DE1064071B - Process for the production of triallyl or trimethallyl cyanurate - Google Patents

Description

GERMAN

The previously known processes for the production of triallyl cyanurate or trimethallyl cyanurate are based on the action of the corresponding unsaturated alcohols on cyanuric halides in Presence of hydrogen halide acceptors. Here one works without (USA.-Patents 2510564 and 2537816) and with (U.S. Patent 2631148) Participation of indifferent solvents or diluents.

The processes according to (US Pat. Nos. 2510564 and 2,537,816) are relatively uneconomical Yields (68 to 85%) and a very high input compared to the cyanuric halide used of allyl or methallyl alcohol (at least 13 moles of unsaturated alcohol per mole of cyanuric halide) on. In the case of the inert organic solution or. Working thinners, in the U.S. Patent 2 631 148 processes described must include the solvents or diluents used be distilled off after the reaction has ended. Here you can start the last remnants It is very difficult to separate solvents or diluents from the end product, which reduces the purity and later application of the same can be influenced.

In the method according to the invention, the above-mentioned inadequacies are largely eliminated. This is characterized in that one cyanuric halide with excess allyl alcohol or methallyl alcohol in the presence of triallyl cyanurate or trimethallyl cyanurate as a solution or Diluent and a hydrogen halide acceptor at a temperature below + 10 ° C with one another lets react.

The advantage of this process, which operates with a relatively high yield, is to be found in the fact that the Task of the inert solvents and diluents used in the already known process is taken over by the unsaturated cyanuric acid ester to be produced in each case. This is not necessary the distillative and complete removal of inert solvents or diluents. Per mole of cyanuric halide are practically only 4.5 mol of unsaturated alcohol in the process according to the invention needed.

When displaying z. B. Triallylcyanurat this is used itself as a diluent. Man The procedure is such that, before the start of the reaction, the pure triallyl cyanurate used as a diluent is added so much allyl alcohol admits that it has little or no tendency at temperatures above 2 ° C shows to crystallization.

The optimal ratio is about 3 parts by volume of triallyl cyanurate to 1 part by volume of allyl alcohol. The amount of unsaturated alcohol

Method of manufacture
of triallyl or trimethallyl cyanurate

Applicant:

German Academy
of the sciences in Berlin,

Berlin-Adlershof,
Rudower Chaussee 116-125

Dipl.-Chem. Dr. Horst Schulze, Berlin-Grünau,
has been named as the inventor

can be increased as required. In addition, the amount of allyl alcohol is added before the start of the reaction too, which is sufficient to remove the triallyl cyanurate formed in the reaction in the case of the above To keep temperatures fluid as well. Each of them is added to this solution to react with cyanuric halide calculated amount of allyl alcohol. You can here to 1 mole of cyanuric halide directly 3 moles Use allyl alcohol or any more. Add to the total solution at the lowest possible temperature, such as B. 2 to 10 ° C, the calculated amount of cyanuric halide with stirring. This suspension will then, by stirring vigorously and carefully cooling, add drop by drop with the calculated amount of concentrated, If possible, 40 to 50% sodium or potassium hydroxide solution or other hydrogen chloride acceptors added in the appropriate amount, the reaction temperature when maximum yields are obtained should be within the temperature range of 2 ° - max. 10 ° C.

The triallyl cyanurate obtained after the reaction and containing water, alcohol and alkali chloride is stirred for a further 1 hour and can be separated from the water, alcohol and alkali metal chloride by known methods (see Example 1). The isolated end product can e.g. B. with CaCl ₂ , Na ₂ SO ₄ , etc. at temperatures above 28 ° C or in a vacuum. Triallyl cyanurate of high purity is obtained with maximum yields of around 90% (based on 100% cyanuric halide).

The excess unsaturated alcohol contained in the washing water can be removed using known methods to be recovered.

909 609/418

example 1
Preparation of triallyl cyanurate

In a solution of 160.0 g (0.64 mol) of triallyl cyanurate in 261.3 g (4.5 mol) of allyl alcohol, 184.4 g (1 mol) of cyanuric chloride (pure) are added at a temperature between 2 and 10 ° C suspended with vigorous stirring. 300.0 g (3 mol) of 40% strength sodium hydroxide solution are added dropwise to this suspension, likewise with vigorous stirring, it being necessary to ensure that the temperature does not exceed 10.degree. C. in order to achieve a maximum yield. It is carefully cooled with a cold mixture of ethanol-resistant carbon dioxide kept at around -20 ° C. After adding the sodium hydroxide solution, about 10 g of 40% caustic solution are added as an excess. The whole reaction takes about IV2 to 2 hours. The mixture is then stirred for a further 1 hour without cooling. The reaction mixture obtained is shaken with 500 cm ^{3 of} hot water and allowed to settle. The lower solution consisting of aqueous sodium chloride solution and allyl alcohol is drained off and the upper layer consisting mainly of triallyl cyanurate is filtered through a glass frit and ^{shaken again with 1100 cm 3 of} hot water. After settling, the lower layer now consists of almost pure triallyl cyanurate, while the upper aqueous layer still contains allyl alcohol and sodium chloride. The remaining amounts of allyl alcohol are removed from the triallyl cyanurate by shaking it again with warm water. The water-moist triallyl cyanurate separated from the aqueous layer is _{dried with CaCl 2} at a temperature above 28 ° C. and nitrated.

380 g of triallyl cyanurate with a melting point of 28 ° C. are obtained, which after deduction of the diluent 160 g of triallyl cyanurate used in a yield of 220 g = 92.3% of theory (based on IOWoiges Cyanuric chloride).

Example 2
Preparation of trimethallyl cyanurate

The representation proceeds analogously to the representation of triallyl cyanurate described in Example 1. Instead of Allyl alcohol, the equivalent amount of methallyl alcohol is used. The reaction product must be complete removal of excess methallyl alcohol shaken several times with hot water will. The yields are lower (about 85%) than indicated in Example 1.

Example 3

Preparation of triallyl or trimethallyl cyanurate using cyanuric bromide

The representations are analogous to those described in Examples 1 and 2. Instead of cyanuric chloride the equivalent amount of cyanuric bromide is used. The yields are the same as in the examples 1 and 2.

Claims (1)

Claim: Process for preparing triallyl cyanurate or Trimethallylcyanurat, characterized in that one leaves a cyanuric halide with excess allyl alcohol or methallyl alcohol in the presence of triallyl cyanurate or Trimethallylcyanurat as solvent or diluent and a Halogenwasserstoffacceptors at temperatures below +10 ⁰ C react with one another. © 909 609/418 8.