CN112608209A

CN112608209A - Green method for synthesizing MDPES raw material phenylacetylene without solvent

Info

Publication number: CN112608209A
Application number: CN202011395312.9A
Authority: CN
Inventors: 陈王志; 杨如; 肖鸿; 马可伟; 郭春燕; 曾庆豪; 李丹
Original assignee: Great Zhuhai Composites Co ltd
Current assignee: Great Zhuhai Composites Co ltd
Priority date: 2020-12-03
Filing date: 2020-12-03
Publication date: 2021-04-06

Abstract

The invention relates to a green new method for synthesizing MDPES raw material phenylacetylene without solvent, which comprises the steps of mixing and stirring 1, 2-dibromoethylbenzene, alkali and a catalyst EB-D uniformly, heating to 40-160 ℃ for reaction to be complete, filtering to remove bromide, filtering to separate a mixture of solid and liquid, filtering again after filtrate is still turbid, distilling the filtrate to obtain the product phenylacetylene, wherein the product detection purity is more than 98 percent, the method overcomes the defects of multiple steps, complex post-treatment, expensive raw materials, high safety risk, large environmental protection pressure, low product purity and the like caused by using the raw materials such as bromine, carbon tetrachloride, methanol, metallic sodium, sodium hydride, lithium amide, palladium chloride and the like in the traditional process, and the specific synthetic route is as follows: under the condition of no solvent, 1, 2-dibromo ethyl benzene is used as a starting material, alkali is used as a dehalogenation agent, a catalyst EB-D is added, one-step dehalogenation reaction is carried out at 40-160 ℃ until the completion, and then filtration and distillation are carried out, so that MDPES raw material phenyl acetylene is obtained.

Description

Green method for synthesizing MDPES raw material phenylacetylene without solvent

Technical Field

The invention relates to a green method for synthesizing MDPES raw material phenylacetylene without solvent, belonging to the field of new polymer materials and the field of biological medicines.

Background

Phenylacetylene, also known as phenylacetylene, can be used as a polymeric monomer for the preparation of polymers due to unsaturation at the carbon-carbon triple bond; due to the conjugation, the phenyl acetylene can be used as a luminescent material and an electroluminescent material, is an essential intermediate for preparing the symmetrical aryne linear condensed ring chemical luminescent agent, and can be dissolved in ethanol, diethyl ether and acetone.

The most important function of the phenylacetylene is to prepare polymer resin, the polyphenylacetylene has the characteristics of light guide, electric conduction, paramagnetic energy migration, conversion and the like, the performance is stable, the polyphenylacetylene is a novel conductive high molecular material, and the phenylacetylene derivative polymer is widely used for liquid crystal materials, luminescent materials, nonlinear optical materials, gas separation membranes, magnetic materials and the like. Phenyl acetylene is also an important organic synthesis intermediate, and has very wide application prospect in the fields of biomedicine, medicine, pesticide and the like. The phenylacetylene of the company is mainly used for preparing a silicon alkyne resin high-end composite material and MDPES (modified poly-phenylethynyl amine), and the silicon alkyne resin high-end composite material and MDPES are widely applied to the fields of military nuclear power, aerospace and aviation, integrated circuit boards, 5G high-frequency communication and the like.

The preparation method of phenylacetylene has been reported and has no patent protection, and the comprehensive analysis mainly comprises the following four routes:

(1) adding bromine into styrene, and removing hydrogen bromide from lithium amide. Its advantage is high output rate up to 90%. However, lithium amide needs to be prepared by reacting metal lithium with liquid ammonia, and the conditions are harsh, so that industrial production is difficult to realize.

(2) Beta-bromostyrene and potassium hydroxide solid are melted and reacted to prepare the catalyst. The method is a high-temperature reaction under a strong alkali condition, has high requirements on equipment materials, is relatively serious in equipment corrosion, high in energy consumption, serious in pollution and poor in production operation feasibility. The yield is low and is less than 50 percent.

(3) Adding bromine into styrene for bromination, removing hydrogen bromide by potassium hydroxide at high temperature in a methanol system, and distilling by water vapor to obtain the styrene. The dehydrobromination reaction in the route is violent in heat release, so that the material is easy to spray, the safety production risk is high, a large amount of high-concentration high-salinity sewage is generated by steam distillation, and the environmental protection pressure is high. The yield is low, and the product purity is not high, about 96 percent.

(4) The aryl halide and the derivatives thereof are used as raw materials, noble metals such as rhodium, platinum, palladium, nickel, ketone and the like are used as catalysts, and the aryl halide is prepared by Sonogashira reaction or improved Sonogashira coupling reaction. The method adopts a pyridine/triethylamine mixed solvent which is difficult to remove, and the post-treatment comprises the complex processes of removing the solvent by decompression, washing, filtering, column chromatography separation, concentration, recrystallization and the like, thus being not beneficial to industrial production and environmental protection requirements. And the use of noble metals such as palladium and the like has high cost, and the industrial application of the catalyst is seriously limited.

The application of the phenylacetylene is very wide, but the popularization and the application of the phenylacetylene are severely limited by factors such as high production safety, environmental protection pressure, high price cost, low quality purity and the like. Therefore, the development of the economical, practical, high-quality, low-price and environment-friendly phenylacetylene production process has very important practical significance.

SUMMARY OF THE PATENT FOR INVENTION

The invention aims to provide a green method for synthesizing MDPES raw material phenylacetylene without solvent, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the green method for synthesizing MDPES raw material phenylacetylene without solvent comprises the following steps:

step 1:1, 2-dibromo ethyl benzene, alkali and a catalyst EB-D are mixed and stirred uniformly, heated to 40-160 ℃ to react completely, and filtered to remove bromide.

Step 2: filtration can separate a mixture of solids and liquid, and after filtration the filtrate is still cloudy and can be filtered again.

And step 3: distilling the filtrate to obtain a product of phenylacetylene, wherein the product detection purity is more than 98%;

preferably, in the step 1, the reaction system does not contain other solvents such as methanol and tetrahydrofuran.

Preferably, in the step 1, the base is inorganic or organic base such as triethylamine, sodium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium amide, sodium methoxide, sodium ethoxide, and the like, and includes single base and mixed base of two or more.

Preferably, in the step 1, the reaction temperature is 40 ℃ to 160 ℃, and the reaction temperature is preferably 80 ℃ to 120 ℃.

Preferably, in the step 3, the distillation method is a distillation separation method such as vacuum distillation, atmospheric distillation, vacuum rectification, atmospheric rectification, pressure rectification, short path distillation, thin film distillation, and the like, and includes a single distillation method and two or more mixed distillation separation methods, preferably a vacuum distillation separation method.

Preferably, in the step 1, the molar ratio of the 1, 2-dibromoethylbenzene to the base is 1: 1-10, and the preferred molar ratio is 1: 2.1.

preferably, in the step 3, the purity of the product is detected by using a gas chromatograph.

Preferably, in the step 2, the filter paper is closely attached to the inner part of the funnel, the edge of the filter paper is lower than the edge of the funnel, the liquid level of the filtrate is lower than the edge of the filter paper, the mouth of the beaker is closely attached to the draining glass rod, and the lower end of the funnel is closely attached to the inner wall of the beaker.

Compared with the prior art, the invention has the following beneficial effects:

the technical problem to be solved by the invention is as follows: the method overcomes the defects of multiple reaction steps, high safety and environmental protection pressure, high price cost, low quality purity and the like in the prior art for preparing the phenylacetylene, and provides a phenylacetylene synthetic route which has high utilization rate of raw materials, recoverable solvent, high product yield and high product purity, is green and environment-friendly and meets the requirement of industrial mass production.

Synthetic reaction equation of phenylacetylene

Drawings

FIG. 1 is a graph showing the results of an analysis according to an embodiment of the present invention;

FIG. 2 is a graph of the results of two analyses performed in accordance with the present invention;

FIG. 3 is a graph showing the results of the analysis in the example of the present invention;

FIG. 4 is a graph showing the analysis results of the patent example of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by a person skilled in the art based on the embodiments in the patent of the invention without any inventive work belong to the protection scope of the patent of the invention.

Referring to fig. 1-4, the present invention provides a technical solution: the green method for synthesizing MDPES raw material phenylacetylene without solvent comprises the following steps:

mixing and stirring 1, 2-dibromoethylbenzene, alkali and a catalyst EB-D uniformly, heating to 40-160 ℃ for reaction to be complete, filtering to remove bromide, wherein the reaction system does not contain other solvents such as methanol and tetrahydrofuran, the alkali is inorganic and organic alkali such as triethylamine, sodium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium amide, sodium methoxide and sodium ethoxide, the reaction system comprises single alkali and two or more mixed alkali, the reaction temperature is 40-160 ℃, the preferred reaction temperature is 80-120 ℃, the molar ratio of 1, 2-dibromoethylbenzene to alkali is 1: 1-10, and the preferred molar ratio is 1: 2.1, filtering to separate a mixture of solid and liquid, filtering again after the filtrate is still turbid, carrying out filtering operation, wherein the filter paper is tightly attached to the inner part of a funnel, the edge of the filter paper is lower than the edge of the funnel, the liquid level of the filtrate is lower than the edge of the filter paper, the opening of a beaker is tightly attached to a drainage glass rod, the lower end of the funnel is tightly attached to the inner wall of the beaker, and the filtrate is distilled to obtain a product phenylacetylene, wherein the product detection purity is higher than 98 percent.

The first embodiment is as follows:

52.8g (0.2mol) of 1, 2-dibromoethylbenzene, a catalyst EB-D100g and 22.68g (0.42mol) of sodium methoxide are added into a 500ml three-neck flask, the mixture is stirred and mixed uniformly, the mixture is heated to 60-80 ℃ to react until the residue of the 1, 2-dibromoethylbenzene is less than or equal to 0.5 percent, bromide is removed by filtration, and the filtrate is rectified to obtain phenylacetylene with the yield of 56.8 percent and the GC purity of 99.31 percent.

Example two:

52.8g (0.2mol) of 1, 2-dibromoethylbenzene, a catalyst EB-D100g and 16.8g (0.42mol) of sodium hydroxide are added into a 500ml three-neck flask, the mixture is stirred and mixed uniformly, the mixture is heated to 100-120 ℃ to react until the residue of the 1, 2-dibromoethylbenzene is less than or equal to 0.5 percent, bromide is removed by filtration, and the filtrate is subjected to pressure distillation to obtain phenylacetylene with the yield of 53.2 percent and the GC purity of 99.66 percent.

Example three:

52.8g (0.2mol) of 1, 2-dibromoethylbenzene, a catalyst EB-D100g and 23.56g (0.42mol) of potassium hydroxide are added into a 500ml three-neck flask, the mixture is stirred and mixed uniformly, the mixture is heated to 120-140 ℃, the reaction is carried out until the residue of the 1, 2-dibromoethylbenzene is less than or equal to 0.5 percent, bromide is removed by filtration, and the filtrate is rectified to obtain phenylacetylene with the yield of 58.4 percent and the GC purity of 99.67 percent.

Example four:

52.8g (0.2mol) of 1, 2-dibromoethylbenzene, a catalyst EB-D100g and 16.38g (0.42mol) of sodium amide are added into a 500ml three-neck flask, the mixture is stirred and mixed uniformly, the mixture is heated to 80-100 ℃ to react until the residue of the 1, 2-dibromoethylbenzene is less than or equal to 0.5 percent, bromide is removed by filtration, and the filtrate is subjected to reduced pressure distillation to obtain phenylacetylene, wherein the yield is 57.2 percent and the GC purity is 99.65 percent.

Although embodiments of the present patent have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the present patent, the scope of which is defined in the appended claims and their equivalents.

Claims

1. The green method for synthesizing MDPES raw material phenylacetylene without solvent is characterized by comprising the following steps: the method comprises the following steps:

step 1:1, 2-dibromo ethyl benzene, alkali and a catalyst EB-D are mixed and stirred uniformly, heated to 40-160 ℃ to react completely, and filtered to remove bromide;

step 2: the mixture of solid and liquid can be separated by filtration, and the filtrate is still turbid after filtration and can be filtered again;

and step 3: and distilling the filtrate to obtain the product phenylacetylene, wherein the product detection purity is more than 98%.

2. The green process for the solventless synthesis of MDPES feedstock phenylacetylene of claim 1, wherein: in the step 1, the reaction system does not contain other solvents such as methanol, tetrahydrofuran and the like.

3. The green process for the solventless synthesis of MDPES feedstock phenylacetylene of claim 1, wherein: in the step 1, the alkali is inorganic or organic alkali such as triethylamine, sodium acetate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium amide, sodium methoxide, sodium ethoxide and the like, and comprises single alkali and mixed alkali of two or more.

4. The green process for the solventless synthesis of MDPES feedstock phenylacetylene of claim 1, wherein: in the step 1, the reaction temperature is 40-160 ℃, and the preferable reaction temperature is 80-120 ℃.

5. The green process for the solventless synthesis of MDPES feedstock phenylacetylene of claim 1, wherein: in the step 3, the distillation method is a distillation separation method such as reduced pressure distillation, atmospheric distillation, reduced pressure rectification, atmospheric rectification, pressurized rectification, short-path distillation, thin film distillation and the like, and comprises a single distillation method and two or more mixed distillation separation methods, preferably the reduced pressure distillation separation method.

6. The green process for the solventless synthesis of MDPES feedstock phenylacetylene of claim 1, wherein: in the step 1, the molar ratio of 1, 2-dibromoethylbenzene to alkali is 1: 1-10, preferably 1: 2.1.

7. the green process for the solventless synthesis of MDPES feedstock phenylacetylene of claim 1, wherein: and in the step 3, the purity of the product is detected by adopting a gas chromatograph.

8. The green process for the solventless synthesis of MDPES feedstock phenylacetylene of claim 1, wherein: in the step 2, the filter paper is closely attached to the inner part of the funnel, the edge of the filter paper is lower than the edge of the funnel, the liquid level of the filtrate is lower than the edge of the filter paper, the opening of the beaker is closely attached to a drainage glass rod, and the lower end of the funnel is closely attached to the inner wall of the beaker.