CN109824705B - Preparation method and application of bis (N- (4-carboxyl) phenyl) perylene bisimide zinc complex catalyst - Google Patents
Preparation method and application of bis (N- (4-carboxyl) phenyl) perylene bisimide zinc complex catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a bis (N- (4-carboxyl) phenyl) perylene imide zinc complex catalyst, which comprises the steps of placing zinc acetate, bis (N- (4-carboxyl) phenyl) perylene imide, triethylamine, water and N, N' -dimethyl imide into a beaker for reaction, filtering after the reaction is finished, and slowly volatilizing filtrate to obtain a crystal of the bis (N- (4-carboxyl) phenyl) perylene imide zinc complex catalyst. The method has the advantages of simple reaction process, high purity of the obtained product and simple post-treatment. In the cycloaddition reaction of carbon dioxide under normal pressure, the conversion rate is as high as 97.5%, and the selectivity is as high as 97.9%.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and relates to a preparation technology of a bis (N- (4-carboxyl) phenyl) perylene bisimide zinc complex catalyst.
Technical Field
The metal organic complex is an organic-inorganic hybrid material with intramolecular pores formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds. The metal organic complex has rich metal active site composition, and strong Lewis acidity and strong oxidizability are determined, so that the metal organic complex shows excellent catalytic characteristics in a plurality of organic catalytic reactions. A large number of documents have been reported (Jiang, et al, coord. chem. rev.2018,362, 1-23). At present, the catalytic synthesis chemistry of metal organic complexes has become one of the most promising research directions in the field of metal organic framework science, and is widely concerned by chemists.
Meanwhile, it is known that excessive emission of carbon dioxide causes global warming. The catalytic conversion of carbon dioxide has therefore become a focus of attention for chemists. Among them, the reaction of carbon dioxide catalytic conversion to cyclic carbonate is one of the most successful routes. However, the current catalytic system has the disadvantages of using high temperature and high pressure or solvent, etc., which causes the problem of inconvenient industrialization (Koria. Andrea, et al, Inorg. chem.2018,57, 13494-. Therefore, the development of greener catalysts is still of great interest from an environmental and economic point of view.
Based on the above documents, it is necessary to design an environment-friendly metal organic complex high-efficiency catalytic system for generating cyclic carbonate through cycloaddition of carbon dioxide under normal pressure according to the development concept of green chemistry.
Through searching, no published patent literature relevant to the application of the invention is found.
Disclosure of Invention
The invention aims to solve the problems of overlarge reaction pressure, large catalyst consumption and the like in the cycloaddition reaction for catalytically converting carbon dioxide under high pressure. Provides a preparation method of a catalyst for synthesizing metal organic complexes, which aims to play a catalytic role in the cycloaddition reaction of carbon dioxide and achieve the aim of realizing the cycloaddition of the carbon dioxide under the normal pressure condition.
The design idea of the invention is as follows:
1. reacting inorganic zinc salt with bis (N- (4-carboxyl) phenyl) perylene bisimide to construct a new metal organic complex, so that metal ions can play a catalytic center role;
2. the catalyst with the metal zinc organic complex is applied to the cycloaddition reaction of carbon dioxide, so that the aim of obtaining the cyclic carbonate with high conversion rate and high selectivity of the carbon dioxide under normal pressure is fulfilled.
The structural information of this type of catalyst is obtained by the following method:
the metal organic complex is synthesized by a conventional solvothermal method, and the specific description experiment method is as follows:
firstly, perylene imide and p-aminobenzoic acid are reacted and refluxed under the condition of acetic acid to synthesize the organic ligand bis (N- (4-carboxyl) phenyl) perylene imide. Then, sequentially adding bis (N- (4-carboxyl) phenyl) perylene bisimide (3-6 mmol), triethylamine (5-13 mmol) and Zn (OAc) into a clean hydrothermal reaction kettle2(2～7mmol) Water (8-15 mL) and N, N' -dimethyl imide (2-5 mL) are intensively stirred for 2-5 hours, then the mixture is put into a stainless steel reaction kettle, the temperature is increased to 90-120 ℃, the reaction is carried out for 72-96 hours, and after the reaction is finished, the mixture is cooled to room temperature to obtain a black-red substance. The yield is about 32-58%.
The product is characterized by single crystal diffraction and powder X-ray diffraction, and accurate information about the bis (N- (4-carboxyl) phenyl) perylene bisimide zinc complex is obtained. The specific results are as follows:
the molecular formula of the crystal is Zn (C)38H18N2O8) Wherein Zn coordinates with oxygen in two carboxyl anions of the bis (N- (4-carboxyl) phenyl) perylene bisimide, which is a four-coordination environment, can provide an environment for ring opening of an epoxy compound, and carbon dioxide is easily combined with central zinc ions under reaction conditions, thereby playing a catalytic role.
The invention mainly synthesizes metal organic complex catalyst which has been applied to carbon dioxide cycloaddition reaction. The catalyst can realize the cycloaddition reaction of carbon dioxide under the condition of normal pressure, the conversion rate is as high as 97.5 percent, and the selectivity is as high as 97.9 percent. The preparation method of the catalyst has simple reaction process.
The cyclic compound is epichlorohydrin, epoxy bromopropane, epoxypropane, epoxystyrene and the like, and the conversion rate and the selectivity are detected by gas chromatography.
The purpose of the invention is realized by the following technical scheme:
the molecular structure is as follows:
the molecular formula is: zn (C)38H18N2O8)
Remarking: the space occupancy rates of two zinc atoms are 0.5 and four oxygen atoms coordinated to the zinc atoms are 0.5 respectively in crystallography, so that the compound has the molecular formula of Zn (C)38H18N2O8)
The metal organic complex catalyst provided by the invention has the following characteristics:
1. the preparation method is simple, and the catalyst has a definite molecular structure, thereby being beneficial to researching a catalytic reaction mechanism.
2. The catalyst has the function of catalyzing the cycloaddition of the carbon dioxide by Zn.
Drawings
FIG. 1 is a crystal structure diagram of a bis (N- (4-carboxy) phenyl) perylene imide zinc complex catalyst
FIG. 2 is a powder diffraction pattern of a bis (N- (4-carboxy) phenyl) perylene imide zinc complex catalyst
Detailed Description
Example 1: compound Zn (C)38H18N2O8) Preparation of
Bis (N- (4-carboxy) phenyl) perylene bisimide (3mmol), triethylamine (5mmol), Zn (OAc) were added in this order to a clean hydrothermal reaction kettle2(2mmol), water (8mL) and N, N' -dimethylidenamide (2mL) are stirred vigorously for 2h, then the mixture is put into a stainless steel reaction kettle, the temperature is raised to 90 ℃, the reaction is carried out for 72h, and after the reaction is finished, the mixture is cooled to room temperature to obtain a black red substance. The yield was about 34%.
Example 2: compound Zn (C)38H18N2O8) Preparation of
In a clean hydrothermal reaction kettle, bis (N- (4-carboxyl) phenyl) perylene bisimide (4mmol), triethylamine (8mmol), Zn (OAc) are added in sequence2(4mmol), water (10mL) and N, N' -dimethylidenamide (5mL) are stirred vigorously for 3h, then the mixture is put into a stainless steel reaction kettle, the temperature is raised to 100 ℃, the reaction lasts for 96h, and after the reaction is finished, the mixture is cooled to room temperature to obtain a black red substance. The yield was about 43%.
Example 3: compound Zn (C)38H18N2O8) Preparation of
In a clean hydrothermal reaction kettle, bis (N- (4-carboxyl) phenyl) perylene bisimide (6mmol), triethylamine (13mmol), Zn (OAc) are added in sequence2(7mmol), water (15mL) and N, N' -dimethylidenamide (5mL) were stirred vigorously for 5h, then charged into a stainless steel reaction vesselAnd heating to 120 ℃, reacting for 80 hours, and cooling to room temperature after the reaction is finished to obtain a black red substance. The yield was about 56%.
Example 4: compound Zn (C)38H18N2O8) Preparation of
In a clean hydrothermal reaction kettle, bis (N- (4-carboxyl) phenyl) perylene bisimide (3mmol), triethylamine (6mmol), Zn (OAc) are added in sequence2(4mmol), water (10mL) and N, N' -dimethylidenamide (4mL) are stirred vigorously for 4h, then the mixture is put into a stainless steel reaction kettle, the temperature is raised to 110 ℃, the reaction lasts for 96h, and after the reaction is finished, the mixture is cooled to room temperature to obtain a black red substance. The yield was about 50%.
Example 5: compound Zn (C)38H18N2O8) Preparation of
In a clean hydrothermal reaction kettle, bis (N- (4-carboxyl) phenyl) perylene bisimide (3mmol), triethylamine (7mmol), Zn (OAc) are added in sequence2(4mmol), water (10mL) and N, N' -dimethylidenamide (5mL) are stirred vigorously for 5h, then the mixture is put into a stainless steel reaction kettle, the temperature is raised to 100 ℃, the reaction is carried out for 90h, and after the reaction is finished, the mixture is cooled to room temperature to obtain a black red substance. The yield was about 53%.
Example 6: compound Zn (C)38H18N2O8) Preparation of
In a clean hydrothermal reaction kettle, bis (N- (4-carboxyl) phenyl) perylene bisimide (5mmol), triethylamine (5mmol), Zn (OAc) are added in sequence2(4mmol), water (15mL) and N, N' -dimethylidenamide (3mL) are stirred vigorously for 3h, then the mixture is put into a stainless steel reaction kettle, the temperature is raised to 90 ℃, the reaction is carried out for 72h, and after the reaction is finished, the mixture is cooled to room temperature to obtain a black red substance. The yield was about 37%.
Example 7: compound Zn (C)38H18N2O8) Preparation of
In a clean hydrothermal reaction kettle, bis (N- (4-carboxyl) phenyl) perylene bisimide (4mmol), triethylamine (8mmol), Zn (OAc) are added in sequence2(5mmol), water (9mL) and N, N' -dimethylidenamide (5mL) were vigorously stirred for 5h, then charged into a stainless steel reaction vessel and heated toReacting for 96 hours at 120 ℃, and cooling to room temperature after the reaction is finished to obtain a black red substance. The yield was about 44%.
Example 8: compound Zn (C)38H18N2O8) Preparation of
Adding bis (N- (4-carboxyl) phenyl) perylene bisimide (3mmol), triethylamine (6mmol) and ZnCl into a clean hydrothermal reaction kettle in sequence2(3mmol), water (15mL) and N, N' -dimethylidenamide (5mL) are stirred vigorously for 5h, then the mixture is put into a stainless steel reaction kettle, the temperature is raised to 120 ℃, the reaction is carried out for 72h, and after the reaction is finished, the mixture is cooled to room temperature to obtain a black red substance. The yield was about 36%.
Example 9: compound Zn (C)38H18N2O8) Preparation of
Adding bis (N- (4-carboxyl) phenyl) perylene bisimide (3mmol), triethylamine (6mmol) and Zn (NO) in a clean hydrothermal reaction kettle in sequence3)2(3mmol), water (15mL) and N, N' -dimethylidenamide (5mL) are stirred vigorously for 5h, then the mixture is put into a stainless steel reaction kettle, the temperature is raised to 120 ℃, the reaction is carried out for 72h, and after the reaction is finished, the mixture is cooled to room temperature to obtain a black red substance. The yield was about 33%.
As shown in Table 1, the crystallographic data of the zinc bis (N- (4-carboxyl) phenyl) perylene imide complex
Example 10: zn (C)38H18N2O8) Application of catalyst to carbon dioxide cycloaddition reaction under normal pressure
Example (c):
placing 30mmol of epoxy compound into a 50mL round-bottom flask, adding 50-70 mg of catalyst and 3-5 mol% of tetrabutylammonium bromide, introducing carbon dioxide under normal pressure, stirring at room temperature for reaction for 12-24 h, detecting by gas chromatography, and converting almost all the epoxy compound in the reaction liquid into cyclic carbonate, wherein the specific data of carbon dioxide cycloaddition are shown in Table 2.
TABLE 2 tabulated results of cycloaddition reaction of bis (N- (4-carboxy) phenyl) perylene bisimide zinc complexes to epoxy compounds
From table 2, it can be seen that the bis (N- (4-carboxy) phenyl) perylene imide zinc complex catalyst has good effects on cycloaddition reactions of different epoxy compounds and carbon dioxide, the conversion rates of the catalysts are all more than 95%, the cycloaddition reaction of the catalysts to carbon dioxide under normal pressure is realized, and the problem of the cycloaddition reaction of carbon dioxide under high pressure conditions in documents is solved.
Claims (3)
1. A preparation method of a bis (N- (4-carboxyl) phenyl) perylene bisimide zinc complex catalyst is characterized by comprising the following steps: the method comprises the following steps: sequentially adding bis (N- (4-carboxyl) phenyl) perylene bisimide, triethylamine, inorganic zinc salt and a reaction solvent into a clean hydrothermal reaction kettle, wherein the molar ratio of bis (N- (4-carboxyl) phenyl) perylene bisimide: triethylamine: the ratio of the inorganic zinc salt to the N, N ' -dimethylformamide is 3-6: 5-13: 2-7, the solvent is water and the N, N ' -dimethylformamide, wherein the volume ratio of the water to the N, N ' -dimethylformamide is as follows: 8-15: 2-5, stirring strongly for 2-5 h, then placing into a stainless steel reaction kettle, heating to a certain temperature, reacting, cooling to room temperature after the reaction is finished, wherein the reaction temperature is 90-120 ℃, and the reaction time is 72-96 h after heating to obtain a black-red substance.
2. The method for preparing a bis (N- (4-carboxy) phenyl) perylene imide zinc complex catalyst according to claim 1, wherein: the inorganic zinc salt is Zn (OAc)2。
3. The method for preparing a bis (N- (4-carboxy) phenyl) perylene imide zinc complex according to claim 1, wherein: the molecular structure of the bis (N- (4-carboxyl) phenyl) perylene bisimide zinc complex catalyst is as follows:
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