CN104801344A - Catalyst for catalyzing oxidation of cyclohexane and preparation method of catalyst - Google Patents

Abstract

The invention provides a method for preparing a catalyst for catalyzing oxidation of cyclohexane. The method comprises steps as follows: (A), preparing 5 (p-propionate) phenyl-10,15,20-tri(pyridyl) porphyrin; (B), preparing 5(p-hydroxy) phenyl-10,15,20-tri(pyridyl) porphyrin from 5 (p-propionate) phenyl-10,15,20-tri(pyridyl) porphyrin; (C), preparing metallic coordinated 5-(p-hydroxy) phenyl-10,15,20-tri(pyridyl) porphyrin from 5 (p-hydroxy) phenyl-10,15,20-tri(pyridyl) porphyrin; (D), attaching the metallic coordinated 5-(p-hydroxy) phenyl-10,15,20-tri(pyridyl) porphyrin to at least one magnetic microsphere, and methylating 5-(p-hydroxy) phenyl-10,15,20-tri(pyridyl) porphyrin by the aid of methyl iodide.

Description

Catalyst for catalyzing cyclohexane oxidation and preparation method thereof

technical field

The invention relates to a catalyst for catalyzing the oxidation of cyclohexane, in particular to a macromolecule magnetic nanometer catalyst solidly loaded with metal cation porphyrin and its application in catalytic oxidation of cyclohexane. The invention also relates to a preparation method of a polymer magnetic nanometer catalyst loaded with metal cation porphyrin.

Background technique

Under mild conditions, the ability of the cytochrome P450 mimic system to catalyze the hydroxylation of the substrate by molecular oxygen is very limited, which is similar to the lack of hydrophobicity formed by protein chain folding in the bonding position of the natural cytochrome P450 around the metalloporphyrin complex related to the microenvironment. In polymer-immobilized metalloporphyrin complexes, the surface groups of the polymer carrier can be used as a chemical simulation of the microenvironment around the enzyme active center, which is expected to improve the catalytic activity of the metal complexes. Therefore, the study of polymer-immobilized metalloporphyrins mimicking cytochrome P450 is of great significance for catalysts that catalyze the hydroxylation of substrates by molecular oxygen.

At present, the research on simulating cytochrome P450 has a new goal and content, that is, to develop new catalysts and follow the research route of selective oxidation of hydrocarbons and innovative development. Some hydrocarbon catalysis experts believe that the ideal catalyst for the oxidation of hydrocarbons in the future should be a combination of high selectivity, environmental friendliness and high stability (see Figure 1).

Chloromethyl polystyrene (Merrifield's resin) is a commonly used polymer carrier. The hydrophobic microenvironment it provides is conducive to the combination of substrate molecules and active intermediates of oxo-high-valent metalloporphyrins, thereby improving the catalytic activity of metalloporphyrins. activity and is thus considered a good mimic of the polypeptide chain surrounding the active center of cytochrome P450. However, the immobilization of active chlorine in chloromethyl polystyrene limits the bonding of metalloporphyrin complexes, which limits its application to a certain extent.

The catalytic active center corresponding to the carrier - metalloporphyrin, is the focus of many researches on simulating cytochrome P450. In order to enhance its catalytic activity, a large number of chemical modifications have been carried out on metalloporphyrins, especially the introduction of substituents in the middle of porphyrins has become a research hotspot. However, according to the reported literature, there are few studies on mesopyridyl porphyrin metal complexes, especially water-soluble pyridyl porphyrin metal complexes, and practical cytochrome P450 mimics are very rare.

The Chinese invention patent whose publication number is CN101116829 teaches a kind of preparation in the presence of magnetic fluid and initiator by copolymerization of styrene and porphyrin acrylate with substituents such as p-methoxyphenyl and p-chlorophenyl A method for magnetic nanopolymer microspheres. However, the yield of porphyrin acrylate in this preparation method is low, and because a large amount of porphyrin is polymerized inside the microsphere, it cannot participate in catalysis, so that the catalytic efficiency of the porphyrin in the magnetic nano-polymer microsphere is low.

The Chinese invention patent whose publication number is CN103111328A teaches a kind of using pyridine-4-carboxaldehyde, pyrrole, brominated alkanes, hydrobromic acid, metal salt and iron tribromide etc. as raw materials to prepare magnetic ions containing paramagnetic anion FeBr4- type metalloporphyrin catalysts. In this invention patent, the porphyrin compound is directly used for catalysis, so that the hydrophobic microenvironment similar to the catalytic environment formed by protein chain folding in the bonding position of natural cytochrome P450 is lacking around the metalloporphyrin complex, so its The catalytic efficiency is not as high as that of porphyrins immobilized on polymer microspheres.

Contents of the invention

The main advantage of the present invention is that it provides a new and practical mimic cytochrome P450 catalyst for the oxidation of cyclohexane.

Another advantage of the present invention is that it provides a new catalyst for catalyzing the oxidation of cyclohexane, wherein the catalyst is suitable for application in petrochemical, ink, resin and other industrial production.

Another advantage of the present invention is that it provides a new catalyst for catalyzing the oxidation of cyclohexane, wherein the catalyst has high catalytic efficiency for the oxidation of cyclohexane, and is convenient for recovery and recycling.

Another advantage of the present invention is that it provides a novel catalyst for catalyzing the oxidation of cyclohexane, wherein in the catalyst, the surface of the magnetic microspheres of the catalyst is hinged with porphyrin and picoline, so that porphyrin The higher utilization rate of morphine and the hydrophilicity of the catalyst surface help the catalyst to play a better catalytic role in the catalytic system.

Another advantage of the present invention is that it provides a new catalyst for catalyzing the oxidation of cyclohexane, wherein the catalyst has high magnetic responsiveness under an external magnetic field, has better targeted catalytic activity for cyclohexane, and High catalytic efficiency can still be maintained after repeated recycling.

Another advantage of the present invention is that it provides a new catalyst for catalyzing the oxidation of cyclohexane, wherein the preparation raw material of the catalyst is cheap and easy to obtain and the manufacturing process is simple.

Another advantage of the present invention is that it provides a new catalyst for catalyzing the oxidation of cyclohexane, wherein the carrier of the catalyst is a styrene-methacrylic acid copolymer, and the catalytic center is a water-soluble cationic metal porphyrin as the catalytic center .

Another advantage of the present invention is that it provides a new catalyst for catalyzing the oxidation of cyclohexane, wherein the catalyst has a simple molecular structure, and its manufacturing process is easy to implement and low in cost.

Another advantage of the present invention is that it provides a new catalyst for catalyzing the oxidation of cyclohexane, wherein the catalyst is a polymer magnetic nanocatalyst of immobilized metal cation porphyrin

Other advantages and features of the present invention will be fully manifested by the following detailed description and can be realized by the combination of means and means particularly pointed out in the appended claims.

According to the present invention, the catalyst for catalyzing the oxidation of cyclohexane, which can achieve the aforementioned object and other objects and advantages, includes a catalytic component and a supporting component, wherein the supporting component includes at least one magnetic microsphere, and the catalytic component is attached to the The loading component, wherein the catalytic component is 5-(p-hydroxyl)phenyl-10,15,20-tripyridyl porphyrin coordinated by metal manganese (cobalt, iron).

According to other aspects of the present invention, the present invention further provides a method for manufacturing a catalyst for catalyzing the oxidation of cyclohexane, which comprises the following steps:

(A) Preparation of 5(p-propionate)phenyl-10,15,20-tripyridylporphyrin (EPTPyP);

(B) Preparation of 5(p-hydroxy)phenyl-10,15,20-tripyridylporphyrin from 5(p-propionate)phenyl-10,15,20-tripyridylporphyrin (EPTPyP) Phenyl (HPTPyP);

(C) 5-(p-hydroxyl)phenyl-10 coordinated by metal manganese (cobalt, iron) using 5(p-hydroxyl)phenyl-10,15,20-tripyridyl porphyrin (HPTPyP), 15,20-tripyridylporphyrin ([HPTPyP]MnCl, Co[HPTPyP], Fe[HPTPyP]); and

(D) 5-(p-hydroxyl)phenyl-10,15,20-tripyridyl porphyrin ([HPTPyP]MnCl, Co[HPTPyP], Fe[HPTPyP] coordinated by metal manganese (cobalt, iron) ) immobilized (or attached) on a magnetic microsphere.

Further objects and advantages of the invention will fully appear from an understanding of the ensuing description and accompanying drawings.

These and other objects, features and advantages of the present invention are fully realized by the following detailed description, drawings and claims.

Description of drawings

Figure 1 shows the ideal catalyst for the oxidation of hydrocarbons.

Fig. 2 is a synthetic route diagram of a metal cationic porphyrin-immobilized microsphere for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

3A is a scanning electron microscope (SEM) image of magnetic microspheres immobilized with metal cation porphyrins for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

3B is a scanning electron microscope (SEM) image of magnetic microspheres immobilized with metal cation porphyrins for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

3C is a scanning electron microscope (SEM) image of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

4A is a transmission electron microscope (TEM) image of magnetic microspheres immobilized with metal cation porphyrins for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

4B is a transmission electron microscope (TEM) image of magnetic microspheres immobilized with metal cation porphyrins for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

4C is a transmission electron microscope (TEM) image of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

FIG. 5A is an ultraviolet spectrum of magnetic microspheres loaded with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

Fig. 5B is an ultraviolet spectrum of the magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

FIG. 5C is an ultraviolet spectrogram of the magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

FIG. 6A is an infrared spectrogram of the metal-cation porphyrin-immobilized magnetic microspheres used to catalyze the oxidation of cyclohexane according to a preferred embodiment of the present invention.

Fig. 6B is an infrared spectrogram of the metal-cation porphyrin-immobilized magnetic microspheres used to catalyze the oxidation of cyclohexane according to a preferred embodiment of the present invention.

FIG. 6C is an infrared spectrum of the magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

7A is a thermogravimetric analysis diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

Fig. 7B is a thermogravimetric analysis diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

FIG. 7C is a thermogravimetric analysis diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

FIG. 8A is a hysteresis loop diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

8B is a hysteresis loop diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

8C is a hysteresis loop diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

Fig. 9A is a diagram showing the effect of natural state sedimentation and separation under strong magnetic field of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

Fig. 9B is a diagram showing the effect of natural state sedimentation and separation under strong magnetic field of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

FIG. 9C is an effect diagram of the natural state sedimentation and the separation under a strong magnetic field of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

Fig. 10A is a graph showing the relationship between the reducing agent ascorbic acid and the catalytic conversion number of cyclohexane when ascorbic acid is used as the catalyst to catalyze cyclohexane.

Fig. 10B is a graph showing the relationship between the reducing agent P[St-co-MAA]-MnTMPyP and the catalytic conversion number of cyclohexane when P[St-co-MAA]-MnTMPyP is used as the catalytic cyclohexane catalyst.

Fig. 11 is a flow chart for producing a catalyst for cyclohexane oxidation according to a preferred embodiment of the present invention.

Detailed ways

The following description is disclosed to enable any person skilled in the art to make and use the invention. The preferred embodiments provided in the following description are only examples and modifications obvious to those skilled in the art, and they are not intended to limit the scope of the present invention. The general principles defined in the following description may be applied to other embodiments, alternatives, modifications, equivalent implementations and applications without departing from the spirit and scope of the invention.

Figure 1 shows the ideal catalyst for the oxidation of hydrocarbons. It can be seen from the figure that an ideal catalyst has the characteristics of high catalytic performance, high stability, oxidation resistance and hydrolysis resistance.

Fig. 2 is a synthetic route diagram of a metal cationic porphyrin-immobilized microsphere for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention.

3A is a scanning electron microscope (SEM) image of magnetic microspheres immobilized with metal cation porphyrins for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Fig. 3A that the morphology of the magnetic microspheres immobilized with metal manganese porphyrin is regular spherical, and the particle size ranges from 100 to 200 nanometers.

3B is a scanning electron microscope (SEM) image of magnetic microspheres immobilized with metal cation porphyrins for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 3B that the morphology of the magnetic microspheres immobilized with metal cobalt porphyrin is regular spherical, and the particle size ranges from 100 to 200 nanometers.

3C is a scanning electron microscope (SEM) image of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Fig. 3C that the magnetic microspheres immobilized with metal iron porphyrin have a regular spherical shape and a particle size range of 100-200 nanometers.

4A is a transmission electron microscope (TEM) image of magnetic microspheres immobilized with metal cation porphyrins for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. From the results in Figure 4A, it can be seen that the magnetic fluid inside the magnetic microspheres immobilized with metal manganese porphyrin is clearly visible, and the polymer material is successfully embedded outside, with regular morphology and a particle size range of 100-200 nanometers

4B is a transmission electron microscope (TEM) image of magnetic microspheres immobilized with metal cation porphyrins for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. From the results in Figure 4B, it can be seen that the magnetic fluid inside the magnetic microspheres immobilized with metal cobalt porphyrin is clearly visible, and the polymer material is successfully embedded outside, with regular morphology and a particle size range of 100-200 nanometers

4C is a transmission electron microscope (TEM) image of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. From the results in Figure 4C, it can be seen that the magnetic fluid inside the magnetic microspheres immobilized with metal iron porphyrin is clearly visible, and the polymer material is successfully embedded on the outside, with regular morphology and a particle size range of 100-200 nanometers

FIG. 5A is an ultraviolet spectrum of magnetic microspheres loaded with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 5A that the ultraviolet spectrum of the magnetic microspheres immobilized with metal manganese porphyrin showed the characteristic Sore absorption peak of porphyrin at around 420 nm, indicating that manganese porphyrin was successfully immobilized on the magnetic microspheres.

Fig. 5B is an ultraviolet spectrum of the magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 5B that the ultraviolet spectrum of the magnetic microspheres immobilized with metal cobalt porphyrin showed the characteristic Soret absorption peak of porphyrin at around 420 nm, indicating that cobalt porphyrin was successfully immobilized on the magnetic microspheres.

FIG. 5C is an ultraviolet spectrogram of the magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 5C that the ultraviolet spectrum of the magnetic microspheres immobilized with metal iron porphyrin showed the characteristic Soret absorption peak of porphyrin at around 420 nm, indicating that iron porphyrin was successfully immobilized on the magnetic microspheres.

FIG. 6A is an infrared spectrogram of the metal-cation porphyrin-immobilized magnetic microspheres used to catalyze the oxidation of cyclohexane according to a preferred embodiment of the present invention. As can be seen from the results in Figure 6A, the infrared spectrum of the magnetic microspheres immobilized with metal manganese porphyrin presents the characteristic peaks of polymer materials, such as the characteristic absorption of polystyrene at 2700-3200cm-1, and the characteristic absorption at 1743cm-1 The characteristic stretching vibration absorption C-O-C stretching vibration absorption peak at 1 and 1183 cm-1 representing the ester bond C=O double bond shows that the manganese porphyrin has been bonded on the nano-polymer magnetic microsphere.

Fig. 6B is an infrared spectrogram of the metal-cation porphyrin-immobilized magnetic microspheres used to catalyze the oxidation of cyclohexane according to a preferred embodiment of the present invention. As can be seen from the results in Figure 6B, the infrared spectrum of the magnetic microspheres immobilized with metal cobalt porphyrin presents the characteristic peaks of polymer materials, such as the characteristic absorption of polystyrene at 2700-3200cm-1, and the characteristic absorption at 1743cm-1 The characteristic stretching vibration absorption C-O-C stretching vibration absorption peak at 1 and 1183 cm-1 representing the ester bond C=O double bond shows that cobalt porphyrin has been bonded on the nano-polymer magnetic microsphere.

FIG. 6C is an infrared spectrum of the magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 6C that the infrared spectrum of the magnetic microspheres immobilized with metal iron porphyrin presents the characteristic peaks of polymer materials, such as the characteristic absorption of polystyrene at 2700-3200cm-1, and the characteristic absorption at 1743cm-1 The characteristic stretching vibration absorption C-O-C stretching vibration absorption peak at 1 and 1183 cm-1 representing the ester bond C=O double bond shows that iron porphyrin has been bonded on the nano-polymer magnetic microsphere.

7A is a thermogravimetric analysis diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 7A that the magnetic microspheres immobilized with metal manganese porphyrin are very stable, and the organic part begins to decompose at about 250°C, and it decomposes completely at about 500°C, and the residual inorganic matter content is between 8%- between 12%.

Fig. 7B is a thermogravimetric analysis diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 7B that the magnetic microspheres immobilized with metal cobalt porphyrin are very stable, and the organic part begins to decompose at about 250°C, and it is decomposed completely at about 500°C, and the residual inorganic content is between 8%- between 12%.

FIG. 7C is a thermogravimetric analysis diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. From the results in Figure 7C, it can be seen that the magnetic microspheres immobilized with metal iron porphyrin are very stable, and the organic part begins to decompose at about 250 °C, and the decomposition is complete at about 500 °C, and the residual inorganic content is between 8% and between 12%.

FIG. 8A is a hysteresis loop diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 8A that the magnetic microspheres immobilized with metal manganese porphyrin have good magnetic responsiveness, and the saturation magnetization is about 3.4emu/g.

8B is a hysteresis loop diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 8B that the magnetic microspheres immobilized with metal cobalt porphyrin have good magnetic responsiveness, and the saturation magnetization is about 3.5 emu/g.

8C is a hysteresis loop diagram of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 8C that the magnetic microspheres immobilized with metal iron porphyrin have good magnetic responsiveness, and the saturation magnetization is about 3.3 emu/g.

Fig. 9A is a diagram showing the effect of natural state sedimentation and separation under strong magnetic field of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 9A that under magnetic field separation, the transmittance of the magnetic microspheres immobilized with metal manganese porphyrin reaches 95% within 20 minutes, while under natural sedimentation conditions, the transmittance reaches 95% after more than 6 hours. Only reached 93%. It shows that the microspheres have good magnetic responsiveness.

Fig. 9B is a diagram showing the effect of natural state sedimentation and separation under strong magnetic field of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 9B that under magnetic separation, the transmittance of the magnetic microspheres immobilized with metal cobalt porphyrin reaches 95% within 20 minutes, while under natural sedimentation conditions, the transmittance reaches 95% after more than 6 hours. Only reached 93%. It shows that the microspheres have good magnetic responsiveness.

FIG. 9C is an effect diagram of the natural state sedimentation and the separation under a strong magnetic field of magnetic microspheres immobilized with metal cation porphyrin for catalyzing the oxidation of cyclohexane according to a preferred embodiment of the present invention. It can be seen from the results in Figure 9C that under magnetic field separation, the transmittance of the magnetic microspheres immobilized with metal iron porphyrin reaches 95% within 20 minutes, while under natural sedimentation conditions, the transmittance reaches 95% after more than 6 hours. Only reached 93%. It shows that the microspheres have good magnetic responsiveness.

Fig. 10A is the change curve of the catalytic effect of catalytic cyclohexane under different dosage conditions of ascorbic acid.

Fig. 10B is a graph showing the change of the substrate produced by the catalyst catalyzing the hydroxylation of cyclohexane with the change of catalysis time.

Fig. 11 is a flow chart for producing a catalyst for cyclohexane oxidation according to a preferred embodiment of the present invention.

Under mild conditions, the ability of the cytochrome P450 mimic system to catalyze the hydroxylation of the substrate by molecular oxygen is very limited, which is similar to the lack of hydrophobicity formed by protein chain folding in the bonding position of the natural cytochrome P450 around the metalloporphyrin complex related to the microenvironment. Therefore, if a hydrophobic microenvironment can be introduced into the simulated cytochrome P450 catalytic system, the catalytic ability of the simulated cytochrome P450 catalytic system may be greatly improved.

In cytochrome P450, the catalytic active center is metalloporphyrin. Therefore, people have carried out a lot of research on metalloporphyrin and developed various types of chemical modifications in order to try to obtain compounds with better catalytic effect. However, so far, the research on mesopyridyl porphyrin metal complexes, especially the water-soluble pyridyl porphyrin metal complexes is not deep enough.

The present invention provides following compounds for the manufacture of catalysts for novel catalytic cyclohexane oxidation, the structural formula of which is:

Wherein M is Mn, Fe or Co molecule.

Above-mentioned compound A, compound B, compound C and compound D all can be used for making the catalyst of the present invention that catalyzes the oxidation of cyclohexane, wherein compound A is 5 (p-propionate group) phenyl-10,15,20-tri Pyridyl porphyrin; compound B is 5 (p-hydroxy) phenyl-10,15,20-tripyridyl porphyrin; compound C is 5-(p-hydroxy) benzene coordinated by manganese (or cobalt or iron) Base-10,15,20-tripyridyl porphyrin; Compound D is 5-(p-hydroxy)phenyl-10,15,20-trimethylpyridyl iodoporphyrin coordinated by manganese (or cobalt or iron) phenoline; wherein compound D can be attached to a load component (such as styrene-methacrylic acid magnetic microspheres) through an esterification reaction (generally, an esterification reaction between the hydroxyl group of compound D and the carboxyl group on the surface of the load component) to make immobilized Magnetic catalyst microspheres of metal cationic porphyrin, so that compound D has better catalytic space and contact with substrate cyclohexane. In addition, the loading components, such as styrene-methacrylic acid magnetic microspheres, have high magnetic response, so that the catalytic components attached to the styrene-methacrylic acid magnetic microspheres, such as compound D, can be recovered. Preferably, the diameter of the styrene-methacrylic acid magnetic microspheres or the final product-magnetic catalyst microspheres loaded with compound D is not more than 1000 nanometers, thereby improving the final product loaded with compound D, the magnetic properties of the immobilized metal cation porphyrin Catalytic efficiency of catalyst microspheres. More preferably, the styrene-methacrylic acid magnetic microspheres have a diameter of 150-210 nanometers.

It is worth noting that, as shown in Figure 2 of the accompanying drawings, the molecular structure and chemical composition of compound D can ionize the local structure of the surface of the catalytic component compound D, so that the immobilized metal cation porphyrin loaded with compound D The magnetic catalyst microspheres are water-soluble, so that the magnetic catalyst microspheres loaded with compound D and immobilized metal cation porphyrin can be dissolved in water and recovered more easily. As shown in Figure 2 of the accompanying drawings, further, in the simulated cytochrome P450 catalyst of the present invention, the water-soluble pyridyl porphyrin metal complex is modified, and its catalytic site or catalyst active center is retained, such as metal cationic porphyrin At the same time, the hydrophobic microenvironment improves its catalytic ability and water solubility.

Shown in Fig. 2 and Fig. 11 with reference to accompanying drawing, the present invention further provides a kind of method for making the novel catalyst of catalytic cyclohexane oxidation, and it comprises the following steps:

(A) Preparation of 5(p-propionate)phenyl-10,15,20-tripyridylporphyrin (EPTPyP);

(B) Preparation of 5(p-hydroxy)phenyl-10,15,20-tripyridylporphyrin from 5(p-propionate)phenyl-10,15,20-tripyridylporphyrin (EPTPyP) morphine (HPTPyP);

(C) 5-(p-hydroxyl)phenyl-10 coordinated by metal manganese (cobalt, iron) using 5(p-hydroxyl)phenyl-10,15,20-tripyridyl porphyrin (HPTPyP), 15,20-tripyridylporphyrin ([HPTPyP]MnCl, Co[HPTPyP], Fe[HPTPyP]); and

(D) 5-(p-hydroxyl)phenyl-10,15,20-tripyridyl porphyrin ([HPTPyP]MnCl, Co[HPTPyP], Fe[HPTPyP] coordinated by metal manganese (cobalt, iron) ) is immobilized on at least one magnetic microsphere, and methylated 5-(p-hydroxy)phenyl-10,15,20-tripyridyl porphyrin by methyl iodide, wherein the magnetic microsphere is styrene-methyl The acrylic microsphere has a diameter of 150-210 nanometers.

Wherein the step (A) comprises the following steps:

(A1) Reaction of p-hydroxybenzaldehyde, propionic acid, acetic anhydride, pyrrole and 4-pyridine formaldehyde and ethanol, wherein based on the quality of p-hydroxybenzaldehyde, 100-120 mL of propionic acid is needed for every 1 g of p-hydroxybenzaldehyde, and Acid anhydride 5-8mL, pyrrole 2-4mL, 4-pyridine formaldehyde 2-4mL, ethanol 100-150mL; and

(A2) After standing for 12 to 18 hours, suction filtration, washing, and column chromatography to obtain 5 (p-propionate) phenyl-10,15,20-tripyridyl porphyrin,

This step (B) comprises the following steps:

(B1) 5 (p-propionate group) phenyl-10,15,20-tripyridyl porphyrin was mixed with methanol solution of chloroform and NaOH and magnetically stirred, and reacted at room temperature for 12 hours; and

(B2) After washing with water, centrifuging to remove water and drying, column chromatography separates to obtain 5 (p-hydroxyl) phenyl-10,15,20-tripyridyl porphyrin;

This step (C) comprises the following steps:

(C1) Mix 5(p-hydroxy)phenyl-10,15,20-tripyridylporphyrin, chloroform, methanol, collidine and a metal acetate such as manganese acetate, iron acetate or cobalt acetate After magnetic stirring, the reaction solution is evaporated under reduced pressure; and

(C2) washing with water, suction filtration, column chromatographic separation to obtain metal-coordinated 5-(p-hydroxy)phenyl-10,15,20-tripyridyl porphyrin,

This step (D) comprises the following steps:

(D1) The magnetic styrene-methacrylic acid microspheres, dichloroethane, thionyl chloride and metal-coordinated 5-(p-hydroxyl)phenyl-10,15,20-tripyridyl porphyrin DMF solution reaction; and

(D2) After the reaction, filter, wash, extract, dry, and add _CH3I to reflux for 8 to 12 hours, distill off the solvent to obtain styrene-methacrylic acid copolymerized magnetic nanospheres loaded with metal pyridine porphyrin , wherein the metal pyridine is manganese, iron or cobalt.

The method for the novel catalyst that the present invention is used to manufacture catalytic hexamethylene oxidation further comprises the following steps:

(E) Add gelatin, dibenzoyl peroxide, methacrylic acid, divinylbenzene and styrene in a weight ratio of 0.4 to 0.7: 1.5 to 3: 2.5 to 3.5: 24 to 25, and add magnetic The fluid is reacted with pure water, filtered, washed and vacuum-dried to prepare magnetic styrene-methacrylic acid microspheres with carboxyl groups on the surface, wherein the step (E) is before the step (D).

It should be noted that in the catalyst used for catalyzing the oxidation of cyclohexane in the present invention, there are two components: a loading component and a catalytic component, wherein the catalytic component is the compound D which is immobilized or attached to the loading component, and the loading The composition is magnetic microspheres made of styrene-methacrylic acid as the main component, wherein the diameter of the styrene-methacrylic acid magnetic microspheres is 150 to 210 nanometers, wherein in the catalyst of the present invention, the metal cationic porphyrin The weight ratio is 0.5%-0.8%, and the active center of the catalyst is metal cationic porphyrin.

The following examples are used to illustrate the catalyst of the present invention or the production method of the intermediate compound (or compound intermediate) used to produce the catalyst of the present invention, which does not constitute a limitation to the scope of the present invention. It will be obvious to those skilled in the art that there are other methods or synthetic routes for making intermediate compounds or compound intermediates of the catalysts of the present invention, or methods for making the catalysts of the present invention.

Example 1:

(A) Preparation of 5(p-propionate)phenyl-10,15,20-tripyridylporphyrin (EPTPyP):

React p-hydroxybenzaldehyde, propionic acid, acetic anhydride, pyrrole and 4-pyridine formaldehyde with ethanol, where the mass of p-hydroxybenzaldehyde is used as a benchmark, and 1g of p-hydroxybenzaldehyde requires 100 to 120 mL of propionic acid and 5 to 50 mL of acetic anhydride. 8mL, pyrrole 2~4mL, 4-pyridinecarbaldehyde 2~4mL, ethanol 100~150mL, after standing for 12~18 hours, suction filtration, washing, and column chromatography to obtain 5(p-propionate)phenyl-10, 15,20-tripyridylporphyrin (EPTPyP).

(B) Preparation of 5(p-hydroxy)phenyl-10,15,20-tripyridylporphyrin (HPTPyP):

The 5 (p-propionate group) phenyl-10,15,20-tripyridyl porphyrin (EPTPyP) prepared in step (A) is mixed with the methanol solution of chloroform and NaOH and magnetically stirred, and reacted at room temperature After 12 hours, washing with water, centrifugation to remove water and drying, column chromatography gave 5(p-hydroxy)phenyl-10,15,20-tripyridylporphyrin (HPTPyP).

(C) Preparation of 5-(p-hydroxy)phenyl-10,15,20-tripyridyl porphyrin ([HPTPyP]MnCl, Co[HPTPyP], Fe[HPTPyP] coordinated by metal manganese (cobalt, iron) ):

Mix 5(p-hydroxy)phenyl-10,15,20-tripyridylporphyrin, chloroform, methanol, collidine and manganese acetate, stir magnetically, evaporate the reaction solution under reduced pressure, wash with water, and filter with suction , column chromatography to obtain 5-(p-hydroxy)phenyl-10,15,20-tripyridyl porphyrin ([HPTPyP]MnCl, Co[HPTPyP], Fe[HPTPyP]) coordinated by metal manganese.

(D) Preparation of styrene-methacrylic acid copolymerized magnetic nanospheres (P[St-co-MAA]-MnPyP, P[St-co-MAA]- CoPyP,P[St-co-MAA]-FePyP):

The magnetic styrene-methacrylic acid microspheres prepared in step (E), ethylene dichloride, thionyl chloride and the 5-(p-hydroxyl) phenyl-10 coordinated by the metal manganese obtained in step (C), 15,20-tripyridyl porphyrin (HPTPyP) was reacted with DMF solution, filtered after the reaction, washed, extracted, dried, and added with CH ₃ I to reflux for 8-12 hours, and the solvent was distilled off to obtain a manganese-loaded methylpyridine Styrene-methacrylic acid copolymerized magnetic nanospheres of porphyrin (P[St-co-MAA]-MnMPyP, P[St-co-MAA]-CoMPyP, P[St-co-MAA]-FeMPyP).

(E) Preparation of magnetic styrene-methacrylic acid microspheres:

Add ferrofluid and pure Water reaction, filtration, washing and vacuum drying to prepare magnetic styrene-methacrylic acid microspheres with carboxyl groups on the surface.

Example 2:

(A) Preparation of 5(p-propionate)phenyl-10,15,20-tripyridylporphyrin (EPTPyP):

Weigh p-hydroxybenzaldehyde and place it in a reaction vessel, then add propionic acid and acetic anhydride, stir and heat with magnetic force, the reaction temperature is 120-130°C, add pyrrole and 4-pyridine formaldehyde dropwise, heat up to 145-145°C and reflux for 2.5 ~3.5 hours, then cooled to 75~85°C, added ethanol while stirring, left overnight, filtered, washed, and separated by column chromatography to obtain purple crystal 5(p-propionate)phenyl-10,15,20-tri Pyridyl porphyrin: Based on the quality of p-hydroxybenzaldehyde, the volume of propionic acid needed to react 1g of p-hydroxybenzaldehyde is 100-120mL, the volume of acetic anhydride is 5-8mL, and the volume of pyrrole is 2-4mL. The required volume of 4-pyridinecarbaldehyde is 2-4mL, and the required volume of ethanol is 100-150mL; the eluent used for column chromatography separation is a mixture of chloroform and ethanol at a volume ratio of 30:1.

(B) Preparation of 5(p-hydroxy)phenyl-10,15,20-tripyridylporphyrin (HPTPyP):

The 5 (p-propionate group) phenyl-10,15,20-tripyridyl porphyrin EPTPyP obtained in step (A) is placed in a reaction vessel, and methanol solution of chloroform and NaOH is added, based on EPTPyP, The volume of chloroform needed for 1g EPTPyP is 20mL, the volume of the methanol solution of NaOH is 10mL, magnetically stirred, and reacted at room temperature for 12 hours, washed with water, spin-dried and dried, and separated by column chromatography to obtain 5 (p-hydroxy)phenyl -10,15,20-tripyridyl porphyrin; wherein the concentration of NaOH in the methanol solution of NaOH is 10%, and the eluent used for column chromatography separation is a mixture of chloroform and ethanol at a volume ratio of 15:1.

(C) 5-(p-hydroxyl)phenyl-10,15,20-tripyridyl porphyrin coordinated by metal manganese (cobalt, iron) ([HPTPyP]MnCl, Co[HPTPyP], Fe[HPTPyP]) Preparation of:

5 (p-hydroxyl) phenyl-10,15,20-tripyridyl porphyrin is placed in a reaction vessel, a mixed solvent of chloroform and methanol and collidine are added, and the magnetic stirring reaction temperature is controlled at 60° C., and the reaction After 15 minutes, manganese acetate was added, and the reaction was continued for 3 hours. After the reaction stopped, the reaction solution was evaporated under reduced pressure, washed with water, filtered by suction, and separated by column chromatography to obtain dark green crystals, which were 5-(p-hydroxyl)benzene coordinated by metal manganese. Base-10,15,20-tripyridyl porphyrin; wherein, the mass ratio of 5(p-hydroxyl)phenyl-10,15,20-tripyridyl porphyrin to manganese acetate is 1:4, with 5( P-hydroxyl) phenyl-10,15,20-tripyridyl porphyrin is a benchmark, 1g 5 (p-hydroxyl) phenyl-10,15,20-tripyridyl porphyrin needs the mixed solvent of chloroform and methanol 20 ～40mL, collidine 100～200μL; the volume ratio of chloroform and methanol in the mixed solvent of chloroform and methanol is 2:1, and the eluent used for column chromatography separation is a mixture of chloroform and ethanol in a volume ratio of 9:1 .

(D) Styrene-methacrylic acid copolymerized magnetic nanospheres (P[St-co-MAA]-MnPyP, P[St-co-MAA]-CoPyP) immobilized manganese (cobalt, iron) picoline porphyrin , P[St-co-MAA]-FePyP):

Weigh the magnetic styrene-methacrylic acid microspheres and place them in a reaction vessel, add dried dichloroethane and thionyl chloride, reflux at 75°C for 12 hours, wash with dried dichloroethane, Suction filtration, drying, then add 5-(p-hydroxyl) phenyl-10,15,20-tripyridyl porphyrin ([HPTPyP]MnCl, Co[HPTPyP], Fe [HPTPyP]) DMF solution, reflux at 80°C for 12 hours, filter, wash, extract, and dry to obtain a light green solid, add CH ₃ I to reflux overnight, and distill off the solvent to obtain immobilized manganese-methylpyridine porphyrin Styrene-methacrylic acid copolymerized magnetic nanospheres (P[St-co-MAA]-MnMPy, P[St-co-MAA]-CoMPyP, P[St-co-MAA]-FeMPyP); The volume ratio of the DMF solution of ethane, thionyl chloride and 5-(p-hydroxy)phenyl-10,15,20-tripyridylporphyrin is 35:10:30, 1g magnetic styrene-methacrylic acid The volume of the DMF solution of 5-(p-hydroxy)phenyl-10,15,20-tripyridyl porphyrin required for microspheres is 10 mL, in which the 5-(p-hydroxyl) coordinated by metal manganese (cobalt, iron) ) The concentration of the DMF solution of phenyl-10,15,20-tripyridyl porphyrin is 15-20 g/L.

(E) Preparation of magnetic styrene-methacrylic acid microspheres:

Put the gelatin in a reaction vessel, heat to 100°C to dissolve the gelatin completely, cool down to 70-80°C to keep a constant temperature, add dibenzoyl peroxide, methacrylic acid, divinylbenzene and styrene, and react under nitrogen protection 1 hour, then heat up to 80-90°C and react for 5.5-6.5 hours, cool down, filter, wash, and vacuum-dry to obtain magnetic styrene-methacrylic acid microspheres with carboxyl groups on the surface; the gelatin, dibenzoyl peroxide, formaldehyde The mass ratio of acrylic acid, divinylbenzene and styrene is 4.5-5.5:0.4-0.7:1.5-3:2.5-3.5:24-25. Based on the mass of gelatin, the volume of magnetic fluid required to dissolve 1g of gelatin is 9 ～12mL, the volume of pure water required is 95～105mL.

Example 3:

(A) Synthesis of 5-(p-hydroxy)phenyl-10,15,20-tripyridyl porphyrin (MnHPTPyP) coordinated by metal manganese:

Add 1.386g p-Hydroxybenzaldehyde, 180ml propionic acid, 7ml acetic anhydride in 500ml three-necked bottle, magnetically stir and heat. The temperature of the oil bath is controlled at about 125°C. Use two dropping funnels to add 3ml of freshly distilled pyrrole and 3ml of 4-pyridinecarbaldehyde diluted with 10ml of propionic acid at the same time. After 20 minutes of addition, the solution gradually turns brownish black. Keep stirring, raise the temperature to 140°C and reflux for 3 hours, then evaporate most of the propionic acid and cool to 80°C. 50ml of ethanol was added under stirring and left overnight. Suction filter and wash the crystals with ethanol to obtain dark purple crystals.

Using a mixed solvent of chloroform and ethanol with a volume ratio of 60:1 as the eluent, the third color band was collected by separation on a silica gel column, and concentrated by rotary evaporation to obtain EPTPyP as purple crystals.

Add 80mg EPTPyP, 20ml chloroform, and 10ml methanol solution containing 10% NaOH to a 500ml round bottom flask. Stir magnetically and react at room temperature for 12 hours. After stopping the reaction, it was washed with water several times until the water phase was neutral, the organic phase was spin-dried, and the solid was vacuum-dried at 78°C. Dissolve the crude product in chloroform, use a mixed solvent with a volume ratio of chloroform and ethanol of 25:1 as the eluent, separate and collect the second color band on a silica gel column, and concentrate by rotary evaporation to obtain 5(p-hydroxy)phenyl-10,15 , 20-tripyridylporphyrin (HPTPyP).

Add 50mg HPTPyP, 30ml mixed solvent of chloroform and methanol (volume ratio 2:1), and 87μl 2,4,6-collidine into a 50ml round bottom flask. Magnetic stirring, oil bath heating, the temperature of the oil bath was controlled at 60°C, after 15 minutes of reaction, 200 mg of manganese acetate was added, the solution gradually turned dark green, and the reaction was continued for 3 hours while stirring. After the reaction stopped, the reaction solution was distilled off under reduced pressure, washed with water several times, and filtered with suction to obtain a dark green solid.

The crude product was dissolved in methanol, and a mixed solvent with a volume ratio of chloroform and methanol of 9:1 was used as the eluent. The second color band was collected by separation on a silica gel column, and concentrated by rotary evaporation to obtain dark green crystals.

(B) Preparation of ferrofluid

Weigh 13.6g of FeCl ₃ .6H ₂ O and 5.0g of FeCl ₂ .4H ₂ O and dissolve them in 60ml of double-distilled water for later use. Add 250ml of newly prepared 4% ammonia water into a 500ml three-necked bottle, and blow the air in the bottle with argon. Empty, heat up to 80°C under mechanical stirring, slowly add the prepared mixed solution of ferrous chloride and ferric chloride dropwise, the inside of the three-necked bottle will soon become black and turbid, after the dropwise addition is completed, continue to react for 2 hours. Cool down to room temperature, separate Fe ₃ O ₄ magnetic fluid from ammonia water under an external magnetic field, add water to wash the newly prepared magnetic fluid until it is neutral and ready for use.

(C) Preparation of P[St-co-MAA]

Weigh 5.0g of gelatin into a 250ml three-necked flask, add 10ml of magnetic fluid, 100ml of pure water, heat to 100°C to dissolve completely, cool down to 75°C and add 0.60g of BPO (dibenzoyl peroxide), α- MAA (methacrylic acid) 2.5 g, DVB (divinylbenzene) 3.0 g, St (styrene) 24.5 g. Keep stirring at 200 rpm, under nitrogen protection, react for 1 hour and heat up to 85°C for 6 hours, cool down to 60°C and filter, wash with hot water and ethanol several times, then extract with acetone for 24 hours, and vacuum dry at 80°C for 24 hours After one hour, brown microspheres of 60-80 meshes were obtained.

(D) Preparation of (P[St-co-MAA]-MnTMPyP)

Weigh 3.0g of white P[St-co-MAA] in a 100ml round-bottomed flask, add 35ml of dried dichloroethane and 10ml of thionyl chloride, reflux at 75°C for 12 hours, then use dried dichloroethane Wash with ethyl chloride several times, vacuum-dry at 85°C for 6 hours after suction filtration, then add 50 mg (HPTPyP)MnCl dissolved in 30 ml of dried DMF, reflux at 80°C for 12 hours, filter and dry, and wash with DMF After several extractions with methanol for 12 hours, vacuum drying at 80°C gave a light green solid.

Example 4

As shown in the following tables 1 to 5, the catalytic cyclohexane efficiency of the catalyst for catalytic cyclohexane oxidation of the present invention is verified and confirmed by experiments, wherein Table 1 represents the catalytic effect of existing various catalysts to cyclohexane; Table 2 and Fig. 11A represent the catalytic effect to cyclohexane under different ascorbic acid dosage conditions; Table 3 represents the catalytic effect to cyclohexane under different axial ligand conditions; Table 4 and Fig. 11B represent different reaction time conditions, the present invention The catalyst catalyzes the reaction product of cyclohexane; Table 5 shows the catalytic effects of the catalyst of the present invention on catalyzing cyclohexane under different reaction time conditions.

Table 1 Catalytic effects of different reducing agents for cyclohexane hydroxylation

Table 1 shows the catalytic efficiency of existing common catalysts for catalyzing the oxidation of cyclohexane, wherein the catalytic ability of ascorbic acid is significantly higher than that of sodium borohydride, zinc powder/glacial acetic acid and ammonium hydrogen hydrochloride.

Table 2 represents the catalytic effect of catalytic cyclohexane under different ascorbic acid dosage conditions

As shown in Table 2 and Figure 11A, under the appropriate dosage of ascorbic acid, the catalytic effect of catalytic cyclohexane is getting better and better with the increase of ascorbic acid dosage, but when the dosage of ascorbic acid exceeds the appropriate dosage range, the catalytic effect of catalytic cyclohexane The improvement of the effect with the increase of the dosage of ascorbic acid is not obvious.

Table 3 shows the catalytic activity of catalytic cyclohexane under different axial ligand conditions

As shown in Table 3, when o-mercaptobenzoic acid is used as the axial ligand, the catalytic effect is the best.

Table 4 shows that with reaction time variation, the catalytic effect of catalyst catalysis cyclohexane hydroxylation of the present invention

As shown in Table 4 and FIG. 11B , with the prolongation of the catalysis time, the catalyst of the present invention catalyzes the changes of the generated substrates for the hydroxylation of cyclohexane.

Table 5 shows that catalyst of the present invention catalyzes cyclohexane hydroxylation result

Fig. 5 shows the catalytic effect of the catalyst of the present invention to catalyze the hydroxylation of cyclohexane under different catalytic cycles, wherein the catalytic reaction is carried out in a self-made reactor with a constant temperature jacket at a constant temperature (30 ± 0.1 ° C). The catalytic system includes catalyst ((P[St-co-MAA]-MnTMPyP), manganese porphyrin content 8×10 ^-5 mmol), substrate (cyclohexane, 5.55 mmol), oxygen source (O ₂ , 1.01×10 ⁵ Pa), axial ligand and reducing agent, mixed solvent (acetone:water=9:1) 10ml. Quantitative analysis of cyclohexane catalytic product was determined by gas chromatography (Tianmei GC7890-II type), calculated and processed by internal standard method (p-chlorotoluene was used as internal standard). The recovery and utilization of the catalyst of the present invention can be realized under an external magnetic field. The catalyst (P[St-co-MAA]-MnTMPyP) of the present invention can be recycled after being quickly and completely settled under the attraction of a 0.4T magnet.

Table 6: Comparison between catalysts of the present invention and existing simulated cytochrome P450 catalysts

What table 6 represents is the comparison of catalyst of the present invention and existing imitation cytochrome P450 catalyst, wherein as can be seen from table 6, the immobilization and attachment design of catalyst of the present invention are more reasonable, and the utilization rate of active center (metalloporphyrin) Higher and better catalytic effect, wherein patent application A represents the Chinese patent application with publication number CN101116829, and patent application B represents the Chinese patent application with publication number CN103111328A.

Those skilled in the art will appreciate that the embodiments of the invention shown in the drawings and described above are only illustrative of the invention and not limiting.

From this it can be seen that the object of the present invention can be sufficiently and effectively accomplished. The embodiments have been fully illustrated and described for explaining the functional and structural principles of the present invention, and the present invention is not limited by changes based on the principles of these embodiments. Accordingly, this invention includes all modifications encompassed within the scope and spirit of the appended claims.

Claims (10)

1. for the manufacture of a compound for the catalyst of catalysis cyclohexane oxidation, it is characterized in that there is following molecular structural formula:

Wherein M is Mn, Fe or Co molecule.

2. for a catalyst for catalysis cyclohexane oxidation, it is characterized in that, comprise catalyst component, the compound wherein forming this catalyst component has following molecular structural formula:

wherein M is Mn, Fe or Co molecule.

3. catalyst according to claim 2, it is characterized in that, comprise load composition further, wherein this load composition comprises at least one magnetic microsphere, this catalyst component is attached to this load composition, and wherein containing weight ratio in this catalyst is 0.5% ~ 0.8% catalyst component.

4. catalyst according to claim 3, is characterized in that, wherein this magnetic microsphere is take styrene-t as the microballoon that main component is made, and its diameter is 150 ~ 210 nanometers.

5. for the manufacture of a method for the catalyst of catalysis cyclohexane oxidation, it is characterized in that, comprise the steps:

(A) 5 (p-propionic acid ester group) phenyl-10,15,20-tri-pyridine radicals porphyrin is prepared;

(B) 5 (p-propionic acid ester group) phenyl-10,15,20-tri-pyridine radicals porphyrin is utilized to prepare 5 (p-hydroxyl) phenyl-10,15,20-tri-pyridine radicals porphyrin;

(C) 5 (p-hydroxyl) phenyl-10,15,20-tri-pyridine radicals porphyrin is utilized to prepare 5-(p-hydroxyl) phenyl-10,15, the 20-tri-pyridine radicals porphyrin of metal-complexing; With

(D) 5-(p-hydroxyl) phenyl-10,15, the 20-tri-pyridine radicals porphyrin of metal-complexing is attached at least one magnetic microsphere, and is methylated 5-(p-hydroxyl) phenyl-10,15,20-tri-pyridine radicals porphyrin by iodomethane.

6. method according to claim 5, is characterized in that, wherein this magnetic microsphere is take styrene-t as the microballoon that main component is made, and its diameter is 150 ~ 210 nanometers.

7. method according to claim 6, is characterized in that, described metal is manganese, cobalt or iron.

8. method according to claim 5, is characterized in that:

This step (A) comprises the following steps:

(A1) by parahydroxyben-zaldehyde, propionic acid, acetic anhydride, pyrroles and 4-pyridine carboxaldehyde and ethanol synthesis, wherein with the quality of parahydroxyben-zaldehyde for benchmark, every 1g parahydroxyben-zaldehyde needs propionic acid 100 ~ 120mL, acetic anhydride 5 ~ 8mL, pyrroles 2 ~ 4mL, 4-pyridine carboxaldehyde 2 ~ 4mL, ethanol 100 ~ 150mL; With

(A2) place after 12 ~ 18 hours, suction filtration, washing, pillar layer separation obtains 5 (p-propionic acid ester group) phenyl-10,15,20-tri-pyridine radicals porphyrin,

This step (B) comprises the following steps:

(B1) 5 (p-propionic acid ester group) phenyl-10,15,20-tri-pyridine radicals porphyrin is mixed and magnetic agitation mutually with the methanol solution of chloroform and NaOH, react 12 hours under room temperature; With

(B2) through washing, centrifugal dewater and drying after, pillar layer separation obtains 5 (p-hydroxyl) phenyl-10,15,20-tri-pyridine radicals porphyrin;

This step (C) comprises the following steps:

(C1) by 5 (p-hydroxyl) phenyl-10,15,20-tri-pyridine radicals porphyrin, chloroform, methyl alcohol, trimethylpyridine mix rear magnetic agitation mutually with metal acetate, and decompression steams reactant liquor, and wherein this metal acetate is manganese acetate, ferric acetate or cobalt acetate; With

(C2) wash, suction filtration, pillar layer separation obtains 5-(p-hydroxyl) phenyl-10,15, the 20-tri-pyridine radicals porphyrin of metal-complexing,

This step (D) comprises the following steps:

(D1) by the DMF solution reaction of 5-(p-hydroxyl) phenyl-10,15, the 20-tri-pyridine radicals porphyrin of magnetic styrene-methacrylic acid microballoon, dichloroethanes, thionyl chloride and metal-complexing; With

(D2) filter after reaction, washing, extracting, dry, and add CH ₃i backflow 8 ~ 12 hours, distillation removes desolventizing and obtains the immobilized styrene-t copolymerization magnetic Nano microsphere having metal picoline porphyrin, and wherein this metal picoline porphyrin is manganese picoline porphyrin, armor yl pyridines porphyrin or cobalt picoline porphyrin.

9. method according to claim 7, is characterized in that:

This step (A) comprises the following steps:

(A1) by parahydroxyben-zaldehyde, propionic acid, acetic anhydride, pyrroles and 4-pyridine carboxaldehyde and ethanol synthesis, wherein with the quality of parahydroxyben-zaldehyde for benchmark, every 1g parahydroxyben-zaldehyde needs propionic acid 100 ~ 120mL, acetic anhydride 5 ~ 8mL, pyrroles 2 ~ 4mL, 4-pyridine carboxaldehyde 2 ~ 4mL, ethanol 100 ~ 150mL; With

(A2) place after 12 ~ 18 hours, suction filtration, washing, pillar layer separation obtains 5 (p-propionic acid ester group) phenyl-10,15,20-tri-pyridine radicals porphyrin,

This step (B) comprises the following steps:

(B1) 5 (p-propionic acid ester group) phenyl-10,15,20-tri-pyridine radicals porphyrin is mixed and magnetic agitation mutually with the methanol solution of chloroform and NaOH, react 12 hours under room temperature; With

(B2) through washing, centrifugal dewater and drying after, pillar layer separation obtains 5 (p-hydroxyl) phenyl-10,15,20-tri-pyridine radicals porphyrin;

This step (C) comprises the following steps:

(C1) by 5 (p-hydroxyl) phenyl-10,15,20-tri-pyridine radicals porphyrin, chloroform, methyl alcohol, trimethylpyridine mix rear magnetic agitation mutually with metal acetate, and decompression steams reactant liquor, and wherein this metal acetate is manganese acetate, ferric acetate or cobalt acetate; With

(C2) wash, suction filtration, pillar layer separation obtains 5-(p-hydroxyl) phenyl-10,15, the 20-tri-pyridine radicals porphyrin of metal-complexing,

This step (D) comprises the following steps:

(D1) by the DMF solution reaction of 5-(p-hydroxyl) phenyl-10,15, the 20-tri-pyridine radicals porphyrin of magnetic styrene-methacrylic acid microballoon, dichloroethanes, thionyl chloride and metal-complexing; With

(D2) filter after reaction, washing, extracting, dry, and add CH ₃i backflow 8 ~ 12 hours, distillation removes desolventizing and obtains the immobilized styrene-t copolymerization magnetic Nano microsphere having metal picoline porphyrin, and wherein this metal picoline porphyrin is manganese picoline porphyrin, armor yl pyridines porphyrin or cobalt picoline porphyrin.

10. the method according to claim 5,6,7,8 or 9, is characterized in that, further comprising the steps:

(E) be 0.4 ~ 0.7:1.5 ~ 3:2.5 ~ 3.5:24 ~ 25 by gelatin, dibenzoyl peroxide, methacrylic acid, divinylbenzene and styrene according to weight ratio; under nitrogen protection; add magnetic fluid and pure water reaction; filter; washing and vacuum drying; wear the magnetic styrene-methacrylic acid microballoon of carboxyl with preparation table, wherein this step (E) is before step (D).