CN111662168A - Method for preparing terephthalaldehyde by catalytic oxidation of terephthalyl alcohol with polyoxometallate - Google Patents

Method for preparing terephthalaldehyde by catalytic oxidation of terephthalyl alcohol with polyoxometallate Download PDF

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CN111662168A
CN111662168A CN202010593435.7A CN202010593435A CN111662168A CN 111662168 A CN111662168 A CN 111662168A CN 202010593435 A CN202010593435 A CN 202010593435A CN 111662168 A CN111662168 A CN 111662168A
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polyoxometallate
reaction
terephthalaldehyde
terephthalyl alcohol
terephthalyl
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魏哲宇
余焓
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Shanghai Institute of Technology
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Abstract

The invention relates to a method for preparing terephthalaldehyde by catalyzing and oxidizing terephthalyl alcohol with polyoxometallate, which comprises the following steps: mixing terephthalyl alcohol and polyoxometallate with a solvent, introducing oxygen, reacting for 8-16h at 80-120 ℃, and then separating to obtain terephthalyl aldehyde. Compared with the prior art, the method adopts the non-noble metal of heteropolyacid with Fe, Cu, Ni, Cr and the like as central metals as the catalyst to catalyze and oxidize the terephthalyl alcohol to prepare the terephthalyl aldehyde, the catalyst has extremely high reaction activity, the used catalyst can be recycled after the reaction is finished and the sample is simply treated, so that the method is environment-friendly, improves the cleanness of the reaction, reduces the production and manufacturing cost and is easy to control and industrially produce.

Description

Method for preparing terephthalaldehyde by catalytic oxidation of terephthalyl alcohol with polyoxometallate
Technical Field
The invention belongs to the technical field of preparation of terephthalaldehyde, and relates to a method for preparing terephthalaldehyde by efficiently catalyzing and oxidizing terephthalyl alcohol with polyoxometallate.
Background
Terephthalaldehyde is an important chemical raw material, is mainly used in industries of dyes, fluorescent whitening agents, medicines, spices and the like, and is an important raw material for organic synthesis and fine chemical engineering. Meanwhile, because it has two active aldehyde groups, it can not only self-polymerize, but also copolymerize with other monomers to form high molecular compounds with various properties, which are important monomers for synthesizing high molecular materials. Due to the wide application, the synthesis and application research of terephthalaldehyde is widely concerned by people.
The main method for preparing terephthalaldehyde at home and abroad currently comprises the following steps: dissolving 0.7g of crystal copper sulfate, 0.2g of sodium sulfite and 1.6g of hydrated sodium acetate, and adding the solution into a 10% formaldehyde oxime solution to turn the solution into grass green; under ice-bath cooling, dropwise adding a diazonium salt solution, and immediately discharging a large amount of bubbles; after the dripping is finished, keeping the low temperature for reaction for 30min to obtain a gray solution; adding 30mL of concentrated hydrochloric acid, heating to 100 ℃, and carrying out reflux reaction for 1h to obtain an orange solution; distilling with water vapor to obtain white yellowish solid, filtering, and drying to obtain terephthalaldehyde crude product; recrystallizing with a mixed solvent of alcohol and water in a ratio of 1:1 to obtain the refined terephthalaldehyde. The preparation method has the advantages of complicated steps, low yield, severe reaction conditions, extremely high unsafe factors, high requirements on reaction equipment, and environment-friendliness of the reaction process and byproducts.
Disclosure of Invention
The invention aims to provide a method for preparing terephthalaldehyde by catalyzing and oxidizing terephthalyl alcohol with polyoxometallate, which simplifies the process flow, improves the product yield, is environment-friendly and can recycle the catalyst.
The purpose of the invention can be realized by the following technical scheme:
the method for preparing terephthalaldehyde by catalyzing and oxidizing terephthalyl alcohol with polyoxometallate comprises the following steps: mixing terephthalyl alcohol and polyoxometallate with a solvent, introducing oxygen, reacting for 8-16h at 80-120 ℃, and then separating to obtain terephthalyl aldehyde. Terephthalyl alcohol is used as raw material, polyoxometallate is used as catalyst. The reaction temperature is preferably 100 ℃ and the reaction time is preferably 10 hours.
Further, the configuration of the polyoxometallate is Keggin type ([ XM)12O40]n-) Wells-Dawson type ([ X ]2M18O62]n-) Of the Anderson type ([ XM)6O24]n-) Lindqvist type ([ M)6O19]n-) Waugh type ([ XM)9O32]n-) Or Silverton type ([ XM)12O42]n-) Of (3), preferably of the Anderson type.
Further, the central metal of the polyoxometallate is a non-noble metal.
Furthermore, the central metal of the polyoxometallate is Fe, Cu, Ni or Cr.
Alternatively, the polyoxometalate is a trialkoxy derivative (Tris derivative) modified polyoxometalate.
That is, the catalyst may be a polyoxometalate centered on a metal such as Fe, Cu, Ni, or Cr, or a polyoxometalate centered on Fe, Cu, Ni, or Cr modified with a trialkoxy derivative.
Further, the molar ratio of the polyoxometallate to the terephthalyl alcohol is 1 (20-1000), and preferably 1: 50.
Further, the solvent is an aprotic polar solvent.
Further, the solvent comprises one or more of DMF, DMSO, acetonitrile or toluene, preferably acetonitrile.
Further, the reaction is carried out under stirring, preferably by magnetic stirring.
The reaction process using the Anderson type polyoxometallate as the catalyst is as follows:
Figure BDA0002556622390000021
wherein X is Fe, Cu, Ni or Cr, and Y is Mo.
Further, after the reaction is finished, the polyoxometallate after the reaction is recovered by using an organic solvent, and the polyoxometallate can be reused after the recovery. The specific recovery process is as follows: after the reaction is finished, adding an organic solvent into the system to separate out polyoxometallate (heteropoly acid), treating the polyoxometallate (heteropoly acid) and recycling the polyoxometallate (heteropoly acid), wherein the recycled catalyst can be used for preparing terephthalaldehyde again.
And screening the solvent, the temperature and the amount of the catalyst of the reaction by using a controlled variable method to obtain the optimal reaction condition.
The polyoxometallate (polyacid) catalyst is a high-efficiency green catalyst, not only has excellent oxidation-reduction catalytic performance, but also has high stability and high activity, and is a green and environment-friendly catalyst with a very promising prospect. Since 1927, more and more researchers are put into research in the field of polyacid catalysis after industrialization of propylene hydration to prepare isopropanol is realized in Japan by using polyacid as a catalyst. The major studies are Dawson structure (2:18 series), Keggin structure (1:12A series), and the like. While the Anderson structure (series 1: 6) is a polyacid with a simpler structure, the current reports on the Anderson polyoxometallate mostly focus on polyacid modification and optimization of the structure. There has been no study of the application of Anderson type polyacid to the field of catalysis.
The invention utilizes polyoxometallate to catalyze and oxidize terephthalyl alcohol to prepare terephthalaldehyde, firstly a catalyst, namely polyoxometallate, is put into a clean reaction tube, then a solvent and the terephthalyl alcohol are added into the reactor, finally a balloon filled with oxygen is sleeved on the upper part of the reaction tube, and the reaction is fully carried out by utilizing a magnetic stirrer under a certain temperature condition, so that the terephthalaldehyde can be obtained. The method adopts the non-noble metal of heteropolyacid with Fe, Cu, Ni, Cr and the like as central metals as the catalyst to catalyze and oxidize the terephthalyl alcohol to prepare the terephthalyl aldehyde, the catalyst has extremely high reaction activity, the used catalyst can be recycled after the reaction is finished and a sample is simply treated, the method is environment-friendly, the cleanness of the reaction is improved, the production and manufacturing cost is reduced, and the method is easy to control and industrially produce.
Compared with the prior art, the method has the characteristics of single raw material, low price, simple preparation process, high product yield, no three wastes, environmental friendliness and the like, the used catalyst is a novel catalyst, namely polyoxometallate (heteropoly acid), the central metal is common non-noble metal, the cost is low, the catalyst is easy to obtain, and the catalyst can be recycled for multiple times after simple treatment, so that the method is very favorable for industrial production and has potential application prospects.
Drawings
FIG. 1 is an infrared spectrum of Anderson polyoxometallate modified with Anderson polyoxometallate and Tris derivatives (with iron as the central metal, i.e., Fe-POM catalyst) in the present invention;
FIG. 2 is a XRD contrast (with iron as the central metal) of Anderson polyoxometallate in the invention before and after multiple recycling;
FIG. 3 is a nuclear magnetic spectrum (with iron as the central metal) of an Anderson polyoxometallate modified with a Tris derivative according to the invention;
FIG. 4 is an SEM image of an Anderson-type polyoxometalate (iron as the central metal) in the present invention;
FIG. 5 is an SEM image of Tris derivative modified Anderson polyoxometallate of the invention (iron as central metal);
FIG. 6 is a graph showing the preparation of terephthalaldehyde by the catalytic oxidation of terephthalyl alcohol with Anderson-type polyoxometallate in accordance with the present invention1HNMR spectra (iron as central metal).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The characterization patterns of a portion of the Anderson-type polyoxometallate salts used in the following examples are shown in fig. 1 to 5 and the product characterization pattern is shown in fig. 6.
Example 1:
a25 mL clean reaction tube was charged with 0.0242g (0.02mmol) of a nickel-centered polyoxometalate [ NH ]4]4[NiMo6O18(OH)6]·7H2O(NiMo6) 5mL of acetonitrile and 2mmol of terephthalyl alcohol, and finally sleeving a balloon filled with oxygen above the reaction tube to react for 10 hours at 100 ℃; after the reaction is finished, sampling and measuring GC-MS, wherein the conversion rate of a reaction substrate is 92 percent, the selectivity of a product is 93 percent, and the product is terephthalaldehyde after separation and purification through nuclear magnetism confirmation.
Example 2:
0.0243g (0.02mmol) of iron-centered polyoxometallate [ NH ] was charged into a 25mL clean reaction tube4]3[FeMo6O18(OH)6]·7H2O(FeMo6) 5mL of acetonitrile and 2mmol of terephthalyl alcohol, and finally sleeving a balloon filled with oxygen above the reaction tube to react for 10 hours at 100 ℃; after the reaction is finished, sampling and measuring GC-MS, wherein the conversion rate of a reaction substrate is 93 percent, the selectivity of a product is 95 percent, and the product is terephthalaldehyde after separation and purification through nuclear magnetism confirmation.
Example 3:
0.0239g (0.02mmol) of copper-centered polyoxometallate [ NH ] was charged into a 25mL clean reaction tube4]4[CuMo6O18(OH)6]·7H2O(CuMo6) 5mL of acetonitrile and 2mmol of terephthalyl alcohol, and finally sleeving a balloon filled with oxygen above the reaction tube to react for 10 hours at 100 ℃; after the reaction is finished, sampling and measuring GC-MS, wherein the conversion rate of a reaction substrate is 92 percent, the selectivity of a product is 91 percent, and the product is terephthalaldehyde after separation and purification through nuclear magnetism confirmation.
Example 4:
a25 mL clean reaction tube was charged with 0.0242g (0.02mmol) of chromium-centered polyoxometallate [ NH ]4]3[CrMo6O18(OH)6]·7H2O(CrMo6) 5mL of acetonitrile and 2mmol of terephthalyl alcohol, and finally sleeving a balloon filled with oxygen above the reaction tube to react for 10 hours at 100 ℃; after the reaction is finished, sampling and measuring GC-MS to obtain the conversion of the reaction substrateThe rate is 94%, the selectivity of the product is 91%, and the product is terephthalaldehyde after separation and purification through nuclear magnetism verification.
Example 5:
0.0405g (0.02mmol) of a Tris derivative single side modified nickel centered polyoxometalate [ N (C) was added to a 25mL clean reaction tube4H9)4]4[NiMo6O18(OH)3{(OCH2)3CCH2OH}]·13H2O(CH2OH-NiMo6) 5mL of acetonitrile and 2mmol of terephthalyl alcohol, and finally sleeving a balloon filled with oxygen above the reaction tube to react for 10 hours at 100 ℃; after the reaction is finished, sampling and measuring GC-MS, wherein the conversion rate of a reaction substrate is 92 percent, the selectivity of a product is 90 percent, and the product is terephthalaldehyde after separation and purification through nuclear magnetism confirmation.
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) 5mL of acetonitrile and 2mmol of terephthalyl alcohol, and finally sleeving a balloon filled with oxygen above the reaction tube to react for 10 hours at 100 ℃; after the reaction is finished, sampling and measuring GC-MS, wherein the conversion rate of a reaction substrate is 94 percent, the selectivity of a product is 93 percent, and the product is terephthalaldehyde after separation and purification through nuclear magnetism confirmation.
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) 5mL of acetonitrile and 2mmol of terephthalyl alcohol, and finally sleeving a balloon filled with oxygen above the reaction tube to react for 10 hours at 100 ℃; after the reaction is finished, sampling and measuring GC-MS, and obtaining that the conversion rate of the reaction substrate is 92And percent, the product selectivity is 92 percent, and the product is terephthalaldehyde after separation and purification through nuclear magnetism verification.
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) 5mL of acetonitrile and 2mmol of terephthalyl alcohol, and finally sleeving a balloon filled with oxygen above the reaction tube to react for 10 hours at 100 ℃; after the reaction is finished, sampling and measuring GC-MS, wherein the conversion rate of a reaction substrate is 93 percent, the selectivity of a product is 93 percent, and the product is terephthalaldehyde after separation and purification is confirmed by nuclear magnetism.
Example 9:
the reaction procedure was the same as example 6 except that the catalyst was recovered for the 1 st use, the conversion of the reaction substrate was 93% by GC-MS analysis, the selectivity was about 90%, the product was isolated and purified, and it was confirmed by nuclear magnetism to be terephthalaldehyde.
Example 10:
the reaction procedure was the same as example 6 except that the catalyst was recovered and used for the 2 nd time, the conversion of the reaction substrate was 91% by GC-MS analysis, the selectivity was about 89%, the product was isolated and purified, and it was confirmed by nuclear magnetism to be terephthalaldehyde.
Example 11:
the reaction procedure was the same as example 6 except that the catalyst was recovered and used 3 rd time, the conversion of the reaction substrate was 89% by GC-MS analysis, the selectivity was about 88%, the product was obtained by separation and purification, and it was confirmed by nuclear magnetism to be terephthalaldehyde.
Example 12:
the reaction procedure is the same as example 6, except that the catalyst used is recovered for the 4 th time, the conversion rate of the reaction substrate is 88% by GC-MS analysis, the selectivity is about 87%, the product is obtained by separation and purification, and the nuclear magnetism confirms that the product is terephthalaldehyde.
Example 13:
the reaction procedure was the same as example 6 except that the catalyst was recovered and used 5 th time, the conversion of the reaction substrate was 85% by GC-MS analysis, the selectivity was about 84%, the product was isolated and purified, and it was confirmed by nuclear magnetism to be terephthalaldehyde.
Example 14:
the reaction procedure was the same as example 6 except that the catalyst was recovered for the 6 th time, the conversion of the reaction substrate was 83% by GC-MS analysis, the selectivity was about 80%, the product was isolated and purified, and it was confirmed by nuclear magnetism to be terephthalaldehyde.
The parameters of the process for preparing terephthalaldehyde by catalytic oxidation of terephthalyl alcohol with polyoxometallate referred to in the above examples can be selected according to actual conditions and actual requirements, for example:
the reaction temperature is 80-120 deg.C (e.g. 90 deg.C, 100 deg.C, 110 deg.C), and the reaction time is 8-16h (e.g. 10h, 12h, 14 h).
The polyoxometallate is configured in one of a Keggin type, a Wells-Dawson type, an Anderson type, a Lindqvist type, a Waugh type, or a Silverton type.
The central metal of the polyoxometallate is Fe, Cu, Ni or Cr.
The molar ratio of polyoxometallate to terephthalyl alcohol is 1 (20-1000), for example 1:100, 1:500, 1: 800.
The solvent comprises one or more of DMF, DMSO, acetonitrile, or toluene.
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 (10)

1. The method for preparing terephthalaldehyde by catalyzing and oxidizing terephthalyl alcohol with polyoxometallate is characterized by comprising the following steps: mixing terephthalyl alcohol and polyoxometallate with a solvent, introducing oxygen, reacting for 8-16h at 80-120 ℃, and then separating to obtain terephthalyl aldehyde.
2. The method of claim 1, wherein the polyoxometalate has a configuration of one of Keggin type, Wells-Dawson type, Anderson type, Lindqvist type, Waugh type, or Silverton type.
3. The method of claim 1, wherein the central metal of the polyoxometalate is a non-noble metal.
4. The method of claim 1, wherein the central metal of the polyoxometalate is Fe, Cu, Ni or Cr.
5. The method of claim 1, wherein the polyoxometalate is modified with a trialkoxy derivative to produce terephthalaldehyde.
6. The method for preparing terephthalaldehyde by catalytic oxidation of terephthalyl alcohol with polyoxometallate according to claim 1, wherein the molar ratio of polyoxometallate to terephthalyl alcohol is 1 (20-1000).
7. The method of claim 1, wherein the solvent is an aprotic polar solvent.
8. The polyoxometallate-catalyzed oxidation of terephthalyl alcohol to terephthaldehyde according to claim 1 wherein the solvent comprises one or more of DMF, DMSO, acetonitrile or toluene.
9. The method of claim 1, wherein the reaction is carried out under agitation.
10. The method for preparing terephthalaldehyde by catalytic oxidation of terephthalyl alcohol with polyoxometallate according to claim 1, wherein after the reaction is finished, the polyoxometallate after the reaction is recovered by using an organic solvent.
CN202010593435.7A 2020-06-27 2020-06-27 Method for preparing terephthalaldehyde by catalytic oxidation of terephthalyl alcohol with polyoxometallate Pending CN111662168A (en)

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CN113292609A (en) * 2021-04-26 2021-08-24 上海应用技术大学 Preparation method and application of polyoxometallate complex
CN115677462A (en) * 2021-07-29 2023-02-03 安徽圣诺贝化学科技有限公司 Method for preparing citronellal by catalytic oxidation of citronellol

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