CN114634396A

CN114634396A - Pentachloropropane and preparation method thereof

Info

Publication number: CN114634396A
Application number: CN202111638534.3A
Authority: CN
Inventors: 李汉生; 丁晨; 田丁磊; 苗宝雨; 王伟; 牛韦
Original assignee: Shandong Dongyue Chemical Co ltd
Current assignee: Shandong Dongyue Chemical Co ltd
Priority date: 2021-12-29
Filing date: 2021-12-29
Publication date: 2022-06-17

Abstract

The invention relates to pentachloropropane and a preparation method thereof, belonging to the technical field of organic synthesis. The preparation method of pentachloropropane takes carbon tetrachloride and chloroethylene as raw materials, and adds solid catalyst and solvent to react to prepare the pentachloropropane; the active component of the solid catalyst is cuprous chloride, and the auxiliary active component is-NH₂Organic amines of the group. The preparation method of pentachloropropane provided by the invention is convenient for recycling the catalyst, is energy-saving and environment-friendly, is beneficial to realizing continuous production, and improves the productivity.

Description

Pentachloropropane and preparation method thereof

Technical Field

The invention relates to pentachloropropane and a preparation method thereof, belonging to the technical field of organic synthesis.

Background

1,1,1,3, 3-pentachloropropane, HCC-240fa for short, is an important chemical intermediate, can prepare HFC-245fa and HCFO-1233zd, and the two substances are important choices for replacing CFCs and HCFCs, and can be applied to the fields of cleaning, foaming, refrigeration and the like. The ODP of the HCFO-1233zd (E) is 0.00024, the GWP is 7.0, the environment-friendly performance is excellent, the toxicity is low, the HCFO-1233zd (E) foaming system is non-inflammable in normal state, the use is safe, the comprehensive performance of the hard foam synthesized by the HCFO-1233zd (E) foaming system is good, the heat insulation performance is excellent, and the requirements of the heat insulation industry can be met.

1,1,1,3, 3-pentachloropropane has similar physical and chemical properties to CFC-11 and HCFC-141b, has zero ODP, is the best substitute of CFC-11 and HCFC-141b, and has become a third generation foaming agent. In addition, HFC-245fa may also be used as refrigerants, cleaning agents, sprays, and heat transfer fluids. Therefore, the synthesis method thereof becomes a hot spot in the research of CFCs substitutes in recent years.

HCC-240fa is currently produced by telomerization of vinyl chloride and carbon tetrachloride, and widely used catalysts are iron-based catalysts as well as copper-based catalysts. Patent CN101913980 describes a preparation method of pentachloropropane, however, the telomerization metal salt catalyst is difficult to recover and has great loss in the post-treatment process because of small investment, and is really little recyclable, which will inevitably affect the improvement of production cost in the industrial production. In addition, the loss of heavy metal salts can cause serious environmental pollution problems.

Disclosure of Invention

The invention aims to provide pentachloropropane and a preparation method, which are convenient for recycling the catalyst, energy-saving and environment-friendly, are beneficial to realizing continuous production and improve the productivity.

The preparation method of pentachloropropane takes carbon tetrachloride and chloroethylene as raw materials, and adds solid catalyst and solvent to react to prepare the pentachloropropane;

preferably, the active component of the solid catalyst is cuprous chloride, and the auxiliary active component is a catalyst containing-NH₂Organic amines of the group.

Preferably, the carrier of the solid catalyst is activated carbon; the particle size of the active carbon is 10-150 meshes.

Preferably, the organic amine is tert-butylamine, monoethanolamine, diethanolamine or triethanolamine.

Preferably, the mass ratio of the carrier, the active component and the auxiliary active component of the solid catalyst is 1: 0.025-0.2: 0.01-0.2.

Preferably, the preparation method of the solid catalyst comprises the following steps:

putting a certain amount of activated carbon into a mortar, grinding to the required particle size, adding into an organic solvent, stirring with a magnetic stirrer, and gradually adding a certain amount of dried cuprous chloride powder and organic amine cocatalyst during stirring. Stirring was continued for 1h, stirring was stopped and filtration was carried out.

Preferably, the mass ratio of the activated carbon carrier to the organic solvent is as follows: 1: 5-20.

Preferably, the organic solvent is acetonitrile, dimethylsulfoxide or tetrahydrofuran.

Preferably, the preparation method of pentachloropropane comprises the following steps:

dissolving chloroethylene in carbon tetrachloride, adding a solvent, and then carrying out reaction in a batch type reaction kettle or a continuous type reaction tube filled with a solid catalyst. After the reaction was completed, the solid catalyst was collected.

Preferably, the molar ratio of carbon tetrachloride to chloroethylene is 1: 1-10, the reaction pressure is 0.3-1.5MPa, the reaction temperature is 100-; the batch reaction time is 5-10h, and the residence time of the continuous reaction is 0.1-3 h.

Pentachloropropane prepared by the preparation method.

The invention prepares HCC-240fa by telomerizing carbon tetrachloride and chloroethylene through a solid catalyst. The method can facilitate the recycling of the catalyst, reduce the environmental pollution and the production cost, and can be applied to batch reaction and continuous reaction.

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

(1) the invention adopts the solid supported catalyst, which is beneficial to the recycling of the catalyst;

(2) the catalyst is used for batch reaction, can realize the recycling of the catalyst, reduces pollution and cost, and is beneficial to realizing continuous production.

Detailed Description

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Any obvious modifications or alterations to the present invention, based on the teachings of the present invention, which are obvious to those skilled in the art, should also be considered as the scope of the present invention.

Example 1

A method for producing pentachloropropane, comprising the steps of:

(1) the preparation process of the solid catalyst is as follows:

putting a certain amount of activated carbon into a mortar, grinding to 100-150 meshes, adding the activated carbon into an acetonitrile organic solvent, stirring by using a magnetic stirrer, and gradually adding a certain amount of dried cuprous chloride powder and triethanolamine cocatalyst in the stirring process. Stirring was continued for 1h, stirring was stopped and filtration was carried out. Wherein the mass ratio of the activated carbon to the acetonitrile solvent is 1:10, and the mass ratio of the activated carbon to the acetonitrile solvent is as follows: cuprous chloride: the triethanolamine mass ratio is as follows: 1:0.05:0.05.

(2) Placing the prepared solid catalyst in a batch type reaction kettle, and introducing the mixed carbon tetrachloride, chloroethylene and acetonitrile. The telomerization is carried out at elevated temperature and pressure. After the reaction was completed, the solid catalyst was collected. Wherein the reaction pressure is 0.5MPa, the reaction temperature is 130 ℃, the mass ratio of carbon tetrachloride to the solid catalyst is 20:1, the mass ratio of carbon tetrachloride to chloroethylene is 10:1, the volume ratio of carbon tetrachloride to acetonitrile is 6:1, and the reaction time is 6 hours.

Example 2

A process for the production of pentachloropropane carried out as in example 1, except that:

the catalyst was placed in a fixed bed reactor with a residence time of 0.1 h.

Example 3

dimethyl sulfoxide is adopted as the organic solvent.

Example 4

diethanolamine is used as the organic amine.

Example 5

the reaction temperature was 120 ℃.

Example 6

the reaction time was 3 hours.

Example 7

activated carbon: cuprous chloride: the triethanolamine comprises the following components in percentage by mass: 1:0.08:0.08.

Example 8

the mass ratio of the activated carbon to the acetonitrile solvent is 1: 20.

Comparative example 1

no organic amine is added in the preparation process of the solid catalyst.

Table 1 results of the different embodiments of the reaction

The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.

Claims

1. A preparation method of pentachloropropane is characterized in that: adding a solid catalyst and a solvent into carbon tetrachloride and chloroethylene serving as raw materials to react to prepare the pentachloropropane;

the active component of the solid catalyst is cuprous chloride, and the auxiliary active component is-NH₂Organic amines of the group.

2. The preparation method of pentachloropropane according to claim 1, characterized in that: the carrier of the solid catalyst is active carbon; the particle size of the active carbon is 10-150 meshes; the active carbon is coconut shell active carbon, wood active carbon, coal active carbon or shell active carbon.

3. The process for the preparation of pentachloropropane according to claim 1, characterized in that: the organic amine is tert-butylamine, monoethanolamine, diethanolamine or triethanolamine.

4. The process for the preparation of pentachloropropane according to claim 1, characterized in that: the mass ratio of the carrier, the active component and the auxiliary active component of the solid catalyst is 1: 0.025-0.2: 0.01-0.2.

5. The preparation method of pentachloropropane according to claim 1, characterized in that: the preparation method of the solid catalyst comprises the following steps:

putting the activated carbon into a mortar, grinding to the required particle size, adding the activated carbon into the organic solvent, stirring, gradually adding the dried cuprous chloride powder and the organic amine cocatalyst during stirring, continuing stirring, and filtering.

6. The method for preparing pentachloropropane according to claim 5, characterized in that: the mass ratio of the activated carbon carrier to the organic solvent is as follows: 1: 5-20.

7. The method for preparing pentachloropropane according to claim 5, characterized in that: the organic solvent is acetonitrile, dimethyl sulfoxide or tetrahydrofuran.

8. The preparation method of pentachloropropane according to claim 1, characterized in that: the method comprises the following steps:

dissolving chloroethylene in carbon tetrachloride, adding a solvent, and reacting in a batch reactor or a continuous reaction tube filled with a solid catalyst.

9. The method for preparing pentachloropropane according to claim 8, characterized in that: the molar ratio of carbon tetrachloride to chloroethylene is 1: 1-10, the reaction pressure is 0.3-1.5MPa, the reaction temperature is 100-; the batch reaction time is 5-10h, and the residence time of the continuous reaction is 0.1-3 h.

10. A pentachloropropane characterized by: prepared by the preparation method of claims 1-9.