitrile rubber with controllable acrylonitrile content, molecular weight and hydrogenation degree and narrow molecular weight distribution, and also relates to a method for realizing hydrogenation of nitrile rubber by using a non-noble metal catalyst system, belonging to the technical field of preparation of hydrogenated nitrile rubber.
Background
Hydrogenated nitrile rubber (HNBR) is an elastomeric material with excellent overall properties. It has good oil resistance, ozone aging resistance, chemical medium resistance and excellent physical and mechanical properties, so that it is widely used in the fields of automobile industry, oil field drilling and aerospace. At present, the main processes for the preparation of hydrogenated nitrile rubbers are homogeneous and heterogeneous solution hydrogenation processes.
The catalyst commonly used in the homogeneous solution hydrogenation method is a transition metal complex of a VIII family, mainly comprising noble metal complexes of rhodium, palladium, ruthenium, iridium, osmium and the like, and has the greatest advantages of high activity and high selectivity. RhCl (PPh) was studied by Bhattachaijee 3 ) 3 The best process condition for NBR hydrogenation is that in chlorobenzene solvent, the concentration of the catalyst is 0.02mmol, the pressure of hydrogen is 5.6MPa, the temperature is 100 ℃, the reaction is carried out for 11 hours, the hydrogenation degree can reach 100 percent, and the defects of (1) high cost of the catalyst and difficult recovery are existed; (2) the reaction conditions are harsh, and the required time is long; (3) it is difficult to realize in industrialization. Hsu partially replaces expensive rhodium with low-cost ruthenium, and adopts a bimetallic catalytic system to hydrogenate NBR, when the molar ratio of rhodium to ruthenium is 4. Although the reaction conditions are improved, milder, haveThe industrialization prospect, but the difficult problem of catalyst recovery still can not be solved.
Heterogeneous hydrogenation is emulsion hydrogenation, and the method has the characteristics of few process steps, low cost, environmental protection, energy conservation and the like. The Remple subject group invented a new method for hydrogenating NBR latex, which uses RCl (PPh) without pretreatment and additional organic solvent to promote the dissolution of catalyst 3 ) 3 As main catalyst, PPh 3 As a cocatalyst system, the hydrogenation degree can reach 95% at 145 ℃ and 6.8MPa of hydrogen pressure, but the biggest defect of the technology is that the hydrogenation efficiency is very low, and further development of the research is limited. Other hydrogenation technologies have the defects of low hydrogenation degree, low reaction efficiency, large catalyst usage amount and the like. In addition, regardless of homogeneous or heterogeneous hydrogenation, NBR hydrogenation is performed by using a noble metal complex as a catalyst, and catalyst recovery is a technical bottleneck and is difficult to break through. The catalyst recovery generally adopts a precipitation method and an adsorption method, and for the precipitation method, an additive used for precipitating the catalyst cannot be completely removed and can be brought into a product HNBR to pollute a final finished product, particularly for a high-viscosity HNBR solution; the adsorption method requires a large amount of resin, involves related recovery and resin activation operations, greatly prolongs the whole treatment time, causes cost increase, and generally causes environmental pollution by adopting landfill or discarding in the open after the resin is used up.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide the hydrogenated nitrile rubber with controllable acrylonitrile content, molecular weight and hydrogenation degree and narrow molecular weight distribution, the acrylonitrile content, the molecular weight and the hydrogenation degree of the hydrogenated nitrile rubber can be designed according to application requirements, and rubber products with excellent oil resistance and heat resistance can be prepared and widely applied to the fields of national defense, aerospace, automobiles, petroleum, medical treatment and the like.
The second purpose of the invention is to provide a preparation method of hydrogenated nitrile rubber, the method can realize the controllable adjustment of the acrylonitrile content and the molecular weight in the nitrile rubber by using a solution polymerization technology, simultaneously adopts a metallocene catalytic hydrogenation technology which is completely different from a traditional noble metal catalytic system, can realize high-selectivity and high-efficiency hydrogenation, has the characteristics of low catalyst cost, mild hydrogenation reaction conditions, wide hydrogenation degree control range and the like, solves the technical problems of high cost and the like of the existing hydrogenated nitrile hydrogenation catalyst, directly uses the solution polymerized nitrile rubber for hydrogenation, and solves the problems of unstable nitrile rubber precursor product batch adopted for hydrogenation, complex nitrile rubber sol process, large solvent treatment capacity and the like.
In order to realize the technical purpose, the invention provides a preparation method of hydrogenated nitrile-butadiene rubber, which comprises the steps of adding an organic solvent, a free radical initiator, a butadiene monomer and an acrylonitrile monomer into a polymerization kettle under anhydrous and anaerobic conditions, carrying out polymerization reaction to obtain solution polymerized nitrile-butadiene rubber glue solution, and carrying out hydrogenation reaction on the solution polymerized nitrile-butadiene rubber glue solution to obtain the hydrogenated nitrile-butadiene rubber.
In a preferred embodiment, the organic solvent is at least one of toluene, ethylbenzene, xylene, chlorobenzene, trifluorotoluene, dichlorobenzene, acetone, and ethyl acetate. The organic solvent is preferably at least one of toluene, ethylbenzene and xylene; toluene is most preferred.
As a preferred embodiment, the radical initiator is azobisisobutyronitrile and/or dibenzoyl peroxide.
As a preferable embodiment, the ratio of the molar amount of the radical initiator to the total molar amount of the butadiene monomer and the acrylonitrile monomer is 1/200 to 1/10000. The molecular weight of the nitrile rubber can be effectively regulated and controlled by controlling the dosage of the free radical initiator. The ratio of the molar amount of the radical initiator to the total molar amount of the butadiene monomer and the acrylonitrile monomer is more preferably 1/500 to 1/5000.
As a preferable scheme, the ratio of the total volume of the butadiene monomer and the acrylonitrile monomer to the volume of the organic solvent is 20-60% to 40-80%.
The technical scheme of the invention selects benign solvent and controls proper solvent dosage, which not only can fully dissolve butadiene monomer and acrylonitrile monomer to realize uniform liquid phase polymerization, but also can fully dissolve the generated nitrile-butadiene rubber polymer chain in the solvent, so that the nitrile-butadiene rubber polymer chain can be fully stretched in the solvent, thereby fully exposing the living radical polymerization end, keeping higher chain growth activity, improving polymerization efficiency and obtaining higher molecular weight.
As a preferable embodiment, the molar ratio of the butadiene monomer to the acrylonitrile monomer is 8/2 to 2/8. The molar ratio of the butadiene monomer to the acrylonitrile monomer is 6/4 to 4/6.
As a preferable scheme, the temperature of the polymerization reaction is 50-100 ℃, and the time is 2-48 h. The preferred polymerization conditions are: the temperature is 60-80 ℃, and the time is 12-24 h. The conversion rate of the butadiene monomer and the acrylonitrile monomer can be controlled between 30 and 75 percent by controlling the reaction conditions.
As a preferable scheme, the mass percent content of acrylonitrile in the solution polymerized nitrile-butadiene rubber is 15-50%, the number average molecular weight is 2-20 ten thousand, the molecular weight distribution is less than or equal to 2.5, and the branched chain content of polybutadiene units is 15-25%.
As a preferred scheme, the process of the hydrogenation reaction of the solution of the polymerized nitrile-butadiene rubber comprises the following steps: after removing residual butadiene monomer and acrylonitrile from the solution of the polymerized nitrile butadiene rubber through stepwise distillation, adding an organic solvent to form a solution of the polymerized nitrile butadiene rubber; firstly adding alkyl lithium and introducing hydrogen into a solution of the solution polymerized nitrile butadiene rubber, then adding a hydrogenation catalytic system and introducing hydrogen, and carrying out hydrogenation reaction to obtain hydrogenated nitrile butadiene rubber; <xnotran> , . </xnotran>
As a preferred scheme, the mass percent concentration of the solution polymerized nitrile-butadiene rubber in the solution polymerized nitrile-butadiene rubber is 5-15%. The hydrogenation efficiency can be improved by fully dissolving and dispersing the solution-polymerized nitrile rubber to a certain concentration.
As a preferable scheme, the hydrogenation catalyst system consists of a main catalyst and a cocatalyst; the cocatalyst comprises at least one of dimethyl phthalate, methyl o-benzoate and isooctanol; the main catalyst comprises at least one of dicyclopentadiene titanium dichloride, dicyclopentadiene cobalt dichloride, dicyclopentadiene nickel dichloride and nickel isooctanoate. The preferable catalyst system has high hydrogenation selectivity, can hydrogenate carbon-carbon double bonds with high selectivity, and the hydrogenation degree is easy to control.
As a preferable scheme, the hydrogenation catalyst system consists of a main catalyst and a cocatalyst according to a molar ratio of 0.1-1.
As a preferable scheme, the adding amount of the hydrogenation catalyst system in the solution of the solution polymerized nitrile-butadiene rubber is measured by adding 5-80 mmol of main catalyst into each kilogram of dry solution polymerized nitrile-butadiene rubber.
As a preferred embodiment, the alkyl lithium comprises butyl lithium and/or secondary lithium. The lithium alkyl is primarily used as a reducing agent to form the active sites of the catalyst.
As a preferable scheme, the addition amount of the alkyl lithium in the solution of the solution polymerized nitrile butadiene rubber is 9 to 15 times of the molar amount of the main catalyst in the hydrogenation catalyst system.
As a preferable scheme, the initial temperature of the hydrogenation reaction is 70-85 ℃, the pressure is 1-3 MPa, and the time is 120-480 min. The hydrogenation degree of the solution polymerized nitrile rubber can be effectively controlled by controlling the hydrogenation reaction conditions, the dosage of a hydrogenation catalytic system and the like, for example, the hydrogenation degree is controlled between 30 and 97 percent.
The invention also provides hydrogenated nitrile rubber which is obtained by the preparation method.
As a preferable scheme, the number average molecular weight of the hydrogenated nitrile rubber is 2-20 ten thousand g/mol, the molecular weight distribution is less than or equal to 2.5, and the hydrogenation degree is 30-97%.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the technical scheme of the invention adopts a solution polymerization technology to realize the controllable regulation of the acrylonitrile content and the molecular weight in the nitrile rubber, simultaneously adopts a metallocene catalytic hydrogenation technology which is completely different from a traditional noble metal catalytic system, can realize the high-selectivity and high-efficiency hydrogenation of the nitrile rubber, can realize the arbitrary regulation and control of the acrylonitrile content of the hydrogenated nitrile rubber within the range of 15-50 percent, has the number average molecular weight of 2-20 ten thousand g/mol, has the molecular weight distribution of less than or equal to 2.5, has narrower distribution and the hydrogenation degree of 30-97 percent, can design the molecular weight, the hydrogenation degree, the acrylonitrile content and the like of the hydrogenated nitrile rubber according to the application requirements, and the prepared hydrogenated nitrile rubber has great application prospects as a rubber product with excellent oil resistance and heat resistance in the fields of national defense, aerospace, automobiles, petroleum, medical treatment and the like.
The hydrogenation technology adopted by the technical scheme of the invention mainly uses a non-noble metal catalyst system, has the characteristics of low cost, mild hydrogenation reaction conditions, wide hydrogenation degree control range and the like, and solves the defects of high cost and the like of the existing hydrogenated butyronitrile hydrogenation catalyst.
The technical scheme of the invention adopts a solution polymerization system to obtain solution-polymerized nitrile rubber, and the rubber solution directly enters the hydrogenation process through separation, so that the process is simple, and the problems of unstable nitrile rubber precursor product batch for hydrogenation, complex nitrile rubber sol process, large solvent treatment capacity and the like in the prior art are solved.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of the solution polymerized nitrile rubber raw rubber obtained in example 1.
FIG. 2 shows the NMR spectra of the hydrogenated nitrile rubber obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited by the examples.
The acrylonitrile content of hydrogenated butyronitrile, the branched chain content of polybutadiene units and the degree of hydrogenation in the following examples were measured by nuclear magnetic hydrogen spectroscopy (1H-NMR), and the specific test conditions were as follows: deuterated chloroform is used as a solvent, and the scanning times are 4 times/s.
The molecular weight and molecular weight distribution of the hydrogenated nitrile rubber were determined by Gel Permeation Chromatography (GPC).
Example 1
1000ml of toluene, 1.0g of azobisisobutyronitrile, 450ml of acrylonitrile and 600ml of butadiene were added in this order to a 5-liter polymerization vessel under a nitrogen atmosphere, and the reaction was stirred at 70 ℃ for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the glue solution was introduced into a 5L hydrogenation reactor. Adding 0.1mol of butyllithium at 75 ℃, introducing a certain amount of hydrogen, then adding 5.4mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 1.2g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 120min under the reaction pressure of 1.2MPa to obtain the hydrogenated nitrile rubber.
Example 2
1000ml of toluene, 1.0g of azobisisobutyronitrile, 450ml of acrylonitrile and 600ml of butadiene were added in this order to a 5-liter polymerization vessel under a nitrogen atmosphere, and the reaction was stirred at 70 ℃ for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the gum solution was introduced into a 5L hydrogenation reactor. Adding 0.1mol of butyl lithium at 75 ℃, introducing a certain amount of hydrogen, then adding 5.4mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 1.2g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 120min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile rubber.
Example 3
1000ml of toluene, 1.0g of azobisisobutyronitrile, 450ml of acrylonitrile and 600ml of butadiene were sequentially charged into a 5-liter polymerization vessel under a nitrogen atmosphere, and charged into a 5-liter hydrogenation vessel. Adding 0.1mol of butyllithium at 75 ℃, introducing a certain amount of hydrogen, then adding 5.4mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 1.2g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile rubber.
Example 4
1000ml of toluene, 1.0g of azobisisobutyronitrile, 450ml of acrylonitrile and 600ml of butadiene were added in this order to a 5-liter polymerization vessel under a nitrogen atmosphere, and the reaction was stirred at 70 ℃ for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the glue solution was introduced into a 5L hydrogenation reactor. Adding 0.2mol of butyllithium at 75 ℃, introducing a certain amount of hydrogen, then adding 7.2mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 2.3g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile rubber.
Example 5
1000ml of toluene, 1.0g of azobisisobutyronitrile, 450ml of acrylonitrile and 600ml of butadiene were added in this order to a 5-liter polymerization vessel under a nitrogen atmosphere, and the reaction was stirred at 70 ℃ for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the glue solution was introduced into a 5L hydrogenation reactor. Adding 0.3mol of butyllithium at 75 ℃, introducing a certain amount of hydrogen, then adding 8.4mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 4.6g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile rubber.
Example 6
1000ml of toluene, 0.7g of azobisisobutyronitrile, 450ml of acrylonitrile and 600ml of butadiene were successively added to a 5-liter polymerization vessel under a nitrogen atmosphere, and reacted at 70 ℃ with stirring for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the glue solution was introduced into a 5L hydrogenation reactor. Adding 0.3mol of butyl lithium at 75 ℃, introducing a certain amount of hydrogen, then adding 8.4mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 4.6g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile-butadiene rubber.
Example 7
1000ml of toluene, 0.5g of azobisisobutyronitrile, 450ml of acrylonitrile and 600ml of butadiene were added in this order to a 5-liter polymerization vessel under a nitrogen atmosphere, and the reaction was stirred at 70 ℃ for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the gum solution was introduced into a 5L hydrogenation reactor. Adding 0.3mol of butyllithium at 75 ℃, introducing a certain amount of hydrogen, then adding 8.4mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 4.6g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile rubber.
Example 8
1000ml of toluene, 0.7g of azobisisobutyronitrile, 350ml of acrylonitrile and 800ml of butadiene were successively added to a 5-liter polymerization vessel under a nitrogen atmosphere, and reacted at 70 ℃ with stirring for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the gum solution was introduced into a 5L hydrogenation reactor. Adding 0.3mol of butyllithium at 75 ℃, introducing a certain amount of hydrogen, then adding 8.4mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 4.6g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile rubber.
Example 9
1000ml of toluene, 0.7g of azobisisobutyronitrile, 250ml of acrylonitrile and 800ml of butadiene were successively added to a 5-liter polymerization vessel under a nitrogen atmosphere, and reacted at 70 ℃ with stirring for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the glue solution was introduced into a 5L hydrogenation reactor. Adding 0.3mol of butyl lithium at 75 ℃, introducing a certain amount of hydrogen, then adding 8.4mmol of dimethyl phthalate as a cocatalyst, fully and uniformly stirring, adding 4.6g of dicyclopentadiene titanium dichloride as a main catalyst, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile rubber.
Example 10
1000ml of toluene, 0.7g of azobisisobutyronitrile, 350ml of acrylonitrile and 800ml of butadiene were successively added to a 5-liter polymerization vessel under a nitrogen atmosphere, and reacted at 70 ℃ with stirring for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the gum solution was introduced into a 5L hydrogenation reactor. At 85 ℃, then adding 2.7mmol of isooctanol, fully stirring uniformly, adding 5.4mmol of nickel isooctanoate as a main catalyst, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile-butadiene rubber.
Example 11
1000ml of toluene, 0.7g of azobisisobutyronitrile, 350ml of acrylonitrile and 800ml of butadiene were added in this order to a 5-liter polymerization vessel under a nitrogen atmosphere, and the reaction was stirred at 70 ℃ for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the gum solution was introduced into a 5L hydrogenation reactor. At 85 ℃, adding 5.4mmol of isooctanol, fully and uniformly stirring, adding 5.4mmol of main catalyst nickel isooctanoate, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile-butadiene rubber.
Example 12
1000ml of toluene, 0.7g of azobisisobutyronitrile, 350ml of acrylonitrile and 800ml of butadiene were successively added to a 5-liter polymerization vessel under a nitrogen atmosphere, and reacted at 70 ℃ with stirring for 24 hours. After the polymerization reaction, unreacted monomers were distilled off, and then the gum solution was introduced into a 5L hydrogenation reactor. At 85 ℃, adding 5.4mmol of isooctanol, fully and uniformly stirring, adding 8.2mmol of main catalyst nickel isooctanoate, introducing hydrogen, and reacting for 240min under the reaction pressure of 2.0MPa to obtain the hydrogenated nitrile-butadiene rubber.
The results of the structural parameter tests for the hydrogenated butyronitriles of examples 1 to 12 are given in the following table:
Claims (16)
1. a preparation method of hydrogenated nitrile rubber is characterized by comprising the following steps: adding an organic solvent, a free radical initiator, a butadiene monomer and an acrylonitrile monomer into a polymerization kettle under anhydrous and anaerobic conditions, carrying out polymerization reaction to obtain solution polymerized nitrile-butadiene rubber glue solution, and carrying out hydrogenation reaction on the solution polymerized nitrile-butadiene rubber glue solution to obtain the product.
2. A process for the preparation of a hydrogenated nitrile rubber according to claim 1, wherein: the organic solvent is at least one of toluene, ethylbenzene, xylene, chlorobenzene, trifluorotoluene, dichlorobenzene, acetone and ethyl acetate.
3. A process for the preparation of a hydrogenated nitrile rubber according to claim 1, wherein: the free radical initiator is azobisisobutyronitrile and/or dibenzoyl peroxide.
4. A process for the preparation of a hydrogenated nitrile rubber according to any of the claims 1 to 3, wherein: the ratio of the molar weight of the free radical initiator to the total molar weight of the butadiene monomer and the acrylonitrile monomer is 1/200-1/10000;
the volume ratio of the total volume of the butadiene monomer and the acrylonitrile monomer to the organic solvent is 20-60 percent to 40-80 percent;
the molar ratio of the butadiene monomer to the acrylonitrile monomer is 8/2 to 2/8.
5. A process for the preparation of a hydrogenated nitrile rubber according to claim 1, wherein: the temperature of the polymerization reaction is 50-100 ℃, and the time is 2-48 h.
6. A process for the preparation of a hydrogenated nitrile rubber according to claim 1, wherein: the mass percentage content of acrylonitrile in the solution polymerized nitrile-butadiene rubber is 15-50%, the number average molecular weight is 2-20 ten thousand, the molecular weight distribution is less than or equal to 2.5, and the branched chain content of polybutadiene units is 15-25%.
7. A process for the preparation of a hydrogenated nitrile rubber according to claim 1, wherein: the hydrogenation reaction process of the solution polymerized nitrile rubber glue solution comprises the following steps: after removing residual butadiene monomer and acrylonitrile from the solution of the polymerized nitrile butadiene rubber through stepwise distillation, adding an organic solvent to form a solution of the polymerized nitrile butadiene rubber; firstly adding alkyl lithium and introducing hydrogen into a solution of the solution polymerized nitrile butadiene rubber, then adding a hydrogenation catalytic system and introducing hydrogen, and carrying out hydrogenation reaction to obtain hydrogenated nitrile butadiene rubber; <xnotran> , . </xnotran>
8. A process for the preparation of a hydrogenated nitrile rubber according to claim 7, wherein: the mass percentage concentration of the solution polymerized nitrile-butadiene rubber in the solution is 5-15%.
9. A process for the preparation of a hydrogenated nitrile rubber according to claim 1, wherein: the hydrogenation catalytic system consists of a main catalyst and a cocatalyst; the cocatalyst comprises at least one of dimethyl phthalate, methyl o-benzoate and isooctyl alcohol; the main catalyst comprises at least one of dicyclopentadiene titanium dichloride, dicyclopentadiene cobalt dichloride, dicyclopentadiene nickel dichloride and nickel isooctanoate.
10. A process for the preparation of a hydrogenated nitrile rubber according to claim 9, wherein: the hydrogenation catalyst system consists of a main catalyst and an auxiliary catalyst according to a molar ratio of 0.1-1.
11. A process for the preparation of a hydrogenated nitrile rubber according to claim 9 or 10, wherein: the adding amount of the hydrogenation catalyst system in the solution of the solution polymerized nitrile-butadiene rubber is measured by adding 5 to 80mmol of main catalyst into each kilogram of dry solution polymerized nitrile-butadiene rubber.
12. A process for the preparation of a hydrogenated nitrile rubber according to claim 7, wherein: the alkyl lithium includes butyl lithium and/or secondary lithium.
13. A process for the preparation of a hydrogenated nitrile rubber according to claim 7, wherein: the alkyl lithium in solution polymerized butyronitrile the addition amount of the rubber solution is the molar weight of the main catalyst in the hydrogenation catalyst system is 9-15 times.
14. A process for the preparation of a hydrogenated nitrile rubber according to claim 7, wherein: the initial temperature of the hydrogenation reaction is 70-85 ℃, the pressure is 1-3 MPa, and the time is 120-480 min.
15. A hydrogenated nitrile rubber characterized by: the method according to any one of claims 1 to 14.
16. A hydrogenated nitrile rubber according to claim 15, characterised in that: the number average molecular weight is 2-20 ten thousand g/mol, the molecular weight distribution is less than or equal to 2.5, and the hydrogenation degree is 30-97%.
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- 2021-08-04 CN CN202110892746.8A patent/CN115703848A/en active Pending
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| US4501857A (en) * | 1983-01-20 | 1985-02-26 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for hydrogenation of polymer |
| US4673714A (en) * | 1984-04-18 | 1987-06-16 | Asahi Kasei Kogyo Kabushiki Kaisha | Olefin hydrogenation catalyst, process for hydrogenating polymers with the catalyst, and hydrogenated block copolymers produced by said processes |
| CN1166498A (en) * | 1997-05-23 | 1997-12-03 | 巴陵石油化工公司岳阳石油化工总厂 | Selective hydrogenation method for conjugated dienes polymer |
| US6951906B1 (en) * | 1998-08-03 | 2005-10-04 | Korea Kumho Petrochemical Co., Ltd. | Process for hydrogenating a conjugated diene polymer |
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