阅读说明：本技术 一种甲基次磷酸酯的合成方法 (Synthesis method of methylphosphinic acid ester ) 是由 姜宇华 周炜 陈佳 纪雷 夏易能 于 2020-06-30 设计创作，主要内容包括：本发明涉及一种甲基次磷酸酯的合成方法,其以甲基二氯化膦和醇为原料进行反应制得,所述反应在连续流反应器中进行。本发明的工艺流程简单,副反应少,能够降低有毒物质的产生,后处理成本低,生产效率高,收率和纯度高,安全性好,适合工业化生产。(The invention relates to a synthesis method of methyl hypophosphite, which is prepared by taking methyl phosphine dichloride and alcohol as raw materials to carry out reaction, wherein the reaction is carried out in a continuous flow reactor. The method has the advantages of simple process flow, less side reaction, capability of reducing the generation of toxic substances, low post-treatment cost, high production efficiency, high yield and purity and good safety, and is suitable for industrial production.)

1. The synthesis method of methyl hypophosphite takes methyl phosphine dichloride and alcohol as raw materials to carry out reaction, and is characterized in that: the reaction is carried out in a continuous flow reactor (1).

2. The method for synthesizing methylphosphinic acid ester according to claim 1, wherein: the continuous flow reactor (1) is a micro-channel reactor, a pipeline reactor or a flat-plate reactor.

3. The method for synthesizing methylphosphinic acid ester according to claim 1, wherein: the continuous flow reactor (1) comprises a plurality of reaction parts (11) which are connected in series in sequence, the alcohol is introduced from the first reaction part (11) of the continuous flow reactor (1), and the methyl phosphine dichloride is introduced from the second reaction part (11) of the continuous flow reactor (1) and is mixed and reacted with the alcohol.

4. The method for synthesizing methylphosphinic acid ester according to claim 1, wherein: the continuous flow reactor (1) comprises a first preheating part (12) for introducing the methyl phosphine dichloride, a second preheating part (13) for introducing the alcohol, and a plurality of reaction parts (11) which are communicated with the first preheating part (12) and the second preheating part (13) and are connected in series in sequence.

5. The method for synthesizing methylphosphinic acid ester according to any one of claims 1 to 4, wherein: the flow rate of the methyl phosphine dichloride is controlled to be 5-50 g/min, preferably 5-35 g/min, and more preferably 5-10 g/min.

6. The method for synthesizing methylphosphinic acid ester according to any one of claims 1 to 4, wherein: the flow rate of the alcohol is controlled to be 5-100 g/min, preferably 10-70 g/min, and more preferably 10-15 g/min.

7. The method for synthesizing methylphosphinic acid ester according to any one of claims 1 to 4, wherein: the residence time of the raw materials in the continuous flow reactor (1) is controlled to be 15 s-30 min, preferably 1-5 min.

8. The method for synthesizing methylphosphinic acid ester according to claim 1, wherein: controlling the reaction temperature in the continuous flow reactor (1) to be 0-150 ℃, wherein the molar ratio of the methyl phosphine dichloride to the alcohol is 1: 2-50, preferably 1: 5-10, and more preferably 1: 3.1 to 10.

9. The method for synthesizing methylphosphinic acid ester according to claim 1, wherein: the discharge from the continuous flow reactor (1) is passed through an evaporator (3) to separate the methylphosphinic acid esters from the by-products.

10. The method for synthesizing methylphosphinic acid ester according to claim 9, wherein: the vacuum degree of a vaporization chamber in the evaporator (3) is controlled to be-0.095 to 100Pa, preferably 100 to 300 Pa.

11. The method for synthesizing methylphosphinic acid ester according to claim 9, wherein: the temperature in the evaporator (3) is controlled to be 0-100 ℃, preferably 35-100 ℃, and more preferably 60-100 ℃.

12. The method for synthesizing methylphosphinic acid ester according to claim 9, wherein: and after the byproducts are condensed by a cold air cooler, hydrogen chloride is collected by an absorption tower, and the rest byproducts are collected by a receiving groove.

Technical Field

The invention belongs to the field of organic chemical synthesis, and particularly relates to a synthetic method of methylphosphinic acid ester.

Background

Disclosure of Invention

The invention aims to provide a synthetic method and production equipment of methylphosphinic acid ester, which have high production efficiency and simple post-treatment.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a synthesis method of methyl hypophosphite, which is prepared by taking methyl phosphine dichloride and alcohol as raw materials to perform reaction, wherein the reaction is performed in a continuous flow reactor.

Preferably, the continuous flow reactor is a microchannel reactor, a pipeline reactor or a flat-plate reactor, such as a G1 reactor, AFR reactor, etc. of Corning.

Preferably, the continuous flow reactor comprises a plurality of reaction parts which are connected in series in sequence, the alcohol is introduced from the first reaction part of the continuous flow reactor, and the methyl phosphine dichloride is introduced from the second reaction part of the continuous flow reactor and is mixed and reacted with the alcohol.

Preferably, the continuous flow reactor comprises a first preheating part for introducing the methyl phosphine dichloride, a second preheating part for introducing the alcohol, and a plurality of reaction parts which are communicated with the first preheating part and the second preheating part and are connected in series in sequence.

Preferably, the flow rate of the methyl phosphine dichloride is controlled to be 5-50 g/min, preferably 5-35 g/min, and more preferably 5-10 g/min.

Preferably, the flow rate of the alcohol is controlled to be 5-100 g/min, preferably 10-70 g/min, and more preferably 10-15 g/min.

Preferably, the residence time of the raw materials in the continuous flow reactor is controlled to be 15 s-30 min, preferably 1-5 min.

Preferably, the reaction temperature in the continuous flow reactor is controlled to be 0-150 ℃.

Preferably, the molar ratio of the methyl phosphine dichloride to the alcohol is 1: 2-50, preferably 1: 5-10, and more preferably 1: 3.1 to 10.

Preferably, the discharge from said continuous flow reactor is passed through an evaporator to separate said methylphosphinic acid esters from said by-products.

Further preferably, the degree of vacuum of the vaporization chamber in the evaporator is controlled to be-0.095 MPa to 100Pa, preferably 100Pa to 300 Pa.

Further preferably, the temperature in the evaporator is controlled to be 0-100 ℃, preferably 35-100 ℃, and further preferably 60-100 ℃.

Further preferably, after the byproduct is condensed by a cold air cooler, hydrogen chloride is collected by an absorption tower, and the rest byproduct is collected by a receiving groove.

The second aspect of the invention provides a production device of methyl hypophosphite, which comprises a continuous flow reactor, an evaporator and a first receiving tank, wherein the continuous flow reactor is provided with a first inlet for introducing methyl phosphine dichloride and a second inlet for introducing alcohol, the evaporator is communicated with the outlet of the continuous flow reactor, and the first receiving tank is communicated with the outlet of the evaporator and is used for collecting the methyl hypophosphite.

Preferably, the continuous flow reactor is a microchannel reactor, a pipeline reactor or a flat-plate reactor, such as a G1 reactor, AFR reactor, etc. of Corning.

Preferably, said continuous flow reactor comprises a plurality of reaction sections connected in series, said first inlet being disposed on a second of said reaction sections and said second inlet being disposed on a first of said reaction sections.

Preferably, the continuous flow reactor comprises a first preheating part provided with the first inlet, a second preheating part provided with the second inlet, and a plurality of reaction parts which are communicated with the first preheating part and the second preheating part and are sequentially connected in series.

Preferably, said production apparatus further comprises a first intermediate tank disposed between said continuous flow reactor and said evaporator, and a pump installed on a pipe of said first intermediate tank and said evaporator.

Further preferably, a liquid level meter is arranged on the first middle groove.

Preferably, the inlet of the evaporator is located at the upper part of the evaporator, and the outlet of the evaporator is located at the lower part of the evaporator.

Preferably, the production equipment further comprises a condenser communicated with the evaporator, a second receiving groove communicated with the condenser and used for collecting byproducts, a vacuum pump communicated with the second receiving groove, and an absorption tower communicated with the vacuum pump.

Further preferably, the first receiving groove and the second receiving groove are provided with liquid level meters.

Further preferably, the production equipment further comprises a second intermediate tank, wherein the upper part of the second intermediate tank is respectively communicated with the lower part of the evaporator and the inlet of the condenser, and the lower part of the second intermediate tank is communicated with the first receiving tank or a pipeline between the first receiving tank and the evaporator.

Further preferably, the top of the first receiving tank is communicated with the condenser.

Preferably, the evaporator comprises a falling film evaporator or a wiped film evaporator.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:

the method has the advantages of simple process flow, less side reaction, capability of reducing the generation of toxic substances, low post-treatment cost, high production efficiency, high yield and purity and good safety, and is suitable for industrial production.

Drawings

FIG. 1 is a schematic configuration diagram of a production apparatus of example 1;

FIG. 2 is a schematic structural view of a production apparatus of example 2;

wherein, 1, a continuous flow reactor; 2. a first intermediate tank; 3. an evaporator; 4. a pump; 5. a first receiving groove; 6. a second intermediate tank; 7. a condenser; 8. a second receiving groove; 9. a vacuum pump; 10. a liquid level meter; 11. a reaction section; 12. a first preheating section; 13. a second preheating part.

Detailed Description

The technical solution of the present invention is further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.

The apparatus for producing methylphosphinic acid ester as shown in FIGS. 1 and 2 comprises a continuous flow reactor 1 having a first inlet for introducing methylphosphine dichloride and a second inlet for introducing alcohol, a first intermediate tank 2 having a top communicating with an outlet of the continuous flow reactor 1, an evaporator 3 having a top communicating with a bottom of the first intermediate tank 2, a pump 4 installed on a pipe of the first intermediate tank 2 and the evaporator 3, a first receiving tank 5 communicating with a bottom of the evaporator 3 for collecting methylphosphinic acid ester, a second intermediate tank 6 with the upper part communicated with the lower part of the evaporator 3, a condenser 7 with the top part communicated with the upper part of the second intermediate tank 6, a second receiving tank 8 with the top part communicated with the bottom part of the condenser 7 and used for collecting byproducts (alkyl chloride and alcohol), a vacuum pump 9 communicated with the top part of the second receiving tank 8, and an absorption tower communicated with the vacuum pump 9. The bottom of the second intermediate tank 6 is communicated with the top of the first intermediate tank 2 or the pipeline between the first intermediate tank 2 and the evaporator 3, and the top of the first receiving tank 5 is communicated with the top of the condenser 7. The first intermediate tank 2, the first receiving tank 5 and the second receiving tank 8 are respectively provided with a liquid level meter 10.

Wherein the continuous flow reactor 1 is a microchannel reactor, a pipeline reactor or a flat-plate reactor, such as a G1 reactor, an AFR reactor, etc. of Corning Corp. The evaporator 3 includes a falling film evaporator or a wiped film evaporator.