CN109453819B - Transition metal oxide supported carbazolyl porous organic polymer catalyst and application - Google Patents
Transition metal oxide supported carbazolyl porous organic polymer catalyst and application Download PDFInfo
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Abstract
The invention discloses a method for preparing p-methoxybenzaldehyde by catalyzing oxidation of p-methoxytoluene by using carbazolyl porous organic polymer loaded transition metal oxide. The catalyst takes a carbazolyl porous organic polymer as a carrier, transition metal salt is loaded after the carbazolyl porous organic polymer is used as the carrier, and the carbazolyl porous organic polymer loaded transition metal oxide catalyst is obtained by roasting. The carbazolyl porous organic polymer has homogeneously distributed nitrogen atoms in the skeleton and certain interaction between the nitrogen atoms and the metal. Thus, the uniformly distributed nitrogen atoms activate the metal oxide active sites on the one hand; on the other hand, the loss of active components in the reaction process is reduced. The catalyst can efficiently catalyze p-methoxy toluene to prepare p-methoxy benzaldehyde, and the conversion rate and the selectivity can both reach more than 70%. Compared with the traditional heterogeneous catalyst, the catalyst has high thermal stability, good catalytic activity, difficult loss of active components and long service life.
Description
Technical Field
The invention relates to the field of chemical engineering, in particular to a carbazolyl porous organic polymer material post-loaded cobalt manganese oxide catalyst and application thereof in preparation of p-methoxybenzaldehyde by oxidation of p-methoxytoluene.
Background
P-methoxybenzaldehyde is also called anisaldehyde, is colorless or light yellow liquid at normal temperature, has lasting hawthorn fragrance, is a perfume with high economic value, is an important organic chemical synthesis intermediate, and is also an intermediate for preparing porphyrin photosensitizer, amino-carbapenem and the like. At present, the method for synthesizing p-methoxybenzaldehyde can be mainly divided into a synthetic route using p-propenyl anisole, methoxy benzyl alcohol, phenol, p-hydroxybenzaldehyde, anisole, p-methoxy toluene and the like as raw materials.
In the process of preparing p-methoxybenzaldehyde by oxidizing p-methoxytoluene, molecular oxygen is used as an oxidant, so that the process is a relatively green oxidation process. Patent CN103694093A discloses a method for preparing p-methoxybenzaldehyde by oxidation of p-methoxytoluene using metalloporphyrin as a catalyst and molecular oxygen as an oxidizing agent; in patent CN102070382A, porphyrin metal salt and porphyrin metal salt loaded on a carrier are used as catalysts to catalyze the oxidation of toluene and substituted toluene, the reaction conditions are harsh, and the yield of p-methoxybenzaldehyde is low; CN1491930 discloses the use of CoO-Al2O3the-R (R is a cocatalyst) catalyzes the process of converting p-methoxytoluene into aldehyde, and a better effect is obtained.
The above case illustrates that using molecular oxygen as the oxidant, it is important to design and prepare a catalyst with high conversion, high selectivity and recoverability. The supported catalyst is a commonly used recyclable catalyst, but often faces the problems of loss of active components in different degrees, insufficient activity of active centers and the like, and the selection of a carrier is crucial to the solution of the problems.
The carbazolyl porous organic polymer is an important polymer material, has the characteristics of large specific surface area and high thermal stability, and has great potential as a catalyst carrier. The carbazolyl porous organic polymer has homogeneously distributed nitrogen atoms in the skeleton and certain interaction between the nitrogen atoms and the metal. Thus, the uniformly distributed nitrogen atoms activate the metal oxide active sites on the one hand; on the other hand, the loss of active components in the reaction process is reduced.
Disclosure of Invention
Aiming at the problems that the active center is further activated and the loss of active components of the catalyst is reduced by the effective selection of the supported catalyst carrier, the carbazolyl porous organic polymer is used as the catalyst carrier, and the carbazolyl porous organic polymer has large specific surface area and high thermal stability, and nitrogen atoms uniformly distributed in a polymer framework, so that the carbazolyl porous organic polymer can activate the active center of metal, and a certain stabilizing effect is generated due to the existence of interaction, thereby achieving the purpose of stabilizing the active center. The invention obtains the carbazolyl porous organic polymer by polymerizing the carbazolyl monomer to obtain a polymer material with uniformly distributed nitrogen atoms in a structural unit, then loads active components cobalt and manganese on a polymer framework by a wet impregnation method, and obtains the supported cobalt-manganese oxide catalyst with high activity and stability by drying and roasting. Under the action of the catalyst, the conversion rate of p-methoxytoluene and the selectivity of p-methoxybenzaldehyde can both reach more than 70%.
According to the invention, the carbazolyl porous organic polymer supported transition metal oxide catalyst can be prepared according to the following method:
1) dissolving 1,3, 5-tri (9-carbazolyl) benzene in anhydrous chloroform, stirring at room temperature for 24-36h under nitrogen atmosphere by using ferric chloride as a catalyst, and after the reaction is finished, washing, filtering, washing with concentrated hydrochloric acid, performing Soxhlet extraction and vacuum drying to obtain the carbazolyl porous organic polymer.
2) Weighing 0.1-2g of carbazolyl porous organic polymer, adding cobalt salt and/or manganese salt accounting for 1-10 wt% of the mass of the carrier, adding 2-50ml of ethanol, and stirring at 20-60 ℃ for 12-24 h;
3) after the impregnation is finished, removing ethanol by a rotary evaporator, drying in an oven at 60-120 ℃ for 6-12h, and roasting in a muffle furnace at 250-400 ℃ for 2-5h to obtain the carbazolyl porous organic polymer-supported cobalt oxide and/or manganese oxide catalyst.
According to the invention, the cobalt salt comprises one or more than two of cobalt chloride, cobalt acetate and cobalt nitrate; the manganese salt comprises one or more of manganese chloride, manganese acetate and manganese sulfate.
According to the invention, the catalyst can be applied to the reaction of oxidizing p-methoxytoluene to generate p-methoxytoluene;
according to the invention, it is characterized in that: the preparation of p-methoxybenzaldehyde from p-methoxytoluene adopts a kettle type reaction, the reaction temperature is 60-150 ℃, and the preferable temperature is 90-130 ℃; the reaction time is 1-12h, preferably 6-8 h; the pressure of the reaction oxygen is 0.1-2.0MPa, preferably 0.8-1.5 MPa; the dosage of the catalyst is 0.1-100% of the mass of the substrate, preferably 0.5-2%
The invention discloses a method for preparing p-methoxybenzaldehyde by catalyzing oxidation of p-methoxytoluene by using carbazolyl porous organic polymer loaded transition metal oxide. The catalyst takes a carbazolyl porous organic polymer as a carrier, transition metal salt is loaded after the carbazolyl porous organic polymer is used as the carrier, and the carbazolyl porous organic polymer loaded transition metal oxide catalyst is obtained by roasting. The carbazolyl porous organic polymer has homogeneously distributed nitrogen atoms in the skeleton and certain interaction between the nitrogen atoms and the metal. Thus, the uniformly distributed nitrogen atoms activate the metal oxide active sites on the one hand; on the other hand, the loss of active components in the reaction process is reduced. The catalyst can efficiently catalyze p-methoxy toluene to prepare p-methoxy benzaldehyde, and the conversion rate and the selectivity can both reach more than 70%. Compared with the traditional heterogeneous catalyst, the catalyst has high thermal stability, good catalytic activity, difficult loss of active components and long service life.
The invention has the beneficial effects that:
1. compared with the traditional activated carbon and silicon dioxide carriers, the carbazolyl porous organic polymer carrier has higher specific surface area and is easier to load active components;
2. due to the existence of nitrogen atoms in the skeleton of the carbazolyl porous organic polymer, the electron density of the metal active component is influenced, so that the purpose of activation is achieved; the stable effect is achieved due to the existence of the interaction of nitrogen atoms and metals; so as to obtain the catalyst with relatively high activity and stability.
3. The catalyst has good reusability and long service life.
Drawings
FIG. 1 is a TEM representation of material A;
FIG. 2 is an infrared spectrum of material A, B, C, D;
fig. 3 is a drawing of physical adsorption of material a.
Detailed Description
The process provided by the present invention is described in detail below with reference to examples, but the present invention is not limited thereto in any way.
EXAMPLE 1 preparation of Material A
1) Weighing 2.0g of ferric chloride, replacing with nitrogen, adding 70ml of anhydrous chloroform, dropwise adding 0.8g of 1,3, 5-tri (9-carbazolyl) benzene dissolved in 70ml of anhydrous chloroform, stirring for 36 hours at room temperature, and obtaining the carbazolyl porous organic polymer through washing, suction filtration, washing with concentrated hydrochloric acid, Soxhlet extraction and vacuum drying.
2) Weighing 0.2g of carbazolyl porous organic polymer, adding 40mg of cobalt acetate tetrahydrate, adding 5ml of ethanol, and stirring at 40 ℃ for 24 hours;
3) after the impregnation is finished, removing ethanol by a rotary evaporator, drying in an oven at 80 ℃ for 12h, and roasting in a muffle furnace at 300 ℃ for 3h to obtain a material A.
EXAMPLE 2 preparation of materials B-E
The preparation of materials B-E was the same as material A, except for the choice of metal salts, loading and calcination temperature, and the materials obtained are listed in Table 1.
TABLE 1 Metal salts, loadings and calcination temperatures for materials B-E
| Material plaiting | Metal salt | Amount of support (wt%) | Calcination temperature (. degree.C.) |
| B | CoCl2·6H2O | 3.0 | 350 |
| C | Co(NO3)2·6H2O | 3.0 | 300 |
| D | Co(NO3)2·6H2O | 7.0 | 300 |
| E | Co(O Ac)2·6H2O | 5.0 | 300 |
Example 3 preparation of Material F
1) Weighing 2.0g of ferric chloride, replacing with nitrogen, adding 70ml of anhydrous chloroform, dropwise adding 0.8g of 1,3, 5-tri (9-carbazolyl) benzene dissolved in 70ml of anhydrous chloroform, stirring for 36 hours at room temperature, and obtaining the carbazolyl porous organic polymer through washing, suction filtration, washing with concentrated hydrochloric acid, Soxhlet extraction and vacuum drying.
2) Weighing 0.2g of carbazolyl porous organic polymer, adding 80mg of manganese acetate tetrahydrate, adding 5ml of ethanol, and stirring at 40 ℃ for 24 hours;
3) and after the impregnation is finished, removing ethanol by using a rotary evaporator, drying in an oven at 80 ℃ for 12h, and roasting in a muffle furnace at 400 ℃ for 3h to obtain a material F.
Example 4
30mg of the synthesized catalyst A and 1.2g of p-methoxytoluene are added into a 60ml high-pressure reaction kettle, 10ml of acetonitrile is used as a reaction solvent, the oxygen pressure is 1.0MPa, the reaction temperature is 130 ℃, and the reaction is carried out for 6 hours. After the reaction is finished and the temperature is reduced to room temperature, a gas phase analysis method is adopted, the conversion rate of the p-methoxy toluene is 70 percent, and the selectivity of the p-methoxy benzaldehyde is 70 percent.
Example 5
30mg of the synthesized catalyst A and 1.2g of p-methoxytoluene are added into a 60ml high-pressure reaction kettle, 10ml of acetonitrile is used as a reaction solvent, the oxygen pressure is 0.2MPa, the reaction temperature is 130 ℃, and the reaction is carried out for 6 hours. After the reaction is finished and the temperature is reduced to room temperature, a gas phase analysis method is adopted, the conversion rate of the p-methoxy toluene is 30 percent, and the selectivity of the p-methoxy benzaldehyde is 60 percent.
Example 6
30mg of the synthesized catalyst A and 1.2g of p-methoxytoluene are added into a 60ml high-pressure reaction kettle, 10ml of acetonitrile is used as a reaction solvent, the oxygen pressure is 1.0MPa, the reaction temperature is 80 ℃, and the reaction is carried out for 12 hours. After the reaction is finished and the temperature is reduced to room temperature, a gas phase analysis method is adopted, the conversion rate of the p-methoxy toluene is 15 percent, and the selectivity of the p-methoxy benzaldehyde is 80 percent.
Example 7
30mg of the synthesized catalyst F and 1.2g of p-methoxytoluene are added into a 60ml high-pressure reaction kettle, 10ml of acetonitrile is used as a reaction solvent, the oxygen pressure is 1.0MPa, the reaction temperature is 130 ℃, and the reaction is carried out for 6 hours. After the reaction is finished and the temperature is reduced to room temperature, a gas phase analysis method is adopted, the conversion rate of the p-methoxy toluene is 50 percent, and the selectivity of the p-methoxy benzaldehyde is 70 percent.
Example 8
The catalyst A used in the example 4 is subjected to repeated use experiments, the experimental steps are completely consistent, the catalyst A is repeatedly used for four times, the conversion rate of p-methoxytoluene is 68%, the selectivity of p-methoxybenzaldehyde is 68%, and the activity is basically maintained.
Claims (9)
1. The catalyst of transition metal oxide loaded on carbazolyl porous organic polymer is characterized in that: taking a carbazolyl porous organic polymer as a carrier, loading transition metal salt on the prepared carrier, and introducing a transition metal oxide active center; the transition metal oxide comprises cobalt oxide and/or manganese oxide; the mass loading of the transition metal oxide in the catalyst is 1-10 wt%;
the carbazolyl porous organic polymer is used as a carrier, and is prepared by dissolving 1,3, 5-tri (9-carbazolyl) benzene in anhydrous chloroform and polymerizing through a Friedel-crafts reaction catalyzed by ferric chloride, wherein the structural formula of the carbazolyl porous organic polymer is as follows:
2. the catalyst of claim 1, wherein: the carbazolyl porous organic polymer carrier is prepared according to the following steps:
dissolving 1,3, 5-tri (9-carbazolyl) benzene in anhydrous chloroform, taking ferric chloride as a catalyst, and stirring at room temperature for 24-36h under the atmosphere of nitrogen; after the reaction is finished, the carbazolyl porous organic polymer is obtained through washing, suction filtration, washing with concentrated hydrochloric acid, Soxhlet extraction and vacuum drying.
3. The catalyst of claim 1, wherein: the active center is introduced by the following steps:
1) weighing 0.1-2g of carbazolyl porous organic polymer, adding cobalt salt and/or manganese salt accounting for 1-10 wt% of the mass of the carrier, adding 2-50ml of ethanol and 20-60 ml of ethanoloStirring for 12-24h under the condition of C;
2) after the impregnation is finished, removing ethanol by a rotary evaporator at 60-120%oDrying in an oven for 6-12h in a muffle furnace at 250-oAnd C, roasting for 2-5h to obtain the carbazolyl porous organic polymer supported cobalt oxide and/or manganese oxide catalyst.
4. A catalyst according to claim 3, characterized in that: in the loading process, the cobalt salt comprises one or more of cobalt chloride, cobalt acetate and cobalt nitrate; the manganese salt comprises one or more of manganese chloride, manganese acetate and manganese sulfate.
5. Use of a catalyst according to any one of claims 1 to 4 in the oxidation of p-methoxytoluene to p-methoxybenzaldehyde.
6. Use according to claim 5, characterized in thatThe method comprises the following steps: the preparation of p-methoxybenzaldehyde from p-methoxytoluene adopts a kettle type reaction at the reaction temperature of 60-150 DEG CoC; the reaction time is 1-12 h; the oxygen pressure in the reaction system is 0.1-2.0 MPa.
7. Use according to claim 6, characterized in that: the reaction temperature is 90-130%oC; the reaction time is 6-8 h; the oxygen pressure in the reaction system is 0.8-1.5 MPa.
8. Use according to claim 5 or 6, characterized in that: the dosage of the catalyst is 0.1-100% of the mass of the substrate p-methoxytoluene.
9. Use according to claim 8, characterized in that: the dosage of the catalyst is 0.5-2% of the mass of the substrate p-methoxytoluene.
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