CN110105249B - Preparation method of 4,4' -diphenylmethane diisocyanate - Google Patents
Preparation method of 4,4' -diphenylmethane diisocyanate Download PDFInfo
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Abstract
The invention relates to a preparation method of 4,4 '-diphenylmethane diisocyanate, which comprises the steps of adding a catalyst polyoxometallate and a solvent into a reaction vessel, adding raw materials of 4,4' -diaminodiphenylmethane, phenyl silane, 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 M-Anderson type heteropoly acid as the catalyst, the catalyst has mild reaction conditions, 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 4,4' -diphenylmethane diisocyanate.
Background
4,4' -diphenylmethane diisocyanate is a downstream main product of aromatic hydrocarbon, and is widely applied to the production fields of polyurethane elastomers, synthetic fibers, artificial leather, solvent-free coatings and other polyurethane materials. The traditional synthesis method uses Pd, Ru, Rh, Au, Ir and other noble metals as catalysts, and has numerous advantages, but the catalysts have the defects of high price, high using amount, incapability of recycling and the like, so that the wide application of the catalysts in industry is limited. Therefore, chemists strive to find a green, efficient, recyclable catalyst.
Conventionally, the preparation of diphenylmethane diisocyanate is carried out by reacting aniline with formaldehyde, neutralizing with alkali, distilling to obtain diphenylmethane diamine (MDA), dissolving diphenylmethane diamine with chlorobenzene or dichlorobenzene, carrying out phosgenation to prepare isocyanate, and removing solvent by vacuum distillation to obtain diphenylmethane diisocyanate. But aldehydes are difficult to transport and maintain for long periods of time due to their relatively reactive chemical nature.
Patent CN1966489B discloses an invention method for preparing diphenylmethane diisocyanate by a two-step method, which comprises the steps of firstly carrying out acid condensation on aniline and formaldehyde to obtain an amine mixture, then reacting the amine mixture with phosgene, and distilling to obtain the diphenylmethane diisocyanate.
Disclosure of Invention
The invention aims to solve the problems and provide a method for preparing 4,4' -diphenylmethane diisocyanate, which is environment-friendly, low in reaction toxicity and low in cost.
The purpose of the invention is realized by the following technical scheme:
a preparation method of 4,4 '-diphenylmethane diisocyanate takes 4,4' -diaminodiphenylmethane 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, 4' -diaminodiphenylmethane, 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 0-50 ℃, the mixture is stirred and reacted for 5-25 hours, and the product is obtained after separation and purification.
Preferably, the catalyst is Fe, Al, Mn or Cu-centered Anderson type polyoxometallate or trialkoxy derivative (Tris derivative) modified Fe, Al, Mn or Cu-centered Anderson type polyoxometallate, 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 mol% to 1 mol%, and is most 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 anhydrous acetonitrile or N, N-dimethylformamide.
Preferably, the reaction temperature is set to be 0-30 ℃, the reaction time is 5-15 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 4,4' -diaminodiphenylmethane, 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 4,4' -diaminodiphenylmethane 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 takes polyoxometallate as a catalyst, and takes 4,4 '-dicyclohexylmethane and carbon dioxide as raw materials to generate 4,4' -diphenylmethane diisocyanate in one step in a carbon dioxide atmosphere, so that the method has the advantages of simple process flow, high yield, less by-products, simple treatment and reutilization of the catalyst for multiple times, is a simple, environment-friendly and efficient synthesis path, is used as a renewable resource, has important significance for resource utilization, can make up the carbon source crisis caused by large consumption of petroleum and natural gas, can effectively solve the greenhouse effect, is economic, green and efficient, adopts a one-step method to directly prepare a target product, and greatly improves the efficiency, and in addition, the catalyst is cheap and recyclable.
Compared with the existing method for preparing 4,4' -diphenylmethane 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 renewable resource carbon dioxide as one of the raw materials, and is a method for preparing 4,4' diphenylmethane 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
To a 25mL clean reaction tube was added 0.0240g (0.0 g)2mmol) copper-centered polyoxometallate [ NH ]4]4[CuMo6O18(OH)6]·7H2O(CuMo6) 0.3966g (2mmol) of 4,4' -diaminodiphenylmethane, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol) of triethylamine, 0.3067g (2mmol) of phosphorus oxychloride and 6mL of solvent toluene, and finally sleeving an oxygen balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of the reaction substrate is more than 89%, the selectivity of the product is 90%, white molten solid is obtained by separation and purification, and the product is the 4,4' -diphenylmethane diisocyanate after nuclear magnetic confirmation.
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) 0.3966g (2mmol) of 4,4' -diaminodiphenylmethane, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol) of triethylamine, 0.3067g (2mmol) of phosphorus oxychloride and 6mL of solvent toluene, and finally sleeving an oxygen balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of the reaction substrate is more than 93 percent, the selectivity of the product is 94 percent, white molten solid is obtained by separation and purification, and the product is the 4,4' -diphenylmethane diisocyanate after nuclear magnetic confirmation.
Example 3
A25 mL clean reaction tube was charged with 0.0234g (0.02mmol) of chromium-centered polyoxometallate [ NH ]4]3[CrMo6O18(OH)6]·7H2O(CrMo6) 0.3966g (2mmol) of 4,4' -diaminodiphenylmethane, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol) of triethylamine, 0.3067g (2mmol) of phosphorus oxychloride and 6mL of solvent toluene, and finally sleeving an oxygen balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of a reaction substrate is more than 92 percent, the selectivity of the product is 91 percent, white molten solid is obtained by separation and purification, and the product is the 4,4' -diphenylmethane diisocyanate after nuclear magnetism confirmation.
Example 4
0.0363g (0.02mmol) of a copper-centered polyoxometalate 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) 0.3966g (2mmol) of 4,4' -diaminodiphenylmethane, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol) of triethylamine, 0.3067g (2mmol) of phosphorus oxychloride and 6mL of solvent toluene, and finally sleeving an oxygen balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of a reaction substrate is more than 90 percent, the selectivity of the product is 89 percent, ether (or ethanol, ethyl acetate and the like) is added into a reaction system, white solid is obtained by filtering, washing and drying are carried out, the white solid is collected and recycled, the filtrate is separated and purified to obtain white molten solid, and the product, namely the 4,4' -diphenylmethane diisocyanate is confirmed by nuclear magnetism.
Example 5
0.0363g (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) 0.3966g (2mmol) of 4,4' -diaminodiphenylmethane, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol) of triethylamine, 0.3067g (2mmol) of phosphorus oxychloride and 6mL of solvent toluene, and finally sleeving an oxygen balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of a reaction substrate is more than 92 percent, the selectivity of the product is 95 percent, ether (or ethanol, ethyl acetate and the like) is added into a reaction system, white solid is obtained by filtering, washing and drying are carried out, the white solid is collected and recycled, the filtrate is separated and purified to obtain white molten solid, and the product, namely the 4,4' -diphenylmethane diisocyanate is confirmed by nuclear magnetism.
Example 6
Into a 25mL clean reaction tube was added 0.0363g (0.02mmol) of a chromium-centered polyoxometalate [ N (C) with a single side modification with a Tris derivative4H9)4]3[CrMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-CrMo6) 0.3966g (2mmol) of 4,4' -diaminodiphenylmethane, 0.2164g (4mmol) of phenylsilane, 0.1012g (1mmol) of triethylamine, 0.3067g (2mmol) of phosphorus oxychloride and 6mL of solvent toluene, and finally sleeving an oxygen balloon filled with carbon dioxide above a reaction tube to react for 12 hours at 30 ℃; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of a reaction substrate is more than 89%, the selectivity of the product is 90%, ether (or ethanol, ethyl acetate and the like) is added into a reaction system, white solid is obtained by filtering, washing and drying are carried out, the white solid is collected and recycled, the filtrate is separated and purified to obtain white molten solid, and the product, namely the 4,4' -diphenylmethane diisocyanate is confirmed by nuclear magnetism.
Example 7
The reaction steps are the same as example 5, and the difference from example 2 is that the catalyst is used for the 1 st time after recovery, GC-MS analysis shows that the substrate conversion rate is more than 92%, the selectivity is about 92%, the product is obtained by separation and purification, and nuclear magnetism confirms that the 4,4' -diphenylmethane diisocyanate has the yield of 92%.
Example 8
The reaction steps are the same as example 5, and the difference from example 2 is that the catalyst is used for the 2 nd time after being recovered, GC-MS analysis shows that the substrate conversion rate is more than 90%, the selectivity is about 92%, the product is obtained by separation and purification, and nuclear magnetism confirms that the product is 4,4' -diphenylmethane diisocyanate, and the yield is 90%.
Example 9
The reaction steps are the same as example 5, and the difference from example 2 is that the catalyst is used for the 3 rd time after being recovered, GC-MS analysis shows that the substrate conversion rate is more than 90%, the selectivity is about 89%, the product is obtained by separation and purification, and the nuclear magnetism confirms that the product is 4,4' -diphenylmethane diisocyanate, and the yield is 88%.
Example 10
The reaction steps are the same as example 5, and are different from example 2 in that the catalyst is used for the 4 th time after recovery, GC-MS analysis shows that the substrate conversion rate is more than 89%, the selectivity is about 88%, the product is obtained by separation and purification, and the nuclear magnetism confirms that the 4,4' -diphenylmethane diisocyanate has the yield of 87%.
Example 11
The reaction steps are the same as example 5, and different from example 2 in that the catalyst is used for the 5 th time after being recovered, GC-MS analysis shows that the substrate conversion rate is more than 88%, the selectivity is about 86%, the product is obtained by separation and purification, and the nuclear magnetism confirms that the product is 4,4' -diphenylmethane diisocyanate, and the yield is 86%.
Example 12
This example is the same as example 1, except that the reaction is carried out at 50 ℃ for 5 h; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of the reaction substrate is more than 82 percent, the selectivity of the product is 83 percent, white molten solid is obtained by separation and purification, and the product is the 4,4' -diphenylmethane diisocyanate after nuclear magnetism confirmation.
Example 13
This example is the same as example 2, except that the reaction is carried out at 40 ℃ for 10 h; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of the reaction substrate is more than 83 percent, the selectivity of the product is 83 percent, white molten solid is obtained by separation and purification, and the product is the 4,4' -diphenylmethane diisocyanate after nuclear magnetism confirmation.
Example 14
This example is the same as example 1, except that the reaction is carried out at 20 ℃ for 18 h; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of the reaction substrate is more than 86 percent, the selectivity of the product is 84 percent, white molten solid is obtained by separation and purification, and the product is the 4,4' -diphenylmethane diisocyanate after nuclear magnetism confirmation.
Example 15
The preparation method is the same as the embodiment 2, except that an acid-binding agent is pyridine, a dehydrating agent is dimethyl sulfoxide, and the reaction is carried out at the temperature of 30 ℃ for 10 hours; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of the reaction substrate is more than 90 percent, the selectivity of the product is 89 percent, white molten solid is obtained by separation and purification, and the product is the 4,4' -diphenylmethane diisocyanate after nuclear magnetism confirmation.
Example 16
The preparation method is the same as the embodiment 2, except that an acid-binding agent is pyridine, a dehydrating agent is dimethyl sulfoxide, and the reaction is carried out at 25 ℃ for 25 h; after the reaction is finished, the sample is taken to measure GC-MS, the conversion rate of the reaction substrate is more than 89%, the selectivity of the product is 90%, white molten solid is obtained by separation and purification, and the product is the 4,4' -diphenylmethane diisocyanate after nuclear magnetic confirmation.
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 4,4 '-diphenylmethane diisocyanate is characterized in that 4,4' -diaminodiphenylmethane and gaseous carbon dioxide are used as raw materials, polyoxometallate is used as a catalyst for coupling reaction;
mixing 4,4' -diaminodiphenylmethane, 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 0-50 ℃, stirring for reaction for 5-25 h, and separating and purifying to obtain a product;
the catalyst is Anderson type polyoxometallate taking Fe, Al, Mn or Cu as a center, or Anderson type polyoxometallate taking Fe, Al, Mn or Cu 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 anhydrous acetonitrile or N, N-dimethylformamide.
2. The method for preparing 4,4' -diphenylmethane diisocyanate according to claim 1, wherein the reaction temperature is set to 0-30 ℃ and the reaction time is set to 5-15 hours.
3. The method of claim 2, wherein the reaction temperature is 30 ℃ and the reaction time is 12 hours.
4. The method for preparing 4,4 '-diphenylmethane diisocyanate according to claim 1, wherein the molar ratio of polyoxometallate, 4' -diaminodiphenylmethane, 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 4,4' -diaminodiphenylmethane is 3 mL/mmol.
5. The process for preparing 4,4' -diphenylmethane diisocyanate 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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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5189205A (en) * | 1992-03-16 | 1993-02-23 | Monsanto Compamy | Process for preparing isocyanates |
| CN1590369A (en) * | 2003-09-05 | 2005-03-09 | 中国科学院兰州化学物理研究所 | Preparation method of isocyanate |
| CN1966489A (en) * | 2005-11-19 | 2007-05-23 | 拜尔材料科学股份公司 | Method for producing 4, 4' -diphenylmethane diisocyanate |
| CN101429138A (en) * | 2008-12-18 | 2009-05-13 | 宁波万华聚氨酯有限公司 | Method for producing isocyanic ester in gas-phase |
| CN101687779A (en) * | 2007-07-02 | 2010-03-31 | 亨茨曼国际有限公司 | Process for the synthesis of carbamates using CO2 |
| CN107567436A (en) * | 2015-05-06 | 2018-01-09 | 巴斯夫欧洲公司 | The method for preparing isocyanate compound |
-
2019
- 2019-05-31 CN CN201910469663.0A patent/CN110105249B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5189205A (en) * | 1992-03-16 | 1993-02-23 | Monsanto Compamy | Process for preparing isocyanates |
| CN1590369A (en) * | 2003-09-05 | 2005-03-09 | 中国科学院兰州化学物理研究所 | Preparation method of isocyanate |
| CN1966489A (en) * | 2005-11-19 | 2007-05-23 | 拜尔材料科学股份公司 | Method for producing 4, 4' -diphenylmethane diisocyanate |
| CN101687779A (en) * | 2007-07-02 | 2010-03-31 | 亨茨曼国际有限公司 | Process for the synthesis of carbamates using CO2 |
| CN101429138A (en) * | 2008-12-18 | 2009-05-13 | 宁波万华聚氨酯有限公司 | Method for producing isocyanic ester in gas-phase |
| CN107567436A (en) * | 2015-05-06 | 2018-01-09 | 巴斯夫欧洲公司 | The method for preparing isocyanate compound |
Non-Patent Citations (5)
| Title |
|---|
| Anderson型杂多酸烷氧化合物催化氧化性能的应用研究;戴国勇;《中国优秀硕士学位论文 工程科技I辑》;20180215(第02期);全文 * |
| Carbon dioxide, carbonyl sulfide, carbon disulfide, isocyanates, isothiocyanates, carbodiimides, and their selenium, tellurium, and phosphorus analogues;Braverman, S.等;《Science of Synthesis》;20051231;第18卷;65-320页 * |
| 二氧化碳的化学利用及催化体系的研究进展;陈红萍等;《化工进展》;20091231;第28卷;第1.3节 * |
| 化学转化二氧化碳为氨基甲酸酯研究;熊文芳;《中国优秀博士学位论文 工程科技I辑》;20190115(第12期);全文 * |
| 翟永彦;Anderson型多金属氧酸盐催化氧化偶联反应的研究;《中国优秀硕士学位论文 工程科技I辑》;20190115(第01期);全文 * |
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