A metalloporphyrin containing a hexafluoropropylene trimer functional group, and its preparation method and application

Abstract

The present invention discloses a metalloporphyrin containing a hexafluoropropylene trimer functional group, a preparation method thereof, and an application thereof. The preparation method of the metalloporphyrin containing a hexafluoropropylene trimer functional group comprises the following steps: dissolving a benzaldehyde derivative containing a hexafluoropropylene trimer functional group, freshly distilled pyrrole, and a metal acetate in a mixed solvent of methanol and chloroform, and reacting the mixture under an N2 atmosphere. After the reaction is completed, the reaction mixture is desolvated under reduced pressure to obtain a crude metalloporphyrin product, which is then washed with water, washed with anhydrous ethanol, and separated by silica gel column chromatography to obtain the metalloporphyrin containing a hexafluoropropylene trimer functional group. The present invention also provides an application of the metalloporphyrin containing a hexafluoropropylene trimer functional group in the O2-catalyzed oxidation of cycloalkanes. The cycloalkane oxidation method provided by the present invention has high selectivity for partial oxidation products (cycloalkyl alcohols and cycloalkyl ketones), low content of explosive peroxides and deep oxidation products, aliphatic diacids, and is a safe, effective, and low-energy-consumption cycloalkane oxidation method.

Description

Technical Field

[0001] The invention relates to a metalloporphyrin containing a hexafluoropropylene trimer functional group, a preparation method thereof and application of the metalloporphyrin as a catalyst in partial oxidation of cycloalkanes, and belongs to the field of organic catalysis and fine organic synthesis. Background Art

[0002] The catalytic oxidation of cycloalkanes can convert hydrocarbons, which are widely found in fossil resources, into high-value-added alcohols and ketones, and has widespread application in the chemical industry (ZL 202111006432.X; ZL 202010884408.5; ZL 201911161924.9). However, because the resulting partial oxidation products (cycloalkyl alcohols and cycloalkyl ketones) are more chemically active than the substrate cycloalkane, they are prone to deep oxidation, forming ring-opening products such as aliphatic diacids and their derivatives. This not only reduces the selectivity of the partial oxidation products and increases energy consumption and equipment requirements for separation and purification, but also the resulting aliphatic diacids and their derivatives are prone to crystallization, clogging production pipelines and significantly complicating industrial production. To ensure optimal selectivity for the partial oxidation products (cycloalkanols and cycloalkanones), the catalytic oxidation of cyclohexane in industry often targets a conversion of around 5% to achieve a selectivity of around 85%. (Chemical Engineering Journal, 2022, 443: 136-126; Chemical Engineering Science, 2022, 260: 117-825; Molecular Catalysis, 2023, 535: 112-853). Further increasing the substrate conversion rate will significantly reduce the selectivity of the partial oxidation products (cyclohexanol and cyclohexanone), making it impossible to simultaneously increase the substrate conversion rate and the selectivity of the partial oxidation products. The root cause of the above problems, in addition to the high reactivity of the oxidation products (cycloalkyl alcohols and cycloalkyl ketones), is another important reason for the frequent contact of the partial oxidation products with the catalytic active centers. In the current chemical industry, the catalysts used for the catalytic oxidation of cycloalkanes are mainly cobalt (II) and manganese (II) salts, complexes, and their derivatives. These catalysts can not only catalyze the oxidation of cycloalkanes to partial oxidation products such as alcohols and ketones by O2, but also catalyze the oxidation of alcohols and ketones to deep oxidation products. Therefore, effectively preventing the partial oxidation products (cycloalkyl alcohols and cycloalkyl ketones) from frequent contact with the catalytic active sites will help avoid deep oxidation of alcohols and ketones during the partial oxidation of cycloalkanes, thereby achieving efficient, selective oxidation of cycloalkanes to the partial oxidation products, cycloalkyl alcohols and cycloalkyl ketones. Achieving highly selective production of cycloalkyl alcohols and cycloalkyl ketones not only reduces the difficulty and equipment requirements for industrial separation and purification of cycloalkane partial oxidation products, lowering separation energy consumption, but also effectively prevents safety accidents caused by pipeline blockages, which is of great significance to the safe, energy-saving, and emission-reducing production of cycloalkanes in industry.

[0003] Fluorochemicals, due to their low polarity, not only have strong hydrophobic properties, but also show strong repulsion to some oily compounds, especially to some organic compounds with greater polarity, with strong oleophobicity (CN115926069A; WO 2022059620A1). The partial oxidation of cycloalkanes to cycloalkyl alcohols and cycloalkyl ketones is a process of increasing polarity. The partial oxidation of cycloalkanes with low polarity generates cycloalkyl alcohols and cycloalkyl ketones with increased polarity. Therefore, the catalytic material for the partial oxidation of cycloalkanes modified with low polarity carbon fluorine chains will be conducive to achieving the separation of cycloalkyl alcohols and cycloalkyl ketones with greater polarity from the catalytic active centers, and avoid their contact with the catalytic active centers during the disordered diffusion process, thereby preventing their deep oxidation. In the above process, since the polarity of cycloalkanes themselves is low, the introduction of carbon fluorine chains has little effect on the contact of cycloalkanes with the catalytic active centers, and can enable the substrate cycloalkanes to smoothly contact the catalytic active centers and be partially oxidized to cycloalkyl alcohols and cycloalkyl ketones. Therefore, modifying the partial oxidation catalyst of cycloalkanes with carbon-fluorine chains will be beneficial to the efficient and selective catalytic oxidation of cycloalkanes to produce cycloalkyl alcohols and cycloalkyl ketones, which is of great significance to the safe, energy-saving and emission-reducing production of cycloalkanes in industry. Summary of the Invention

[0004] In response to the above-mentioned technical problems existing in the prior art, the present invention aims to provide a metalloporphyrin containing a hexafluoropropylene trimer functional group, a preparation method thereof, and its use as a catalyst in the partial oxidation of cycloalkanes. The present invention uses a hexafluoropropylene trimer as a modifying group to promptly separate the partial oxidation products, cycloalkyl alcohols and cycloalkyl ketones, from the catalytically active center, and prevents contact between the partial oxidation products and the catalytically active center, thereby preventing deep oxidation and improving the selectivity of the partial oxidation products. The branched structure of the hexafluoropropylene trimer functional group constructs high-energy C—H bonds near the metal catalytically active center, preventing oxidative degradation of the metalloporphyrin catalyst itself, enhancing the catalytic conversion ratio of the cycloalkane oxidation process, further improving the selectivity of cycloalkyl alcohols and cycloalkyl ketones, and preventing accidents caused by peroxide accumulation. The present method for partial oxidation of cycloalkanes not only achieves high selectivity for cycloalkyl alcohols and cycloalkyl ketones, but also has a low cycloalkyl hydroperoxide content and a high safety factor. It is an efficient, feasible, and safe method for the partial catalytic oxidation of cycloalkanes to synthesize cycloalkyl alcohols and cycloalkyl ketones.

[0005] The technical solution adopted in the present invention is as follows:

[0006] A metalloporphyrin containing a hexafluoropropylene trimer functional group, the structure of which is shown in formula (I):

[0007]

[0008] The metal center M of the metalloporphyrin containing a hexafluoropropylene trimer functional group is Co(II), Mn(II), Fe(II), Ni(II) or Cu(II), preferably Co(II).

[0009] The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group comprises the following steps: dissolving a benzaldehyde derivative containing a hexafluoropropylene trimer functional group, freshly distilled pyrrole, and a metal M salt in a reaction solvent, stirring and reacting at 0-80°C under a nitrogen atmosphere for 6-168 hours; after completion of the reaction, desolventizing the reaction mixture to obtain a crude metalloporphyrin product; washing the crude metalloporphyrin product with water and anhydrous ethanol, and separating the product by silica gel column chromatography to obtain the metalloporphyrin product containing a hexafluoropropylene trimer functional group. The reaction temperature is preferably 20-50°C, and the reaction time is preferably 72-168 hours.

[0010] Furthermore, the benzaldehyde derivative containing the hexafluoropropylene trimer functional group has a branched structure as shown in formula (II):

[0011]

[0012] The preparation method comprises the following steps: adding hexafluoropropylene trimer and 3,5-dihydroxybenzaldehyde to a halogenated methane solvent, heating to 35-45°C under an N2 atmosphere, and stirring under reflux for reaction for 6-10 hours; after the reaction, cooling the reaction solution to room temperature, adding deionized water, extracting and separating the liquid, and then drying the organic phase with anhydrous sodium sulfate; collecting the organic phase through chromatographic column chromatography, and drying it to obtain a colorless liquid, thereby completing the preparation; wherein the molar ratio of the hexafluoropropylene trimer to the 3,5-dihydroxybenzaldehyde is 1:0.5-2, preferably 1:1; and the eluent for chromatographic column chromatography separation is a cyclohexane-dichloromethane mixed solvent with a volume ratio of 4-6:1, and the volume ratio of cyclohexane-dichloromethane is preferably 5:1.

[0013] The molar ratio of the benzaldehyde derivative containing the hexafluoropropylene trimer functional group to the freshly distilled pyrrole is 1:1-10.

[0014] Furthermore, the molar ratio of the metal M salt to the benzaldehyde derivative containing the hexafluoropropylene trimer functional group is 0.10 to 10:1, preferably 0.40 to 10:1.

[0015] Furthermore, the reaction solvent is a mixture of methanol and chloroform, and the volume ratio of methanol to chloroform is 1:0.10-10.0, preferably 1:0.80-10.0.

[0016] The present invention also provides the use of a metalloporphyrin containing a hexafluoropropylene trimer functional group in the partial oxidation of cycloalkanes. The method comprises: dispersing the metalloporphyrin containing a hexafluoropropylene trimer functional group in a cycloalkane, sealing the reaction system, heating to 100-150°C with stirring, introducing oxygen to 0.40 MPa-2.0 MPa, maintaining the set temperature and oxygen pressure, and stirring for 3.0-15.0 hours; then, cooling the reaction solution to room temperature with stirring, and stirring for 3.0-12.0 hours at room temperature to obtain a reaction mixture containing the partial oxidation products, cycloalkyl alcohol and cycloalkyl ketone. The reaction temperature is preferably 120-150°C, the oxygen pressure is preferably 1.0-2.0 MPa, and the stirring reaction time is preferably 6-12 hours.

[0017] Furthermore, the feed ratio of the metalloporphyrin containing a hexafluoropropylene trimer functional group to the cycloalkane is 1 mg: 0.2 to 235 mmol, preferably 1 mg: 0.2 to 12 mmol. The cycloalkane is at least one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, and cyclododecane, and the corresponding partial oxidation products are cycloalkyl alcohols and cycloalkyl ketones.

[0018] The technical concept of the present invention is as follows: the present invention uses a metalloporphyrin modified with a branched hexafluoropropylene trimer as a catalyst to catalyze the partial oxidation of cycloalkanes by O2 to produce partial oxidation products, cycloalkyl alcohols and cycloalkyl ketones. The branched hexafluoropropylene trimer is used as a modifying group to promptly separate the partial oxidation products, cycloalkyl alcohols and cycloalkyl ketones, from the catalytic active center and prevent contact between the partial oxidation products and the catalytic active center, thereby preventing deep oxidation and improving the selectivity of the partial oxidation products. The branched structure of the hexafluoropropylene trimer functional group forms high-energy C—H bonds near the metal catalytic active center, preventing oxidative degradation of the metalloporphyrin catalyst itself, enhancing the catalytic conversion ratio of the cycloalkane oxidation process, further improving the selectivity of cycloalkyl alcohols and cycloalkyl ketones, and preventing accidents that may be caused by peroxide accumulation. Therefore, the cycloalkane partial oxidation method of the present invention not only has high selectivity for cycloalkyl alcohols and cycloalkyl ketones, but also has a low cycloalkyl hydroperoxide content and a high safety factor. It has the potential to address the problem of cycloalkyl alcohols and cycloalkyl ketones being easily deeply oxidized to form byproducts such as aliphatic diacids during the industrial catalytic oxidation of cycloalkane, thereby achieving efficient synthesis of partial oxidation products. The method not only has important industrial application value and theoretical research value, but also has certain reference value for improving the selectivity of other catalytic oxidation systems.

[0019] The beneficial effects of the present invention are mainly reflected in the following aspects: the present invention uses a metalloporphyrin modified with a branched hexafluoropropylene trimer as a catalyst, which has an ingenious design, a novel structure and a wide range of applications. In the partial oxidation reaction of cycloalkanes, cycloalkyl alcohols and cycloalkyl ketones have high selectivity, which effectively inhibits the deep oxidation of the partial oxidation products and the generation of aliphatic diacids and their derivatives. The low selectivity of aliphatic diacids and their derivatives is also beneficial to the continuous partial oxidation process of cycloalkanes and the low-energy separation of the products. It has the potential to solve the problem that in the industrial catalytic oxidation process of cycloalkanes, the partial oxidation products cycloalkyl alcohols and cycloalkyl ketones are easily deeply oxidized to generate by-products such as aliphatic diacids, and to achieve efficient synthesis of partial oxidation products. It not only has important industrial application value and theoretical research value, but also has a certain reference value for improving the selectivity of other catalytic oxidation systems. The present invention is a new method for the efficient and feasible selective catalytic oxidation of cycloalkanes. DETAILED DESCRIPTION

[0020] The present invention will be further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.

[0021] Example 1 is the synthesis of a benzaldehyde derivative containing a hexafluoropropylene trimer functional group;

[0022] Example 2-25 is the synthesis of a metalloporphyrin catalyst containing a hexafluoropropylene trimer functional group;

[0023] Examples 26-63 are the use of a metalloporphyrin catalyst containing a hexafluoropropylene trimer functional group in the partial oxidation of cycloalkanes;

[0024] Examples 64-65 are comparative experiments on the application of metalloporphyrin catalysts containing hexafluoropropylene trimer functional groups in the partial oxidation of cycloalkanes;

[0025] Example 66 is a scaled-up experiment of the application of a metalloporphyrin catalyst containing a hexafluoropropylene trimer functional group in the partial oxidation of cycloalkanes.

[0026] The benzaldehyde derivative containing a hexafluoropropylene trimer functional group used in the present invention has a branched structure as shown in formula (II) and is homemade in the laboratory (Journal of Chemical Engineering of Universities, 2009, 23(4): 679-683; Pesticides, 2007, 46(8): 520-522). All other reagents used were commercially available analytical grade.

[0027]

[0028] Nomenclature of metalloporphyrin catalysts containing hexafluoropropylene trimer functional groups. T(3,5-diC9F 17)PPCo-2.00@2.40@1.20@60@80 represents porphyrin cobalt (II) containing a hexafluoropropylene trimer functional group. In the synthesis reaction, the molar ratio of the benzaldehyde derivative containing a hexafluoropropylene trimer functional group to freshly distilled pyrrole is 1:2.00, the molar ratio of the metal acetate to freshly distilled pyrrole is 1:2.40, the volume ratio of methanol to chloroform is 1:1.20, the reaction temperature is 60°C, and the reaction time is 80.0 h.

[0029] Example 1

[0030] In a 100 mL three-necked flask, hexafluoropropylene trimer (C9F 18 ) (4.5006g, 10.0mmol), 3,5-dihydroxybenzaldehyde (1.3812g, 10.00mmol), added to 30mL of dichloromethane. Under N2 atmosphere, heated to 40 ° C, stirred under reflux for 8.0h. After the reaction was completed, the reaction solution was cooled to room temperature, and then 20mL of deionized water was added, and the extract was separated (washed twice with 2×20mL water), and then the organic phase was dried over anhydrous sodium sulfate. Purified by column chromatography (silica gel is 200-300 mesh, eluent is V 环己烷 :V 二氯甲烷 =5:1) The organic phase was collected and dried in a rotary evaporation cycle to obtain 2.3842 g of a colorless liquid benzaldehyde derivative containing a hexafluoropropylene trimer functional group, with a yield of 43.2%.

[0031] Example 2

[0032] In a 25 mL glass reaction tube, a benzaldehyde derivative (II) containing a hexafluoropropylene trimer functional group (1.9405 g, 2.0 mmol), freshly distilled pyrrole (0.2684 g, 4.00 mmol), and anhydrous cobalt acetate (0.7081 g, 4.00 mmol) were dissolved in 20 mL of a mixture of methanol and chloroform (volume ratio 1:1). The reaction was stirred at 30°C under a nitrogen atmosphere for 84.0 h. After completion of the reaction, the reaction mixture was desolvated under reduced pressure to obtain a crude metalloporphyrin. The crude metalloporphyrin was washed with water (5 × 20 mL) and anhydrous ethanol (5 × 20 mL), and separated by silica gel column chromatography (eluent: dichloromethane) to obtain the metalloporphyrin T (3,5-diC9F) containing a hexafluoropropylene trimer functional group. 17 )PPCo-2.00@1.00@1.00@30@84, purple-red solid powder 0.1762 g, yield 8.3%.

[0033] Example 3

[0034] The preparation process of the catalyst of Example 3 was repeated in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was replaced with "anhydrous manganese acetate (0.8981 g, 4.00 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPMn-2.00@1.00@1.00@30@84, purple-black solid powder 0.2485g, yield 10.5%.

[0035] Example 4

[0036] The preparation process of the catalyst of Example 4 was repeated in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was replaced with "anhydrous ferric acetate (0.7758 g, 4.00 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPFe-2.00@1.00@1.00@30@84, purple-black solid powder 0.2146 g, yield 10.1%.

[0037] Example 5

[0038] The preparation process of the catalyst of Example 5 was repeated in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was replaced with "nickel acetate, tetrahydrate (0.9954 g, 4.00 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F) with hexafluoropropylene trimer functional group was obtained. 17 )PPNi-2.00@1.00@1.00@30@84, 0.2835 g of purple-black solid powder, yield 11.0%.

[0039] Example 6

[0040] The preparation process of the catalyst of Example 6 was repeated in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was replaced with "anhydrous copper acetate (0.7266 g, 4.00 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCu-2.00@1.00@1.00@30@84, purple-red solid powder 0.3148 g, yield 12.3%.

[0041] Example 7

[0042] The preparation process of the catalyst of Example 7 was repeated in Example 2, except that "freshly steamed pyrrole (0.2684 g, 4.00 mmol)" was replaced with "freshly steamed pyrrole (0.1342 g, 2.00 mmol)". The remaining conditions were the same as those of Example 1, and the metalloporphyrin T (3,5-diC9F) with hexafluoropropylene trimer functional group was obtained. 17 )PPCo-1.00@1.00@1.00@30@84, purple-red solid powder 0.1685 g, yield 7.9%.

[0043] Example 8

[0044] The preparation process of the catalyst of Example 8 was repeated in Example 2, except that "freshly steamed pyrrole (0.2684 g, 4.00 mmol)" was replaced with "freshly steamed pyrrole (0.4025 g, 6.00 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-3.00@1.00@1.00@30@84, purple-red solid powder 0.1791 g, yield 8.5%.

[0045] Example 9

[0046] The preparation process of the catalyst of Example 9 was repeated in Example 2, except that "freshly steamed pyrrole (0.2684 g, 4.00 mmol)" was replaced with "freshly steamed pyrrole (1.3148 g, 20.00 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-10.00@1.00@1.00@30@84, purple-red solid powder 0.1815 g, yield 8.6%.

[0047] Example 10

[0048] The preparation process of the catalyst of Example 10 was repeated in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was replaced with "anhydrous cobalt acetate (3.5405 g, 20.00 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F) with hexafluoropropylene trimer functional group was obtained. 17 )PPCo-2.00@0.20@1.00@30@84, purple-red solid powder 0.1815 g, yield 8.8%.

[0049] Example 11

[0050] The preparation process of the catalyst of Example 11 was repeated in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was replaced with "anhydrous cobalt acetate (0.8851 g, 5.00 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@0.80@1.00@30@84, purple-red solid powder 0.1762 g, yield 8.5%.

[0051] Example 12

[0052] The preparation process of the catalyst of Example 12 was repeated in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was replaced with "anhydrous cobalt acetate (0.1416 g, 0.80 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@5.00@1.00@30@84, purple-red solid powder 0.1582 g, yield 7.2%.

[0053] Example 13

[0054] The preparation process of the catalyst of Example 13 was repeated in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was replaced with "anhydrous cobalt acetate (0.0354 g, 0.20 mmol)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@20.00@1.00@30@84, purple-red solid powder 0.1246 g, yield 5.9%.

[0055] Example 14

[0056] The preparation process of the catalyst of Example 14 was repeated in Example 2, except that "in a mixed solvent of 20 mL of methanol and chloroform (volume ratio 1:1)" was changed to "in a mixed solvent of 20 mL of methanol and chloroform (volume ratio 1:0.1)". The remaining conditions were the same as in Example 2, and the metalloporphyrin T (3,5-diC9F) with a hexafluoropropylene trimer functional group was obtained. 17 )PPCo-2.00@1.00@0.10@30@84, purple-red solid powder 0.1671 g, yield 7.9%.

[0057] Example 15

[0058] The preparation process of the catalyst of Example 15 was repeated in Example 2, except that "in a mixed solvent of 20 mL of methanol and chloroform (volume ratio 1:1)" was changed to "in a mixed solvent of 20 mL of methanol and chloroform (volume ratio 1:0.8)". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F) with a hexafluoropropylene trimer functional group was obtained. 17 )PPCo-2.00@1.00@0.80@30@84, purple-red solid powder 0.1754 g, yield 8.3%.

[0059] Example 16

[0060] The catalyst preparation process of Example 16 was repeated in Example 2, except that "in a mixed solvent of 20 mL of methanol and chloroform (volume ratio 1:1)" was replaced with "in a mixed solvent of 20 mL of methanol and chloroform (volume ratio 1:2)". The remaining conditions were the same as in Example 2, and the metalloporphyrin T (3,5-diC9F) with a hexafluoropropylene trimer functional group was obtained. 17 )PPCo-2.00@1.00@2.00@30@84, purple-red solid powder 0.1778 g, yield 8.4%.

[0061] Example 17

[0062] The catalyst preparation process of Example 17 was repeated in Example 2, except that "in a mixed solvent of 20 mL of methanol and chloroform (volume ratio 1:1)" was replaced with "in a mixed solvent of 20 mL of methanol and chloroform (volume ratio 1:10)". The remaining conditions were the same as in Example 2, and the metalloporphyrin TT (3,5-diC9F) with a hexafluoropropylene trimer functional group was obtained. 17 )PPCo-2.00@1.00@10.00@30@84, purple-red solid powder 0.1765 g, yield 8.7%.

[0063] Example 18

[0064] The preparation process of the catalyst of Example 18 was repeated in Example 2, except that "under N2 atmosphere, 30°C" was changed to "under N2 atmosphere, 0°C". The other conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@1.00@1.00@0@84, purple-red solid powder 0.0596 g, yield 2.6%.

[0065] Example 19

[0066] The preparation process of the catalyst of Example 19 was repeated in Example 2, except that "under N2 atmosphere, 30°C" was changed to "under N2 atmosphere, 20°C". The other conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@1.00@1.00@20@84, purple-red solid powder 0.1753 g, yield 8.2%.

[0067] Example 20

[0068] The preparation process of the catalyst of Example 20 was repeated in Example 2, except that "under N2 atmosphere, 30°C" was changed to "under N2 atmosphere, 50°C". The other conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@1.00@1.00@50@84, purple-red solid powder 0.1771 g, yield 8.5%.

[0069] Example 21

[0070] The preparation process of the catalyst of Example 21 was repeated in Example 2, except that "under N2 atmosphere, 30°C" was changed to "under N2 atmosphere, 80°C". The other conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@1.00@1.00@80@84, purple-red solid powder 0.1784 g, yield 8.4%.

[0071] Example 22

[0072] The preparation process of the catalyst of Example 22 was repeated in Example 2, except that the stirring reaction time was changed from "84.0 h" to "6.0 h". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@6, purple-red solid powder 0.0849 g, yield 4.0%.

[0073] Example 23

[0074] The preparation process of the catalyst of Example 23 was repeated in Example 2, except that the stirring reaction time was changed from "84.0 h" to "72.0 h". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@72, purple-red solid powder 0.1744 g, yield 8.2%.

[0075] Example 24

[0076] The preparation process of the catalyst of Example 24 was repeated in Example 2, except that the stirring reaction time was changed from "84.0 h" to "96.0 h". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@96, purple-red solid powder 0.1766 g, yield 8.3%.

[0077] Example 25

[0078] The preparation process of the catalyst of Example 25 was repeated in Example 2, except that the stirring reaction time was changed from "84.0 h" to "168.0 h". The remaining conditions were the same as those of Example 2, and the metalloporphyrin T (3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@168, purple-red solid powder 0.1789 g, yield 8.5%.

[0079] Example 26

[0080] In a 100 mL stainless steel autoclave lined with polytetrafluoroethylene, the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional groups prepared in Example 2 was added to the mixture. 17 PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was dispersed in cyclohexane (16.8320 g, 200 mmol), the reaction system was sealed, and the temperature was raised to 125°C with stirring. When the temperature reached the set temperature, oxygen was introduced to 1.00 MPa. The set temperature and oxygen pressure were maintained and the reaction was stirred for 8.0 hours. After the reaction was completed, the reaction solution was stirred and cooled to room temperature. The reaction was stirred at room temperature for 6.0 hours to completely decompose and convert the small amount of residual cycloalkyl hydroperoxide. After the reaction was completed, the residual gas was slowly released, the reactor was opened, and the volume was adjusted to 100 mL with anhydrous methanol. 10 mL of the fixed volume solution was accurately pipetted, and toluene (0.1843 g, 2.0 mmol) was added as an internal standard for gas phase analysis to conduct GC analysis to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partial oxidation products cyclohexanol and cyclohexanone. 10 mL of the fixed volume solution was accurately pipetted, and benzoic acid (0.1221 g, 1.0 mmol) was added as an internal standard for liquid phase analysis to conduct HPLC analysis to determine the yields and selectivities of the deep oxidation products adipic acid and glutaric acid. GC and HPLC analysis revealed a cyclohexane conversion of 10.2%, a cyclohexanol selectivity of 32%, a cyclohexanone selectivity of 64%, and an adipic acid selectivity of 4%. No glutaric acid or other byproducts were detected.

[0081] Example 27

[0082] The only difference between Example 27 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 3. 17 )PPMn-2.00@1.00@1.00@30@84 (16.9 mg, 0.004 mmol). The experimental results of Example 27 were: cyclohexane conversion 8.7%, cyclohexanol selectivity 33%, cyclohexanone selectivity 62%, adipic acid selectivity 5%, and no glutaric acid or other by-products were detected.

[0083] Example 28

[0084] The only difference between Example 28 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 4. 17 )PPFe-2.00@1.00@1.00@30@84 (16.9 mg, 0.004 mmol). The experimental results of Example 28 were: cyclohexane conversion 7.3%, cyclohexanol selectivity 30%, cyclohexanone selectivity 61%, adipic acid selectivity 9%, and no glutaric acid or other byproducts were detected.

[0085] Example 29

[0086] The only difference between Example 29 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 5. 17 )PPNi-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 29 were: cyclohexane conversion 6.5%, cyclohexanol selectivity 29%, cyclohexanone selectivity 59%, adipic acid selectivity 12%, and no glutaric acid or other byproducts were detected.

[0087] Example 30

[0088] The only difference between Example 30 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 6. 17 )PPCu-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 30 were: cyclohexane conversion 6.3%, cyclohexanol selectivity 28%, cyclohexanone selectivity 59%, adipic acid selectivity 13%, and no glutaric acid or other byproducts were detected.

[0089] Example 31

[0090] The only difference between Example 31 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with 0.8480 g, 0.2 mmol. The experimental results of Example 31 were: cyclohexane conversion 11.9%, cyclohexanol selectivity 35%, cyclohexanone selectivity 63%, adipic acid selectivity 2%, and no glutaric acid or other byproducts were detected.

[0091] Example 32

[0092] The only difference between Example 32 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with 0.0848 g, 0.02 mmol. The experimental results of Example 32 were: cyclohexane conversion 11.1%, cyclohexanol selectivity 34%, cyclohexanone selectivity 63%, adipic acid selectivity 3%, and no glutaric acid or other byproducts were detected.

[0093] Example 33

[0094] The only difference between Example 33 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with 0.85 mg, 0.0002 mmol. The experimental results of Example 33 were: cyclohexane conversion 8.1%, cyclohexanol selectivity 33%, cyclohexanone selectivity 61%, adipic acid selectivity 6%, and no glutaric acid or other byproducts were detected.

[0095] Example 34

[0096] Example 34 differs from Example 26 only in that the reaction temperature is changed to 120° C. The experimental results of Example 34 are: cyclohexane conversion rate 9.9%, cyclohexanol selectivity 32%, cyclohexanone selectivity 65%, adipic acid selectivity 3%, and no glutaric acid or other byproducts are detected.

[0097] Example 35

[0098] The only difference between Example 35 and Example 26 is that the reaction temperature was changed to 135° C. The experimental results of Example 35 were: cyclohexane conversion rate 10.4%, cyclohexanol selectivity 32%, cyclohexanone selectivity 64%, adipic acid selectivity 4%, and no glutaric acid or other byproducts were detected.

[0099] Example 36

[0100] Example 36 differs from Example 26 only in that the reaction temperature is changed to 150° C. The experimental results of Example 36 are: cyclohexane conversion rate 10.7%, cyclohexanol selectivity 32%, cyclohexanone selectivity 63%, adipic acid selectivity 5%, and no glutaric acid or other byproducts are detected.

[0101] Example 37

[0102] Example 37 differs from Example 26 only in that the reaction oxygen pressure is changed to 0.40 MPa. The experimental results of Example 37 are: cyclohexane conversion 7.4%, cyclohexanol selectivity 31%, cyclohexanone selectivity 62%, adipic acid selectivity 7%, and no glutaric acid or other byproducts are detected.

[0103] Example 38

[0104] Example 38 differs from Example 26 only in that the reaction oxygen pressure is changed to 1.20 MPa. The experimental results of Example 38 are: cyclohexane conversion 10.6%, cyclohexanol selectivity 34%, cyclohexanone selectivity 64%, adipic acid selectivity 2%, and no glutaric acid or other byproducts are detected.

[0105] Example 39

[0106] Example 39 differed from Example 26 only in that the set temperature and oxygen pressure were maintained, and the stirring reaction time was changed to 6.0 hours. The experimental results of Example 39 were: cyclohexane conversion 9.1%, cyclohexanol selectivity 33%, cyclohexanone selectivity 62%, adipic acid selectivity 5%, and no glutaric acid or other byproducts were detected.

[0107] Example 40

[0108] Example 40 differed from Example 26 only in that the set temperature and oxygen pressure were maintained, and the stirring reaction time was changed to 12.0 hours. The experimental results of Example 40 were: cyclohexane conversion 11.0%, cyclohexanol selectivity 33%, cyclohexanone selectivity 64%, adipic acid selectivity 3%, and no glutaric acid or other byproducts were detected.

[0109] Example 41

[0110] Example 41 differed from Example 26 only in that cyclohexane (16.8320 g, 200 mmol) was replaced with cyclopentane (14.0260 g, 200 mmol). The experimental results of Example 41 were: cyclopentane conversion of 10.5%, cyclopentanol selectivity of 34%, cyclopentanone selectivity of 63%, glutaric acid selectivity of 3%, and no succinic acid or other byproducts were detected.

[0111] Example 42

[0112] Example 42 differed from Example 26 only in that cyclohexane (16.8320 g, 200 mmol) was replaced with cycloheptane (19.6372 g, 200 mmol). The experimental results of Example 42 were: cycloheptane conversion of 13.7%, cycloheptanol selectivity of 33%, cycloheptanone selectivity of 64%, and pimelic acid selectivity of 3%. No adipic acid or other byproducts were detected.

[0113] Example 43

[0114] Example 43 differed from Example 26 only in that cyclohexane (16.8320 g, 200 mmol) was replaced with cyclooctane (22.4426 g, 200 mmol). The experimental results of Example 43 were: cyclooctane conversion of 16.8%, cyclooctanol selectivity of 32%, cyclooctanone selectivity of 66%, suberic acid selectivity of 2%, and no pimelic acid or other byproducts were detected.

[0115] Example 44

[0116] Example 44 differs from Example 26 only in that cyclohexane (16.8320 g, 200 mmol) is replaced with cyclododecane (33.6640 g, 200 mmol). The experimental results of Example 44 are: cyclododecane conversion 18.6%, cyclododecanol selectivity 35%, cyclododecanone selectivity 65%, and no aliphatic diacid is detected.

[0117] Example 45

[0118] The only difference between Example 45 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 7. 17 )PPCo-1.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 45 were: cyclohexane conversion 9.9%, cyclohexanol selectivity 33%, cyclohexanone selectivity 63%, adipic acid selectivity 4%, and no glutaric acid or other byproducts were detected.

[0119] Example 46

[0120] The only difference between Example 46 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 8. 17 )PPCo-3.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 46 were: cyclohexane conversion 9.6%, cyclohexanol selectivity 34%, cyclohexanone selectivity 61%, adipic acid selectivity 5%, and no glutaric acid or other byproducts were detected.

[0121] Example 47

[0122] The only difference between Example 47 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 9. 17)PPCo-10.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 47 were: cyclohexane conversion 10.4%, cyclohexanol selectivity 32%, cyclohexanone selectivity 65%, adipic acid selectivity 3%, and no glutaric acid or other byproducts were detected.

[0123] Example 48

[0124] The only difference between Example 48 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 10. 17 )PPCo-2.00@0.20@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 48 were: cyclohexane conversion 9.3%, cyclohexanol selectivity 31%, cyclohexanone selectivity 64%, adipic acid selectivity 5%, and no glutaric acid or other byproducts were detected.

[0125] Example 49

[0126] The only difference between Example 49 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 11. 17 )PPCo-2.00@0.80@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 49 were: cyclohexane conversion 10.1%, cyclohexanol selectivity 33%, cyclohexanone selectivity 64%, adipic acid selectivity 3%, and no glutaric acid or other byproducts were detected.

[0127] Example 50

[0128] The only difference between Example 50 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 12. 17)PPCo-2.00@5.00@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 50 were: cyclohexane conversion 9.4%, cyclohexanol selectivity 33%, cyclohexanone selectivity 61%, adipic acid selectivity 6%, and no glutaric acid or other byproducts were detected.

[0129] Example 51

[0130] The only difference between Example 51 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 13. 17 )PPCo-2.00@20.00@1.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 51 were: cyclohexane conversion 8.5%, cyclohexanol selectivity 32%, cyclohexanone selectivity 62%, adipic acid selectivity 6%, and no glutaric acid or other byproducts were detected.

[0131] Example 52

[0132] The only difference between Example 52 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 14. 17 )PPCo-2.00@1.00@0.10@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 52 were: cyclohexane conversion 9.7%, cyclohexanol selectivity 34%, cyclohexanone selectivity 62%, adipic acid selectivity 4%, and no glutaric acid or other byproducts were detected.

[0133] Example 53

[0134] The only difference between Example 53 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 15. 17)PPCo-2.00@1.00@0.80@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 53 were: cyclohexane conversion 10.1%, cyclohexanol selectivity 32%, cyclohexanone selectivity 65%, adipic acid selectivity 3%, and no glutaric acid or other byproducts were detected.

[0135] Example 54

[0136] The only difference between Example 54 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 16. 17 )PPCo-2.00@1.00@2.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 54 were: cyclohexane conversion 10.5%, cyclohexanol selectivity 33%, cyclohexanone selectivity 64%, adipic acid selectivity 3%, and no glutaric acid or other byproducts were detected.

[0137] Example 55

[0138] The only difference between Example 55 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin TT (3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 17. 17 )PPCo-2.00@1.00@10.00@30@84 (17.0 mg, 0.004 mmol). The experimental results of Example 55 were: cyclohexane conversion 10.7%, cyclohexanol selectivity 32%, cyclohexanone selectivity 64%, adipic acid selectivity 4%, and no glutaric acid or other by-products were detected.

[0139] Example 56

[0140] The only difference between Example 56 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 18. 17)PPCo-2.00@1.00@1.00@0@84 (17.0 mg, 0.004 mmol). The experimental results of Example 56 were: cyclohexane conversion 7.9%, cyclohexanol selectivity 33%, cyclohexanone selectivity 60%, adipic acid selectivity 7%, and no glutaric acid or other byproducts were detected.

[0141] Example 57

[0142] The only difference between Example 57 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 19. 17 )PPCo-2.00@1.00@1.00@20@84 (17.0 mg, 0.004 mmol). The experimental results of Example 57 were: cyclohexane conversion 10.0%, cyclohexanol selectivity 34%, cyclohexanone selectivity 62%, adipic acid selectivity 4%, and no glutaric acid or other byproducts were detected.

[0143] Example 58

[0144] The only difference between Example 58 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced by the metalloporphyrin T(3,5-diC9F) containing hexafluoropropylene trimer functional group obtained in Example 20. 17 )PPCo-2.00@1.00@1.00@50@84 (17.0 mg, 0.004 mmol). The experimental results of Example 58 were: cyclohexane conversion 10.2%, cyclohexanol selectivity 31%, cyclohexanone selectivity 66%, adipic acid selectivity 3%, and no glutaric acid or other byproducts were detected.

[0145] Example 59

[0146] The only difference between Example 59 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 21. 17)PPCo-2.00@1.00@1.00@80@84 (17.0 mg, 0.004 mmol). The experimental results of Example 59 were: cyclohexane conversion 9.2%, cyclohexanol selectivity 32%, cyclohexanone selectivity 64%, adipic acid selectivity 4%, and no glutaric acid or other byproducts were detected.

[0147] Example 60

[0148] The only difference between Example 60 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 22. 17 )PPCo-2.00@1.00@1.00@30@6 (17.0 mg, 0.004 mmol). The experimental results of Example 60 were: cyclohexane conversion 7.6%, cyclohexanol selectivity 31%, cyclohexanone selectivity 61%, adipic acid selectivity 8%, and no glutaric acid or other byproducts were detected.

[0149] Example 61

[0150] The only difference between Example 61 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 23. 17 )PPCo-2.00@1.00@1.00@30@72 (17.0 mg, 0.004 mmol). The experimental results of Example 61 were: cyclohexane conversion 10.3%, cyclohexanol selectivity 33%, cyclohexanone selectivity 63%, adipic acid selectivity 4%, and no glutaric acid or other by-products were detected.

[0151] Example 62

[0152] The only difference between Example 62 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 24. 17)PPCo-2.00@1.00@1.00@30@96 (17.0 mg, 0.004 mmol). The experimental results of Example 62 were: cyclohexane conversion 10.6%, cyclohexanol selectivity 32%, cyclohexanone selectivity 63%, adipic acid selectivity 5%, and no glutaric acid or other byproducts were detected.

[0153] Example 63

[0154] The only difference between Example 63 and Example 26 is that the metalloporphyrin T(3,5-diC9F 17 )PPCo-2.00@1.00@1.00@30@84 (17.0 mg, 0.004 mmol) was replaced with the metalloporphyrin T(3,5-diC9F) containing a hexafluoropropylene trimer functional group obtained in Example 25. 17 )PPCo-2.00@1.00@1.00@30@168 (17.0 mg, 0.004 mmol). The experimental results of Example 63 were: cyclohexane conversion 10.5%, cyclohexanol selectivity 34%, cyclohexanone selectivity 63%, adipic acid selectivity 3%, and no glutaric acid or other byproducts were detected.

[0155] Example 64 (comparative experiment)

[0156] Preparation of TPPCo-2.00@1.00@1.00@30@84

[0157] In a 25 mL glass reaction tube, benzaldehyde (0.2122 g, 2.0 mmol), freshly distilled pyrrole (0.2684 g, 4.00 mmol), and anhydrous cobalt acetate (0.7081 g, 4.00 mmol) were dissolved in 20 mL of a mixture of methanol and chloroform (volume ratio 1:1). The reaction was stirred at 30°C under a nitrogen atmosphere for 84 h. After completion of the reaction, the reaction mixture was desolvated under reduced pressure to obtain a crude metalloporphyrin. The crude metalloporphyrin was washed with water (5 × 20 mL) and anhydrous ethanol (5 × 20 mL), and then separated by silica gel column chromatography (eluent: dichloromethane) to obtain the metalloporphyrin TPPCo-2.00@1.00@1.00@30@84 as a purple-black solid powder (0.1238 g, yield 18.1%).

[0158] In a 100 mL polytetrafluoroethylene-lined stainless steel autoclave, the metalloporphyrin TPPCo-2.00@1.00@1.00@30@84 (2.7 mg, 0.004 mmol) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 125°C with stirring. When the temperature reached the set point, oxygen was introduced to 1.00 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 hours. After the reaction was completed, the reaction solution was cooled to room temperature with stirring and then stirred at room temperature for 6.0 hours to completely decompose and convert any residual cycloalkyl hydroperoxide. After the reaction was complete, the residual gas was slowly released, the reactor was opened, and the volume was adjusted to 100 mL with anhydrous methanol. 10 mL of the fixed volume solution was accurately pipetted, and toluene (0.1843 g, 2.0 mmol) was added as the internal standard for gas phase analysis for GC analysis to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partial oxidation products cyclohexanol and cyclohexanone. 10 mL of the fixed volume solution was accurately pipetted, and benzoic acid (0.1221 g, 1.0 mmol) was added as the internal standard for liquid phase analysis for HPLC analysis to determine the yields and selectivities of the deep oxidation products adipic acid and glutaric acid. GC and HPLC analysis revealed a cyclohexane conversion of 6.5%, a cyclohexanol selectivity of 34%, a cyclohexanone selectivity of 48%, and an adipic acid selectivity of 18%. No glutaric acid or other byproducts were detected.

[0159] Example 65 (comparative experiment)

[0160] Preparation of T(4-Cl)PPCo-2.00@1.00@1.00@30@84

[0161] In a 25 mL glass reaction tube, 4-chlorobenzaldehyde (0.2811 g, 2.0 mmol), freshly distilled pyrrole (0.2684 g, 4.00 mmol), and anhydrous cobalt acetate (0.7081 g, 4.00 mmol) were dissolved in 20 mL of a mixture of methanol and chloroform (volume ratio 1:1). The reaction was stirred at 30°C under a nitrogen atmosphere for 84 h. After completion of the reaction, the reaction mixture was desolvated under reduced pressure to obtain a crude metalloporphyrin. The crude metalloporphyrin was washed with water (5 × 20 mL) and anhydrous ethanol (5 × 20 mL), and then separated by silica gel column chromatography (eluent: dichloromethane) to obtain the metalloporphyrin T(4-Cl)PPCo-2.00@1.00@1.00@30@84 as a purple-red solid powder (0.1457 g, yield 15.4%).

[0162] In a 100 mL stainless steel autoclave lined with polytetrafluoroethylene, the metalloporphyrin T(4-Cl)PPCo-2.00@1.00@1.00@30@84 (3.3 mg, 0.004 mmol) was dispersed in cyclohexane (16.8320 g, 200 mmol). The reaction system was sealed and heated to 125°C with stirring. Once the temperature reached the set point, oxygen was introduced to 1.00 MPa. The set temperature and oxygen pressure were maintained, and the reaction was stirred for 8 hours. Upon completion of the reaction, the reaction mixture was cooled to room temperature with stirring and then stirred for 6 hours at room temperature to completely decompose and convert any residual cycloalkyl hydroperoxide. After the reaction was complete, the residual gas was slowly released, the reactor was opened, and the volume was brought to 100 mL with anhydrous methanol. 10 mL of the fixed volume solution was accurately pipetted, and toluene (0.1843 g, 2.0 mmol) was added as the internal standard for gas phase analysis for GC analysis to determine the conversion of the substrate cyclohexane and the yields and selectivities of the partial oxidation products cyclohexanol and cyclohexanone. 10 mL of the fixed volume solution was accurately pipetted, and benzoic acid (0.1221 g, 1.0 mmol) was added as the internal standard for liquid phase analysis for HPLC analysis to determine the yields and selectivities of the deep oxidation products adipic acid and glutaric acid. GC and HPLC analysis revealed a cyclohexane conversion of 6.8%, a cyclohexanol selectivity of 34%, a cyclohexanone selectivity of 50%, and an adipic acid selectivity of 16%. No glutaric acid or other byproducts were detected.

[0163] By comparing catalysts and conducting comparative experiments, it can be clearly seen that the catalyst prepared by the present invention can catalyze the oxidation of cycloalkanes with O2, which not only improves the conversion rate of cycloalkanes, but also greatly improves the selectivity of partial oxidation products (cycloalkanols and cycloalkanones), significantly reduces the selectivity of by-product aliphatic diacids, and effectively inhibits deep oxidation.

[0164] Example 66 (Scale-up experiment)

[0165] In a 1.0 L stainless steel autoclave lined with polytetrafluoroethylene, the metalloporphyrin T(3,5-diC9F 17)PPCo-2.00@1.00@1.00@30@84 (170.0 mg, 0.04 mmol) was dispersed in cyclohexane (168.320 g, 2.0 mol), the reaction system was sealed, and the temperature was raised to 125°C with stirring. When the temperature reached the set temperature, oxygen was introduced to 1.00 MPa, the set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 hours. After the reaction was completed, the reaction solution was stirred and cooled to room temperature, and the reaction was stirred at room temperature for 6.0 hours to completely decompose and convert the small amount of residual cycloalkyl hydroperoxide. After the reaction was completed, the residual gas was slowly released and the reactor was opened. This experiment was repeated three times, the reaction mixtures were combined, and the cyclohexane was separated by atmospheric distillation to obtain 415.6 g of cyclohexane, which was then distilled under reduced pressure. The first fraction received was taken as cyclohexanone, and 14.64 g was obtained; the second fraction received was taken as cyclohexanol, and 7.1 g was obtained. The remaining mixture after vacuum distillation was recrystallized from isopropanol / cyclohexane (1:1) to yield 3.6 g of white crystals. Calculations showed a cyclohexane conversion of 15%, a cyclohexanol selectivity of 28%, a cyclohexanone selectivity of 58%, and adipic acid selectivity of 14%.

[0166] The contents described in this specification are merely an enumeration of implementation forms of the inventive concept, and the protection scope of the present invention should not be considered as being limited to the specific forms described in the embodiments.

Claims

1. A metalloporphyrin containing a hexafluoropropylene trimer functional group, characterized in that: Its structure is shown in formula (I): The metal center M of the metal porphyrin containing the hexafluoropropylene trimer functional group is Co(II), Mn(II), Fe(II), Ni(II) or Cu(II).

2. The metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 1, wherein: The metal center M of the metal porphyrin containing a hexafluoropropylene trimer functional group is Co(II).

3. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 1, wherein: The following steps are involved: A benzaldehyde derivative containing a hexafluoropropylene trimer functional group, freshly distilled pyrrole, and a metal M salt are dissolved in a reaction solvent, and the mixture is stirred and reacted at a temperature of 0 to 80° C. under a nitrogen atmosphere for 6.0 to 168.0 hours. After the reaction is completed, the reaction mixture is desolvated under reduced pressure to obtain a crude metalloporphyrin product. The obtained crude metalloporphyrin product is washed with water and anhydrous ethanol in sequence, and separated by silica gel column chromatography to obtain a metalloporphyrin product containing a hexafluoropropylene trimer functional group.

4. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 3, wherein: The reaction temperature is 20-50° C., and the reaction time is 72.0-168.0 h.

5. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 3, wherein: The benzaldehyde derivative containing a hexafluoropropylene trimer functional group has a branched structure as shown in formula (II): The molar ratio of the benzaldehyde derivative containing the hexafluoropropylene trimer functional group to the freshly distilled pyrrole is 1:1-10.

6. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 5, wherein: The benzaldehyde derivative containing a hexafluoropropylene trimer functional group has a preparation method comprising the following steps: adding hexafluoropropylene trimer and 3,5-dihydroxybenzaldehyde to a methyl halide solvent, heating to 35-45° C. under an N2 atmosphere, and stirring under reflux for reaction for 6-10 hours; after the reaction is completed, cooling the reaction solution to room temperature, adding deionized water, extracting and separating the liquids, and then drying the organic phase with anhydrous sodium sulfate; separating and purifying the organic phase by column chromatography, collecting the organic phase, and drying it to obtain a colorless liquid, thereby completing the preparation; The molar ratio of hexafluoropropylene trimer to 3,5-dihydroxybenzaldehyde is 1:0.5-2; The eluent for column chromatography separation is a cyclohexane-dichloromethane mixed solvent with a volume ratio of 4-6:

1.

7. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 6, wherein: The molar ratio of hexafluoropropylene trimer to 3,5-dihydroxybenzaldehyde is 1:1; The eluent for column chromatography separation was a cyclohexane-dichloromethane mixed solvent with a volume ratio of 5:

1.

8. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 3, wherein: The molar ratio of the metal M salt to the benzaldehyde derivative containing the hexafluoropropylene trimer functional group is 0.10 to 10:

1.

9. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 8, wherein: The molar ratio of the metal M salt to the benzaldehyde derivative containing the hexafluoropropylene trimer functional group is 0.40 to 10:

1.

10. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 3, wherein: The reaction solvent is a mixture of methanol and chloroform, and the volume ratio of methanol to chloroform is 1:0.10-10.

0.

11. The method for preparing a metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 10, wherein: The reaction solvent is a mixture of methanol and chloroform, and the volume ratio of methanol to chloroform is 1:0.80-10.

0.

12. Use of the metalloporphyrin containing a hexafluoropropylene trimer functional group as claimed in claim 1 in the partial oxidation of cycloalkanes.

13. The use according to claim 12, characterized in that The application method comprises the following steps: dispersing the metalloporphyrin containing a hexafluoropropylene trimer functional group according to claim 1 in a cycloalkane, sealing the reaction system, heating the system to 100 to 150° C. while stirring, introducing oxygen to 0.40 MPa to 2.0 MPa, maintaining the set temperature and oxygen pressure, and stirring the reaction for 3.0 to 15.0 hours; stirring the reaction solution and cooling it to room temperature, and stirring the reaction at room temperature for 3.0 to 12.0 hours to obtain a reaction mixture containing partially oxidized products, cycloalkyl alcohol and cycloalkyl ketone.

14. The use according to claim 13, characterized in that The reaction temperature is 120-150° C., the reaction oxygen pressure is 1.0-2.0 MPa, and the stirring reaction time is 6-12 hours.

15. The use according to claim 13, characterized in that The feeding ratio of the metal porphyrin containing hexafluoropropylene trimer functional group to cycloalkane is 1 mg: 0.2-235 mmol.

16. The use according to claim 15, characterized in that The feeding ratio of the metal porphyrin containing hexafluoropropylene trimer functional group to cycloalkane is 1 mg: 0.2-12 mmol.

17. The use according to claim 13, wherein: The cycloalkane is at least one of cyclopentane, cyclohexane, cycloheptane, cyclooctane and cyclododecane, and the corresponding partial oxidation products are cycloalkyl alcohols and cycloalkyl ketones.

Images