No-solvent process of epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide

A technology of epoxycyclohexane and hydrogen peroxide, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of activity or selectivity reduction and production capacity reduction , the process is difficult to industrialize and other issues, to achieve high selectivity and yield, reduce interfacial tension, simple reaction system effect

Inactive Publication Date: 2007-08-22
ZHENGZHOU UNIV
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Problems solved by technology

Due to the requirements of green chemistry, the method of using hydrogen peroxide as a green oxidizing agent has been put on the agenda, but the chemical properties of epoxycyclohexane are active and easily hydrolyzed, so the existing methods for preparing cyclohexene oxide from cyclohexene with hydrogen peroxide are general A large amount of organic solvents such as chloroform, dichloromethane, 1,2-dichloroethane, etc. will be added to slow down the hydrolysis of cyclohexane [Li Kunlan, Zhou Ning, Xi Zuwei. Quaternary in solvents and heteropolyacid salts] The effect of ammonium cations on the control of phase transfer catalysis in cyclohexene epoxidation [J]. Acta Catalytica Sinica, 2002, 23(2): 125-126]. The concentrations are respectively 13%-16% of cyclohexene, 11%-15% of epoxycyclohexane, and 65%-75% of dichloroethane, and the amount of solvent accounts for almost more than 2/3. It will reduce the production capacity, increase the recovery cost of solvent and then increase the production cost of epoxycyclohexane. On the other hand, because of the use of toxic and harmful organic solvents, the advantages of hydrogen peroxide as a green oxidant are greatly weakened
In 1996, Kazuhiko Sato et al [AHalide-Free Method for Olefin Epoxidation with 30% ydrogen Peroxide[J].Bull.Chem.Soc.Jpn., 1997, 70(4):905-915.][A Practical Method for Epoxidation ofTerminal Olefins with 30% Hydrogen Peroxide under Halide-Free Conditions[J].J.Org.Chem., 1996,61(23):8310-8311.] have carried out the exploration of preparing olefin epoxide by solvent-free method, but this The method is mainly applied to the preparation of epoxides of terminal olefins, and cannot be used for the preparation of epoxides of olefins sensitive to water, and the catalytic system used in the reaction system is composed of Na

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  • No-solvent process of epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide
  • No-solvent process of epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide
  • No-solvent process of epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide

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Embodiment 1

[0036] Example 1, cyclohexene 40mL, 35% hydrogen peroxide 20mL (molar ratio 1.75: 1), chloromethylated polystyrene (PS) supports N, N-dimethyl octadecyl phosphotungstic heteropoly acid (PS-CH 2 N(CH 3 ) 2 C 18 h 37 h 2 PW 4 o 16 )2g, NaHCO 3 0.05g, react at 50°C for 6h, filter out chloromethylated polystyrene (PS) supported by N,N-dimethyloctadecyl phosphotungstic heteropolyacid, separate the oil phase, and rectify to obtain epoxy Cyclohexane. Gas chromatographic analysis of the oil phase and determination of the hydrogen peroxide content in the water phase show that the conversion rate of hydrogen peroxide can reach 95.1%, the selectivity of epoxycyclohexane can reach 98.5%, and the yield of epoxycyclohexane can reach 93.3%. The infrared spectrum data of product epoxy cyclohexane is as follows (cm -1 ): 2936.8, 2936.8, 2672.9, 1458.5, 1437.9, 1356.9, 1260.0, 1187.4, 1168.3, 1086.6, 1036.6, 989.1, 966.2, 890.8, 877.0, 837.1, 780.9, 746.0.

[0037] Under the above-m...

Embodiment 2

[0038] Example 2, cyclohexene 40mL, 30% hydrogen peroxide 25mL (molar ratio 1.6:1), chloromethylated polystyrene supported polyethylene glycol N, N-dimethyl octadecyl ammonium phosphotungstic heteropoly Acid (PS-(OCH 2 CH 2 ) 15 N(CH 3 ) 2 C 18 h 37 NaHPW 4 o 16 )2.5g, CaCl 2 0.025g, react at 40°C for 8h, filter out chloromethylated polystyrene-supported polyethylene glycol N,N-dimethyloctadecylammonium phosphotungstic heteropolyacid, separate the oil phase, and rectify to obtain cyclo Oxycyclohexane. The infrared spectroscopic data of product epoxycyclohexane is as embodiment 1, and oil phase carries out gas chromatography analysis, and water phase measures hydrogen peroxide content as can be known, and the conversion rate of hydrogen peroxide reaches 97.4%, and the selectivity of epoxycyclohexane can reach 97.5%, The yield of epoxycyclohexane can reach 94.5%.

[0039] Under the above reaction conditions, catalyst A component --- chloromethylated polystyrene suppo...

Embodiment 3

[0040] Example 3, cyclohexene 40mL, 30% hydrogen peroxide 20mL (molar ratio 2: 1), chloromethylated polystyrene resin supported N, N-dimethyldodecamonium phosphotungstic heteropolyacid (PS-CH 2 N(CH 3 ) 2 C 12 h 25 h 2 PW 4 o 16 ) 0.2g, KCl 0.2g, react at 60°C for 4h, filter out chloromethylated polystyrene resin supported N,N-dimethyldodecamonium phosphotungstic heteropolyacid, separate the oil phase, and rectify to obtain ring Oxycyclohexane. The infrared spectroscopic data of product epoxycyclohexane is as embodiment 1, and oil phase carries out gas chromatography analysis, and water phase measures hydrogen peroxide content as can be known, and the conversion rate of hydrogen peroxide reaches 94.3%, and the selectivity of epoxycyclohexane can reach 95.4%, The yield of epoxycyclohexane can reach 90.0%.

[0041] Under the above reaction conditions, catalyst A component --- chloromethylated polystyrene resin supported N, N-dimethyldodecamonium phosphotungstic heteropol...

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Abstract

The present invention discloses process of epoxidizing cyclohexene with hydrogen peroxide to prepare cyclohexane epoxide. The process includes the following steps: adding hydrogen peroxide and composite catalyst into cyclohexene to react at 20-70 deg.c for 2-10 hr, filtering off catalyst after finishing reaction, separating oil phase, and rectifying to obtain cyclohexane epoxide. The composite catalyst consists of component A and component B, the component A is C-[(R1)n0-(OCH2OCH2)n1-YR2R3R4]m1(Q1)m2Xn2D, and component B is salt. The process of the present invention has the features of no use of solvent, high catalytic activity, high reaction selectivity, high yield, recoverability of component A of catalyst and no pollution.

Description

technical field [0001] The invention relates to a method for preparing epoxycyclohexane by oxidizing cyclohexene with hydrogen peroxide. Background technique [0002] Cyclohexene Oxide is a very versatile organic intermediate, which can be widely used in a wide range of fields such as epoxy resins, surfactants, paints, adhesives, medicines, pesticides, and polymer materials. Due to the requirements of green chemistry, the method of using hydrogen peroxide as a green oxidizing agent has been put on the agenda, but the chemical properties of epoxycyclohexane are active and easily hydrolyzed, so the existing methods for preparing cyclohexene oxide from cyclohexene with hydrogen peroxide are general A large amount of organic solvents such as chloroform, dichloromethane, 1,2-dichloroethane, etc. will be added to slow down the hydrolysis of cyclohexane [Li Kunlan, Zhou Ning, Xi Zuwei. Quaternary in solvents and heteropolyacid salts] The effect of ammonium cations on the control o...

Claims

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Application Information

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IPC IPC(8): C07D301/12C07D303/06B01J31/06B01J31/02
Inventor 章亚东王振兴苏媛
Owner ZHENGZHOU UNIV
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