阅读说明：本技术 一种腈橡胶的协同催化加氢方法 (Cooperative catalytic hydrogenation method of nitrile rubber ) 是由 李跃辉 邓理 赵娇娇 陈娜娜 董亚楠 孙玉霞 李洋 于 2021-08-09 设计创作，主要内容包括：本发明涉及一种腈橡胶的协同催化加氢方法,该方法是指在浓度为1～10wt%的腈橡胶溶液中加入羰基金属化合物和主催化剂,于氢气气氛下反应,即得氢化腈橡胶。本发明所采用的羰基金属化合物具有催化加氢的性能,可以快速消除反应体系中大量的氰基、残存自由基、盐等杂质对于催化剂活性的负面影响,降低主催化剂(贵金属催化剂)的用量,有效提高贵金属催化剂的活性,从而降低腈橡胶的生产成本。(The invention relates to a synergetic catalytic hydrogenation method of nitrile rubber, which comprises the steps of adding a carbonyl metal compound and a main catalyst into a nitrile rubber solution with the concentration of 1-10 wt%, and reacting in a hydrogen atmosphere to obtain the hydrogenated nitrile rubber. The carbonyl metal compound adopted by the invention has the performance of catalytic hydrogenation, can quickly eliminate the negative influence of a large amount of impurities such as cyano-groups, residual free radicals, salts and the like in a reaction system on the activity of the catalyst, reduces the dosage of a main catalyst (noble metal catalyst), and effectively improves the activity of the noble metal catalyst, thereby reducing the production cost of nitrile rubber.)

1. A method for the concerted catalytic hydrogenation of nitrile rubber is characterized in that: the method comprises the steps of adding a metal carbonyl compound and a main catalyst into a nitrile rubber solution with the concentration of 1-10 wt%, reacting in a hydrogen atmosphere,obtaining hydrogenated nitrile rubber; the amount of the metal carbonyl compound is 1 x 10 of the mass of the nitrile rubber^-5~1×10^-2Doubling; the dosage of the main catalyst is 1 multiplied by 10 of the mass of the nitrile rubber^-5~1×10^-2And (4) doubling.

2. A process for the co-catalytic hydrogenation of nitrile rubber as in claim 1, wherein: the nitrile rubber solution with the concentration of 1-10 wt% is formed by dissolving nitrile rubber in an organic solvent and uniformly dissolving the nitrile rubber by ultrasonic.

3. A process for the co-catalytic hydrogenation of nitrile rubber as in claim 2, wherein: the nitrile rubber is nitrile rubber or valeronitrile rubber.

4. A process for the co-catalytic hydrogenation of nitrile rubber as in claim 2, wherein: the organic solvent is one of toluene, xylene, chlorobenzene and butanone.

5. A process for the co-catalytic hydrogenation of nitrile rubber as in claim 1, wherein: the metal carbonyl compound has the general formula M_x(CO)_yWherein the metal M is one of Mn, Fe, Co, Cr, Mo, Re and Ru, and x = 1-4 and y = 1-12.

6. A process for the co-catalytic hydrogenation of nitrile rubber as in claim 5, wherein: the metal carbonyl compound is MnBr (CO)₅、Mn₂(CO)₁₀、[Mn(CO)₆ ⁺][AlCl₄ ^-]、ReBr(CO)₅、Re₂(CO)₁₀、Mo(CO)₆、Cr(CO)₆、Fe(CO)₅、Fe₂(CO)₉、Fe₃(CO)₁₂、Na[HFe(CO)₄]、RuHCl(CO)(PPh₃)₂、Rh₄(CO)₁₂、RuCo₂(CO)₁₁、Co₂(CO)₈、NaCo(CO)₄、Ni(CO)₄、Na[HFe(CO)₄]One kind of (1).

7. A process for the co-catalytic hydrogenation of nitrile rubber as in claim 1, wherein: the main catalyst is RhCl (PPh)₃)₃、RuCl₂(PPh₃)₃Pd @ C and Raney nickel.

8. A process for the co-catalytic hydrogenation of nitrile rubber as in claim 1, wherein: the reaction conditions are that the hydrogen pressure is 0.5-10 MPa, the temperature is 30-190 ℃, and the reaction time is 1-96 h.

Technical Field

The invention relates to the field of polymer hydrogenation modification, in particular to a method for the concerted catalytic hydrogenation of nitrile rubber.

Background

The hydrogenated nitrile rubber is a product obtained by selectively hydrogenating nitrile rubber, and is a special rubber. The hydrogenated nitrile rubber keeps the oil resistance and the wear resistance of the nitrile rubber, has excellent heat resistance, weather resistance, oxygen resistance, thermal aging resistance and chemical corrosion resistance, has excellent comprehensive performance, and is widely applied to the automobile industry and the oil and gas industry. In current industrial production, hydrogenated nitrile rubber is prepared by catalytic hydrogenation of nitrile rubber, and a hydrogenation catalyst is the core of a hydrogenated nitrile rubber preparation technology.

At present, the solution hydrogenation method is the main method for the industrial production of hydrogenated nitrile rubber, and generally, nitrile rubber is dissolved and then is subjected to reduction hydrogenation under the action of a catalyst and hydrogen. The existing catalyst systems can be divided into RhCl (PPh)₃)₃Homogeneous noble metal catalysts represented by and heterogeneous noble metal catalysts represented by Pd @ C, and ziegler-type homogeneous non-noble metal catalysts. Because the nitrile rubber contains a large amount of cyano-groups, the cyano-groups can complex metal centers, so that the concentration of an active catalyst is reduced, and the dosage of the catalyst is higher. The use of a large amount of noble metal catalysts leads to high cost of hydrogenated nitrile rubber, and therefore, the reduction of the use cost of the catalysts is an important breakthrough in the research of the hydrogenated nitrile rubber. The same applies to valeronitrile rubber. In order to reduce the cost, patent CN107308985A discloses a hydrogenation catalyst using silica to support noble metal, which can realize the recovery of the catalyst. Patent US Patent 6207795 discloses a process for recovering catalyst by acid-base precipitation; patent USPatent 6646059 discloses a method for recovering catalyst by using ion exchange resin, but the consumption of noble metal catalyst is still one of the main reasons for the high cost of hydrogenated nitrile rubber.

Disclosure of Invention

The invention aims to provide a method for the concerted catalytic hydrogenation of nitrile rubber, which effectively reduces the cost.

In order to solve the problems, the invention provides a method for the concerted catalytic hydrogenation of nitrile rubber, which is characterized by comprising the following steps: adding a carbonyl metal compound and a main catalyst into a nitrile rubber solution with the concentration of 1-10 wt%, and reacting in a hydrogen atmosphere to obtain hydrogenated nitrile rubber; the amount of the metal carbonyl compound is 1 x 10 of the mass of the nitrile rubber^-5~1×10^-2Doubling; the dosage of the main catalyst is 1 multiplied by 10 of the mass of the nitrile rubber^-5~1×10^-2And (4) doubling.

The nitrile rubber solution with the concentration of 1-10 wt% is formed by dissolving nitrile rubber in an organic solvent and uniformly dissolving the nitrile rubber by ultrasonic.

The nitrile rubber is nitrile rubber or valeronitrile rubber.

The organic solvent is one of toluene, xylene, chlorobenzene and butanone.

The metal carbonyl compound has the general formula M_x(CO)_yWherein the metal M is one of Mn, Fe, Co, Cr, Mo, Re and Ru, and x = 1-4 and y = 1-12.

The metal carbonyl compound is MnBr (CO)₅、Mn₂(CO)₁₀、[Mn(CO)₆ ⁺][AlCl₄ ^-]、ReBr(CO)₅、Re₂(CO)₁₀、Mo(CO)₆、Cr(CO)₆、Fe(CO)₅、Fe₂(CO)₉、Fe₃(CO)₁₂、Na[HFe(CO)₄]、RuHCl(CO)(PPh₃)₂、Rh₄(CO)₁₂、RuCo₂(CO)₁₁、Co₂(CO)₈、NaCo(CO)₄、Ni(CO)₄、Na[HFe(CO)₄]One kind of (1).

The main catalyst is RhCl (PPh)₃)₃、RuCl₂(PPh₃)₃Pd @ C and Raney nickel (Raney nickel).

The reaction conditions are that the hydrogen pressure is 0.5-10 MPa, the temperature is 30-190 ℃, and the reaction time is 1-96 h.

Compared with the prior art, the invention has the following advantages:

1. the invention effectively improves the hydrogenation efficiency of nitrile rubber by adopting the synergistic effect of the metal carbonyl compound and the main catalyst.

2. The carbonyl metal compound adopted by the invention has the performance of catalytic hydrogenation, can quickly eliminate the negative influence of a large amount of impurities such as cyano-groups, residual free radicals, salts and the like in a reaction system on the activity of the catalyst, reduces the dosage of a main catalyst (noble metal catalyst), and effectively improves the activity of the noble metal catalyst, thereby reducing the production cost of nitrile rubber.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 shows the preparation of nitrile rubber¹H NMR spectrum.

FIG. 2 shows the preparation of hydrogenated nitrile rubbers according to the invention¹H NMR spectrum.

FIG. 3 shows the FT-IR spectrum of the nitrile rubber as the starting material.

FIG. 4 shows the FT-IR spectrum of a hydrogenated nitrile rubber according to the invention.

Detailed Description

A method for the concerted catalytic hydrogenation of nitrile rubber comprises the steps of adding a carbonyl metal compound and a main catalyst into a nitrile rubber solution with the concentration of 1-10 wt%, and reacting for 1-96 hours under the conditions of the pressure of 0.5-10 MPa and the temperature of 30-190 ℃ in a hydrogen atmosphere to obtain the hydrogenated nitrile rubber.

Wherein: the amount of the metal carbonyl compound is 1X 10 times the mass of the nitrile rubber^-5~1×10^-2Doubling; the dosage of the main catalyst is 1 multiplied by 10 of the mass of the nitrile rubber^-5~1×10^-2And (4) doubling.

The nitrile rubber solution with the concentration of 1-10 wt% is a solution formed by dissolving nitrile rubber in an organic solvent and uniformly dissolving the nitrile rubber by ultrasonic. Nitrile rubber means nitrile rubber or valeronitrile rubber. The organic solvent is one of toluene, xylene, chlorobenzene and butanone.

The metal carbonyl compound has the formula M_x(CO)_yWherein the metal M is one of Mn, Fe, Co, Cr, Mo, Re and Ru, and x = 1-4 and y = 1-12. The metal carbonyl compound is preferably MnBr (CO)₅、Mn₂(CO)₁₀、[Mn(CO)₆ ⁺][AlCl₄ ^-]、ReBr(CO)₅、Re₂(CO)₁₀、Mo(CO)₆、Cr(CO)₆、Fe(CO)₅、Fe₂(CO)₉、Fe₃(CO)₁₂、Na[HFe(CO)₄]、RuHCl(CO)(PPh₃)₂、Rh₄(CO)₁₂、RuCo₂(CO)₁₁、Co₂(CO)₈、NaCo(CO)₄、Ni(CO)₄、Na[HFe(CO)₄]One kind of (1).

The main catalyst is RhCl (PPh)₃)₃、RuCl₂(PPh₃)₃Pd @ C and Raney nickel.

Example 1 a process for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Fe₃(CO)₁₂1 ml of a solution containing 0.1 mg of RhCl (PPh) was added₃)₃Toluene solution (i.e. main catalyst RhCl (PPh)₃)₃The amount of the rubber is 1X 10 of the mass of the nitrile rubber^-4Doubling), and stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 9. The iodine number of the nitrile rubber feedstock is 305, i.e.The degree of hydrogenation of the hydrogenated nitrile rubber was 97%.

Wherein: the nitrile rubber solution of 5wt% is a solution prepared by dissolving 1 g of nitrile rubber in 19 g of chlorobenzene and dissolving the mixture uniformly by ultrasonic.

Of the resulting product¹An H NMR spectrum (see figure 2) and an FT-IR spectrum (see figure 4) are respectively compared with those of the raw material nitrile rubber¹Comparing the H NMR spectrum (see FIG. 1) with the FT-IR spectrum (see FIG. 3), it can be seen that: after hydrogenation reaction, the nuclear magnetic resonance signal of hydrogen on the carbon-carbon double bond at 5-6 ppm disappears, 970 cm^-1The infrared absorption peak at the carbon-carbon double bond disappeared, indicating that the carbon-carbon double bond was reduced by hydrogenation.

Comparative example a process for the co-catalytic hydrogenation of nitrile rubber (without addition of metal carbonyl compound):

a5 wt% nitrile rubber solution was added to a 50 ml autoclave, and 1 ml of a solution containing 0.1 mg of RhCl (PPh)₃)₃In toluene (i.e., RhCl (PPh)₃)₃The amount of the rubber is 1X 10 of the mass of the nitrile rubber^-4Doubling), and stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 88. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 71%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

As can be seen from the comparative examples, the addition of the metal carbonyl compound effectively increases the catalytic efficiency and increases the hydrogenation degree of the hydrogenated nitrile rubber.

Example 2 a method for the co-catalytic hydrogenation of nitrile rubber:

the 10wt% nitrile rubber solution was added to a 250 ml autoclave, and 1 ml of a solution containing 0.1 mg Fe was added₃(CO)₁₂To the toluene solution of (1 ml) was added 0.1 mg of RhCl (PPh)₃)₃(ii) toluene solution, (i.e. RhCl (PPh)₃)₃The amount of the rubber is 1X 10 of the mass of the nitrile rubber^-5Multiple times) stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then filling hydrogen into the high-pressure reaction kettle under the pressure of 10MPa, heating to control the reaction temperature to 190 ℃, and continuously stirring for reaction for 96 hours. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 27. The iodine value of the nitrile rubber feedstock is 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 91%.

Wherein: the nitrile rubber solution with 10wt% is a solution formed by dissolving 10 g of nitrile rubber in 90 g of chlorobenzene and dissolving uniformly by ultrasonic.

Example 3 a method for the co-catalytic hydrogenation of nitrile rubber:

adding 1wt% of nitrile rubber solution into a 250 ml high-pressure reaction kettle, and adding 10 mg of Fe₃(CO)₁₂With 10 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then filling hydrogen into the high-pressure reaction kettle under the pressure of 1 MPa, heating to control the reaction temperature to be 30 ℃, and continuously stirring for reaction for 1 hour. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 192. The iodine value of the nitrile rubber feedstock is 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 37%.

Wherein: the 1wt% nitrile rubber solution is a solution prepared by dissolving 1 g nitrile rubber in 99 g chlorobenzene and dissolving the mixture uniformly by ultrasonic.

Example 4 a method for the co-catalytic hydrogenation of nitrile rubber:

adding 5wt% nitrile rubber solution into 50 ml high-pressure reactor1 mg of Fe was added to the kettle₃(CO)₁₂With 0.5 mg of RuCl₂(PPh₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 88. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 71%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 5a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Fe₃(CO)₁₂And 5 mg of Pd @ C, and stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 101. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 67%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 6 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Fe₃(CO)₁₂And 5 mg of Raney nickel are stirred uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then filling hydrogen into the high-pressure reaction kettle under the pressure of 5 MPa, and heating to control the reactionThe reaction was continued at 140 ℃ with stirring for 24 hours. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 64. The iodine value of the nitrile rubber feedstock is 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 79%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 7 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of MnBr (CO)₅With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 31. The iodine value of the nitrile rubber feedstock is 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 90%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 8 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Mn₂(CO)₁₀With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane into the mixture,settling to obtain the target product with iodine value of 15. The iodine value of the nitrile rubber feedstock is 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 95%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 9 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Mn₂(CO)₁₀With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 25. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 92%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 10 a method for the co-catalytic hydrogenation of nitrile rubber:

5wt% nitrile rubber solution was charged into a 50 ml autoclave, to which 1 mg Fe (CO) was added₅With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 79. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 74%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 11 a process for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Fe₂(CO)₉With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 40. The iodine value of the nitrile rubber feedstock is 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 87%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 12 a process for the co-catalytic hydrogenation of nitrile rubber:

a5 wt% nitrile rubber solution was added to a 50 ml autoclave, to which was added 1 mg of RuHCl (CO) (PPh)₃)₂With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 116. The iodine value of the nitrile rubber feedstock is 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 62%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 13 a process for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Co₂(CO)₈And 0.5 mgRhCl(PPh₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 14 a process for the co-catalytic hydrogenation of nitrile rubber:

5wt% nitrile rubber solution was charged into a 50 ml autoclave, to which was added 1 mg of [ Mn (CO) ]₆ ⁺][AlCl₄ ^-]With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 15 a method for the co-catalytic hydrogenation of nitrile rubber:

5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg ReBr (CO)₅With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then filling hydrogen into the high-pressure reaction kettle under the pressure of 5 MPa, and heating to control the reactionThe reaction was continued at 140 ℃ with stirring for 24 hours. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 16 a process for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Re₂(CO)₁₀With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 17 a method for the co-catalytic hydrogenation of nitrile rubber:

5wt% nitrile rubber solution was charged to a 50 ml autoclave and 1 mg of Mo (CO) was added₆With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexaneAnd settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 18 a method for the co-catalytic hydrogenation of nitrile rubber:

5wt% nitrile rubber solution was charged into a 50 ml autoclave, to which 1 mg Cr (CO) was added₆With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 19 a method for the co-catalytic hydrogenation of nitrile rubber:

5wt% nitrile rubber solution was charged into a 50 ml autoclave, to which 1 mg Na [ HFe (CO)₄]With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 20 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Rh₄(CO)₁₂With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 21 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of RuCo₂(CO)₁₁With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 22 a method for the co-catalytic hydrogenation of nitrile rubber:

the nitrile rubber solution (5 wt%) was charged into a 50 ml autoclave, and 1 mg of NaCo (CO) was added₄With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 23 a process for the co-catalytic hydrogenation of nitrile rubber:

5wt% nitrile rubber solution was charged into a 50 ml autoclave, to which 1 mg of Ni (CO) was added₄With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 24 a method for the co-catalytic hydrogenation of nitrile rubber:

5wt% nitrile rubber solution was charged into a 50 ml autoclave, to which 1 mg Na [ HFe (CO)₄]With 0.5 mg of RhCl (PPh)₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then filling hydrogen into the high-pressure reaction kettle under the pressure of 5 MPa, heating to control the reaction temperature to be 140 ℃, and continuously stirring for 24 hours. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 139. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 54%.

Wherein: a5 wt.% nitrile rubber solution was prepared as in example 1.

Example 25 a method for the co-catalytic hydrogenation of nitrile rubber:

5wt% of valeronitrile rubber solution was added to a 50 ml autoclave, and 1 mg of Fe was added₃(CO)₁₂1 ml of a solution containing 0.1 mg of RhCl (PPh) was added₃)₃Toluene solution (i.e. main catalyst RhCl (PPh)₃)₃The amount of the rubber is 1X 10 of the mass of the nitrile rubber^-4Doubling), and stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 38. The iodine value of the starting material for the valeronitrile rubber is 296, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 87%.

Wherein: the 5wt% solution of valeronitrile rubber is a solution prepared by dissolving 1 g of valeronitrile rubber in 19 g of chlorobenzene and dissolving the resulting solution uniformly by sonication.

Example 26 a process for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Fe₃(CO)₁₂1 ml of a solution containing 0.1 mg of RhCl (PPh) was added₃)₃Toluene solution (i.e. main catalyst RhCl (PPh)₃)₃The amount of the rubber is 1X 10 of the mass of the nitrile rubber^-4Doubling), and stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then to the rearFilling hydrogen into the high-pressure reaction kettle under the pressure of 5 MPa, heating to control the reaction temperature to be 140 ℃, and continuously stirring for 24 hours. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 37. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 88%.

Wherein: the nitrile rubber solution with the weight percent of 5 is formed by dissolving 1 g of nitrile rubber in 19 g of toluene and uniformly dissolving by ultrasonic.

Example 27 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Fe₃(CO)₁₂1 ml of a solution containing 0.1 mg of RhCl (PPh) was added₃)₃Toluene solution (i.e. main catalyst RhCl (PPh)₃)₃The amount of the rubber is 1X 10 of the mass of the nitrile rubber^-4Doubling), and stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 19. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 94%.

Wherein: the nitrile rubber solution with the weight percent of 5 is formed by dissolving 1 g of nitrile rubber in 19 g of dimethylbenzene and uniformly dissolving by ultrasonic.

Example 28 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 50 ml high-pressure reaction kettle, and adding 1 mg of Fe₃(CO)₁₂1 ml of a solution containing 0.1 mg of RhCl (PPh) was added₃)₃Toluene solution (i.e. main catalyst RhCl (PPh)₃)₃The amount of the rubber is 1X 10 of the mass of the nitrile rubber^-4Doubling), and stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 162. The iodine value of the nitrile rubber feedstock was 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber was 47%.

Wherein: the nitrile rubber solution with the weight percent of 5 is formed by dissolving 1 g of nitrile rubber in 19 g of butanone and uniformly dissolving by ultrasonic.

Example 29 a method for the co-catalytic hydrogenation of nitrile rubber:

adding a nitrile rubber solution with the concentration of 5wt% into a 500 ml high-pressure reaction kettle, and adding 10 mg of Fe₃(CO)₁₂1 mg of RhCl (PPh) was added₃)₃And stirring uniformly. The autoclave was purged with 1 MPa of nitrogen to displace the air in the autoclave and repeated 3 times. Then, hydrogen gas is filled into the high-pressure reaction kettle under the pressure of 5 MPa, the reaction temperature is controlled by heating to 140 ℃, and the reaction time is 24 hours with continuous stirring. And after the reaction time is reached, cooling the high-pressure reaction kettle to room temperature, slowly opening an air release valve, reducing the pressure to normal pressure, opening the reaction kettle, and taking out the reaction mixture. Adding a poor solvent n-hexane, and settling to obtain a target product, wherein the iodine value of the product is 12. The iodine value of the nitrile rubber feedstock is 305, i.e. the degree of hydrogenation of the hydrogenated nitrile rubber is 96%.

Wherein: the nitrile rubber solution of 5wt% is a solution prepared by dissolving 10 g of nitrile rubber in 200 g of chlorobenzene and dissolving the nitrile rubber uniformly by ultrasonic.