A metal porphyrin containing hexafluoropropylene trimer groups, a preparation method thereof, and applications thereof

Abstract

The present invention discloses a metal porphyrin containing a hexafluoropropylene trimer group, a preparation method thereof and an application; a benzaldehyde derivative containing a hexafluoropropylene trimer group, freshly distilled pyrrole, and a metal acetate are dissolved in a mixed solvent of methanol and chloroform, and under a nitrogen atmosphere, the reaction is stirred at 0 to 80 °C for 6.0 to 168.0 h. After the reaction is completed, through post-treatment, a metal porphyrin containing a hexafluoropropylene trimer group is obtained; the metal porphyrin containing a hexafluoropropylene trimer group described in the present invention can be used in the reaction of catalytic oxidation of cycloalkanes by O2. The cycloalkane oxidation method provided by the present invention has high selectivity for partial oxidation products (cycloalkyl alcohols and cycloalkyl ketones), low contents of explosive peroxides and deeply oxidized product aliphatic diacids, and is a safe, effective cycloalkane oxidation method with low separation energy consumption.

Description

Technical Field

[0001] The present invention relates to a metal porphyrin containing a hexafluoropropylene trimer group, a preparation method thereof, and an application as a catalyst in the partial oxidation of cycloalkanes, belonging to the fields of organic catalysis and fine organic synthesis. Background Art

[0002] The catalytic oxidation of cycloalkanes can convert hydrocarbons widely present in fossil resources into high-value-added alcohol and ketone compounds, which has extensive applications in the chemical industry (ZL 202111006432.X; ZL202010884408.5; ZL 201911161924.9). However, due to the higher chemical activity of some of the generated oxidation products (cycloalkyl alcohols and cycloalkyl ketones) than the substrate cycloalkanes, some of the oxidation products are prone to deep oxidation, generating ring-opening products, aliphatic diacids and their derivatives. This not only reduces the selectivity of the partial oxidation products, increases the energy consumption and equipment requirements for separation and purification, but also the generated aliphatic diacids and their derivatives are prone to crystallization, clogging the production pipelines, causing great difficulties in industrial production. In the industrial catalytic oxidation of cyclohexane, in order to ensure a better selectivity of the partial oxidation products (cyclohexanol and cyclohexanone), the conversion of cyclohexane is often controlled at about 5% to achieve a selectivity of about 85% for the partial oxidation products. (Chemical Engineering Journal, 2022, 443:136126; Chemical Engineering Science, 2022, 260:117825; Molecular Catalysis, 2023, 535:112853). Further increasing the substrate conversion rate will significantly reduce the selectivity of the partial oxidation products (cyclohexanol and cyclohexanone), and it is 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 relatively high reactivity of the oxidation products (cycloalkyl alcohols and cycloalkyl ketones), another important reason is the frequent contact between the partial oxidation products and the catalytic active centers. In the current chemical industry, the catalysts used for the catalytic oxidation of cycloalkanes are mainly salts, complexes and their derivatives of cobalt(II) and manganese(II). The above catalysts can not only catalyze the oxidation of the C-H bond of cycloalkanes by O2 to partial oxidation products such as alcohols and ketones, but also catalyze the oxidation of alcohol and ketone compounds by O2 to deep oxidation products. Therefore, effectively avoiding the frequent contact between the partial oxidation products (cycloalkyl alcohols and cycloalkyl ketones) and the catalytic active centers will be conducive to avoiding the deep oxidation of alcohol and ketone compounds during the partial oxidation process of cycloalkanes, and realizing the efficient and selective oxidation of O2 to cycloalkanes to partial oxidation products, cycloalkyl alcohols and cycloalkyl ketones. By achieving the highly selective preparation of cycloalkyl alcohols and cycloalkyl ketones, it is not only conducive to reducing the difficulty and equipment requirements for the separation and purification of industrial cycloalkane partial oxidation products, reducing the separation energy consumption, but also can effectively prevent safety accidents caused by pipeline blockage, which is of great significance for the safe, energy-saving and emission-reduction production of industrial cycloalkanes.

[0003] Fluorine-containing compounds, due to their low polarity, not only have strong hydrophobic properties but also exhibit strong repellency to some oil compounds, especially to some organic compounds with relatively high polarity, showing strong lipophobicity (CN115926069A; WO 2022059620A1). The partial oxidation of cycloalkanes to cycloalkyl alcohols and cycloalkyl ketones is a process of increasing polarity, where low-polarity cycloalkanes are partially oxidized to form cycloalkyl alcohols and cycloalkyl ketones with increased polarity. Therefore, modifying the catalytic material for the partial oxidation of cycloalkanes with low-polarity carbon-fluorine chains will facilitate the detachment of relatively high-polarity cycloalkyl alcohols and cycloalkyl ketones from the catalytic active centers, avoid their contact with the catalytic active centers during the disordered diffusion process, and prevent their deep oxidation. In the above process, due to the low polarity of cycloalkanes themselves, the introduction of carbon-fluorine chains has little impact on the contact between cycloalkanes and catalytic active centers, allowing the substrate cycloalkanes to smoothly contact the catalytic active centers and be partially oxidized to cycloalkyl alcohols and cycloalkyl ketones. Therefore, modifying the catalyst for the partial oxidation of cycloalkanes with carbon-fluorine chains will be conducive to the efficient and selective catalytic oxidation of cycloalkanes to form cycloalkyl alcohols and cycloalkyl ketones, which is of great significance for the safe, energy-saving, and emission-reducing production of cycloalkanes in industry. Summary of the Invention

[0004] In view of the above problems existing in the prior art, the present invention provides a metal porphyrin containing a hexafluoropropylene trimer group, a preparation method thereof, and its application as a catalyst in the partial oxidation of cycloalkanes.

[0005] The present invention uses a hexafluoropropylene trimer as a modifying group to enable the timely detachment of the partially oxidized products, cycloalkyl alcohols and cycloalkyl ketones, from the catalytic active centers, prevent the contact between the partially oxidized products and the catalytic active centers, prevent their deep oxidation, and improve the selectivity of the partially oxidized products; with the branched-chain structure of the hexafluoropropylene trimer group, high-bond-energy C-F bonds are constructed near the metal catalytic active centers to prevent the oxidative degradation of the metal porphyrin catalyst itself, strengthen the catalytic conversion ratio in the cycloalkane oxidation process, further improve the selectivity of cycloalkyl alcohols and cycloalkyl ketones, and prevent accidents that may be caused by the accumulation of peroxides.

[0006] The method for the partial oxidation of cycloalkanes in the present invention not only has high selectivity for cycloalkyl alcohols and cycloalkyl ketones but also has a low content of cycloalkyl hydroperoxides and a high safety factor, and is an efficient, feasible, and safe method for the partial catalytic oxidation of cycloalkanes to synthesize cycloalkyl alcohols and cycloalkyl ketones.

[0007] The technical solution of the present invention is as follows:

[0008] A metal porphyrin containing a hexafluoropropylene trimer group, whose structure is shown in formula (I):

[0009]

[0010] In formula (I), the metal center M is Co(II), Mn(II), Fe(II), Ni(II) or Cu(II), preferably Co(II).

[0011] The preparation method of the metal porphyrin containing a hexafluoropropylene trimer group according to the present invention is as follows:

[0012] Dissolve the benzaldehyde derivative containing a hexafluoropropylene trimer group, pyrrole (freshly distilled), and metal acetate in a reaction solvent. Under a nitrogen atmosphere, stir and react at 0 - 80 °C for 6.0 - 168.0 h; after the reaction is completed, the reaction mixture is concentrated under reduced pressure to obtain a crude metal porphyrin product; the obtained crude metal porphyrin product is washed with water and then with absolute ethanol successively, and separated by silica gel column chromatography to obtain the metal porphyrin containing a hexafluoropropylene trimer group;

[0013] Among them,

[0014] The molar ratio of the benzaldehyde derivative containing a hexafluoropropylene trimer group to pyrrole is 1:1 - 10;

[0015] The molar ratio of metal acetate to pyrrole is 1:0.20 - 20;

[0016] The molar ratio of metal acetate to the benzaldehyde derivative containing a hexafluoropropylene trimer group is 0.10 - 10:1, preferably 0.40 - 10:1;

[0017] 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;

[0018] Preferably, the reaction temperature is 20 - 50 °C and the reaction time is 72.0 - 168.0 h;

[0019] The eluent for silica gel column chromatography separation is dichloromethane;

[0020] In the above preparation method, the structure of the benzaldehyde derivative containing a hexafluoropropylene trimer group is shown in formula (II):

[0021]

[0022] The preparation method of the benzaldehyde derivative containing a hexafluoropropylene trimer group is:

[0023] Add hexafluoropropylene trimer and 4-hydroxybenzaldehyde to a halogenated methane solvent. Under a nitrogen atmosphere, stir and react under reflux at 35 - 45 °C for 6 - 10 h; after the reaction is completed, cool the reaction solution to room temperature, then add deionized water, extract and separate the liquid, dry the organic phase with anhydrous sodium sulfate, concentrate and then purify by column chromatography to obtain the benzaldehyde derivative containing a hexafluoropropylene trimer group (colorless liquid);

[0024] Among them,

[0025] the molar ratio of hexafluoropropylene trimer to 4-hydroxybenzaldehyde is 1:0.5 - 2, preferably 1:1;

[0026] the eluent for column chromatography separation is a cyclohexane-dichloromethane mixed solvent with a volume ratio of 4 - 6:1, preferably a cyclohexane-dichloromethane volume ratio of 5:1.

[0027] The metal porphyrin containing a hexafluoropropylene trimer group of the present invention can be applied to the partial oxidation reaction of cycloalkanes. The specific application method is as follows:

[0028] Disperse the metal porphyrin containing a hexafluoropropylene trimer group in cycloalkanes, seal the reaction system, heat it to 100 - 150 °C with stirring, introduce oxygen to 0.40 - 2.0 MPa, maintain the set temperature and oxygen pressure, and stir and react for 3.0 - 15.0 h; then, cool the reaction solution to room temperature with stirring and stir and react at room temperature for 3.0 - 12.0 h to obtain a reaction mixture containing the partial oxidation products cycloalkyl alcohol and cycloalkyl ketone;

[0029] Among them, the feeding ratio of the metal porphyrin containing a hexafluoropropylene trimer group to cycloalkanes is 1 mg:0.2 - 235 mmol, preferably 1 mg:0.2 - 12 mmol;

[0030] Preferably, the reaction temperature is 120 - 150 °C, the oxygen pressure is 1.0 - 2.0 MPa, and the stirring reaction time is 6 - 12 h;

[0031] The cycloalkane is selected from at least one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, and cyclododecane, and the corresponding partial oxidation products are cycloalkyl alcohol and cycloalkyl ketone.

[0032] The technical concept of the present invention is:

[0033] The present invention uses a metal porphyrin modified with a branched hexafluoropropylene trimer as a catalyst to catalytically oxidize cycloalkanes with O2 to prepare partial oxidation products cycloalkyl alcohol and cycloalkyl ketone. Using a branched hexafluoropropylene trimer as a modifying group enables the partial oxidation products cycloalkyl alcohol and cycloalkyl ketone to promptly detach from the catalytic active center, prevents the contact of the partial oxidation products with the catalytic active center, prevents their deep oxidation, and improves the selectivity of the partial oxidation products; with the branched structure of the hexafluoropropylene trimer group, a high bond energy C-F bond is constructed near the metal catalytic active center, preventing the oxidative degradation of the metal porphyrin catalyst itself, strengthening the catalytic conversion ratio in the cycloalkane oxidation process, further improving the selectivity of cycloalkyl alcohol and cycloalkyl ketone, and preventing accidents that may be caused by the accumulation of peroxides.

[0034] Therefore, the method for partial oxidation of cycloalkanes in the present invention not only has high selectivity for cycloalkyl alcohols and cycloalkyl ketones, but also has a low content of cycloalkyl hydroperoxides, high safety factor, and 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 prone to deep oxidation to form by-products such as aliphatic diacids, and to achieve the efficient synthesis of partial oxidation products. It 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.

[0035] The beneficial effects of the present invention are mainly reflected in:

[0036] The present invention uses a metal porphyrin modified with a branched hexafluoropropylene trimer as a catalyst, which is ingeniously designed, novel in structure, and has a wide application range. In the partial oxidation reaction of cycloalkanes, the selectivity of cycloalkyl alcohols and cycloalkyl ketones is high, effectively inhibiting the deep oxidation of partial oxidation products and the formation of aliphatic diacids and their derivatives. The low selectivity of aliphatic diacids and their derivatives is also conducive to the continuous operation of the cycloalkane partial oxidation process and the low-energy consumption separation of products.

[0037] The present invention 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 prone to deep oxidation to form by-products such as aliphatic diacids, and to achieve the efficient synthesis of partial oxidation products. It 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. The present invention is a new method for selective catalytic oxidation of cycloalkanes that is efficient and feasible. Specific Embodiments

[0038] The present invention will be further described below through specific examples, but the protection scope of the present invention is not limited thereto.

[0039] Example 1 is the synthesis of a benzaldehyde derivative containing a hexafluoropropylene trimer group.

[0040] Examples 2-25 are the syntheses of metal porphyrin catalysts containing a hexafluoropropylene trimer group.

[0041] Examples 26-63 are the applications of metal porphyrin catalysts containing a hexafluoropropylene trimer group in the partial oxidation reaction of cycloalkanes.

[0042] Examples 64-65 are comparative experiments on the application of metal porphyrin catalysts containing a hexafluoropropylene trimer group in the partial oxidation reaction of cycloalkanes.

[0043] Example 66 is a scale-up experiment on the application of a metal porphyrin catalyst containing a hexafluoropropylene trimer group in the partial oxidation reaction of cycloalkanes.

[0044] The benzaldehyde derivative containing a hexafluoropropylene trimer group used in the present invention has a branched structure as shown in formula (II) and is prepared in the laboratory (Journal of Chemical Engineering of Chinese Universities, 2009, 23(4): 679-683; Pesticides, 2007, 46(8): 520-522.). Other reagents used are all commercially available analytical pure.

[0045]

[0046] Nomenclature rules for metal porphyrin catalysts containing hexafluoropropylene trimer groups:

[0047] T(4-C9F 17 )PPCo-2.00@2.40@1.20@60@80 represents porphyrin cobalt (II) containing a hexafluoropropylene trimer group. In the synthesis reaction, the molar ratio of the benzaldehyde derivative containing a hexafluoropropylene trimer group to freshly distilled pyrrole is 1:2.00, the molar ratio of 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.

[0048] Example 1

[0049] In a 100 mL three-necked flask, hexafluoropropylene trimer (C9F 18 )(4.5006 g, 10.0 mmol) and 4-hydroxybenzaldehyde (1.2212 g, 10.00 mmol) were added to 30 mL of dichloromethane. Under a N2 atmosphere, it was heated to 40 °C and stirred and reacted under reflux for 8.0 h. After the reaction was completed, the reaction solution was cooled to room temperature, then 20 mL of deionized water was added, and extraction and liquid separation were carried out (washed twice with 2×20 mL of water), and then the organic phase was dried with anhydrous sodium sulfate. After purification by column chromatography (silica gel was 200-300 mesh, and the eluent was V 环己烷 :V 二氯甲烷 = 5:1), the organic phase was collected and rotary evaporated to obtain 2.1742 g of a colorless liquid benzaldehyde derivative containing a hexafluoropropylene trimer group, with a yield of 39.3%.

[0050] Example 2

[0051] In a 25 mL glass reaction tube, a benzaldehyde derivative (II) containing a hexafluoropropylene trimer group (1.1044 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 a mixed solvent of 20 mL methanol and chloroform (volume ratio 1:1). Under a nitrogen atmosphere, the reaction was stirred at 30 °C for 84.0 h. After the reaction was completed, the reaction mixture was concentrated under reduced pressure to obtain a crude product of metal porphyrin. The obtained crude product of metal porphyrin was washed with water (5 × 20 mL), washed with absolute ethanol (5 × 20 mL), and separated by silica gel column chromatography (the eluent was dichloromethane) to obtain metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@1.00@30@84, 0.1762 g of purple-red solid powder, with a yield of 14.3%. 1 1H NMR (500 MHz, CDCl3): δ = 9.14 (s, 8H), 8.36 (d, 8H), 8.19 (d, 8H), -2.58 (s, 2H).

[0052] Example 3

[0053] The preparation process of the catalyst in Example 3 was repeated as in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was changed to "anhydrous manganese acetate (0.8981 g, 4.00 mmol)". The other conditions were the same as in Example 2, and metal porphyrin T(4-C9F 17 )PPMn-2.00@1.00@1.00@30@84, 0.2355 g of purple-black solid powder, with a yield of 19.2%. 1 1H NMR (500 MHz, CDCl3): δ = 9.10 (s, 8H), 8.33 (d, 8H), 8.14 (d, 8H), -2.59 (s, 2H).

[0054] Example 4

[0055] The preparation process of the catalyst in Example 4 was repeated as in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was changed to "anhydrous iron acetate (0.7758 g, 4.00 mmol)". The other conditions were the same as in Example 2, and metal porphyrin T(4-C9F 17 )PPFe-2.00@1.00@1.00@30@84, 0.2016 g of purple-black solid powder, with a yield of 16.4%. 11H NMR (500 MHz, CDCl3): δ = 9.11 (s, 8H), 8.33 (d, 8H), 8.16 (d, 8H), -2.61 (s, 2H).

[0056] Example 5

[0057] The preparation process of the catalyst in Example 5 was repeated as in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was changed to "nickel acetate tetrahydrate (0.9954 g, 4.00 mmol)". Other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPNi-2.00@1.00@1.00@30@84, 0.2335 g of purple-black solid powder, yield 19.0%. 1 1H NMR (500 MHz, CDCl3): δ = 9.10 (s, 8H), 8.34 (d, 8H), 8.18 (d, 8H), -2.59 (s, 2H).

[0058] Example 6

[0059] The preparation process of the catalyst in Example 6 was repeated as in Example 2, except that "anhydrous cobalt acetate (0.7081 g, 4.00 mmol)" was changed to "anhydrous copper acetate (0.7266 g, 4.00 mmol)". Other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPNi-2.00@1.00@1.00@30@84, 0.2861 g of purple-red solid powder, yield 23.3%. 1 1H NMR (500 MHz, CDCl3): δ = 9.18 (s, 8H), 8.41 (d, 8H), 8.23 (d, 8H), -2.62 (s, 2H).

[0060] Example 7

[0061] The preparation process of the catalyst in Example 7 was repeated as in Example 2, except that "freshly distilled pyrrole (0.2684 g, 4.00 mmol)" was changed to "freshly distilled pyrrole (0.1342 g, 2.00 mmol)". Other conditions were the same as in Example 1, and the metal porphyrin T(4-C9F 17 )PPCo-1.00@1.00@1.00@30@84, 0.1312 g of purple-red solid powder, yield 10.7%.

[0062] Example 8

[0063] The preparation process of the catalyst in Example 8 was repeated as in Example 2, except that "freshly distilled pyrrole (0.2684 g, 4.00 mmol)" was changed to "freshly distilled pyrrole (0.4025 g, 6.00 mmol)". The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-3.00@1.00@1.00@30@84, 0.1791 g of purple-red solid powder was obtained, with a yield of 14.6%.

[0064] Example 9

[0065] The preparation process of the catalyst in Example 9 was repeated as in Example 2, except that "freshly distilled pyrrole (0.2684 g, 4.00 mmol)" was changed to "freshly distilled pyrrole (1.3148 g, 20.00 mmol)". The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-10.00@1.00@1.00@30@84, 0.1815 g of purple-red solid powder was obtained, with a yield of 14.7%.

[0066] Example 10

[0067] The preparation process of the catalyst in Example 10 was repeated as in Example 2, except that "cobalt acetate anhydrous (0.7081 g, 4.00 mmol)" was changed to "cobalt acetate anhydrous (3.5405 g, 20.00 mmol)". The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-2.00@0.20@1.00@30@84, 0.1835 g of purple-red solid powder was obtained, with a yield of 14.9%.

[0068] Example 11

[0069] The preparation process of the catalyst in Example 11 was repeated as in Example 2, except that "cobalt acetate anhydrous (0.7081 g, 4.00 mmol)" was changed to "cobalt acetate anhydrous (0.8851 g, 5.00 mmol)". The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-2.00@0.80@1.00@30@84, 0.1124 g of purple-red solid powder was obtained, with a yield of 9.2%.

[0070] Example 12

[0071] Example 12 The preparation process of the catalyst was repeated as in Example 2, except that “cobalt acetate anhydrous (0.7081 g, 4.00 mmol)” was changed to “cobalt acetate anhydrous (0.1416 g, 0.80 mmol)”. Other conditions were the same as in Example 2, and metal porphyrin T(4-C9F 17 )PPCo-2.00@5.00@1.00@30@84, 0.1582 g of purple-red solid powder was obtained, with a yield of 7.5%.

[0072] Example 13

[0073] Example 13 The preparation process of the catalyst was repeated as in Example 2, except that “cobalt acetate anhydrous (0.7081 g, 4.00 mmol)” was changed to “cobalt acetate anhydrous (0.0354 g, 0.20 mmol)”. Other conditions were the same as in Example 2, and metal porphyrin T(4-C9F 17 )PPCo-2.00@20.00@1.00@30@84, 0.0168 g of purple-red solid powder was obtained, with a yield of 3.4%.

[0074] Example 14

[0075] Example 14 The preparation process of the catalyst was repeated as in Example 2, except that “in a 20 mL mixed solvent of methanol and chloroform (volume ratio 1:1)” was changed to “in a 20 mL mixed solvent of methanol and chloroform (volume ratio 1:0.1)”. Other conditions were the same as in Example 2, and metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@0.10@30@84, 0.1171 g of purple-red solid powder was obtained, with a yield of 9.5%.

[0076] Example 15

[0077] Example 15 The preparation process of the catalyst was repeated as in Example 2, except that “in a 20 mL mixed solvent of methanol and chloroform (volume ratio 1:1)” was changed to “in a 20 mL mixed solvent of methanol and chloroform (volume ratio 1:0.8)”. Other conditions were the same as in Example 2, and metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@0.80@30@84, 0.1254 g of purple-red solid powder was obtained, with a yield of 10.2%.

[0078] Example 16

[0079] Example 16 The preparation process of the catalyst was repeated as 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 1:2)”. The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@2.00@30@84, 0.1138 g of purple-red solid powder was obtained, and the yield was 9.3%.

[0080] Example 17

[0081] Example 17 The preparation process of the catalyst was repeated as 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 1:10)”. The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@10.00@30@84, 0.1345 g of purple-red solid powder was obtained, and the yield was 10.9%.

[0082] Example 18

[0083] Example 18 The preparation process of the catalyst was repeated as 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 in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@1.00@0@84, 0.0341 g of purple-red solid powder was obtained, and the yield was 2.8%.

[0084] Example 19

[0085] Example 19 The preparation process of the catalyst was repeated as 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 in Example 2, and the metal porphyrin T(4-C9F17)PPCo-2.00@1.00@1.00@20@84, 0.1019 g of purple-red solid powder was obtained, and the yield was 8.3%.

[0086] Example 20

[0087] Example 20 The preparation process of the catalyst was repeated as 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 in Example 2, and the metal porphyrin T(4-C9F 17)PPCo-2.00@1.00@1.00@50@84, 0.1031 g of purple-red solid powder, yield 8.4%.

[0088] Example 21

[0089] The preparation process of the catalyst in Example 21 was repeated as 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 in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@1.00@80@84, 0.1125 g of purple-red solid powder, yield 9.2%.

[0090] Example 22

[0091] The preparation process of the catalyst in Example 22 was repeated as in Example 2, except that "stirring reaction for 84.0 h" was changed to "stirring reaction for 6.0 h". The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@1.00@30@6, 0.0491 g of purple-red solid powder, yield 4.0%.

[0092] Example 23

[0093] The preparation process of the catalyst in Example 23 was repeated as in Example 2, except that "stirring reaction for 84.0 h" was changed to "stirring reaction for 72.0 h". The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@1.00@30@72, 0.1058 g of purple-red solid powder, yield 8.2%.

[0094] Example 24

[0095] The preparation process of the catalyst in Example 24 was repeated as in Example 2, except that "stirring reaction for 84.0 h" was changed to "stirring reaction for 96.0 h". The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F17)PPCo-2.00@1.00@1.00@30@96, 0.1003 g of purple-red solid powder, yield 8.3%.

[0096] Example 25

[0097] Example 25 The preparation process of the catalyst was repeated as in Example 2, except that "stirring reaction for 84.0 h" was changed to "stirring reaction for 168.0 h". The other conditions were the same as in Example 2, and the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups was obtained. 17 )PPCo-2.00@1.00@1.00@30@168, 0.1278 g of purple-red solid powder, yield 10.4%.

[0098] Example 26

[0099] In a 100 mL stainless steel autoclave with a PTFE liner, the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups 17 )PPCo-2.00@1.00@1.00@30@84 (9.8 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, and the set temperature and oxygen pressure were maintained, and the reaction was stirred for 8.0 h. After the reaction ended, the reaction solution was cooled to room temperature with stirring and stirred at room temperature for 6.0 h to completely decompose and convert a small amount of residual cycloalkyl hydroperoxide. After the reaction was completed, the residual gas was slowly released, the autoclave was opened, and the volume was fixed to 100 mL with anhydrous methanol. Exactly 10 mL of the fixed-volume solution was accurately taken, and the internal standard toluene for gas phase analysis (0.1843 g, 2.0 mmol) was added for GC analysis to determine the conversion rate of the substrate cyclohexane, the yields and selectivities of the partially oxidized products cyclohexanol and cyclohexanone; exactly 10 mL of the fixed-volume solution was accurately taken, and the internal standard benzoic acid for liquid phase analysis (0.1221 g, 1.0 mmol) was added for HPLC analysis to determine the yields and selectivities of the deeply oxidized products adipic acid and glutaric acid. By GC and HPLC analysis, the conversion rate of cyclohexane was 11.5%, the selectivity of cyclohexanol was 46%, the selectivity of cyclohexanone was 52%, the selectivity of adipic acid was 2%, and glutaric acid and other by-products were not detected.

[0100] Example 27

[0101] The difference between Example 27 and Example 26 was only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 2 17 )PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 3 17)PPMn - 2.00@1.00@1.00@30@84 (9.7 mg, 0.004 mmol). The experimental results of Example 27 were as follows: the conversion rate of cyclohexane was 10.7%, the selectivity for cyclohexanol was 39%, the selectivity for cyclohexanone was 57%, the selectivity for adipic acid was 4%, and glutaric acid and other by-products were not detected.

[0102] Example 28

[0103] The difference between Example 28 and Example 26 was only that the metal porphyrin T(4-C9F 17 )PPCo - 2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) prepared in Example 2 was replaced with the metal porphyrin T(4-C9F 17 )PPFe - 2.00@1.00@1.00@30@84 (9.7 mg, 0.004 mmol) prepared in Example 4. The experimental results of Example 28 were as follows: the conversion rate of cyclohexane was 10.1%, the selectivity for cyclohexanol was 42%, the selectivity for cyclohexanone was 56%, the selectivity for adipic acid was 2%, and glutaric acid and other by-products were not detected.

[0104] Example 29

[0105] The difference between Example 29 and Example 26 was only that the metal porphyrin T(4-C9F 17 )PPCo - 2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) prepared in Example 2 was replaced with the metal porphyrin T(4-C9F 17 )PPNi - 2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) prepared in Example 5. The experimental results of Example 29 were as follows: the conversion rate of cyclohexane was 9.8%, the selectivity for cyclohexanol was 47%, the selectivity for cyclohexanone was 51%, the selectivity for adipic acid was 2%, and glutaric acid and other by-products were not detected.

[0106] Example 30

[0107] The difference between Example 30 and Example 26 was only that the metal porphyrin T(4-C9F 17 )PPCo - 2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) prepared in Example 2 was replaced with the metal porphyrin T(4-C9F 17) PPCu-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 30 were as follows: cyclohexane conversion rate 9.6%, cyclohexanol selectivity 39%, cyclohexanone selectivity 60%, adipic acid selectivity 1%, and glutaric acid and other by-products were not detected.

[0108] Example 31

[0109] The difference between Example 31 and Example 26 was only that the metal porphyrin T(4-C9F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) prepared in Example 2 was replaced with a dosage of (0.4912 g, 0.2 mmol). The experimental results of Example 31 were as follows: cyclohexane conversion rate 11.9%, cyclohexanol selectivity 31%, cyclohexanone selectivity 63%, adipic acid selectivity 6%, and glutaric acid and other by-products were not detected.

[0110] Example 32

[0111] The difference between Example 32 and Example 26 was only that the metal porphyrin T(4-C9F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) prepared in Example 2 was replaced with a dosage of 0.0491 g, 0.02 mmol). The experimental results of Example 32 were as follows: cyclohexane conversion rate 11.3%, cyclohexanol selectivity 47%, cyclohexanone selectivity 49%, adipic acid selectivity 4%, and glutaric acid and other by-products were not detected.

[0112] Example 33

[0113] The difference between Example 33 and Example 26 was only that the metal porphyrin T(4-C9F 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) prepared in Example 2 was replaced with a dosage of (4.9 mg, 0.002 mmol). The experimental results of Example 33 were as follows: cyclohexane conversion rate 10.6%, cyclohexanol selectivity 48%, cyclohexanone selectivity 49%, adipic acid selectivity 3%, and glutaric acid and other by-products were not detected.

[0114] Example 34

[0115] Example 34 is different from Example 26 only in that the reaction temperature is changed to 120 °C. The experimental results of Example 34 are as follows: the conversion rate of cyclohexane is 9.7%, the selectivity of cyclohexanol is 46%, the selectivity of cyclohexanone is 53%, the selectivity of adipic acid is 1%, and glutaric acid and other by-products are not detected.

[0116] Example 35

[0117] Example 35 is different from Example 26 only in that the reaction temperature is changed to 135 °C. The experimental results of Example 35 are as follows: the conversion rate of cyclohexane is 11.7%, the selectivity of cyclohexanol is 42%, the selectivity of cyclohexanone is 53%, the selectivity of adipic acid is 5%, and glutaric acid and other by-products are not detected.

[0118] Example 36

[0119] Example 36 is different from Example 26 only in that the reaction temperature is changed to 150 °C. The experimental results of Example 36 are as follows: the conversion rate of cyclohexane is 12.0%, the selectivity of cyclohexanol is 38%, the selectivity of cyclohexanone is 57%, the selectivity of adipic acid is 5%, and glutaric acid and other by-products are not detected.

[0120] Example 37

[0121] Example 37 is different from Example 26 only in that the reaction oxygen pressure is changed to 0.40 MPa. The experimental results of Example 37 are as follows: the conversion rate of cyclohexane is 10.0%, the selectivity of cyclohexanol is 42%, the selectivity of cyclohexanone is 56%, the selectivity of adipic acid is 2%, and glutaric acid and other by-products are not detected.

[0122] Example 38

[0123] Example 38 is different from Example 26 only in that the reaction oxygen pressure is changed to 1.20 MPa. The experimental results of Example 38 are as follows: the conversion rate of cyclohexane is 11.1%, the selectivity of cyclohexanol is 41%, the selectivity of cyclohexanone is 55%, the selectivity of adipic acid is 4%, and glutaric acid and other by-products are not detected.

[0124] Example 39

[0125] Example 39 is different from Example 26 only in that the set temperature and oxygen pressure are maintained, and the stirring reaction time is changed to 6.0 h. The conversion rate of cyclohexane is 10.0%, the selectivity of cyclohexanol is 34%, the selectivity of cyclohexanone is 62%, the selectivity of adipic acid is 4%, and glutaric acid and other by-products are not detected.

[0126] Example 40

[0127] Example 40 is different from Example 26 only in that the set temperature and oxygen pressure are maintained, and the stirring reaction time is changed to 12.0 h. The conversion rate of cyclohexane is 10.4%, the selectivity of cyclohexanol is 33%, the selectivity of cyclohexanone is 65%, the selectivity of adipic acid is 2%, and no glutaric acid and other by-products are detected.

[0128] Example 41

[0129] Example 41 is different from Example 26 only in that cyclohexane (16.8320 g, 200 mmol) is replaced with cyclopentane (14.0260 g, 200 mmol). The experimental results of Example 41 are as follows: the conversion rate of cyclopentane is 11.4%, the selectivity of cyclopentanol is 20%, the selectivity of cyclopentanone is 65%, the selectivity of glutaric acid is 15%, and no succinic acid and other by-products are detected.

[0130] Example 42

[0131] Example 42 is different from Example 26 only in that cyclohexane (16.8320 g, 200 mmol) is replaced with cycloheptane (19.6372 g, 200 mmol). The experimental results of Example 42 are as follows: the conversion rate of cycloheptane is 24.5%, the selectivity of cycloheptanol is 26%, the selectivity of cycloheptanone is 61%, the selectivity of pimelic acid is 3%, and no adipic acid and other by-products are detected..

[0132] Example 43

[0133] Example 43 is different from Example 26 only in that cyclohexane (16.8320 g, 200 mmol) is replaced with cyclooctane (22.4426 g, 200 mmol). The experimental results of Example 43 are as follows: the conversion rate of cyclooctane is 30.1%, the selectivity of cyclooctanol is 46%, the selectivity of cyclooctanone is 51%, the selectivity of suberic acid is 3%, and no pimelic acid and other by-products are detected.

[0134] Example 44

[0135] Example 44 is different 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 as follows: the conversion rate of cyclododecane is 38.6%, the selectivity of cyclododecanol is 46%, the selectivity of cyclododecanone is 54%, and no cyclododecanoic acid, cycloundecanoic acid and other by-products are detected.

[0136] Example 45

[0137] Example 45 is different from Example 26 only in that the metal porphyrin T(4-C9F prepared in Example 2 17) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol), replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 7 17 ) PPCo-1.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 45 were as follows: cyclohexane conversion rate 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and glutaric acid and other by-products were not detected.

[0138] Example 46

[0139] The difference between Example 46 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 8 17 ) PPCo-3.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 46 were as follows: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and glutaric acid and other by-products were not detected.

[0140] Example 47

[0141] The difference between Example 47 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 9 17 ) PPCo-10.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 47 were as follows: cyclohexane conversion rate 11.5%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and glutaric acid and other by-products were not detected.

[0142] Example 48

[0143] The difference between Example 48 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol), replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 10 17 ) PPCo-2.00@0.20@1.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 48 were as follows: cyclohexane conversion rate 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0144] Example 49

[0145] The difference between Example 49 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 11 17 ) PPCo-2.00@0.80@1.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 49 were as follows: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0146] Example 50

[0147] The difference between Example 50 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 12 17 ) PPCo-2.00@5.00@1.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 50 were as follows: cyclohexane conversion rate 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0148] Example 51

[0149] The difference between Example 51 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17)PPCo - 2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol), replaced with the metal porphyrin T(4 - C9F containing hexafluoropropylene trimer group prepared in Example 13 17 )PPCo - 2.00@20.00@1.00@30@84(9.8 mg, 0.004 mmol). The experimental results of Example 51 were: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by - products were detected.

[0150] Example 52

[0151] The difference between Example 52 and Example 26 is only that the metal porphyrin T(4 - C9F containing hexafluoropropylene trimer group prepared in Example 2 17 )PPCo - 2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4 - C9F containing hexafluoropropylene trimer group prepared in Example 14 17 )PPCo - 2.00@1.00@0.10@30@84(9.8 mg, 0.004 mmol). The experimental results of Example 52 were: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by - products were detected.

[0152] Example 53

[0153] The difference between Example 53 and Example 26 is only that the metal porphyrin T(4 - C9F containing hexafluoropropylene trimer group prepared in Example 2 17 )PPCo - 2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4 - C9F containing hexafluoropropylene trimer group prepared in Example 15 17 )PPCo - 2.00@1.00@0.80@30@84(9.8 mg, 0.004 mmol). The experimental results of Example 53 were: cyclohexane conversion rate 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by - products were detected.

[0154] Example 54

[0155] The difference between Example 54 and Example 26 is only that the metal porphyrin T(4 - C9F containing hexafluoropropylene trimer group prepared in Example 2 17) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol), replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 16 17 ) PPCo-2.00@1.00@2.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 54 were: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0156] Example 55

[0157] The difference between Example 55 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 2 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) was replaced with the metal porphyrin TT(4-C9F containing hexafluoropropylene trimer groups prepared in Example 17 17 ) PPCo-2.00@1.00@10.00@30@84 (9.8 mg, 0.004 mmol). The experimental results of Example 55 were: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0158] Example 56

[0159] The difference between Example 56 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 2 17 ) PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 18 17 ) PPCo-2.00@1.00@1.00@0@84 (9.8 mg, 0.004 mmol). The experimental results of Example 56 were: cyclohexane conversion rate 11.3%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0160] Example 57

[0161] The difference between Example 57 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 2 17)PPCo-2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol), replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 19 17 )PPCo-2.00@1.00@1.00@20@84(9.8 mg, 0.004 mmol). The experimental results of Example 57 were as follows: cyclohexane conversion rate 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0162] Example 58

[0163] The difference between Example 58 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17 )PPCo-2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 20 17 )PPCo-2.00@1.00@1.00@50@84(9.8 mg, 0.004 mmol). The experimental results of Example 58 were as follows: cyclohexane conversion rate 11.3%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0164] Example 59

[0165] The difference between Example 59 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17 )PPCo-2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 21 17 )PPCo-2.00@1.00@1.00@80@84(9.8 mg, 0.004 mmol). The experimental results of Example 59 were as follows: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0166] Example 60

[0167] The difference between Example 60 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17) PPCo-2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol), replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 22 17 ) PPCo-2.00@1.00@1.00@30@6(9.8 mg, 0.004 mmol). The experimental results of Example 60 were: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0168] Example 61

[0169] The difference between Example 61 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17 ) PPCo-2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 23 17 ) PPCo-2.00@1.00@1.00@30@72(9.8 mg, 0.004 mmol). The experimental results of Example 61 were: cyclohexane conversion rate 11.5%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0170] Example 62

[0171] The difference between Example 62 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17 ) PPCo-2.00@1.00@1.00@30@84(9.8 mg, 0.004 mmol) was replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 24 17 ) PPCo-2.00@1.00@1.00@30@96(9.8 mg, 0.004 mmol). The experimental results of Example 62 were: cyclohexane conversion rate 11.6%, cyclohexanol selectivity 46%, cyclohexanone selectivity 52%, adipic acid selectivity 2%, and no glutaric acid and other by-products were detected.

[0172] Example 63

[0173] The difference between Example 63 and Example 26 is only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer group prepared in Example 2 17)PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol), replaced with the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 25 17 )PPCo-2.00@1.00@1.00@30@168 (9.8 mg, 0.004 mmol). The experimental results of Example 63 were as follows: cyclohexane conversion rate 11.4%, cyclohexanol selectivity 47%, cyclohexanone selectivity 51%, adipic acid selectivity 2%, and glutaric acid and other by-products were not detected.

[0174] Example 64 (comparative experiment)

[0175] Preparation and catalysis of TPPCo-2.00@1.00@1.00@30@84

[0176] Preparation: 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 a mixed solvent of 20 mL methanol and chloroform (volume ratio 1:1). Under a N2 atmosphere, the reaction was stirred at 30 °C for 84.0 h. After the reaction was completed, the reaction mixture was concentrated under reduced pressure to obtain a crude metal porphyrin product. The obtained crude metal porphyrin product was washed with water (5 × 20 mL), washed with absolute ethanol (5 × 20 mL), and separated by silica gel column chromatography (eluent: dichloromethane) to obtain the metal porphyrin TPPCo-2.00@1.00@1.00@30@84, 0.1238 g of purple-black solid powder, and the yield was 18.1%.

[0177] Catalysis: The difference between Example 64 and Example 26 was only that the metal porphyrin T(4-C9F containing hexafluoropropylene trimer groups prepared in Example 2 17 )PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) was replaced with the metal porphyrin TPPCo-2.00@1.00@1.00@30@84 prepared in Example 64. The cyclohexane conversion rate was 6.5%, the cyclohexanol selectivity was 29%, the cyclohexanone selectivity was 48%, the adipic acid selectivity was 17%, and the glutaric acid selectivity was 6%.

[0178] Example 65 (comparative experiment)

[0179] Preparation and catalysis of T(4-Cl)PPCo-2.00@1.00@1.00@30@84

[0180] Preparation: The difference between Example 65 and Example 64 is only that the benzaldehyde (0.2122 g, 2.0 mmol) in Example 64 is replaced by 4-chlorobenzaldehyde (0.2811 g, 2.0 mmol), obtaining metal porphyrin T(4-Cl)PPCo-2.00@1.00@1.00@30@84, 0.1457 g of purple-red solid powder, with a yield of 15.4%.

[0181] Catalysis: The difference between Example 65 and Example 26 is only that the metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@1.00@30@84 (9.8 mg, 0.004 mmol) prepared in Example 2 is replaced by the metal porphyrin T(4-Cl)PPCo-2.00@1.00@1.00@30@84 prepared in Example 65. The conversion rate of cyclohexane is 6.8%, the selectivity of cyclohexanol is 32%, the selectivity of cyclohexanone is 50%, the selectivity of adipic acid is 15%, and the selectivity of glutaric acid is 3%.

[0182] Through comparison of the catalyst and comparative experiments, it can be clearly seen that the catalyst prepared by the present invention for catalyzing the oxidation of cycloalkanes with O2 can not only improve the conversion rate of cycloalkanes, but also greatly improve the selectivity of some oxidation products (cycloalkanols and cycloalkanones), significantly reduce the selectivity of by-product aliphatic diacids, and effectively inhibit deep oxidation.

[0183] Example 66 (scale-up experiment)

[0184] In a 1 L stainless steel autoclave with a PTFE lining, disperse the metal porphyrin T(4-C9F 17 )PPCo-2.00@1.00@1.00@30@84 (0.0980 g, 0.004 mmol) in cyclohexane (168.32 g, 2 mol), seal the reaction system, and heat it to 125 °C with stirring. When the temperature reaches the set temperature, introduce oxygen to 1.00 MPa, maintain the set temperature and oxygen pressure, and stir the reaction for 8.0 h. After the reaction is completed, cool the reaction solution to room temperature with stirring and stir the reaction for 6.0 h at room temperature to completely decompose and convert a small amount of residual cycloalkyl hydroperoxide.

[0185] The experiment was repeated three times. After the reaction, the reaction mixtures were combined and distilled under atmospheric pressure to separate cyclohexane, obtaining 437.29 g of cyclohexane. Then, it was subjected to vacuum rectification. The fraction at 156 °C, 29.19 g, was cyclohexanone; the fraction at 162 °C, 43.48 g, was cyclohexanol. The remaining mixture after vacuum rectification was recrystallized in isopropanol / cyclohexane (1:1) to obtain 10.57 g of white crystals. After calculation, the conversion rate of cyclohexane was 13.4%, the selectivity of cyclohexanol was 37%, the selectivity of cyclohexanone was 54%, and the selectivity of adipic acid was 9%.

[0186] The content described in this specification is only a list of the implementation forms of the inventive concept, and the protection scope of the present invention should not be regarded as limited to the specific forms stated in the embodiments.

Claims

1. A metal porphyrin containing a hexafluoropropylene trimer group, and its structure is shown in formula (I): In formula (I), the metal center M is Co(II), Mn(II), Fe(II), Ni(II) or Cu(II).

2. A preparation method of the metal porphyrin containing a hexafluoropropylene trimer group as described in claim 1, characterized in that The preparation method is as follows: Dissolve the benzaldehyde derivative containing a hexafluoropropylene trimer group, pyrrole, and metal acetate in a reaction solvent. Under a nitrogen atmosphere, stir and react at 0 - 80 °C for 6.0 - 168.0 h. After the reaction is completed, the reaction mixture is concentrated under reduced pressure to obtain a crude metal porphyrin product. The obtained crude metal porphyrin product is washed with water and then with absolute ethanol successively, and separated by silica gel column chromatography to obtain the metal porphyrin containing a hexafluoropropylene trimer group; Among them, the structure of the benzaldehyde derivative containing a hexafluoropropylene trimer group is shown in formula (II):

3. The preparation method as described in claim 2, characterized in that The molar ratio of the benzaldehyde derivative containing a hexafluoropropylene trimer group to pyrrole is 1:1 - 10.

4. The preparation method as described in claim 2, characterized in that The molar ratio of metal acetate to pyrrole is 1:0.20 - 20.

5. The preparation method as described in claim 2, characterized in that The molar ratio of metal acetate to the benzaldehyde derivative containing a hexafluoropropylene trimer group is 0.10 - 10:

1.

6. The preparation method as described in claim 2, characterized in that The reaction solvent is a mixture of methanol and chloroform, and the volume ratio of methanol to chloroform is 1:0.10 - 10.

0.

7. The preparation method as described in claim 2, characterized in that The eluent for silica gel column chromatography separation is dichloromethane.

8. Application of the metal porphyrin containing a hexafluoropropylene trimer group as described in claim 1 in the partial oxidation reaction of cycloalkanes.

9. The application as described in claim 8, characterized in that The application method is as follows: Disperse the metal porphyrin containing a hexafluoropropylene trimer group in a cycloalkane, seal the reaction system, heat it to 100 - 150 °C with stirring, introduce oxygen to 0.40 - 2.0 MPa, maintain the set temperature and oxygen pressure, and stir and react for 3.0 - 15.0 h. Then, cool the reaction solution to room temperature with stirring and stir and react at room temperature for 3.0 - 12.0 h to obtain a reaction mixture containing partially oxidized products cycloalkyl alcohol and cycloalkyl ketone; Among them, the cycloalkane is selected from at least one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, and cyclododecane.

10. The application as described in claim 9, characterized in that The feeding ratio of the metal porphyrin containing a hexafluoropropylene trimer group to the cycloalkane is 1 mg:0.2 - 235 mmol.

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