CN113980239B - Method for preparing thermoplastic polyurethane elastomer by using nitroaniline isomer mixture and product thereof - Google Patents
Method for preparing thermoplastic polyurethane elastomer by using nitroaniline isomer mixture and product thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a thermoplastic polyurethane elastomer by utilizing a nitroaniline isomer mixture and a product thereof. The method comprises the following steps: (1) Reacting the isomer mixture of para-position and ortho-position of nitroaniline in an organic solvent at the reaction temperature of 90-160 ℃, the hydrogen pressure of 3-10MPa and the action of a Raney nickel catalyst to obtain a mixture of phenylenediamine and cyclohexanediamine containing para-position and ortho-position isomers; (2) Heating the diamine mixture obtained in the step (1) and phosgene to 300-400 ℃ respectively for gasification, removing hydrogen chloride and phosgene after phosgenation reaction, and distilling to obtain an isocyanate composition containing p-phenylene diisocyanate, o-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate and 1, 2-cyclohexane diisocyanate; (3) And (3) mixing the isocyanate composition obtained in the step (2) with macromolecular polyol and micromolecular diol chain extender to react to obtain the thermoplastic polyurethane elastomer.
Description
Technical Field
The invention relates to the field of thermoplastic polyurethane elastomers, in particular to a method for preparing a thermoplastic polyurethane elastomer by utilizing a nitroaniline isomer mixture and a product thereof.
Background
Nitroaniline is generally prepared by acetylating aniline and then reacting with mixed acid (the research on synthesis of o-nitroaniline, the ministry of Qi, liu, etc.) the nitration position in the reaction process is sensitive to the reaction temperature, the obtained product is generally a nitroaniline isomer mixture, and the product needs to be separated again to obtain p-nitroaniline or o-nitroaniline which is then used subsequently.
The separation and purification of nitroaniline isomer mixture and hydrogenated mixed phenylenediamine generally requires complicated operations such as rectification (such as patent technologies with publication numbers of CN107619373A and CN 102491905A), and has high requirements on equipment and process.
Isocyanate is an important organic compound, and diisocyanates such as diphenylmethane diisocyanate, toluene diisocyanate and the like are widely applied to the field of polyurethane material synthesis, but conventionally used isocyanates are generally pure substances, the preparation process needs more complicated purification and separation work, and the flow is complicated.
Disclosure of Invention
The invention provides a method for preparing a thermoplastic polyurethane elastomer by utilizing a nitroaniline isomer mixture, which has a simple technical route, utilizes a nitroaniline raw material which is not subjected to isomer separation and purification to prepare a special isocyanate composition, is applied to the synthesis of a polyurethane material, improves the comprehensive properties of the product, such as dynamic mechanical property, transparency, rebound resilience, yellowing resistance, heat resistance and the like, and realizes the direct and effective utilization of the nitroaniline isomer mixture.
A process for preparing a thermoplastic polyurethane elastomer from a mixture of nitroaniline isomers comprising the steps of:
(1) Reacting the isomer mixture of para-position and ortho-position of nitroaniline in an organic solvent at the reaction temperature of 90-160 ℃, the hydrogen pressure of 3-10MPa and the action of a Raney nickel catalyst to obtain a mixture of phenylenediamine and cyclohexanediamine containing para-position and ortho-position isomers;
(2) Mixing the diamine mixture obtained in the step (1) and phosgene (COCl) 2 ) Respectively heating to 300-400 ℃ for gasification, removing hydrogen chloride and phosgene after phosgenation reaction, and distilling to obtain an isocyanate composition containing p-phenylene diisocyanate, o-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate and 1, 2-cyclohexane diisocyanate;
(3) And (3) mixing the isocyanate composition obtained in the step (2) with macromolecular polyol and micromolecular diol chain extender to react to obtain the thermoplastic polyurethane elastomer.
The invention adopts the isomer mixture of para position and ortho position of nitroaniline as the unseparated product after the acylation nitration of aniline, reduces the steps of separating and purifying raw materials and products, and uses a relatively cheap Raney nickel catalyst to carry out one-step hydrogenation to obtain the composition containing aromatic and aliphatic diisocyanate, which is applied to the synthesis of polyurethane materials.
In a preferable example, in the step (1), in the isomer mixture of the para-position and the ortho-position of nitroaniline, the mass ratio of p-nitroaniline to o-nitroaniline is 4-9.
In a preferred example, in the step (1), the mass ratio of the p-position and ortho-position isomer mixture of nitroaniline to the total mass of the organic solvent is 20-60%, based on 100% of the total mass of the p-position and ortho-position isomer mixture of nitroaniline and the organic solvent.
In the step (1), the organic solvent is preferably at least one of cyclohexane, dioxane, tetrahydrofuran, cyclohexylamine, dicyclohexylamine, isopropanol, ethanol, methanol, n-butanol, 2-butanol, toluene, xylene, and ethyl acetate, and more preferably at least one of ethanol, isopropanol, and methanol.
In the step (1), the mass of the raney nickel catalyst is preferably 0.1 to 10% of the mass of the nitroaniline para-position and ortho-position isomer mixture, and more preferably 1 to 5% of the mass of the nitroaniline para-position and ortho-position isomer mixture.
In a preferable example, in the step (1), the reaction temperature is 100-140 ℃, and the hydrogen pressure is 4-8MPa.
In a preferred embodiment, in the step (2), the diamine mixture obtained in the step (1) and phosgene are respectively heated to 330-380 ℃ for gasification.
In a preferred embodiment, in the step (2), the molar ratio of the phosgene to the amine groups in the diamine mixture is 1.5 to 3.
In a preferred example, in step (2), the phosgenation reaction is carried out in a tubular reactor.
In a preferred embodiment, the absolute pressure in the feed pipe of the tubular reactor is from 500 to 2000mbar, the outlet pressure of the tubular reactor is from 300 to 1300mbar, and the residence time of the reaction mixture in the tubular reactor is from 1 to 3s.
In a preferable example, in the step (2), in the isocyanate composition, the mass ratio of p-phenylene diisocyanate is 50% to 70%, the mass ratio of o-phenylene diisocyanate is 5% to 15%, the mass ratio of 1, 4-cyclohexane diisocyanate is 20% to 40%, and the mass ratio of 1, 2-cyclohexane diisocyanate is 3% to 10%.
In a preferred embodiment, in the step (2), the mass content X of the-NCO (isocyanate group) in the isocyanate composition is 50.6% < X < 52.5%.
In the step (3), the method of the present invention can calculate the ratio of the suitable macromolecular polyol (polyester polyol and/or polyether polyol, etc.) and the chain extender of the small molecular diol according to the content of the isocyanate group in the obtained isocyanate composition, and the three components are mixed in a reactor or a twin-screw extruder for reaction, cooled and granulated to obtain the thermoplastic polyurethane elastomer. The reaction zone temperature may be 170-200 ℃.
The invention also provides the thermoplastic polyurethane elastomer prepared by the method.
Compared with the prior art, the invention has the main advantages that:
1) The direct product of aniline acetylation nitration, namely nitroaniline mixture without separating isomers, is different from the conventional separation and purification inertia thinking in the prior art, the technical scheme of the invention develops a new way, the nitroaniline mixture is directly used as an initial raw material, separation and purification are not carried out, and aromatic and aliphatic diisocyanate compositions are prepared by direct hydrogenation and phosgenation reaction, so that the thermoplastic polyurethane elastomer with excellent performance is further prepared, the process route is simple and efficient, and the direct, sufficient and more valuable utilization of the isomer mixture at the para position and the ortho position of the nitroaniline is realized at low cost.
2) According to the technical scheme, only a Raney nickel catalyst is used in the hydrogenation reaction process, noble metal catalysts such as ruthenium and rhodium are not used, the catalyst cost is low, the hydrogenation reaction degree does not need to be controlled in the hydrogenation reaction process, the performance and the application of a final product are not influenced due to the simultaneous existence of nitro hydrogenation and benzene ring hydrogenation, and the requirements on the selection of the catalyst and the process conditions are lower.
3) The isocyanate composition containing p-phenylene diisocyanate, o-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate and 1, 2-cyclohexane diisocyanate is obtained by the technical route, subsequent separation is not needed for the composition, the composition is directly applied to polyurethane reaction, the reaction activities of the p-phenylene diisocyanate, the o-phenylene diisocyanate, the 1, 4-cyclohexane diisocyanate and the 1, 2-cyclohexane diisocyanate are balanced, and the existence of the aromatic diisocyanate and the aliphatic diisocyanate enables the transparency, the yellowing resistance, the weather resistance and the like of the product to be obviously improved.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
a) Mixing an isomer mixture of para-position and ortho-position of nitroaniline (wherein the p-nitroaniline accounts for 90wt%, and the o-nitroaniline accounts for 10 wt%) with an ethanol solvent according to a mass ratio of 1:1, adding 3wt% (relative to the mass of nitroaniline) of Raney nickel catalyst into a high-pressure stirring kettle, sealing for reaction, detecting nitrogen leakage, introducing hydrogen to 4MPa to replace gas for 3 times after no gas leakage is confirmed, introducing the hydrogen to 4MPa, heating to 100 ℃, maintaining the temperature, maintaining the hydrogen pressure in the kettle at 4MPa, keeping for 4 hours, cooling to 40 ℃, relieving pressure for replacement, settling and separating reaction liquid and the catalyst, filtering the reaction liquid in the kettle, flushing the intercepted solid catalyst into the reaction kettle through back flushing operation to continue hydrogenation reaction of the next batch, freezing the reaction liquid with salt water, filtering and drying to obtain a mixture of phenylenediamine and cyclohexanediamine containing para-position and ortho-position isomers.
b) Mixing the diamine mixture obtained in step a), phosgene and nitrogen in a molar ratio of 1:4:1 are heated to 360 ℃ by respective heat exchangers and continuously flow into a reactor, and a gas jet absorption device for condensation and an excess phosgene and hydrogen chloride absorption tower are connected at the downstream of the reactor. The internal diameter of the tubular reactor was 15mm, the pressure in the reactor tube was 600mbar, the flow rate of the diamine mixture vapor and nitrogen flowing through the outlet of the reactor tube was about 28m/s, the flow rate of phosgene was about 5m/s, and after staying in the reactor for 1.5s, a photochemical solution of a diisocyanate composition was obtained, and after distillation, an isocyanate composition was obtained, which, according to gas phase tests, accounted for 63.8wt% for p-phenylene diisocyanate, 6.7wt% for o-phenylene diisocyanate, 26.2wt% for 1, 4-cyclohexane diisocyanate, and 3.3wt% for 1, 2-cyclohexane diisocyanate.
Example 2
a) Mixing a p-nitroaniline isomer mixture and an ortho-nitroaniline isomer mixture (wherein the p-nitroaniline accounts for 86wt%, and the o-nitroaniline accounts for 14 wt%) with an ethanol solvent according to a mass ratio of 1:1.5, adding the mixture into a high-pressure stirring kettle, adding 4wt% (relative to the mass of nitroaniline) of Raney nickel catalyst into the kettle, sealing the mixture for reaction, detecting the leakage of nitrogen, introducing hydrogen to 5.5MPa after no air leakage is confirmed, replacing gas for 3 times, introducing the hydrogen to 5.5MPa, heating to 110 ℃ to maintain the temperature, maintaining the hydrogen pressure in the kettle at 5.5MPa, keeping the pressure for 4 hours, cooling to 40 ℃ and decompressing and replacing, then separating reaction liquid and catalyst by settling, filtering the reaction liquid in the kettle, flushing the intercepted solid catalyst into the reaction kettle by back flushing operation to continue the hydrogenation reaction of the next batch, carrying out frozen brine treatment on the reaction liquid, and filtering and drying to obtain a phenylenediamine and cyclohexanediamine mixture containing para and ortho isomers.
b) Mixing the diamine mixture obtained in step a), phosgene and nitrogen in a ratio of 1:4:1 are heated to 350 ℃ via respective heat exchangers and continuously flow into a reactor, and a gas jet absorption device for condensation and an excess phosgene and hydrogen chloride absorption tower are connected at the downstream of the reactor. The internal diameter of the tubular reactor was 15mm, the pressure in the reactor tube was 800mbar, the flow rate of the diamine mixture vapor and nitrogen flowing through the outlet of the reactor tube was about 28m/s, the flow rate of phosgene was about 5m/s, the diisocyanate composition photochemical solution was obtained after staying in the reactor for 2s, and the isocyanate composition was obtained after distillation treatment, the proportion of p-phenylene diisocyanate was 62.4wt%, the proportion of o-phenylene diisocyanate was 7.5wt%, the proportion of 1, 4-cyclohexane diisocyanate was 23.6wt%, and the proportion of 1, 2-cyclohexane diisocyanate was 6.5wt% according to the gas phase test.
Example 3
a) Mixing a p-nitroaniline isomer mixture and an ortho-nitroaniline isomer mixture (wherein the p-nitroaniline accounts for 80wt%, and the o-nitroaniline accounts for 20 wt%) with an isopropanol solvent according to a mass ratio of 1: adding 1 into a high-pressure stirring kettle, adding 5wt% (relative to the mass of nitroaniline) of Raney nickel catalyst into the kettle, sealing for reaction, detecting nitrogen leakage, introducing hydrogen to 7MPa for replacing gas for 3 times after confirming no gas leakage, introducing the hydrogen to 7MPa, heating to 125 ℃, maintaining the temperature, maintaining the hydrogen pressure in the kettle at 7MPa, keeping for 6 hours, cooling to 40 ℃, decompressing and replacing, then separating reaction liquid and catalyst by settling, filtering the reaction liquid in the kettle, flushing the intercepted solid catalyst into the reaction kettle by back flushing operation for continuous hydrogenation reaction of the next batch, freezing the reaction liquid with salt water, filtering and drying to obtain a mixture of phenylenediamine and cyclohexanediamine containing para-isomer and ortho-isomer.
b) Mixing the diamine mixture obtained in step a), phosgene and nitrogen in a ratio of 1:5:1 are heated to 360 ℃ by respective heat exchangers and continuously flow into a reactor, and a gas jet absorption device for condensation and an excess phosgene and hydrogen chloride absorption tower are connected at the downstream of the reactor. The internal diameter of the tubular reactor was 15mm, the pressure in the reactor tube was 1000mbar, the flow rate of the diamine mixture vapor and nitrogen flowing through the outlet of the reactor tube was about 29m/s, the flow rate of phosgene was about 5.5m/s, and after 3s of residence time in the reactor, the photochemical solution of the diisocyanate composition was obtained, and after distillation treatment, the isocyanate composition was obtained, which, according to gas phase tests, accounted for 51.2wt% for p-phenylene diisocyanate, 10.6wt% for o-phenylene diisocyanate, 28.8wt% for 1, 4-cyclohexane diisocyanate, and 9.4wt% for 1, 2-cyclohexane diisocyanate.
Example 4
a) Mixing an isomer mixture of para-position and ortho-position of nitroaniline (wherein the p-nitroaniline accounts for 88wt%, and the o-nitroaniline accounts for 12 wt%) with a methanol solvent according to a mass ratio of 1: adding 1 into a high-pressure stirring kettle, adding 2.8wt% (relative to the mass of nitroaniline) of Raney nickel catalyst into the kettle, sealing for reaction, detecting nitrogen leakage, introducing hydrogen to 9MPa after no gas leakage is confirmed, replacing gas for 3 times, introducing the hydrogen to 9MPa, heating to 140 ℃ to maintain the temperature, maintaining the hydrogen pressure in the kettle at 9MPa, keeping for 3 hours, cooling to 40 ℃, decompressing and replacing, then separating reaction liquid and catalyst by settling, filtering the reaction liquid in the kettle, flushing the intercepted solid catalyst into the reaction kettle by back flushing operation for continuous hydrogenation reaction of the next batch, carrying out frozen brine treatment on the reaction liquid, filtering and drying to obtain a phenylenediamine and cyclohexanediamine mixture containing para-position and ortho-position isomers.
b) Mixing the diamine mixture obtained in step a), phosgene and nitrogen in a ratio of 1:4:1 are heated to 370 ℃ via respective heat exchangers and continuously fed into a reactor, and a gas jet absorption device for condensation and an excess phosgene and hydrogen chloride absorption tower are connected at the downstream of the reactor. The inner diameter of the tubular reactor is 15mm, the pressure in the reactor tube is 900mbar, wherein the flow rate of the diamine mixture steam and nitrogen flowing through the outlet of the reactor tube is about 28m/s, the flow rate of phosgene is about 5m/s, the photochemical solution of the diisocyanate composition is obtained after the diamine mixture steam and nitrogen stay in the reactor for 1.9s, and the isocyanate composition is obtained after distillation treatment, wherein the proportion of p-phenylene diisocyanate is 66.2wt%, the proportion of o-phenylene diisocyanate is 7.6wt%, the proportion of 1, 4-cyclohexane diisocyanate is 21.8wt%, and the proportion of 1, 2-cyclohexane diisocyanate is 4.4wt% according to gas phase tests.
Example 5
a) Mixing an isomer mixture of para-position and ortho-position of nitroaniline (wherein the p-nitroaniline accounts for 90wt%, and the o-nitroaniline accounts for 10 wt%) with an ethanol solvent according to a mass ratio of 1:2, adding 3.3wt% (relative to the mass of nitroaniline) of Raney nickel catalyst into a high-pressure stirring kettle, sealing for reaction, detecting nitrogen leakage, introducing hydrogen to 8MPa for replacing gas for 3 times after confirming no gas leakage, introducing the hydrogen to 8MPa, heating to 135 ℃ for maintaining the temperature, maintaining the hydrogen pressure in the kettle at 8MPa, keeping for 6 hours, cooling to 40 ℃, decompressing and replacing, then separating reaction liquid and catalyst by settling, filtering the reaction liquid in the kettle, flushing the intercepted solid catalyst into the reaction kettle by back flushing operation for continuous hydrogenation reaction of the next batch, carrying out frozen brine treatment on the reaction liquid, filtering and drying to obtain the mixture of phenylenediamine and cyclohexanediamine containing para-isomer and ortho-isomer.
b) Mixing the diamine mixture obtained in step a), phosgene and nitrogen in a ratio of 1:4:1 are heated to 360 ℃ by respective heat exchangers and continuously flow into a reactor, and a gas jet absorption device for condensation and an excess phosgene and hydrogen chloride absorption tower are connected at the downstream of the reactor. The internal diameter of the tubular reactor was 15mm, the pressure in the reactor tube was 1200mbar, the flow rate of the diamine mixture vapor flowing through the outlet of the reactor tube and nitrogen was about 29m/s, the flow rate of phosgene was about 5.5m/s, the photochemical solution of the diisocyanate composition was obtained after staying in the reactor for 2.2s, and the isocyanate composition was obtained after distillation treatment, and the content of p-phenylene diisocyanate, o-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, and 1, 2-cyclohexane diisocyanate, respectively, was 55.9wt%, 5.1wt%, 34.1wt%, and 4.9wt%, respectively, according to the gas phase test.
Example 6
Using the isocyanate composition prepared in example 5, a mixture of a polybutylene adipate polyol (molecular weight 2000 g/mol), 1, 4-butanediol in a ratio of 21.35% by weight: 70wt%:8.65wt% of the mixture is added into a double-screw extruder to be extruded in a reaction mode, the temperature of a reaction zone is 170-200 ℃, and the thermoplastic polyurethane elastomer is obtained after cooling and grain cutting.
Example 7
Using the isocyanate composition prepared in example 3, with polycaprolactone polyol (molecular weight 2100 g/mol), 1, 4-butanediol in a ratio of 21.21% by weight: 70wt%:8.79wt% of the mixture is added into a double-screw extruder for reaction and extrusion, the temperature of a reaction zone is 180-200 ℃, and the thermoplastic polyurethane elastomer is obtained after cooling and grain cutting.
Example 8
Using the isocyanate composition prepared in example 5, in a ratio of 21.58% by weight with polytetrahydrofuran polyol (molecular weight 1800 g/mol), 1, 4-butanediol: 70wt%:8.42wt% of the mixture is added into a double-screw extruder for reaction and extrusion, the temperature of a reaction zone is 180-200 ℃, and the thermoplastic polyurethane elastomer is obtained after cooling and grain cutting.
Example 9
Using the isocyanate composition prepared in example 1, a 23.89% by weight ratio to the polytetramethylene adipate polyol (molecular weight 1950 g/mol), 1, 4-butanediol was used: 66wt%:10.11wt% of the mixture is added into a double-screw extruder to be extruded in a reaction way, the temperature of a reaction zone is 180-200 ℃, and the thermoplastic polyurethane elastomer is obtained after cooling and grain cutting.
Example 10
Using the isocyanate composition prepared in example 1, with polycaprolactone polyol (molecular weight 2240 g/mol), 1, 4-butanediol in a ratio of 23.63wt%:66wt%:10.37wt% of the mixture is added into a double-screw extruder to be extruded in a reaction mode, the temperature of a reaction zone is 180-200 ℃, and the thermoplastic polyurethane elastomer is obtained after cooling and grain cutting.
Example 11
Using the isocyanate composition prepared in example 2, in a ratio of 24.61% by weight with polytetrahydrofuran polyol (molecular weight 1850 g/mol), 1, 4-butanediol: 65wt%:10.39wt% of the mixture is added into a double-screw extruder to be extruded in a reaction mode, the temperature of a reaction zone is 180-200 ℃, and the thermoplastic polyurethane elastomer is obtained after cooling and grain cutting.
Comparative example 1
4,4' -diphenylmethane diisocyanate (MDI) is adopted, and the mixture is mixed with polybutylene adipate-butanediol ester polyol (molecular weight 2000 g/mol) and 1, 4-butanediol according to the proportion of 24.44 percent by weight: 70wt%:5.56wt% of the mixture is added into a double-screw extruder to be extruded in a reaction mode, the temperature of a reaction zone is 180-200 ℃, and the thermoplastic polyurethane elastomer is obtained after cooling and grain cutting.
Comparative example 2
4,4' -dicyclohexyl methane diisocyanate (HMDI) is adopted to be mixed with polycaprolactone polyol (molecular weight of 2240 g/mol) and 1, 4-butanediol according to the proportion of 35.23wt%:55wt%:9.77wt% of the mixture is added into a double-screw extruder to be extruded in a reaction way, the temperature of a reaction zone is 180-200 ℃, and the thermoplastic polyurethane elastomer is obtained after cooling and grain cutting.
The performance tests of the thermoplastic polyurethane elastomers of examples 6 to 8 and comparative example 1 with commercially available E90 (Merrill materials Co., ltd.) are shown in the following table:
the performance tests of the thermoplastic polyurethane elastomers of examples 9 to 11 and comparative example 2 with commercially available E95 (Merrill materials Co., ltd.) are shown in the following table:
as can be seen from the data in the above table, the thermoplastic polyurethane elastomer prepared based on the isocyanate composition of the present invention has the same excellent mechanical properties as the commercially available E90, E95 (conventional 4,4' -diphenylmethane diisocyanate MDI based thermoplastic polyurethane elastomer) and the comparative example (thermoplastic polyurethane elastomer prepared by using conventional MDI and HMDI), the 2mm turbidity is significantly lower than that of E90, E95 and the comparative example, the QUV grade is higher than that of E90 and E95 and the comparative example shows that the thermoplastic polyurethane elastomer prepared based on the isocyanate composition of the present invention has more excellent transparency and yellowing resistance and weather resistance, the dynamic mechanical property Tan delta is significantly lower than that of E90, E95 and the comparative example, and the Tan delta is almost unchanged along with the temperature, which shows that the mechanical loss at the same temperature is lower and the heat resistance is better, thereby showing that the thermoplastic polyurethane elastomer prepared by directly using the nitroaniline isomer mixture in the technical scheme of the present invention has excellent comprehensive properties.
Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention defined by the appended claims.
Claims (8)
1. A method for preparing a thermoplastic polyurethane elastomer from a nitroaniline isomer mixture, which is characterized by comprising the following steps:
(1) Reacting the p-position isomer mixture and the ortho-position isomer mixture of nitroaniline in an organic solvent at the reaction temperature of 90-160 ℃, the hydrogen pressure of 3-10MPa and the action of a Raney nickel catalyst to obtain a p-position isomer-containing phenylenediamine and an ortho-position isomer-containing cyclohexanediamine mixture;
in the isomer mixture of para-position and ortho-position of nitroaniline, the mass ratio of p-nitroaniline to o-nitroaniline is 4-9;
the mass of the Raney nickel catalyst is 0.1-10% of the mass of the nitroaniline para-position and ortho-position isomer mixture;
(2) Respectively heating the diamine mixture obtained in the step (1) and phosgene to 300-400 ℃ for gasification, removing hydrogen chloride and phosgene after carrying out phosgenation reaction, and distilling to obtain an isocyanate composition containing p-phenylene diisocyanate, o-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate and 1, 2-cyclohexane diisocyanate;
in the isocyanate composition, the mass percentage of p-phenylene diisocyanate is 50-70%, the mass percentage of o-phenylene diisocyanate is 5-15%, the mass percentage of 1, 4-cyclohexane diisocyanate is 20-40%, and the mass percentage of 1, 2-cyclohexane diisocyanate is 3-10%;
(3) And (3) mixing the isocyanate composition obtained in the step (2) with macromolecular polyol and micromolecular diol chain extender to react to obtain the thermoplastic polyurethane elastomer.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the isomer mixture of the para-position and the ortho-position of the nitroaniline is 20-60% based on the total mass of the isomer mixture of the para-position and the ortho-position of the nitroaniline and the organic solvent being 100%.
3. The method according to claim 1, wherein in the step (1), the organic solvent is at least one of cyclohexane, dioxane, tetrahydrofuran, cyclohexylamine, dicyclohexylamine, isopropanol, ethanol, methanol, n-butanol, 2-butanol, toluene, xylene, and ethyl acetate.
4. The method according to claim 1, wherein in the step (1), the reaction temperature is 100 to 140 ℃ and the hydrogen pressure is 4 to 8MPa.
5. The method of claim 1, wherein in step (2):
heating the diamine mixture obtained in the step (1) and phosgene to 330-380 ℃ respectively for gasification;
the molar ratio of the phosgene to the amine groups in the diamine mixture is 1.5 to 3.
6. The method of claim 1, wherein in step (2):
the phosgenation reaction is carried out in a tubular reactor;
the absolute pressure in the feed pipe of the tubular reactor is 500-2000mbar, the outlet pressure of the tubular reactor is 300-1300mbar, and the residence time of the reaction mixture in the tubular reactor is 1-3s.
7. The process according to claim 1, wherein in step (2), the isocyanate composition has a mass X of-NCO content of 50.6% < X < 52.5%.
8. The thermoplastic polyurethane elastomer prepared by the process according to any one of claims 1 to 7.
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