A kind of preparation method of 1,10-decanediol

A technology of decanediol and decenoic acid ester, which is applied in the field of preparation of 1,10-decanediol, can solve the problems of low total yield, low total product yield, difficult practical application value, etc., and increase the conversion rate From and selectivity, improving yield and selectivity, and solving the effect of product separation difficulties

Active Publication Date: 2021-01-15
WANHUA CHEM GRP CO LTD
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0006] The traditional manufacturing method has the following problems: long production cycle, poor product quality, toxic phenolic substances, corrosion of equipment, and pollution of the environment
[0009] Hydrogenation reaction is one of the commonly used reaction types in industry, but due to the extremely flammable and explosive risks of hydrogen, hydrogenation reaction is often accompanied by great danger; at the same time, in order to improve selectivity and conversion rate, hydrogenation reaction is generally It is carried out under high pressure, which requires a series of high-pressure-resistant equipment such as high-pressure reactors, which will not only increase equipment investment, but also increase the complexity of operation. High-pressure reactions also have the risk of hydrogen leakage, and the safety hazard is very prominent.
Therefore, although the above method provides a new idea for the synthesis of decanediol, the total yield is too low to have practical application value, and the high-pressure hydrogenation reaction increases equipment investment and safety hazards
[0010] As can be seen from the above, the preparation of decanediol from castor oil has the disadvantages of harsh reaction conditions and prominent waste problems; the two-step method of preparing decanediol with 1,9-decadiene as a raw material has low total product yields and poor equipment Disadvantages such as large investment and high risk of operation

Method used

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  • A kind of preparation method of 1,10-decanediol
  • A kind of preparation method of 1,10-decanediol
  • A kind of preparation method of 1,10-decanediol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055]Add 184.15 g 9-decenoic acid methyl ester, 209.3 g tert-butanol solution containing 47.3 wt% tert-butyl hydroperoxide (TBHP) and 65.2 mg molybdenum acetylacetonate to the flask, replace the flask with nitrogen 3 times, Reaction at 60℃ for 2 hours, the conversion rate of 9-decenoic acid methyl ester is 99.8% by gas-phase internal standard method (qualitative and quantitative) and 1H NMR measurement (assisted qualitative), the choice of 9,10-epoxydecanoic acid methyl ester The purity is 98.6%. 191.1 grams of pure methyl 9,10-epoxydecanoate is obtained by distillation. Starting from methyl 9-decenoate, the yield of methyl 9,10-epoxydecanoate is 95.5% .

[0056]Add 70.0 g of 9,10-epoxydecanoic acid methyl ester and 1 ml of catalyst solution (615 mg of PdCl2Dissolve in 1000 ml of dichloromethane, take 1 ml of it), add 440.9 g of ammonium formate and 616 mg of vitamin C, replace the flask with nitrogen 3 times, react at 50°C for 300 minutes, measured by gas phase internal standard meth...

Embodiment 2

[0058]Add 200 grams of 9-decenoic acid methyl ester, 506.6 grams of ethylbenzene solution containing 35.5% by weight of ethylbenzene hydrogen peroxide (EBHP) and 1.84 grams of molybdenum naphthenate to the flask. Replace the flask with nitrogen 3 times at 200°C. After 3.5 hours of reaction, the conversion rate of 9-decenoic acid methyl ester was determined by gas phase internal standard method and 1HNMR to be 99.2%, the selectivity of 9,10-epoxydecanoic acid methyl ester was 98.3%, and 9,10 was obtained by distillation. -209.5 grams of pure methyl epoxydecanoate. Starting from methyl 9-decenoate, the yield of methyl 9,10-epoxydecanoate is 96.4%.

[0059]Add 90.0 g 9,10-epoxydecanoic acid methyl ester and 1 ml catalyst solution (5.034 g Pd(OAc) to the reaction flask2Dissolve in 1000ml of dichloromethane, take 1ml of it), add 1528.7g of sodium formate and 194mg of vitamin E, replace the flask with nitrogen 3 times, react at 80°C for 10 seconds, determine by gas phase internal standard me...

Embodiment 3

[0061]Add 120 grams of 9-decenoic acid methyl ester, 204 grams of cumene solution containing 55.8 wt% cumene hydroperoxide (CHP) and 0.39 grams of molybdenum stearate to the flask. Replace the flask with nitrogen 3 times. After reacting at 120°C for 12 hours, the conversion rate of 9-decenoic acid methyl ester was determined by gas-phase internal standard method and 1HNMR to be 99.5%, and the selectivity of 9,10-epoxydecanoic acid methyl ester was 99.1%. 9 , 124 grams of pure 10-epoxydecanoate methyl ester, starting from 9-decenoic acid methyl ester, the yield of 9,10-epoxydecanoic acid methyl ester is 95.1%.

[0062]Add 150.0 g of 9,10-epoxydecanoic acid methyl ester and 1 ml of catalyst solution (96.6 mg of CoCl2Dissolve in 1000 ml of dichloromethane, take 1 ml of it), then add 737.2 g of formic acid / triethylamine azeotrope (the content of formic acid is 46.8wt%, based on the total mass of formic acid and triethylamine azeotrope) And 2.7 g of glucose, replace the flask with nitrogen ...

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Abstract

The present invention relates to a preparation method of 1,10-decanediol. The method is characterized by using 9-decenoic acid ester as a raw material, adopting a two-step epoxidation-transfer hydrogenation reaction to obtain 1,10-decanediol, and the epoxidation step uses a molybdenum catalyst and an organic peroxide, and 9 , The yield of 10-epoxidized methyl decanoate is greater than 95%; the hydrogen donor is used in the transfer hydrogenation reaction to replace hydrogen, and a reducing additive is introduced to reduce the epoxy group and the ester group to a hydroxyl group in one step under normal pressure. The method does not need to use high-pressure hydrogen, which not only reduces the investment of the reaction device, reduces the complexity of the operation, but also increases the safety of the reaction, improves the yield of the target product, and solves the difficulty of product separation and a large number of difficulties in the traditional production technology. To deal with problems such as industrial waste water, the raw material 9-decenoate is cheap and easy to obtain, the preparation process is simple, the equipment requirements are not high, and it is suitable for industrial production.

Description

Technical field[0001]The invention relates to a preparation method of 1,10-decanediol, which belongs to the field of fine organic chemical industry.Background technique[0002]1,10-Decanediol (1,10-Decanediol), also known as 1,10-dihydroxydecane, is an important chemical raw material and pharmaceutical intermediates, mainly used in the manufacture of medicines and materials, such as the production of double Iododecane is used to prepare medicines such as antibacterial and antimycotic drugs (double) clonidine and octenidine, and can also be used to prepare functional materials, adhesives, polymer materials, etc., and has a wide range of uses.[0003]In the traditional process, 1,10-decanediol is firstly prepared from ricinoleic acid through high-temperature cracking to obtain 1,10-sebacic acid, and then obtained through esterification and hydrogenation reactions. Among them, both esterification and hydrogenation reduction are very important. Mature reaction, so castor oil pyrolysis to pr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C29/149C07C31/20C07D301/19C07D303/42
CPCC07C29/149C07D301/19C07D303/42C07C31/20Y02P20/52
Inventor 杜旺明王明永陈海波张彦雨赵晶边新建丰茂英王文黎源
Owner WANHUA CHEM GRP CO LTD
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