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Method for synergistically catalyzing oxidization of cycloalkane by using metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt

A mofspcn-224, metalloporphyrin technology is applied in the field of industrial catalysis and fine organic synthesis, and can solve the problems of reducing the selectivity of cycloalkyl alcohols and cycloalkyl ketones, increasing the uncontrollability of the reaction system, poor selectivity of target products, and the like, Achieve high selectivity, inhibition of disordered diffusion, and small environmental impact

Pending Publication Date: 2020-11-17
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, the industrial catalytic oxidation of naphthenes is mainly based on homogeneous Mn 2+ or Mn 2+ As a catalyst, oxygen (O 2 ) is an oxidizing agent, which is carried out at 150°C to 170°C. The main problems are that the reaction temperature is high, the conversion rate of the substrate is low, and the selectivity of the target product is poor, especially the formation of aliphatic diacids is difficult to suppress (Applied Catalysis A, General 2019,575:120-131; Catalysis Communications 2019,132:105809)
The main root causes of the above problems are: (1) O 2 Oxidation of cycloalkanes mainly undergoes a disordered free radical diffusion process; (2) the oxidation intermediate product, cycloalkyl hydroperoxide, converts to the target oxidation products cycloalkanol and cycloalkanone through a free radical thermal decomposition path, which increases the inability of the reaction system. controllability, reducing the selectivity of cycloalkyl alcohols and cycloalkyl ketones

Method used

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  • Method for synergistically catalyzing oxidization of cycloalkane by using metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt
  • Method for synergistically catalyzing oxidization of cycloalkane by using metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt
  • Method for synergistically catalyzing oxidization of cycloalkane by using metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Synthesis of PCN-224(Mn)-m: In a 35mL pressure-resistant reaction tube, T(3-COOH)PPMn(II) (0.0847g, 0.1mmol), ZrCl 4 (0.1400g, 0.6mmol), benzoic acid (5.4000g, 44.3mmol) was dissolved in 16.0mL DMF, ultrasonic 30min until completely dissolved. The mixture was placed in an electric constant temperature blast drying oven at 120° C. for 48.0 hours of static reaction. After the reaction is complete, turn off the heating, cool naturally to room temperature, filter the crude product with suction and rinse with DMF and acetone successively, then transfer to a 10.0 mL centrifuge tube, centrifuge for 5.0 min (3000 rpm) in a low-speed centrifuge, pour out the upper layer, and dry DMF leaching (3×8.0mL) until the upper layer is clear, dry acetone leaching (3×8.0mL) until the upper layer is clear, remove the solid in the lower layer, and dry at 90°C for 8.0h to obtain a brick red powder (0.0680g, 44.7% yield).

Embodiment 2

[0030] Synthesis of PCN-224(Mn)-p: In a 35mL pressure-resistant reaction tube, T(4-COOH)PPMn(II) (0.0847g, 0.1mmol), ZrCl 4(0.1400g, 0.6mmol), benzoic acid (5.4000g, 44.3mmol) was dissolved in 16.0mL DMF, ultrasonic 30min until completely dissolved. The mixture was placed in an electric constant temperature blast drying oven at 120° C. for 48.0 hours of static reaction. After the reaction is complete, turn off the heating, cool naturally to room temperature, filter the crude product with suction and rinse with DMF and acetone successively, then transfer to a 10.0 mL centrifuge tube, centrifuge for 5.0 min (3000 rpm) in a low-speed centrifuge, pour out the upper layer, and dry DMF leaching (3×8.0mL) until the upper layer is clear, dry acetone leaching (3×8.0mL) until the upper layer is clear, remove the solid in the lower layer, and dry at 90°C for 8.0h to obtain a brick red powder (0.0690g, 45.3% yield).

Embodiment 3

[0032] Synthesis of PCN-224(Mn)-d: In a 35mL pressure-resistant reaction tube, [T(4-(4-COOH)P)PPMn(II)](0.1152g, 0.1mmol), ZrCl 4 (0.1400g, 0.6mmol), benzoic acid (5.4000g, 44.3mmol) was dissolved in 16.0mL DMF, ultrasonic 30min until completely dissolved. The mixture was placed in an electric constant temperature blast drying oven at 120° C. for 48.0 hours of static reaction. After the reaction is completed, turn off the heating, cool to room temperature naturally, filter the crude product with suction and rinse with DMF and acetone successively, then transfer to a 10.0mL centrifuge tube, centrifuge at 5.0m (3000.0rpm) in a low-speed centrifuge, pour out the upper layer liquid, Dry DMF leaching (3×8.0mL) until the upper layer is clear, dry acetone leaching (3×8.0mL) until the upper layer is clear, remove the solid in the lower layer, and dry at 90°C for 8.0h to obtain a brick red powder (0.0670g, 43.3% yield).

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Abstract

The invention provides a method for synergistically catalyzing oxidation of cycloalkane by using metalloporphyrin MOFs PCN-224(Mn) / Zn (II) salt. The method comprises the following steps: dispersing PCN-224(Mn) (0.001%-5% g / mol) and Zn (II) salt (0.01%-10% mol / mol) in cycloalkane, sealing a reaction system, conducting heating to 90-150 DEG C while stirring, introducing an oxidant, keeping the reaction system at a set temperature and a set pressure, carrying out stirring and reacting for 2.0-24.0 h, and conducting post-treatment on a reaction solution so as to obtain products, namely cloalkyl alcohol and cycloalkyl ketone. The method provided by the invention has the advantages of high selectivity of cycloalkyl alcohol and cycloalkyl ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of cycloalkyl hydroperoxide is low, and a safety coefficient is high The invention provides the efficient, feasible and safe method for synthesizing alkyl alcohol and cycloalkyl ketone through selective catalytic oxidation of cycloalkane.

Description

technical field [0001] The invention relates to a method for synergistically catalyzing the oxidation of cycloalkane to cycloalkanol and cycloalkanone by metalloporphyrin MOFs PCN-224(Mn) / Zn(II) salt, which belongs to the field of industrial catalysis and fine organic synthesis. Background technique [0002] Catalytic oxidation of naphthenes is a very important conversion process in the chemical industry. The oxidation products cycloalkanol and cycloalkanone are not only important organic solvents, but also important fine chemical intermediates, widely used in pesticides, medicines, dyes, surface Synthesis of fine chemical products such as active agents and resins, especially the production of polyamide fibers nylon-6 and nylon-66. At present, the industrial catalytic oxidation of naphthenes is mainly based on homogeneous Mn 2+ or Mn 2+ As a catalyst, oxygen (O 2 ) is an oxidizing agent, which is carried out at 150°C to 170°C. The main problems are that the reaction tempe...

Claims

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Application Information

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IPC IPC(8): C07C29/50C07C35/08C07C45/33C07C49/403B01J31/22B01J31/26C07C29/76C07C29/78C07C29/80C07C45/81C07C45/82
CPCC07C29/50C07C45/33B01J31/183B01J31/26B01J31/1691C07C29/76C07C29/78C07C29/80C07C45/81C07C45/82C07C2601/14B01J2231/70B01J2531/025B01J2531/72C07C35/08C07C49/403
Inventor 佘远斌黄浩沈海民
Owner ZHEJIANG UNIV OF TECH
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