CN110105248B - Preparation method of toluene diisocyanate - Google Patents
Preparation method of toluene diisocyanate Download PDFInfo
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- CN110105248B CN110105248B CN201910469661.1A CN201910469661A CN110105248B CN 110105248 B CN110105248 B CN 110105248B CN 201910469661 A CN201910469661 A CN 201910469661A CN 110105248 B CN110105248 B CN 110105248B
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Abstract
The invention relates to a preparation method of toluene diisocyanate, which comprises the steps of adding a catalyst polyoxometallate and a solvent into a reaction container, adding raw materials of 2, 6-diaminotoluene, phenylsilane, an acid binding agent and a dehydrating agent, uniformly mixing, finally adding gaseous carbon dioxide, and carrying out magnetic stirring and full reaction at a certain temperature to obtain a product. The method of the invention adopts Anderson type heteropoly acid as the catalyst, the catalyst has mild reaction conditions and high specific selectivity, can be recycled and is environment-friendly, the cleanness of industrial reaction is improved, the economical efficiency of the process is improved, the manufacturing cost and the generation of three wastes are reduced, the environmental protection pressure is reduced, and the method is beneficial to industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of toluene diisocyanate.
Background
The toluene diisocyanate is mainly used as a production raw material of polyurethane resin, is used for producing polyvinyl chloride foam-coated plastics, coatings, rubber, sealants, adhesives and the like, and can also be used as a rubber vulcanizing agent, a protein crosslinking agent and the like. Comprises a foamed plastic; a polyurethane coating; a urethane rubber; polyimide fibers and adhesives have also found some applications. The synthesis and application research of toluene diisocyanate is widely concerned due to the wide application range.
The traditional preparation of toluene diisocyanate is to nitrify toluene to generate dinitrotoluene, and then to reduce the dinitrotoluene to obtain toluenediamine. The toluene diamine reacts with phosgene to obtain toluene diisocyanate TDI, but the preparation method is complicated and has low yield, and the most fatal defects are that phosgene has strong toxicity and high equipment requirement.
In the patent CN108570135A, in a nitrogen atmosphere, a phenolic substance, an aldehyde substance, a catalyst and a solvent are first added into a reactor, after a certain period of reaction, an amine substance and formaldehyde are added to continue the reaction, and the target product toluene diisocyanate is obtained by reduced pressure distillation. The catalyst used in the invention has good stability, and the trimerization reaction of the toluene diisocyanate has higher catalytic activity and excellent catalytic selectivity, but the purification mode of reduced pressure distillation has the disadvantages that when the pressure is improperly controlled or the pressure is unstable, the distillation fails and the container needs to be resistant to vacuum.
Disclosure of Invention
The present invention is directed to solving the above problems and providing a simple process for preparing toluene diisocyanate.
The purpose of the invention is realized by the following technical scheme:
a preparation method of toluene diisocyanate takes 2, 6-diaminotoluene and gaseous carbon dioxide as raw materials, takes polyoxometallate as a catalyst to carry out coupling reaction, and the general reaction formula is as follows:
preferably, 2, 6-diaminotoluene, polyoxometallate and a solvent are mixed and added into a reaction vessel, then phenylsilane, an acid-binding agent and a dehydrating agent are added, the mixture is uniformly mixed, finally gaseous carbon dioxide is introduced, the reaction temperature is set to be 0-40 ℃, the mixture is stirred and reacted for 6-24 hours, and the product is obtained after separation and purification.
Preferably, the catalyst is Fe, Cu, Ni or Cr-centered Anderson type polyoxometallate or Fe, Cu, Ni or Cr-centered Anderson type polyoxometallate modified by trialkoxy derivatives (Tris derivatives), and the characterization map is shown in the attached figures 1-5. The Fe-POM catalyst is most preferably used, and the amount of the catalyst is preferably 0.1 to 5 mol%, more preferably 1 mol%.
Preferably, the acid-binding agent is pyridine or triethylamine, and the acid-binding agent is added to absorb acid generated in the reaction process so as to improve the reaction yield.
Preferably, the dehydrating agent is dimethyl sulfoxide or phosphorus oxychloride.
Preferably, the solvent is selected from N, N-dimethylformamide, dimethyl sulfoxide, toluene or anhydrous acetonitrile, preferably the solvent is toluene.
Preferably, the reaction temperature is set to be 0-30 ℃, the reaction time is 6-12 h, and further preferably, the reaction temperature is set to be 30 ℃, and the reaction time is 12 h.
Preferably, the molar ratio of the polyoxometallate, the 2, 6-diaminotoluene, the phenylsilane, the acid-binding agent and the dehydrating agent is 0.02: 2: 4: 1: and 2, the ratio of the using amount of the solvent to the 2, 6-diaminotoluene is 3 mL/mmol.
Preferably, the polyoxometallate catalyst after the reaction is recovered by using an organic solvent, and the recovered catalyst is recycled, wherein the organic solvent adopts diethyl ether, ethanol, ethyl acetate, methanol and the like.
The method utilizes 2, 6-diaminotoluene and carbon dioxide as reaction raw materials, generates toluene diisocyanate by one-step coupling, has simple process flow and simple raw materials, greatly improves atom economy, and has important significance in the research of carbon dioxide fixation and chemical transformation in view of environmental protection and resource utilization because carbon dioxide is a main source of greenhouse effect and is also the most abundant resource in the nature. The catalyst can be reused for many times after being simply treated, is a simple, environment-friendly and efficient synthesis path, is economical, green and efficient, and is used for directly preparing a target product by a one-step method, so that the efficiency is greatly improved.
Compared with the existing method for preparing toluene diisocyanate, the method has the following advantages:
1. the method has the characteristics of simple process flow, low production cost, no three wastes, high product yield and the like, adopts nontoxic and harmless carbon dioxide which is a renewable resource as one of raw materials, and is a method for preparing the toluene diisocyanate with high atom economy and environmental friendliness.
2. The adopted catalyst is a novel catalyst, the polyoxometallate (heteropoly acid) mainly in an Anderson type is adopted, the central metal is common non-noble metal, the catalyst is an efficient multifunctional catalyst, the catalyst has higher reaction activity and stability, the oxidation-reduction catalytic performance is excellent, the catalyst belongs to a green efficient catalyst, the catalyst can be recycled for a plurality of times after being simply treated, the corrosivity to equipment is extremely low, and the catalyst is favorable for industrial production.
Drawings
FIG. 1 is an infrared spectrum of an Anderson-type polyoxometalate modified with an Anderson-type or Tris derivative of the invention (taking iron as a metal center as an example);
FIG. 2 is a comparison of XRD patterns of the Anderson-based polyoxometallates of the invention (iron being the metal center for example) versus multiple recycles;
FIG. 3 is a nuclear magnetic spectrum of an Anderson-type polyoxometalate modified with a Tris derivative of the invention (taking iron as a metal center as an example);
FIG. 4 is an SEM image of an Anderson-type polyoxometalate of the present invention (taking iron as a metal center as an example);
FIG. 5 is an SEM image of an Anderson-type polyacid modified with a Tris derivative of the present invention (taking iron as a metal center as an example).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A25 mL clean reaction tube was charged with 0.0240g (0.02mmol) of nickel-centered polyoxometallate [ NH ]4]4[NiMo6O18(OH)6]·7H2O(NiMo6) 6mL of a toluene solvent, 0.2484g (2mmol) of 2, 6-diaminotoluene, 0.3067g (2mmol) of phosphorus oxychloride, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol)l) triethylamine, and finally sleeving a balloon filled with carbon dioxide on the reaction tube to react for 12 hours at the temperature of 30 ℃; after the reaction is finished, sampling and measuring GC-MS, and obtaining that the conversion rate of a reaction substrate is more than 93 percent, the selectivity of a product is 90 percent, separating and purifying to obtain a light yellow liquid, and confirming that the product is the toluene diisocyanate through nuclear magnetism.
Example 2
A25 mL clean reaction tube was charged with 0.0240g (0.02mmol) of iron-centered polyoxometallate [ NH ]4]3[FeMo6O18(OH)6]·7H2O(FeMo6) 6mL of toluene solvent, 0.2484g (2mmol) of 2, 6-diaminotoluene, 0.3067g (2mmol) of phosphorus oxychloride, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol) of triethylamine, and finally covering a balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, sampling and measuring GC-MS, obtaining that the conversion rate of a reaction substrate is more than 95 percent, the selectivity of a product is 91 percent, separating and purifying to obtain a light yellow liquid, and confirming that the product is the toluene diisocyanate through nuclear magnetism.
Example 3
A25 mL clean reaction tube was charged with 0.0240g (0.02mmol) of copper-centered polyoxometallate [ NH ]4]4[CuMo6O18(OH)6]·7H2O(CuMo6) 6mL of toluene solvent, 0.2484g (2mmol) of 2, 6-diaminotoluene, 0.3067g (2mmol) of phosphorus oxychloride, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol) of triethylamine, and finally covering a balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, sampling and measuring GC-MS, knowing that the conversion rate of the reaction substrate is more than 91 percent, the selectivity of the product is 89 percent, separating and purifying to obtain light yellow liquid, and confirming that the product is the toluene diisocyanate through nuclear magnetism.
Example 4
A25 mL clean reaction tube was charged with 0.0240g (0.02mmol) of chromium-centered polyoxometallate [ NH ]4]3[CrMo6O18(OH)6]·7H2O(CrMo6) 6mL of a toluene solvent, 0.2484g (2mmol) of 2, 6-diaminotoluene, 0.3067g (2mmol) of phosphorus oxychloride, 0.2164g (4mmol) of phenylsilane, 0.1012g of (A), (B), (C), (D) and (D)1mmol) of triethylamine, and finally sleeving a balloon filled with carbon dioxide on the reaction tube to react for 12 hours at the temperature of 30 ℃; after the reaction is finished, sampling and measuring GC-MS, obtaining that the conversion rate of a reaction substrate is more than 90 percent, the selectivity of a product is 89 percent, separating and purifying to obtain a light yellow liquid, and confirming that the product is the toluene diisocyanate through nuclear magnetism.
Example 5
0.0407g (0.02mmol) of a Tris derivative single-side modified nickel-centered polyoxometalate [ N (C) ]was put into a 25mL clean reaction tube4H9)4]4[NiMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-NiMo6) 6mL of solvent toluene, 0.4207g (2mmol) of 4, 4' -diaminodicyclohexylmethane, 0.1012g (1mmol) of triethylamine, 0.2164g (4mmol) of phenylsilane, 0.3067g (2mmol) of phosphorus oxychloride, and finally covering a balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, sampling and measuring GC-MS, and obtaining that the conversion rate of a reaction substrate is more than 89 percent and the selectivity of a product is 88 percent; adding diethyl ether (or organic solvent such as ethyl acetate) into the final reaction system, filtering to obtain white solid, washing, drying, collecting and recycling. Separating and purifying to obtain light yellow liquid, and confirming the product toluene diisocyanate by nuclear magnetic test analysis.
Example 6
0.0407g (0.02mmol) of an iron-centered polyoxometalate modified on one side with a Tris derivative [ [ N (C) ] was added to a 25mL clean reaction tube4H9)4]3[FeMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-FeMo6) 6mL of solvent toluene, 0.4207g (2mmol) of 4, 4' -diaminodicyclohexylmethane, 0.0641g (2mmol) of methanol, 0.1012g (1mmol) of triethylamine, 0.2164g (4mmol) of phenylsilane, 0.3067g (2mmol) of phosphorus oxychloride, and finally sleeving a balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, sampling and measuring GC-MS, and obtaining that the conversion rate of a reaction substrate is more than 92 percent and the selectivity of a product is 93 percent; to the final reaction bodyAdding diethyl ether (or organic solvent such as ethyl acetate), filtering to obtain white solid, washing, drying, and collecting for recycling. Separating and purifying to obtain light yellow liquid, and confirming the product toluene diisocyanate by nuclear magnetic test analysis.
Example 7
0.0407g (0.02mmol) of copper-centered polyoxometallate modified on one side with a Tris derivative [ [ N (C) ] was added to a 25mL clean reaction tube4H9)4]4[CuMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-CuMo6) 6mL of solvent toluene, 0.4207g (2mmol) of 4, 4' -diaminodicyclohexylmethane, 0.1012g (1mmol) of triethylamine, 0.2164g (4mmol) of phenylsilane, 0.3067g (2mmol) of phosphorus oxychloride, and finally covering a balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, sampling and measuring GC-MS, and obtaining that the conversion rate of a reaction substrate is more than 90 percent and the selectivity of a product is 89 percent; adding diethyl ether (or organic solvent such as ethyl acetate) into the final reaction system, filtering to obtain white solid, washing, drying, collecting and recycling. Separating and purifying to obtain light yellow liquid, and confirming the product toluene diisocyanate by nuclear magnetic test analysis.
Example 8
0.0407g (0.02mmol) of chromium-centered polyoxometallate modified on one side with a Tris derivative [ [ N (C) ] was added to a 25mL clean reaction tube4H9)4]3[CrMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-CrMo6) 6mL of solvent toluene, 0.4207g (2mmol) of 4, 4' -diaminodicyclohexylmethane, 0.1012g (1mmol) of triethylamine, 0.2164g (4mmol) of phenylsilane, 0.3067g (2mmol) of phosphorus oxychloride, and finally covering a balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, sampling and measuring GC-MS, and obtaining that the conversion rate of a reaction substrate is more than 89 percent and the selectivity of a product is 89 percent; adding diethyl ether (or organic solvent such as ethyl acetate) into the final reaction system, filtering to obtain white solid, washing, and dryingAnd collecting and recycling. Separating and purifying to obtain light yellow liquid, and confirming the product toluene diisocyanate by nuclear magnetic test analysis.
Example 9
The reaction steps are the same as example 6, and are different from example 2 in that the catalyst is recovered and used for the 1 st time, GC-MS analysis shows that the conversion rate of the reaction substrate is more than 91%, the selectivity is about 89%, the product is obtained by separation and purification, and nuclear magnetism confirms that the product is toluene diisocyanate.
Example 10
The reaction steps are the same as example 6, and are different from example 2 in that the catalyst is used for the 2 nd time after being recovered, GC-MS analysis shows that the conversion rate of the reaction substrate is more than 90%, the selectivity is about 88%, the product is obtained by separation and purification, and nuclear magnetism confirms that the product is toluene diisocyanate.
Example 11
The reaction procedure is the same as that in example 6, and is different from example 2 in that the catalyst is recovered and used for the 3 rd time, GC-MS analysis shows that the conversion rate of the reaction substrate is 89%, the selectivity is about 88%, the product is obtained by separation and purification, and nuclear magnetism confirms that the product is toluene diisocyanate.
Example 12
The reaction procedure is the same as that of example 6, and is different from example 2 in that the catalyst is used for the 4 th time after recovery, GC-MS analysis shows that the conversion rate of the reaction substrate is 88%, the selectivity is about 86%, the product is obtained by separation and purification, and nuclear magnetism confirms that the product is toluene diisocyanate.
Example 13
The reaction procedure is the same as that of example 6, and is different from example 2 in that the catalyst is used for the 5 th time after being recovered, the GC-MS analysis shows that the conversion rate of the reaction substrate is 87%, the selectivity is about 85%, the product is obtained by separation and purification, and the nuclear magnetism confirms that the product is toluene diisocyanate.
Example 12
The reaction procedure is the same as that of example 6, and is different from example 2 in that the catalyst is used for the 6 th time after being recovered, GC-MS analysis shows that the conversion rate of the reaction substrate is 83%, the selectivity is about 84%, the product is obtained by separation and purification, and nuclear magnetism confirms that the product is toluene diisocyanate.
Example 13
This example is the same as example 1, except that the reaction is carried out at 40 ℃ for 6 h; after the reaction is finished, sampling and measuring GC-MS, obtaining that the conversion rate of a reaction substrate is more than 86 percent, the selectivity of a product is 87 percent, separating and purifying to obtain a light yellow liquid, and confirming that the product is the toluene diisocyanate through nuclear magnetism.
Example 14
The preparation method is the same as the embodiment 1, except that dimethyl sulfoxide is used as a dehydrating agent, pyridine is used as an acid-binding agent, anhydrous acetonitrile is used as a solvent, and the reaction is carried out for 8 hours at 35 ℃; after the reaction is finished, sampling and measuring GC-MS, obtaining that the conversion rate of a reaction substrate is more than 88 percent, the selectivity of a product is 87 percent, separating and purifying to obtain a light yellow liquid, and confirming that the product is the toluene diisocyanate through nuclear magnetism.
Example 15
This example is the same as example 2, except that the reaction is carried out at 25 ℃ for 15 h; after the reaction is finished, sampling and measuring GC-MS, obtaining that the conversion rate of a reaction substrate is more than 90 percent, the selectivity of a product is 89 percent, separating and purifying to obtain a light yellow liquid, and confirming that the product is the toluene diisocyanate through nuclear magnetism.
Example 16
This example was the same as example 2 except that dimethyl sulfoxide was used as the dehydrating agent and N, N-dimethylformamide was used as the solvent, and the reaction was carried out at 25 ℃ for 15 hours; after the reaction is finished, sampling and measuring GC-MS, obtaining that the conversion rate of a reaction substrate is more than 89%, the selectivity of a product is 87%, separating and purifying to obtain a light yellow liquid, and confirming that the product is the toluene diisocyanate through nuclear magnetism.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (5)
1. A preparation method of toluene diisocyanate is characterized in that 2, 6-diaminotoluene and gaseous carbon dioxide are used as raw materials, polyoxometallate is used as a catalyst to carry out coupling reaction;
mixing 2, 6-diaminotoluene, polyoxometallate and a solvent, adding the mixture into a reaction container, adding phenylsilane, an acid binding agent and a dehydrating agent, uniformly mixing, finally introducing gaseous carbon dioxide, setting the reaction temperature to be 0-40 ℃, stirring for reacting for 6-24 hours, and separating and purifying to obtain a product;
the catalyst is Anderson type polyoxometallate taking Fe, Cu, Ni or Cr as a center, or Anderson type polyoxometallate taking Fe, Cu, Ni or Cr modified by trialkoxy derivatives as a center metal;
the acid-binding agent is pyridine or triethylamine; the dehydrating agent is dimethyl sulfoxide or phosphorus oxychloride; the solvent is selected from N, N-dimethylformamide, dimethyl sulfoxide, toluene or anhydrous acetonitrile.
2. The method for preparing toluene diisocyanate according to claim 1, wherein the reaction temperature is set to 0-30 ℃ and the reaction time is 6-12 h.
3. The process according to claim 2, wherein the reaction temperature is set at 30 ℃ and the reaction time is set at 12 hours.
4. The method for preparing toluene diisocyanate according to claim 1, wherein the molar ratio of said polyoxometallate, 2, 6-diaminotoluene, phenylsilane, acid-binding agent and dehydrating agent is 0.02: 2: 4: 1: and 2, the ratio of the using amount of the solvent to the 2, 6-diaminotoluene is 3 mL/mmol.
5. The process according to any one of claims 1 to 4, wherein the polyoxometallate catalyst after the reaction is recovered by using an organic solvent and recycled.
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| CN111662328B (en) * | 2020-06-12 | 2021-10-15 | 万华节能科技集团股份有限公司 | Derivative of flame-retardant environment-friendly toluene diisocyanate and synthetic method thereof |
| CN111807970A (en) * | 2020-06-28 | 2020-10-23 | 上海应用技术大学 | Method for preparing N-benzylaniline by catalytic oxidation of aniline with polyoxometallate |
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