CN113583155B - Cooperative catalytic hydrogenation method of nitrile rubber - Google Patents

Abstract

The invention relates to a method for synergistic catalytic hydrogenation of nitrile rubber. The method refers to adding metal carbonyl compounds and a main catalyst to a nitrile rubber solution with a concentration of 1-10 wt% and reacting in a hydrogen atmosphere to obtain hydrogenated nitrile rubber. The carbonyl metal compound used in the present invention has the performance of catalytic hydrogenation, can quickly eliminate the negative impact of a large number of cyano groups, residual free radicals, salts and other impurities in the reaction system on the catalyst activity, reduce the amount of the main catalyst (precious metal catalyst), Effectively improve the activity of precious metal catalyst, thereby reducing the production cost of nitrile rubber.

Description

A kind of synergistic catalytic hydrogenation method of nitrile rubber

technical field

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

Background technique

Hydrogenated nitrile rubber is the product of selective hydrogenation of nitrile rubber, which is a kind of special rubber. Hydrogenated nitrile rubber retains the oil resistance and wear resistance of nitrile rubber, and also has excellent heat resistance, weather resistance, oxygen resistance, heat aging resistance and chemical corrosion resistance. It has excellent comprehensive properties and is widely used in the automotive industry and oil and gas. industry. In the current industrial production, hydrogenated nitrile rubber is prepared by catalytic hydrogenation of nitrile rubber, and the hydrogenation catalyst is the core of the preparation technology of hydrogenated nitrile rubber.

At present, the solution hydrogenation method is the main method for the industrial production of hydrogenated nitrile rubber. This method is generally to first dissolve the nitrile rubber, and then perform reductive hydrogenation under the action of catalyst and hydrogen. The existing catalyst systems can be divided into homogeneous noble metal catalysts represented by RhCl(PPh ₃ ) ₃ , heterogeneous noble metal catalysts represented by Pd@C, and Ziegler-type homogeneous non-precious metal catalysts. Since nitrile rubber contains a large amount of cyano groups, the cyano groups can complex the metal center, resulting in a decrease in the concentration of active catalyst and a higher amount of catalyst. The large-scale use of precious metal catalysts keeps the cost of hydrogenated nitrile rubber high. Therefore, reducing the cost of catalyst use is an important breakthrough in the research of hydrogenated nitrile rubber. The same applies to valeronitrile rubber. In order to reduce the cost, patent CN107308985A discloses a hydrogenation catalyst using silica-supported precious metal, which can realize the recovery of the catalyst. Patent US Patent 6207795 discloses a method for recovering catalyst by using acid-base precipitation; Patent US Patent 6646059 discloses a method for recovering catalyst by using ion exchange resin, but the consumption of precious metal catalyst is still the main reason for the high cost of hydrogenated nitrile rubber one of the reasons.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a synergistic catalytic hydrogenation method of nitrile rubber which can effectively reduce the cost.

In order to solve the above problems, the method for synergistic catalytic hydrogenation of nitrile rubber according to the present invention is characterized in that: the method refers to adding metal carbonyl compound and main catalyst to the nitrile rubber solution with a concentration of 1 to 10 wt %, The hydrogenated nitrile rubber is obtained by reacting in a hydrogen atmosphere; the amount of the carbonyl metal compound is 1×10 ^-5 to 1×10 ^-2 times the mass of the nitrile rubber; the amount of the main catalyst is 1×10 the mass of the nitrile rubber. ^-5 ~1×10 ^-2 times.

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

The nitrile rubber refers to nitrile rubber or valer nitrile rubber.

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

The general formula of the metal carbonyl compound is M _x (CO) _y , wherein metal M refers to one of Mn, Fe, Co, Cr, Mo, Re, and Ru, and x=1~4, y=1~ 12.

The metal carbonyl compound refers to MnBr(CO) ₅ , Mn ₂ (CO) ₁₀ , [Mn(CO) ₆ ⁺ ][AlCl ₄ ⁻ ], ReBr(CO) ₅ , Re ₂ (CO) ₁₀ , Mo(CO ) ₆ , Cr(CO) ₆ , Fe(CO) ₅ , Fe ₂ (CO) ₉ , Fe ₃ (CO) ₁₂ , Na[HFe(CO) ₄ ], RuHCl(CO)(PPh ₃ ) ₂ , Rh ₄ One of (CO) ₁₂ , RuCo ₂ (CO) ₁₁ , Co ₂ (CO) ₈ , NaCo(CO) ₄ , Ni(CO) ₄ , and Na[HFe(CO) ₄ ].

The main catalyst refers to one of RhCl(PPh ₃ ) ₃ , RuCl ₂ (PPh ₃ ) ₃ , Pd@C, and Raney nickel.

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

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

1. The present invention adopts the synergistic effect of carbonyl metal compound and main catalyst to effectively improve the hydrogenation efficiency of nitrile rubber.

2. The metal carbonyl compound used in the present invention has the performance of catalytic hydrogenation, which can quickly eliminate the negative impact of a large number of cyano groups, residual free radicals, salts and other impurities in the reaction system on the catalyst activity, and reduce the main catalyst (precious metal catalyst). The dosage can effectively improve the activity of the precious metal catalyst, thereby reducing the production cost of nitrile rubber.

Description of drawings

The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

Figure 1 is the ¹ H NMR spectrum of the raw nitrile rubber.

Fig. 2 is the ¹ H NMR spectrum of the hydrogenated nitrile rubber of the present invention.

Figure 3 is the FT-IR spectrum of the raw nitrile rubber.

Fig. 4 is the FT-IR spectrogram of the hydrogenated nitrile rubber of the present invention.

Detailed ways

A method for synergistic catalytic hydrogenation of nitrile rubber. The method refers to adding metal carbonyl compounds and a main catalyst to a nitrile rubber solution with a concentration of 1 to 10 wt %, and in a hydrogen atmosphere, the pressure is 0.5-10 MPa and the temperature is 30- The hydrogenated nitrile rubber is obtained by reacting at 190°C for 1~96h.

Among them: the amount of metal carbonyl compound is 1×10 ^-5 ~ 1×10 ^-2 times the mass of the nitrile rubber; the amount of the main catalyst is 1×10 ^-5 ~ 1×10 ^-2 times the mass of the nitrile rubber.

The nitrile rubber solution with a concentration of 1~10wt% refers to a solution formed by dissolving nitrile rubber in an organic solvent and uniformly dissolving it by ultrasonic. Nitrile rubber refers to nitrile rubber or valer nitrile rubber. The organic solvent refers to one of toluene, xylene, chlorobenzene and butanone.

The general formula of metal carbonyl compound is M _x (CO) _y , wherein metal M refers to one of Mn, Fe, Co, Cr, Mo, Re, Ru, and x=1~4, y=1~12. The metal carbonyl compound is preferably MnBr(CO) ₅ , Mn ₂ (CO) ₁₀ , [Mn(CO) ₆ ⁺ ][AlCl ₄ ⁻ ], ReBr(CO) ₅ , Re ₂ (CO) ₁₀ , Mo(CO) ₆ , Cr(CO) ₆ , Fe(CO) ₅ , Fe ₂ (CO) ₉ , Fe ₃ (CO) ₁₂ , Na[HFe(CO) ₄ ], RuHCl(CO)(PPh ₃ ) ₂ , Rh ₄ (CO) _12. One of RuCo ₂ (CO) ₁₁ , Co ₂ (CO) ₈ , NaCo(CO) ₄ , Ni(CO) ₄ , and Na[HFe(CO) ₄ ].

The main catalyst refers to one of RhCl(PPh ₃ ) ₃ , RuCl ₂ (PPh ₃ ) ₃ , Pd@C, and Raney nickel.

Embodiment 1 A kind of synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of Fe ₃ (CO) ₁₂ was added, and 1 ml of a toluene solution containing 0.1 mg of RhCl(PPh ₃ ) ₃ (that is, the main catalyst RhCl(PPh _{3 )} was added. ) The dosage of ₃ is 1×10 ^-4 times the mass of nitrile rubber), and stir well. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and the procedure was repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation, and the iodine value of the product was 9. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 97%.

Among them: 5wt% nitrile rubber solution refers to the solution formed by dissolving 1 gram of nitrile rubber in 19 grams of chlorobenzene, and ultrasonically dissolving it uniformly.

Compare the 1 H NMR spectrum (see Figure 2) and FT-IR spectrum (see Figure 4) of the obtained product with the ¹ H NMR spectrum (see Figure 1) and FT-IR spectrum (see Figure ¹ ) of the raw nitrile rubber, respectively. Figure 3) By comparison, it can be seen that: after the hydrogenation reaction, the NMR signal of the hydrogen on the carbon-carbon double bond at 5~6 ppm disappears, and the infrared absorption peak of the carbon-carbon double bond at 970 cm ^-1 disappears, indicating that the carbon-carbon double bond disappears. The carbon double bonds are reduced by hydrogenation.

Comparative example A synergistic catalytic hydrogenation method of nitrile rubber (without the addition of metal carbonyl compounds):

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, and 1 ml of a toluene solution containing 0.1 mg RhCl(PPh ₃ ) ₃ was added (that is, the amount of RhCl(PPh ₃ ) ₃ was 1×10 of the quality of the nitrile rubber. ^-4 times), stir well. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 88. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 71%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

It can be seen from the comparative example that the addition of metal carbonyl compounds can effectively improve the catalytic efficiency and improve the hydrogenation degree of the hydrogenated nitrile rubber.

Embodiment 2 A kind of synergistic catalytic hydrogenation method of nitrile rubber:

A 10 wt% nitrile rubber solution was added to a 250-ml autoclave, 1 ml of a toluene solution containing 0.1 mg Fe ₃ (CO) ₁₂ was added, 1 ml of a toluene solution containing 0.1 mg RhCl(PPh ₃ ) ₃ was added, ( That is, the dosage of RhCl(PPh ₃ ) ₃ is 1×10 ^-5 times the mass of the nitrile rubber) and stir well. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 10 MPa, and the reaction temperature was controlled by heating to 190 degrees Celsius, and the reaction time was continuously stirred for 96 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 27. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 91%.

Among them: 10wt% nitrile rubber solution refers to the solution formed by dissolving 10 grams of nitrile rubber in 90 grams of chlorobenzene, and ultrasonically dissolving it uniformly.

Embodiment 3 A kind of synergistic catalytic hydrogenation method of nitrile rubber:

1 wt % nitrile rubber solution was added into a 250 ml autoclave, 10 mg of Fe ₃ (CO) ₁₂ and 10 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 1 MPa, and the reaction temperature was controlled by heating to 30 degrees Celsius, and the reaction time was continuously stirred for 1 hour. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 192. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 37%.

Among them: 1 wt% nitrile rubber solution refers to a solution formed by dissolving 1 gram of nitrile rubber in 99 grams of chlorobenzene, and ultrasonically dissolving it uniformly.

Embodiment 4 A kind of synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of Fe ₃ (CO) ₁₂ and 0.5 mg of RuCl ₂ (PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 88. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 71%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Embodiment 5 A kind of synergistic catalytic hydrogenation method of nitrile rubber:

The 5 wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of Fe ₃ (CO) ₁₂ and 5 mg of Pd@C were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation, and the iodine value of the product was 101. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 67%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 6 A synergistic catalytic hydrogenation method of nitrile rubber:

A 5 wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of Fe ₃ (CO) ₁₂ and 5 mg of Raney nickel were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation, and the iodine value of the product was 64. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 79%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 7 A synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of MnBr(CO) ₅ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 31. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 90%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 8 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Mn ₂ (CO) ₁₀ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 15. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 95%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 9 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Mn ₂ (CO) ₁₀ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 25. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 92%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Embodiment 10 A kind of synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Fe(CO) ₅ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settle to obtain the target product, and the iodine value of the product is 79. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 74%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Embodiment 11 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Fe ₂ (CO) ₉ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, sedimentation to obtain the target product, the iodine value of the product is 40. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 87%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 12 A synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of RuHCl(CO)(PPh ₃ ) ₂ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation, and the iodine value of the product was 116. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 62%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 13 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Co ₂ (CO) ₈ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 14 A synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg [Mn(CO) ₆ ⁺ ][AlCl ₄ ^- ] and 0.5 mg RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 15 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of ReBr(CO) ₅ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 16 A synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of Re ₂ (CO) ₁₀ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 17 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Mo(CO) ₆ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 18 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Cr(CO) ₆ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 19 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Na[HFe(CO) ₄ ] and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 20 A synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of Rh ₄ (CO) ₁₂ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 21 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of RuCo ₂ (CO) ₁₁ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 22 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of NaCo(CO) ₄ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 23 A synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 50 ml autoclave, 1 mg of Ni(CO) ₄ and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 24 A synergistic catalytic hydrogenation method of nitrile rubber:

5 wt % nitrile rubber solution was added into a 50 ml autoclave, 1 mg of Na[HFe(CO) ₄ ] and 0.5 mg of RhCl(PPh ₃ ) ₃ were added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. Add the poor solvent n-hexane, settling to obtain the target product, the iodine value of the product is 139. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 54%.

Wherein: the nitrile rubber solution of 5wt% is the same as in Example 1.

Example 25 A synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% valeronitrile rubber solution was added to a 50 ml autoclave, 1 mg Fe ₃ (CO) ₁₂ was added, and 1 ml of a toluene solution containing 0.1 mg RhCl(PPh ₃ ) ₃ (i.e. the main catalyst RhCl(PPh _{3 )} was added. ) The dosage of ₃ is 1×10 ^-4 times the mass of nitrile rubber), and stir well. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 38. The iodine value of the valeronitrile rubber raw material is 296, that is, the hydrogenation degree of hydrogenated nitrile rubber is 87%.

Wherein: 5wt% valeronitrile rubber solution refers to a solution formed by dissolving 1 gram of valeronitrile rubber in 19 grams of chlorobenzene, and ultrasonically dissolving it uniformly.

Example 26 A synergistic catalytic hydrogenation method of nitrile rubber:

A 5wt% nitrile rubber solution was added to a 50-milliliter autoclave, 1 mg of Fe ₃ (CO) ₁₂ was added, and 1 ml of a toluene solution containing 0.1 mg of RhCl(PPh ₃ ) ₃ (i.e. the main catalyst RhCl(PPh _{3 )} was added. ) The dosage of ₃ is 1×10 ^-4 times the mass of nitrile rubber), and stir well. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 37. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 88%.

Among them: 5wt% nitrile rubber solution refers to the solution formed by dissolving 1 gram of nitrile rubber in 19 grams of toluene, and ultrasonically dissolving it uniformly.

Example 27 A synergistic catalytic hydrogenation method of nitrile rubber:

A 5wt% nitrile rubber solution was added to a 50-milliliter autoclave, 1 mg of Fe ₃ (CO) ₁₂ was added, and 1 ml of a toluene solution containing 0.1 mg of RhCl(PPh ₃ ) ₃ (i.e. the main catalyst RhCl(PPh _{3 )} was added. ) The dosage of ₃ is 1×10 ^-4 times the mass of nitrile rubber), and stir well. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation. The iodine value of the product was 19. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 94%.

Among them: 5 wt% nitrile rubber solution refers to a solution formed by dissolving 1 gram of nitrile rubber in 19 grams of xylene, and ultrasonically dissolving it uniformly.

Example 28 A synergistic catalytic hydrogenation method of nitrile rubber:

A 5wt% nitrile rubber solution was added to a 50-milliliter autoclave, 1 mg of Fe ₃ (CO) ₁₂ was added, and 1 ml of a toluene solution containing 0.1 mg of RhCl(PPh ₃ ) ₃ (i.e. the main catalyst RhCl(PPh _{3 )} was added. ) The dosage of ₃ is 1×10 ^-4 times the mass of nitrile rubber), and stir well. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the vent valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation, and the iodine value of the product was 162. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 47%.

Among them: 5wt% nitrile rubber solution refers to the solution formed by dissolving 1 gram of nitrile rubber in 19 grams of butanone, and ultrasonically dissolving it uniformly.

Example 29 A synergistic catalytic hydrogenation method of nitrile rubber:

The 5wt% nitrile rubber solution was added to a 500-ml high pressure reactor, 10 mg Fe ₃ (CO) ₁₂ was added, 1 mg RhCl(PPh ₃ ) ₃ was added, and the mixture was stirred uniformly. The autoclave was filled with 1 MPa nitrogen to replace the air in the autoclave, and repeated 3 times. Then, the high pressure reaction kettle was filled with hydrogen at a pressure of 5 MPa, and the reaction temperature was controlled by heating to 140 degrees Celsius, and the reaction time was continuously stirred for 24 hours. After reaching the reaction time, the above-mentioned high-pressure reaction kettle was cooled to room temperature, the gas release valve was slowly opened, the pressure was reduced to normal pressure, the reaction kettle was opened, and the reaction mixture was taken out. The poor solvent n-hexane was added, and the target product was obtained by sedimentation, and the iodine value of the product was 12. The iodine value of the nitrile rubber raw material is 305, that is, the hydrogenation degree of the hydrogenated nitrile rubber is 96%.

Among them: 5wt% nitrile rubber solution refers to the solution formed by dissolving 10 grams of nitrile rubber in 200 grams of chlorobenzene, and ultrasonically dissolving it uniformly.

Claims (1)

1. A method for the concerted catalytic hydrogenation of nitrile rubber is characterized in that: 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^-2Doubling; the nitrile rubber is nitrile rubber or valeronitrile rubber; the main catalyst refers to RhCl (PPh)₃)₃(ii) a The metal carbonyl compound is MnBr (CO)₅、Mn₂(CO)₁₀、Fe₃(CO)₁₂、Fe₂(CO)₉One of (a) and (b); 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 waves; the organic solvent is one of toluene, xylene and chlorobenzene; the reaction conditions are that the hydrogen pressure is 0.5-10 MPa, the temperature is 140-190 ℃, and the reaction time is 24-96 h.

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