Catalyst for producing diamines by hydrogenation of dinitriles, method for producing same and use thereof

Abstract

The present invention discloses a catalyst for producing diamines by hydrogenating dinitriles, the catalyst comprising the following components: a) an active component, the active component comprising Ni and / or an oxide thereof; b) an auxiliary, the auxiliary comprising one or more of Mg, Cu, Co, Zn, Zr, Mo, and / or an oxide thereof; and C) a support; or a reaction product thereof, wherein the relative content of α-NiO in the catalyst is less than 2.0 au. The present invention also discloses a process for producing diamines by hydrogenating dinitriles. The catalyst and process of the present invention significantly reduce the production of excess hydrogenation by-products and improve overall selectivity to the target product.

Description

Detailed Description of the Invention

[0001] [Technical Field] The present invention belongs to the field of dibasic amine production, and in particular relates to a catalyst for producing dibasic amines by hydrogenation of dibasic nitriles and a method for producing the same, a method for producing dibasic amines by hydrogenation of dibasic nitriles, and uses thereof.

[0002] [Background technology] m-Xylylenediamine (meta-benzenedimethanamine) can be used as a raw material for epoxy resin curing agents. Curing agents made from m-xylylenediamine contain aromatic aliphatic amines, so they can be used as modified epoxy resin curing agents. Their properties include accelerated curing speed at room temperature, good heat resistance, water and chemical resistance, and good wet cure ability and surface gloss. Curing agents made from m-xylylenediamine are widely used in coatings, adhesives, and electronics.

[0003] m-Xylylenediamine is also used as a raw material for synthesizing MX nylon and its derivatives, especially MXD6 (produced with adipic acid). This nylon is characterized by high strength and elasticity at high temperatures, a high deformation temperature, and a low coefficient of thermal expansion (similar to that of alloys). This nylon is suitable for precision molding and can be used for high-temperature baking and coating. The resulting films have high transparency and oxygen impermeability, making them suitable for food packaging. The resulting fibers have high strength.

[0004] m-Xylylenediamine can also be used as a raw material for polyurethane resins. m-Xylylenediamine can be used to produce meta-bis(isocyanatomethyl)benzene, which can then be used to synthesize polyurethane resins. This resin is similar to hexamethylene diisocyanate and has better yellowing resistance than the latter. This resin can be used in light-colored coatings, has high coating hardness, and low toxicity, and can also be used in synthetic leather.

[0005] Currently, m-xylylenediamine is primarily produced by catalytic hydrogenation of isophthalonitrile.

[0006] Patent application CN200680036084.8 discloses a process flow for producing MXDA (m-xylylenediamine) from IPN (isophthalonitrile) by fixed-bed continuous hydrogenation. The IPN is melted at 170-200°C and mixed in liquid form with liquid ammonia and recycled materials to dissolve (60°C). Under conditions of 60-130°C and 150-200 bar, the conversion per pass is >99% and the selectivity is >92% in a fixed-bed reactor catalyzed by a Mn-doped unsupported Co catalyst.

[0007] Patent application CN200680035201.9 discusses using recycled MXDA as an IPN solvent and dissolving it at 55-70°C. Patent applications CN201010150757.0 and CN201010150725.0 primarily involve adding a modified Raney Ni catalyst to a stirred reactor, followed by the addition of isophthalonitrile and a ternary solvent mixture (aromatic hydrocarbon, low-carbon alcohol, aliphatic halogenated derivative), and a secondary amine inhibitor. After dissolution, the reaction is carried out in a stirred tank at 40-120°C and 2-10 MPa, followed by intermittent production of MXDA by hydrogenation.

[0008] However, the prior art still suffers from problems such as high catalyst consumption, insufficient product selectivity, and intermittent operation of the high-pressure autoclave, etc. Therefore, there is a need to develop a new catalyst with high activity and high selectivity to realize continuous industrial production.

[0009] Summary of the Invention The technical problem to be solved by the present invention is to provide a novel catalyst for producing m-xylylenediamine with high selectivity, in contrast to the low selectivity achieved in the production of m-xylylenediamine by hydrogenation of isophthalonitrile in the prior art, and a method for producing the same.

[0010] Accordingly, a first aspect of the present invention provides a catalyst for the production of a dibasic amine by hydrogenation of a dibasic nitrile, the catalyst comprising the following components or reaction products thereof: a) an active component, the active component comprising Ni and / or its oxides; b) an additive, the additive comprising one or more of Mg, Cu, Co, Zn, Zr, Mo and / or oxides thereof; c) carrier; Here, the relative content of α-NiO in the catalyst is less than 2.0 au.

[0011] According to some embodiments of the present invention, the relative content of α-NiO in the catalyst is less than 1.5 au, preferably less than 0.2 au.

[0012] According to some embodiments of the present invention, the adjuvant comprises one or more of Cu, Co, Zr, Mo and / or oxides thereof.

[0013] The "relative content" of the present invention does not refer to an absolute concept of content, but rather refers to the relative content of a substance determined by comparing the integrated areas of peaks in the same graph in the same coordinate system. Here, the size of the integrated area of ​​the peak represents the content of the substance in the catalyst. Specifically, for the relative content of α-NiO of the present invention (using au as the unit), the same graph in the same coordinate system refers to the H2-TPR diagram of the catalyst. Here, the horizontal axis is Celsius temperature (°C), and the vertical axis is the signal value of the TCD (thermal conductivity detector) (which is a quantitative value expressed, for example, in the form of a percentage or decimal). When measuring the H2-TPR for the relative content of α-NiO of the present invention, a fully oxidized catalyst is used, and the amount of catalyst is 50 mg.

[0014] In the present invention, au is an abbreviation for arbitrary unit, refers to a relative value, and is dimensionless.

[0015] According to some embodiments of the present invention, the total weight of the catalyst is 100% by weight.

[0016] The content of the active ingredient is 5 to 70% by weight, preferably 10 to 60% by weight, more preferably 15 to 50% by weight; the content of the adjuvant is 0.1 to 60% by weight, preferably 1 to 50% by weight, more preferably 5 to 45% by weight; and the content of the carrier is 10 to 90% by weight, preferably 15 to 80% by weight, more preferably 20 to 70% by weight.

[0017] According to some other examples of the present invention, the content of the active ingredient is, on a weight basis, 10 to 60 parts, preferably 15 to 55 parts; the content of the adjuvant is 0.1 to 120 parts, preferably 0.2 to 90 parts; and the content of the carrier is 0.1 to 45 parts, preferably 1 to 35 parts.

[0018] According to some embodiments of the present invention, the support is at least one of alumina, silica and zeolite, preferably alumina.

[0019] According to some embodiments of the present invention, the support is a support that has been treated at a high temperature of 500° C. or higher.

[0020] A second aspect of the present invention provides a method for producing a catalyst according to the first aspect of the present invention, the method comprising the steps of: 1) treating the support at a temperature of 500°C or higher to produce a modified support, and then carrying out a first contact of a solution of an auxiliary salt (i.e., an auxiliary salt), a solution of a first precipitant, the support, and water; 2) carrying out a second contact of the nickel salt solution, the second precipitant solution, the modified support obtained from step 1), and water, followed by filtering and calcination to produce a catalyst; Includes.

[0021] According to some embodiments of the present invention, in step 1), the first contacting is carried out by simultaneously adding a solution of an auxiliary salt and a solution of a first precipitant to water containing a carrier.

[0022] According to some embodiments of the present invention, in step 2), a solution of an auxiliary salt and a solution of a second precipitant are simultaneously added to the water containing the modified carrier obtained from step 1) to carry out the second contacting.

[0023] According to some embodiments of the present invention, in step 1), the solution obtained in the first contact is controlled to a final pH of 6.0 to 10.0, for example, 6.0 to 8.0.

[0024] According to some embodiments of the present invention, in step 2), the solution obtained in the second contact is controlled to a final pH of 6.0 to 10.0, for example, 6.0 to 8.0.

[0025] According to some embodiments of the present invention, the temperature of the first contact is 50 to 90°C, and in some embodiments, the temperature is 70°C.

[0026] According to some embodiments of the present invention, the first contact time is 3 to 6 hours.

[0027] According to some embodiments of the present invention, the temperature of the second contact is 50 to 90°C.

[0028] According to some embodiments of the present invention, the second contact time is 3 to 6 hours.

[0029] According to some embodiments of the invention, the auxiliary salt is selected from one or more of Mg(NO3)2, Cu(NO3)2, Co(NO3)2, Zn(NO3)2, Zr(NO3)4 and (NH4)2MoO4, preferably selected from one or more of Cu(NO3)2, Zr(NO3)4, (NH4)2MoO4 and Co(NO3)2.

[0030] According to some embodiments of the present invention, the auxiliary salt may be a salt hydrate, such as one or more of Mg(NO3)2·6H2O, Cu(NO3)2·3H2O, Co(NO3)2·6H2O, Zn(NO3)2·6H2O, and Zr(NO3)4·5H2O.

[0031] According to some embodiments of the invention, the first precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and aqueous ammonia, preferably sodium hydroxide and / or aqueous ammonia.

[0032] According to some embodiments of the present invention, the nickel salt is nickel sulfate and / or nickel nitrate, preferably nickel nitrate.

[0033] According to some embodiments of the invention, the second precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and aqueous ammonia, preferably selected from one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.

[0034] According to some embodiments of the present invention, in step 1), the solution of the auxiliary salt has a concentration of 0.1 to 1.5 mol / L, preferably 0.3 to 1.2 mol / L.

[0035] According to some embodiments of the present invention, in step 1), the solution of the first precipitant has a concentration of 0.4 to 2.0 mol / L, preferably 0.6 to 1.6 mol / L.

[0036] According to some embodiments of the present invention, in step 1), the content of the carrier in water is 5 to 100 g / L, for example, 20 to 80 g / L, or 5 to 20 g / L, for example, 8 to 15 g / L.

[0037] According to some embodiments of the present invention, in step 2), the nickel salt solution has a concentration of 0.2 to 1.5 mol / L, preferably 0.5 to 1.2 mol / L.

[0038] According to some embodiments of the present invention, in step 2), the solution of the second precipitant has a concentration of 0.4 to 2.0 mol / L, preferably 0.6 to 1.5 mol / L.

[0039] According to some embodiments of the present invention, in step 2), the content of the modified support in water is 10-100 g / L, for example, 20-85 g / L, or 10-30 g / L, for example, 12-25 g / L.

[0040] According to some embodiments of the present invention, in step 2), the calcination is carried out in an air atmosphere.

[0041] According to some embodiments of the present invention, in step 2), the firing temperature is 300 to 600°C.

[0042] According to some embodiments of the present invention, in step 2), a nickel salt solution and a second precipitant solution are simultaneously added to water containing the modified support at 50 to 90°C, mixed, and the mixed solution is controlled to a final pH of 6.0 to 10.0, for example 6.0 to 8.0, stirred for 3 to 6 hours, filtered, washed, dried, and calcined in an oxygen-containing atmosphere (such as air or pure oxygen) at 300 to 600°C to produce a catalyst.

[0043] A third aspect of the present invention provides a process for producing a dibasic amine by hydrogenation of a dibasic nitrile, the process comprising contacting and reacting the dibasic nitrile with hydrogen gas in the presence of a catalyst according to the first aspect of the present invention or a catalyst produced by a process according to the second aspect of the present invention to produce the dibasic amine.

[0044] According to some embodiments of the present invention, the reaction temperature is 50 to 120°C, preferably 60 to 80°C.

[0045] According to some embodiments of the present invention, the reaction pressure is 4.0 to 15.0 MPa, for example, 4.0 to 12.0 MPa, or 6.0 to 10.0 MPa.

[0046] According to some embodiments of the present invention, the liquid hourly space velocity of the reaction is 1 to 12 h -1 , preferably 2 to 10 hours -1 is.

[0047] According to some embodiments of the present invention, the molar ratio of hydrogen gas to dibasic nitrile in the reaction is 3:1 to 70:1, preferably 5:1 to 20:1.

[0048] According to some embodiments of the present invention, the isophthalonitrile is dissolved in liquid ammonia. In some embodiments, the mass fraction of isophthalonitrile is 10%. In some embodiments, the mass fraction of the liquid ammonia is 90%.

[0049] A fourth aspect of the present invention provides the use of a catalyst according to the first aspect of the present invention, or a catalyst produced by a process according to the second aspect of the present invention, or a process according to the third aspect of the present invention, in the production of dibasic amines by hydrogenation of dibasic nitriles, in particular in the production of m-xylylenediamine by hydrogenation of isophthalonitrile.

[0050] In general, the present invention provides the following technical solutions:

[0051] 1. A catalyst comprising: a) an active ingredient, the active ingredient comprising an oxide of Ni; b) an adjuvant, preferably the adjuvant comprises one or more of the oxides of Mg, Cu, Co, Zn, Zr and Mo, more preferably the adjuvant comprises one or more of the oxides of Cu, Co, Zr and Mo; c) carrier; Including, The relative content of α-NiO in the catalyst is less than 2.0 au, such as less than or equal to 1.5 au, further such as less than or equal to 0.2 au; catalyst.

[0052] 2. A catalyst in a fully oxidized state: a) an active ingredient, the active ingredient comprising an oxide of Ni; b) an adjuvant, preferably the adjuvant comprises one or more of the oxides of Mg, Cu, Co, Zn, Zr and Mo, more preferably the adjuvant comprises one or more of the oxides of Cu, Co, Zr and Mo; c) carrier; Including, The content of α-NiO in the catalyst is less than 55 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 10 wt%, for example, less than 5 wt%. catalyst.

[0053] The term "fully oxidized state" used herein refers to a catalyst obtained by calcining the corresponding catalyst in an oxygen-containing atmosphere (such as air or pure oxygen) at a calcination temperature (e.g., 300-600°C) for a sufficiently long time (e.g., 4 hours, 8 hours, 12 hours, 24 hours, 48 ​​hours, 96 hours, 1 week, 2 weeks, 4 weeks, or more). The fully oxidized state can also be achieved by other methods and is not limited to the above-mentioned calcination methods.

[0054] 3. A catalyst comprising: a) an active component, wherein the active component is Ni and / or its oxide; b) an adjuvant, preferably the adjuvant comprises one or more of Mg, Cu, Co, Zn, Zr, Mo and / or oxides thereof, more preferably the adjuvant comprises one or more of Cu, Co, Zr, Mo and / or oxides thereof; c) carrier; Including, When the catalyst is in its fully oxidized state, the content of α-NiO in the catalyst is less than 55 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, less than 10 wt%, for example less than 5 wt%. catalyst.

[0055] 4. A catalyst comprising: a) an active component, wherein the active component is Ni and / or its oxide; b) an adjuvant, preferably the adjuvant comprises one or more of Mg, Cu, Co, Zn, Zr, Mo and / or oxides thereof, more preferably the adjuvant comprises one or more of Cu, Co, Zr, Mo and / or oxides thereof; c) carrier; Including, When the catalyst is in its fully oxidized state, the relative content of α-NiO in the catalyst is less than 2.0 au, such as 1.5 au or less, further such as 0.2 au or less. catalyst.

[0056] 5. By weight, The content of the active ingredient is 10 to 60 parts by weight, for example, 15 to 55 parts by weight; The content of the adjuvant is 0.1 to 120 parts by weight, for example, 0.2 to 90 parts by weight; The content of the carrier is 0.1 to 45 parts by weight, for example, 1 to 35 parts by weight; or The total weight of the catalyst is 100% by weight. The content of the active ingredient is 5 to 70% by weight, preferably 10 to 60% by weight, more preferably 15 to 50% by weight; The content of the adjuvant is 0.1 to 60% by weight, preferably 1 to 50% by weight, more preferably 5 to 45% by weight; The content of the carrier is 10 to 90% by weight, preferably 15 to 80% by weight, and more preferably 20 to 70% by weight; or The total weight of the catalyst is 100% by weight. The content of the active ingredient is 30-35% by weight; The content of the adjuvant is 15-50% by weight; The content of the carrier is 15 to 60% by weight; Preferably, the adjuvant is Co, Mo or Zr, more preferably, the adjuvant is Co. The catalyst according to any of the above technical solutions, characterized in that

[0057] 6. The support is at least one of alumina, silica and zeolite, for example alumina; preferably, the support is a support treated at a temperature of 500 ° C or higher; The catalyst according to any of the above technical solutions, characterized in that

[0058] 7. The support contains alumina, and the proportions of α-alumina, β-alumina, γ-alumina, δ-alumina, and θ-alumina are 0.1 to 99%, 0.1 to 99%, 0.1 to 99%, 0.1 to 99%, 0.1 to 99%, and 0.1 to 99%, preferably 10 to 95%, 1 to 70%, 2 to 90%, 5 to 90%, and 3 to 80%, respectively, based on the weight of the alumina. The catalyst according to any of the above technical solutions, characterized in that

[0059] 8. The catalyst is a catalyst for producing dibasic amines by hydrogenation of dibasic nitriles; The catalyst according to any of the above technical solutions, characterized in that

[0060] 9. The relative content of α-NiO in the catalyst is greater than 0.0001 au, such as greater than 0.001 au, further such as greater than 0.01 au; or the content of α-NiO in the catalyst is greater than 0.0001 wt%, such as greater than 0.001 wt%, further such as greater than 0.01 wt%; The catalyst according to any of the above technical solutions, characterized in that

[0061] 10. A method for producing a catalyst according to any one of the above technical solutions, comprising: The method comprises the steps of: 1) carrying out a first contact of a solution of auxiliary salt, a solution of a first precipitant, a support, and water to produce a modified support; 2) carrying out a second contact of the nickel salt solution, the second precipitant solution, the modified support obtained from step 1), and water, followed by filtering and calcination to produce a catalyst; Including, For example, in step 1), a solution of an auxiliary salt and a solution of a first precipitant are simultaneously added to water containing the support to carry out the first contact; and / or in step 2), a solution of a nickel salt and a solution of a second precipitant are simultaneously added to water containing the modified support obtained from step 1) to carry out the second contact; A method characterized by:

[0062] 11. In step 1), the support used is a support treated at a temperature of 500°C or higher, preferably a support treated at a temperature above 500°C; The method according to technical solution 10, characterized in that:

[0063] 12. The solution obtained in the first contact and the solution obtained in the second contact are controlled to a final pH of 6.0 to 10.0, for example, 6.0 to 8.0; For example, the temperature of the first contact and / or the second contact is 50 to 90°C, and / or the time of the first contact and / or the second contact is 3 to 6 hours. The method according to any one of technical solutions 10 to 11, characterized in that:

[0064] 13. The auxiliary salt is selected from one or more of Mg(NO3)2, Cu(NO3)2, Co(NO3)2, Zn(NO3)2, Zr(NO3)4, (NH4)2MoO4, Mg(NO3)2·6H2O, Cu(NO3)2·3H2O, Co(NO3)2·6H2O, Zn(NO3)2·6H2O and Zr(NO3)4·5H2O, for example, selected from one or more of Cu(NO3)2, Zr(NO3)4, (NH4)2MoO4 and Co(NO3)2; and / or said first precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and aqueous ammonia, preferably the first precipitating agent does not contain carbon, more preferably the first precipitating agent is sodium hydroxide and / or aqueous ammonia; and / or the nickel salt is nickel sulfate and / or nickel nitrate, e.g., nickel nitrate; and / or the second precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and aqueous ammonia, preferably the second precipitating agent comprises carbon, more preferably the second precipitating agent is sodium carbonate and / or sodium bicarbonate; The method according to any one of technical solutions 10 to 12, characterized in that

[0065] 14. In step (1), the solution of the auxiliary salt has a concentration of 0.1 to 1.5 mol / L, for example, 0.3 to 1.2 mol / L; and / or the solution of the first precipitant has a concentration of 0.4 to 2.0 mol / L, for example, 0.6 to 1.6 mol / L; and / or the content of the carrier in water is 5 to 100 g / L, for example, 20 to 80 g / L, or 5 to 20 g / L, for example, 8 to 15 g / L. The method according to any one of technical solutions 10 to 13,

[0066] 15. In step 2), the nickel salt solution has a concentration of 0.2-1.5 mol / L, for example, 0.5-1.2 mol / L; and / or the second precipitant solution has a concentration of 0.4-2.0 mol / L, for example, 0.6-1.5 mol / L; and / or the content of the carrier in water is 10-100 g / L, for example, 20-85 g / L, or 10-30 g / L, for example, 12-25 g / L; The method according to any one of technical solutions 10 to 14,

[0067] 16. A method for producing a dibasic amine by hydrogenation of a dibasic nitrile, comprising the step of contacting and reacting the dibasic nitrile with hydrogen gas in the presence of a catalyst according to any one of Technical Solutions 1 to 9 or a catalyst prepared by the method according to any one of Technical Solutions 10 to 15 to produce a dibasic amine, wherein, for example, the molar ratio of the hydrogen gas to the dibasic nitrile is 3:1 to 70:1, for example, 5:1 to 20:1; method.

[0068] For example, the reaction temperature is 50 to 120°C, for example, 60 to 80°C; and / or the reaction pressure is 4.0 to 15.0 MPa, for example, 4.0 to 12.0 MPa, further for example, 6.0 to 10.0 MPa; and / or the liquid hourly space velocity of the reaction is 1 to 12 h-1 , for example, 2 to 10 hours -1 is.

[0069] In the present invention, the dibasic amine and the dibasic nitrile are not particularly limited. The dibasic nitrile is an aliphatic C4-C 24 Dibasic nitriles, such as adiponitrile, pimelonitrile, suberonitrile, nonanedinitrile, decanedinitrile, undecanedinitrile, dodecanedinitrile, tridecanedinitrile, tetradecanedinitrile, pentadecanedinitrile, hexadecanedinitrile, heptadecanedinitrile, or octadecanedinitrile, or aromatic C6-C 18 It may be a dibasic nitrile, such as phthalonitrile, isophthalonitrile, or terephthalonitrile; Dibasic amines are aliphatic C4-C 24 Dibasic amines, such as hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, or octadecanediamine, or aromatic C6-C 18 It may also be a dibasic amine, for example, ortho-benzenedimethanamine, meta-benzenedimethanamine, or para-benzenedimethanamine.

[0070] 17. A catalyst according to any one of technical solutions 1 to 9, or a catalyst prepared by the method according to any one of technical solutions 10 to 15, or a method according to technical solution 13, in the preparation of dibasic amines by hydrogenation of dibasic nitriles, In particular, aliphatic C4~C 24 Dibasic nitriles (such as adiponitrile, pimelonitrile, suberonitrile, nonanedinitrile, decanedinitrile, undecanedinitrile, dodecanedinitrile, tridecanedinitrile, tetradecanedinitrile, pentadecanedinitrile, hexadecanedinitrile, heptadecanedinitrile, or octadecanedinitrile), or aromatic C6-C18 Aliphatic C4-C by hydrogenation of dibasic nitriles (such as phthalonitrile, isophthalonitrile, or terephthalonitrile) 24 Dibasic amines (such as hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, or octadecanediamine), or aromatic C6-C 18 In the production of dibasic amines (such as ortho-benzenedimethanamine, meta-benzenedimethanamine, or para-benzenedimethanamine), use.

[0071] Supported nickel-based catalysts typically have three forms of NiO: free amorphous α-NiO, β1-NiO, which interacts weakly with the support, and β2-NiO, which interacts strongly with the support. Too much free amorphous α-NiO in the catalyst leads to excessive hydrogenation side reactions, producing hydrogenolysis by-products such as 3-methylbenzylamine and m-xylene.

[0072] Here, the content of α-NiO means the weight percentage or relative content of α-NiO relative to the total amount of nickel species as NiO in the catalyst when the catalyst is converted to a fully oxidized state.

[0073] The present invention focuses on the effect of various NiO-type nickel-based catalysts on the selectivity of the target product, and provides a catalyst and method for the hydrogenation of dibasic nitriles to produce diamines, particularly m-xylylenediamine, by hydrogenating isophthalonitrile. The catalyst and method of the present invention significantly reduce the production of excess hydrogenation by-products and improve the overall selectivity of the target product.

[0074] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the H2-TPR diagrams produced in Examples 1 and 2 and Comparative Example 1.

[0075] Here, (1) α-NiO (300-400 °C): due to free amorphous NiO species on the surface; (2) β1-NiO (400-500 °C): due to NiO species that weakly interact with the support; (3) β2-NiO (500-600 °C): due to NiO species that strongly interact with the support.

[0076] Detailed Description In order to make the present invention easier to understand, the present invention will be described in detail below in conjunction with the embodiments and the accompanying drawings. These embodiments are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. In the examples, no specific conditions are shown, but they are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or equipment used are not specified by manufacturer in this specification, but are commercially available or can be obtained by conventional methods.

[0077] The range endpoints and any values ​​disclosed herein are not limited to the exact ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the range endpoints, range endpoints and individual point values, and individual point values ​​can be combined with each other to create one or more new numerical ranges, and these new numerical ranges should be construed as specifically disclosed herein.

[0078] In the concept used in the present invention, the conversion and selectivity for the production of m-xylylenediamine by hydrogenation of isophthalonitrile are calculated by the following formulas:

[0079]

number

[0080] where n: amount of substance (in moles); IPN: isophthalonitrile; MXDA: m-xylylenediamine; 1: raw material; 2: product.

[0081] Test Method: 1. Test method for the relative content of each NiO type: The area of ​​the H2-TPR curve (vertical axis: %TCD, horizontal axis: temperature) was integrated to calculate the relative content of each NiO type based on the hydrogen consumption of the sample. The unit is au (arbitrary unit). The magnitude of the peak area actually represents the relative content of each NiO type and is used for intercomparison of NiO between different samples.

[0082] In the following examples, the isophthalonitrile used is of industrial grade and is dissolved in liquid ammonia, the mass fraction of isophthalonitrile is 10%, and the mass fraction of liquid ammonia is 90%; the volume fraction of hydrogen gas used is 99.9%.

[0083] The structure of the catalyst is measured by X-ray fluorescence ("Petrochemical Analysis Method (RIPP Test Method)", edited by Yang Cuiding et al., Science Press, 1990).

[0084] Example 1 (1) Catalyst production Preparation of modified support: The auxiliary salt Co(NO3)2 was added to Solution I at a concentration of 0.8 mol / L, and sodium hydroxide was added to Solution II at a concentration of 1.0 mol / L. The precursor of the aluminum hydroxide support (pseudoboehmite) was pretreated at a high temperature of 500°C and then added to 1 L of water. Solutions I and II were co-currently precipitated at 70°C, and the final pH was controlled at 7.0. The mixture was aged with stirring for 3 to 6 hours to produce the modified alumina support.

[0085] Catalyst preparation: Nickel nitrate was added to Solution III at a concentration of 0.8 mol / L, sodium carbonate was added to Solution IV at a concentration of 1.2 mol / L, and the resulting modified alumina support (50 g) was added to 1 L of water. Solutions III and IV were precipitated in parallel at 70 °C, with the final pH controlled at 7.5. The mixture was aged for 4 hours with stirring, then filtered, washed, dried, and calcined at 500 °C in an air atmosphere for 6 hours to produce the catalyst. The weight of the resulting catalyst was 0.75 g of CoO, 5.25 g of the active component (nickel oxide), and 9.0 g of the alumina support. The H2-TPR diagram is shown in Figure 1, and the results are listed in Table 1.

[0086] (2) Catalyst reduction 15 g of the resulting catalyst was collected. This catalyst contained CoO (0.75 g) in the catalyst component. The catalyst was packed into 15 mL and reduced with pure hydrogen gas at 500 °C for 24 hours to produce a reduced catalyst.

[0087] (3) Hydrogenation of isophthalonitrile to produce m-xylylenediamine The raw materials were a liquid ammonia solution of isophthalonitrile (3000 mL, mass fraction of isophthalonitrile 10%, mass fraction of liquid ammonia 90%) and pure hydrogen gas (volume fraction of hydrogen gas 99.9%). The amount of reduction catalyst used was 15 g, the reaction temperature was 80°C, the reaction pressure was 8.0 MPa, the molar ratio of hydrogen gas to isophthalonitrile was 5:1, and the liquid hourly space velocity was 10 h . -1 A hydrogenation test was carried out under the conditions shown in Table 1. The reaction results are shown in Table 1. The IPN conversion was 99.9%, and the MXDA selectivity was 97.1%. The 3-methylbenzylamine content was 0.32% (measured by liquid chromatography).

[0088] Example 2 The catalysts in this example were prepared according to the catalyst preparation method in Example 1, except that different CoO contents were used in the catalyst: the weight of CoO in the catalyst was 2.25 g. The H2-TPR diagram is shown in Figure 1, and the results are listed in Table 1.

[0089] (1) Catalyst reduction: 15 g of catalyst was collected. This catalyst contained CoO (2.25 g) in the catalyst. The catalyst was packed into 15 mL and reduced with pure hydrogen gas at 500 °C for 24 hours to produce a reduced catalyst.

[0090] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.9%, the MXDA selectivity was 98.3%, and the content of 3-methylbenzylamine was 0.13%.

[0091] Example 3 The catalysts of this example were prepared according to the catalyst preparation method of Example 1, except that different Co contents were used in the catalyst: the weight of CoO in the catalyst was 0.5 g. The results of the relative content of α-NiO are shown in Table 1.

[0092] (1) Catalyst reduction: 15 g of catalyst was collected. This catalyst contained CoO (0.5 g) in the catalyst. The catalyst was filled into 15 mL and reduced with pure hydrogen gas at 500 °C for 24 hours to produce a reduced catalyst.

[0093] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.9%, the MXDA selectivity was 96.4%, and the content of 3-methylbenzylamine was 0.42%.

[0094] Example 4 The catalysts of this example were prepared according to the catalyst preparation method of Example 1, except that different Co contents were used in the catalyst: the weight of CoO in the catalyst was 4.5 g. The results of the relative content of α-NiO are shown in Table 1.

[0095] (1) Catalytic reduction: 15 g of catalyst was collected. This catalyst contained CoO (4.5 g) in the catalyst. The catalyst was packed into 15 mL and reduced with pure hydrogen gas at 500 °C for 24 hours to produce a reduced catalyst.

[0096] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.9%, the MXDA selectivity was 98.4%, and the content of 3-methylbenzylamine was 0.11%.

[0097] Example 5 The catalysts of this example were prepared according to the catalyst preparation method of Example 1, except that different Co contents were used in the catalyst: the weight of CoO in the catalyst was 7.5 g. The results of the relative content of α-NiO are shown in Table 1.

[0098] (1) Catalytic reduction: 15 g of catalyst was collected. This catalyst contained CoO (7.5 g) in the catalyst. The catalyst was filled into 15 mL and reduced with pure hydrogen gas at 500 °C for 24 hours to produce a reduced catalyst.

[0099] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.9%, the MXDA selectivity was 98.5%, and the content of 3-methylbenzylamine was 0.09%.

[0100] Example 6 The catalyst of this example was prepared according to the catalyst preparation method of Example 2, except that a different auxiliary salt was used: the auxiliary salt was Zr(NO3)4. The relative content of α-NiO in the catalyst was shown in Table 1.

[0101] (1) Catalyst reduction: 15 g of catalyst was collected, packed into 15 mL of water, and reduced with pure hydrogen gas at 500°C for 24 hours to produce a reduced catalyst.

[0102] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.9%, the MXDA selectivity was 98.0%, and the content of 3-methylbenzylamine was 0.17%.

[0103] Example 7 The catalyst of this example was prepared according to the catalyst preparation method of Example 2, except that a different auxiliary salt was used: the auxiliary salt was Mg(NO3)2. The relative content of α-NiO in the catalyst was shown in Table 1.

[0104] (1) Catalytic reduction: 15 g of catalyst was collected, packed into 15 mL of water, and reduced with pure hydrogen gas at 500°C for 24 hours to produce a reduced catalyst.

[0105] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.9%, the MXDA selectivity was 97.8%, and the content of 3-methylbenzylamine was 0.23%.

[0106] Example 8 The catalyst of this example was prepared according to the catalyst preparation method of Example 2, except that a different auxiliary salt was used: the auxiliary salt was Cu(NO3)2. The relative content of α-NiO in the catalyst was shown in Table 1.

[0107] (1) Catalyst reduction: 15 g of catalyst was collected, packed into 15 mL of water, and reduced with pure hydrogen gas at 500°C for 24 hours to produce a reduced catalyst.

[0108] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.7%, the MXDA selectivity was 96.9%, and the content of 3-methylbenzylamine was 0.36%.

[0109] Example 9 The catalyst of this example was prepared according to the catalyst preparation method of Example 2, except that a different auxiliary salt was used: the auxiliary salt was Zn(NO3)2. The relative content of α-NiO in the catalyst was shown in Table 1.

[0110] (1) Catalyst reduction: 15 g of catalyst was collected, packed into 15 mL of water, and reduced with pure hydrogen gas at 500°C for 24 hours to produce a reduced catalyst.

[0111] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.8%, the MXDA selectivity was 96.4%, and the content of 3-methylbenzylamine was 0.41%.

[0112] Example 10 The catalyst of this example was prepared according to the catalyst preparation method of Example 2, except that a different auxiliary salt was used: the auxiliary salt was (NH)MoO. The relative content of α-NiO in the catalyst was shown in Table 1.

[0113] (1) Catalyst reduction: 15 g of catalyst was collected, packed into 15 mL of water, and reduced with pure hydrogen gas at 500°C for 24 hours to produce a reduced catalyst.

[0114] (2) Catalytic hydrogenation of catalysts The method was the same as in Example 1, and the reaction results are shown in Table 1. The IPN conversion was 99.9%, the MXDA selectivity was 98.1%, and the content of 3-methylbenzylamine was 0.19%.

[0115] Example 11 (1) Catalyst production The auxiliary salt Co(NO3)2 solution, nickel nitrate solution III, and precipitant solution from Example 1 were added together to water containing aluminum hydroxide support treated at a high temperature of 500°C, and the final pH of the solution was controlled to 7.0, causing the nickel salt, auxiliary salt, and precipitant to precipitate together on the support alumina. The relative content of α-NiO in the catalyst was shown in Table 1.

[0116] (2) Catalyst reduction 15 g of the resulting catalyst was collected, packed into a 15 mL container, and reduced with pure hydrogen gas at 500°C for 24 hours to produce a reduced catalyst.

[0117] (3) Hydrogenation of isophthalonitrile to produce m-xylylenediamine The raw materials were a liquid ammonia solution of isophthalonitrile (3000 mL, mass fraction of isophthalonitrile 10%, mass fraction of liquid ammonia 90%) and pure hydrogen gas (volume fraction of hydrogen gas 99.9%). The catalyst amount was 15 g, the reaction temperature was 80°C, the reaction pressure was 8.0 MPa, the hydrogen gas / isophthalonitrile molar ratio was 5:1, and the liquid hourly space velocity was 10 h . -1 A hydrogenation test was carried out under the conditions shown in Table 1. The reaction results are shown in Table 1. The IPN conversion was 99.9%, and the MXDA selectivity was 95.2%. The 3-methylbenzylamine content was 0.49%.

[0118] Comparative Example 1 (1) Catalyst production The procedure was the same as in Example 1, except that no solution of auxiliary salt Co(NO3)2 was added during the preparation of the catalyst. The H2-TPR diagram is shown in Figure 1, and the results are listed in Table 1.

[0119] (2) Catalyst reduction 15 g of the resulting catalyst was collected. This catalyst did not contain CoO in the catalyst components. The catalyst was packed into 15 mL and reduced with pure hydrogen gas at 500°C for 24 hours.

[0120] (3) Hydrogenation of isophthalonitrile to produce m-xylylenediamine The raw materials were a liquid ammonia solution of isophthalonitrile (3000 mL, mass fraction of isophthalonitrile 10%, mass fraction of liquid ammonia 90%) and pure hydrogen gas (volume fraction of hydrogen gas 99.9%). The amount of reduction catalyst used was 15 g, the reaction temperature was 80°C, the reaction pressure was 8.0 MPa, the molar ratio of hydrogen gas to isophthalonitrile was 5:1, and the liquid hourly space velocity was 10 h . -1A hydrogenation test was carried out under the conditions shown in Table 1. The reaction results are shown in Table 1. The IPN conversion was 99.9%, and the MXDA selectivity was 95.6%. The 3-methylbenzylamine content was 0.58%.

[0121] Comparative Example 2 (1) Catalyst production The treatment was the same as in Example 1, except that the alumina support was not treated at a high temperature of 500° C. The results of the relative content of α-NiO in the catalyst are shown in Table 1.

[0122] (2) Catalytic reduction 15 g of the resulting catalyst was collected, packed into a 15 mL container, and reduced with pure hydrogen gas at 500°C for 24 hours to produce a reduced catalyst.

[0123] (3) Hydrogenation of isophthalonitrile to produce m-xylylenediamine The raw materials were a liquid ammonia solution of isophthalonitrile (3000 mL, mass fraction of isophthalonitrile 10%, mass fraction of liquid ammonia 90%) and pure hydrogen gas (volume fraction of hydrogen gas 99.9%). The catalyst amount was 15 g, the reaction temperature was 80°C, the reaction pressure was 8.0 MPa, the hydrogen gas / isophthalonitrile molar ratio was 5:1, and the liquid hourly space velocity was 10 h . -1 A hydrogenation test was carried out under the conditions shown in Table 1. The reaction results are shown in Table 1. The IPN conversion was 99.8%, and the MXDA selectivity was 94.9%. The 3-methylbenzylamine content was 0.45%.

[0124] It should be noted that the above-described embodiments are used only to explain the present invention and are not intended to limit the present invention. Although the present invention has been described with reference to exemplary embodiments, it should be understood that the terms used therein are words of description and description, rather than words of limitation. The present invention can be modified within the scope of the claims of the present invention, and can be modified without departing from the scope and spirit of the present invention. While the present invention described herein refers to specific methods, materials, and embodiments, it is not intended to be limited to the specific examples disclosed herein; rather, the present invention extends to all other methods and applications having the same functionality.

[0125] [Table 1] [Brief explanation of the drawings]

[0126] [Figure 1] FIG. 1 shows the H2-TPR diagrams produced in Examples 1 and 2 and Comparative Example 1.

Claims

1. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile, comprising: a) an active component, said active component being Ni and / or its oxides; b) an additive, said additive comprising one or more of Mg, Cu, Co, Zn, Zr, Mo and / or oxides thereof; c) an alumina support; Including, when the catalyst is in its fully oxidized state, the relative content of α-NiO in the catalyst is less than or equal to 1.5 a.u.; The relative content of α-NiO in the catalyst was determined by using 50 mg of the catalyst in a fully oxidized state; ２ - Using the TPR diagram, H ２ - Determined by integrating the area of ​​the TPR curve, where the vertical axis is %TCD and the horizontal axis is temperature; and calculating the relative content of each NiO type based on the hydrogen consumption of the sample, in units of a.u. (arbitrary units); The support is an alumina support treated at a temperature of 500°C or higher. characterized in that A catalyst for the production of dibasic amines by hydrogenation of dibasic nitriles.

2. the adjuvant comprises one or more of Mg, Co, Zr, Mo and / or their oxides; and / or When the catalyst is in its fully oxidized state, the relative content of α-NiO in the catalyst is less than or equal to 0.2 a.u.

2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

3. In parts by weight, The content of the active ingredient is 10 to 60 parts; The content of the adjuvant is 0.1 to 120 parts; The content of the carrier is 0.1 to 45 parts.

2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

4. In parts by weight, The content of the active ingredient is 15 to 55 parts; The content of the adjuvant is 0.2 to 90 parts; The content of the carrier is 1 to 35 parts.

2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

5. The proportions of α-alumina, β-alumina, γ-alumina, δ-alumina, and θ-alumina are 0.1 to 99%, 0.1 to 99%, 0.1 to 99%, 0.1 to 99%, and 0.1 to 99%, respectively, based on the weight of the alumina carrier.

2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

6. The proportions of α-alumina, β-alumina, γ-alumina, δ-alumina, and θ-alumina are 10 to 95%, 1 to 70%, 2 to 90%, 5 to 90%, and 3 to 80%, respectively, based on the weight of the alumina carrier.

2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

7. the relative content of α-NiO in the catalyst is greater than 0.0001 a.u.; 2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

8. the relative content of α-NiO in the catalyst is greater than 0.001 a.u.; 2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

9. the relative content of α-NiO in the catalyst is greater than 0.01 a.u.; 2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

10. The content of α-NiO in the catalyst is more than 0.0001 wt.%.

2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

11. The content of α-NiO in the catalyst is more than 0.001 wt.%.

2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

12. The content of α-NiO in the catalyst is more than 0.01 wt.%.

2. A catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to claim 1.

13. A process for producing a catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to any one of claims 1 to 12, comprising the steps of: The method comprises the following steps: 1) carrying out a first contacting of a solution of an auxiliary salt, a solution of a first precipitant, a support, and water to produce a modified support, wherein the support is an alumina support treated at a temperature of 500°C or greater; 2) carrying out a second contact of a solution of a nickel salt, a solution of a second precipitant, the modified support obtained from step 1), and water, followed by filtering and calcination to produce a catalyst; Including, The adjuvant salt is a salt of the adjuvant. A method characterized by:

14. In step 1), to carry out the first contact, the auxiliary salt solution and the first precipitant solution are simultaneously added to the water containing the support; and / or in step 2), to carry out the second contact, the nickel salt solution and the second precipitant solution are simultaneously added to the water containing the modified support obtained from step 1).

14. The method according to claim 13.

15. In step 1), the support used is an alumina support treated at a temperature above 500°C; 14. The method according to claim 13.

16. The solution obtained from the first contact and the solution obtained from the second contact are controlled to a final pH of 6.0 to 10.0; the temperature of the first contact and / or the second contact is 50 to 90°C, and / or the time of the first contact and / or the second contact is 3 to 6 hours; 14. The method according to claim 13.

17. The auxiliary salt is Mg(NO ３ ) ２ , Cu(NO ３ ) ２ , Co(NO ３ ) ２ , Zn(NO ３ ) ２ , Zr(NO ３ ) ４ , (NH ４ ) ２ MoO ４ , Mg(NO ３ ) ２ ・6H ２ O, Cu(NO ３ ) ２ ・3H ２ O, Co(NO ３ ) ２ ・6H ２ O, Zn(NO ３ ) ２ ・6H ２ O and Zr(NO ３ ) ４ ・5H ２ O; and / or said first precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and aqueous ammonia; and / or the nickel salt is nickel sulfate and / or nickel nitrate; and / or the second precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and aqueous ammonia; 14. The method according to claim 13.

18. The auxiliary salt is Mg(NO ３ ) ２ , Mg(NO ３ ) ２ ・6H ２ O, Zr(NO ３ ) 4, (NH ４ ) ２ MoO ４ and Co(NO ３ ) ２ selected from one or more of: and / or the first precipitating agent is sodium hydroxide and / or aqueous ammonia; and / or the nickel salt is nickel nitrate; and / or the second precipitating agent is sodium carbonate and / or sodium bicarbonate; 14. The method according to claim 13.

19. In step 1), the solution of the auxiliary salt has a concentration of 0.1-1.5 mol / L; and / or the solution of the first precipitant has a concentration of 0.4-2.0 mol / L; and / or the content of the carrier in water is 5-100 g / L. and / or in step 2), the nickel salt solution has a concentration of 0.2-1.5 mol / L; and / or the second precipitant solution has a concentration of 0.4-2.0 mol / L; and / or the content of the carrier in water is 10-100 g / L; 14. The method according to claim 13.

20. In step 1), the solution of the auxiliary salt has a concentration of 0.3-1.2 mol / L; and / or the solution of the first precipitant has a concentration of 0.6-1.6 mol / L; and / or the content of the carrier in water is 20-80 g / L, or 5-20 g / L; and / or in step 2), the nickel salt solution has a concentration of 0.5-1.2 mol / L; and / or the second precipitant solution has a concentration of 0.6-1.5 mol / L; and / or the content of the carrier in water is 20-85 g / L, or 10-30 g / L; 14. The method according to claim 13.

21. 1. A process for producing a dibasic amine by hydrogenation of a dibasic nitrile, comprising: contacting the dibasic nitrile with hydrogen gas in the presence of the catalyst of any one of claims 1 to 12 to produce the dibasic amine, wherein the molar ratio of hydrogen gas to dibasic nitrile is from 3:1 to 70:1; The reaction temperature is 50 to 120°C; and / or the reaction pressure is 4.0 to 15.0 MPa; and / or the liquid hourly space velocity is 1 to 12 h －１ That is, method.

22. Use of the catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to any one of claims 1 to 12 in producing a dibasic amine by hydrogenation of a dibasic nitrile.

23. The catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to any one of claims 1 to 12, ４ ~C ２４ Dibasic nitrile, or aromatic C ６ ~C １８ Aliphatic C by hydrogenation of dibasic nitriles ４ ~C ２４ Dibasic amine, or aromatic C ６ ~C １８ Use in the production of dibasic amines.

24. The catalyst for producing a dibasic amine by hydrogenation of a dibasic nitrile according to any one of claims 1 to 12, ４ ~C ２４ Dibasic nitrile, or aromatic C ６ ~C １８ Aliphatic C by hydrogenation of dibasic nitriles ４ ~C ２４ Dibasic amine, or aromatic C ６ ~C １８ Use in the production of a dibasic amine; The aliphatic C ４ ~C ２４ the dibasic amine is selected from hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, and octadecanediamine; The aromatic C ６ ~C １８ the dibasic amine is selected from ortho-benzenedimethaneamine, meta-benzenedimethaneamine, and para-benzenedimethaneamine; aliphatic C ４ ~C ２４ the dibasic nitrile is selected from adiponitrile, pimelonitrile, suberonitrile, nonanedinitrile, decanedinitrile, undecanedinitrile, dodecanedinitrile, tridecanedinitrile, tetradecanedinitrile, pentadecanedinitrile, hexadecanedinitrile, heptadecanedinitrile, and octadecanedinitrile; aromatic C ６ ~C １８ The dibasic nitrile is selected from phthalonitrile, isophthalonitrile, or terephthalonitrile; use.

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