DE1207364B - Process for the production of 1, 1, 1, 3-tetrachloropropane - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

Number:
File number:
Registration date:
Display day:

C07c

German class: 12 ο -2/01

1 207 364
D41002IVb / 12o
February 28, 1963
December 23, 1965

It is known from US Pat. No. 2,440,800 that carbon tetrachloride can be mixed with ethylene in the presence of benzoyl peroxide with the formation of 1,1,1,3-tetrachloropropane can be implemented. But the conversion into the desired product is only about 10%, based on the tetrachloromethane used (cf. J. Amer. Former Soc. 70 [1948], p. 2529 ff). Attempts to improve conversion by increasing the concentration of ethylene or by increasing it the temperature are extraordinarily daring because of the possibility of explosion and also because of the formation of undesirable by-products. As a result, the previously known method for Commercial production of 1,1.1.3-tetrachloropropane not feasible.

However, this invention proposes an industrially feasible method of making 1,1,1,3-tetrachloropropane and enables the production of this compound in yields of up to 50% in one step.

This process of the present invention for the preparation of 1.1,1.3-tetrachloropropane is characterized in that a mixture of carbon tetrachloride and di- (tert-butyl) peroxide is used for the preparation of ethylene
1,1,1,3-tetrachloropropane

Applicant:

Dow Corning Corporation, Midland, Mich.

(V. St. A.)

Representative:

Dr.-Ing. H. Ruschke and Dipl.-Ing. H. Agular,
Patent Attorneys, Munich 27, Pienzenauer Str. 2

Named as inventor:

Eldon E. Fresh,

Ogden R. Pierce, Midland, Mich. (V. St. A.)

Claimed priority:

V. St. v. America July 18, 1962 (210 853)

H ₃ C

CH ₃

H ₃ CCOOC-CH ₃

H ₃ C

CH ₃

and the mixture is heated before or during the addition of ethylene to a temperature of 100 to less than 140 ⁰ C at an ethylene pressure of 3.5 to 10.6 kg / cm ² or that the reaction is carried out in the same way, but so that the carbon tetrachloride is slightly Di- (tert-butyl) peroxide is added before the addition of ethylene and the remainder is added in the course of the reaction.

It has been found that contrary to what is expected in the prior art, these conditions give excellent yields of 1,1,1,3-tetrachloropropane with a minimum of side reactions to form telomers of this material. The aforementioned conditions are critical. The reaction temperature must be kept in the range of 100 to less than 140 ⁰ C. At temperatures below this range, the reaction is practically too slow, and at temperatures above this range, decomposition of the product occurs with the formation of extremely low yields.

The pressure of the ethylene is also critical than the predominant ones if the ethylene concentration is too high Products are telomeres of propane.

The reaction time is not critical, although in general under the specified conditions satisfactory yields can be obtained after 1 to 2 days. Likewise is the concentration of the Peroxides in the carbon tetrachloride are not critical. Understandably, the amount of peroxide should sufficient for implementation to proceed at a reasonable pace. It it was found that amounts of 0.5 to 10 percent by weight of di- (tert-butyl) peroxide, based on the weight of the carbon tetrachloride, although more or less as the case may be Peroxide can be used.

The process of the present invention converts 40 to 50% of the carbon tetrachloride in one operation in 1,1,1,3-tetrachloropropane. The unreacted carbon tetrachloride is removed from the reaction mixture distilled off and can be washed free of peroxide by-products and reused will. The conversion, based on the ethylene used, extends up to a maximum of 90%.

1,1,1.3-Tetrachloropropane is used as a paint remover and useful as a degreaser for industrial plants.

The following examples illustrate the invention.

509 759/561

example 1

18,000 g of carbon tetrachloride were placed in a reaction vessel and 220 g of di (tert-butyl) peroxide were added. The mixture was ^{heated to 120 °} C. and ethylene was added to the container at 7.03 kg / cm ² . The reaction came quickly in transition, and it had to be cooled to maintain the temperature in the range of 120 ⁰ C. After 24 hours, the reaction was terminated and the product was distilled to obtain 1,1,1,3-tetrachloropropane in an amount of 43%, based on the carbon tetrachloride used. 57% of the carbon tetrachloride was recovered unchanged.

Example 2

18 455 g of carbon tetrachloride and 277 g of di (tert-butyl) -peroxyd were placed in a container, and the mixture was heated to 110 ⁰ C. Ethylene was introduced at 4.9 kg / cm ² overpressure. The container was heated and stirred for 20 hours and a 37% yield of 1,1,1,3-tetrachloropropane based on the tetrachloromethane used was obtained.

B e i s ρ i e 1 3

4762.7 kg of carbon tetrachloride were mixed with 1.5 percent by weight of di (tert-butyl) peroxide. That

The mixture was heated to 115 to 125 ° C. while ethylene was added at 4.2 kg / cm ² overpressure. After 3 days the reaction mixture was distilled; 50% of the carbon tetrachloride had been converted to 1,1,1,3-tetrachloropropane.

Claims (1)

Claim: Process for the preparation of 1,1,1,3-tetrachloropropane by reacting carbon tetrachloride with ethylene in the presence of a peroxide as a catalyst, characterized in that ethylene is added to a mixture of carbon tetrachloride and di- (tert-butyl) peroxide and that The mixture is heated before or during the addition of ethylene to a temperature in the range from 100 to less than 140 ° C at an ethylene pressure of 3.5 to 10.6 kg / cm ² or that the reaction is carried out in the same way, but in such a way that the Tetrachloromethane some di- (tert-butyl) peroxide before the addition of ethylene and the remainder is added in the course of the reaction. Considered publications:
U.S. Patent No. 2,440,800. 509 759/561 12.65 © Bundesdruckerei Berlin