PL192726B1 - Derivative of isocyanuric acid and method of obtaining same - Google Patents

Abstract

A method for producing an isocyanuric acid derivative characterized by the fact that the reaction isocyanuric acid with 2-bromoethylallyl ether is carried out while maintaining the ratio by weight like 1: 3, in an alkaline medium, in the presence of a solvent, in the presence of a catalyst phase transfer and in an inert gas atmosphere, the product of the mixture The reaction mixture is isolated by extraction with methylene chloride or diethyl ether and washed with water and dried using known methods.

Description

Description of the invention

The subject of the invention is a process for the preparation of an isocyanuric acid derivative used as a monomer in the copolymerization process of unsaturated polyesters.

It is known from the publication of M. Chiron, P. Caubere, Synthetic Communications, 23 (19), 659-2672 (1993) for the preparation of trialkyl derivatives of isocyanuric acid (ICA): tribenzylisocyanurate, tris (2-hydroxyethyl) isocyanurate, tricyanomethylisocyanurate and others, in the presence of strong bases, i.e. sodium hydride. The solvent in this process is the aprotic solvent phosphoric acid hexamethylamide (HMPA).

The method of obtaining triallyl isocyanurate (TAIC) in the cyclotrimerization of potassium cyanate in the presence of allyl chloride is also known from the US Patent No. 2,536,849 (1951). This process is carried out at elevated temperature.

The process according to the invention consists in reacting isocyanuric acid (ICA) with 2-bromoethylallyl ether at a weight ratio of 1: 3, in an alkaline medium, in the presence of a solvent and phase transfer catalyst and in an inert gas atmosphere. The product from the reaction mixture is isolated by extraction with methylene chloride or diethyl ether, and washed with water and dried according to known methods. Preferably, the reaction between 2-bromoethylallyl ether and isocyanuric acid is carried out at a temperature of 323-373K. Preferably, N, N-dimethylformamide (DMF) is used as the solvent.

Preferably, isocyanuric acid trisodium or trilithium salt is used in the reaction or generated in situ in the reaction medium. Preferably, NaOH, LiH in N, N-dimethylformamide is used as the basic medium. ^{Preferably, Bu4N +} HSO4 ^- or Bu4N ⁺ I ^- or [18] -corona-6 ether is used as the catalyst.

The 2-bromoethyl allyl ether (BEAE) used to obtain the isocyanuric acid derivative according to the invention is obtained in the first stage of the process in the presence of allyl bromide and ethylene oxide under autogenous pressure in the presence of the catalysts: tetraethylammonium bromide and metallic copper.

The advantage of the obtained tris (2-allylethoxy) isocyanurate ether is its high purity of 92 to 96%.

The process of the invention produces an isocyanuric acid derivative in the form of a monomer, which can be used in the copolymerization process of unsaturated polyesters and can be used as a cross-linking agent for other polymers. The use of an isocyanuric acid derivative as a crosslinking agent or as a monomer will significantly increase the thermal resistance of the polymers obtained.

P r z k ł a d I

A mixture of 5 g (0.04 mol) of isocyanuric acid (ICA) and powdered NaOH in the amount of 4.7 g (0.12 mol) dissolved in 60 ml of anhydrous N, N-dimethylformamide (DMF) was heated for 3 hours at 373 K stirring the reagents intensively. After this time, the solution is cooled to 363 K, 50 mg of [18] crown-6 ether together with 19.3 g (0.12 mol) of 2-bromoethylallyl ether (BEAE) and a catalytic amount of potassium iodide (one crystal) are added. The reaction is carried out for 16 hours, then the solvent is removed from the reaction medium under reduced pressure, and the residue obtained is extracted with diethyl ether and washed with water. The ether extract was dried over anhydrous magnesium sulfate (MgSO4) and then the ether was removed under reduced pressure. The residue, 6.5 g, is a yellow, viscous liquid. The efficiency of the process in terms of ICA is 56 mol%, the boiling point is 415K / 0.1 mmHg (bath temperature).

The product was analyzed by ¹³ C NMR, and ¹ H NMR. The results of the analyzes are as follows:

¹³ C NMR (CDCl 3) (d ppm); 42 (N-CH2); 66.2 (N-CH2 CH2); 71.7 (-CH2-CH = CH2); 117.3 (= CH2);

134.5 (-CH2 =); 149 (-C = O).

¹ H NMR (CDCl3) (ppm d); 5.8 (m, 1H); 5.2 (m, 2H); 4.1 (d 2H); 4.0 (t 2H); 3.7 (t 2H).

Example II

A mixture of 5 g (0.04 mol) of isocyanuric acid (ICA) and 0.96 g (0.12 mol) of lithium hydride in 60 ml of N, N-dimethylformamide (DMF) was heated to 363 K. After this time was added. 50 mg of tetraethylammonium iodide along with 19.3 g (0.12 mol) of 2-bromoethylallyl ether (BEAE). After the reaction is carried out for 12 hours, the solvent is removed from the reaction medium under reduced pressure, and the residue obtained is extracted with methylene chloride and washed with water. The extract is dried over anhydrous magnesium sulfate (MgSO4) and then the methylene chloride is removed under

PL 192 726B1 under reduced pressure. The residue, 11 g, is a yellow, viscous liquid. The process yield in terms of isocyanuric acid (ICA) is 72 mol%. The product was analyzed by ¹³ C NMR, and ¹ H NMR. The results of the analyzes are as follows:

¹³ C NMR (CDCl 3) (d ppm); 42 (N-CH2); 66.2 (N-CH2-CH2); 71.7 (-CH2-CH = CH2); 117.3 (= CH2);

134.5 (-CH2 =); 149 (-C = O).

¹ H NMR (CDCl3) (ppm d); 5.8 (m, 1H); 5.2 (m, 2H); 4.1 (d 2H); 4.0 (t 2H); 3.7 (t 2H).

P r x l a d III.

A suspension of 5 g (0.03 mol) of isocyanuric acid trilithium salt in 100 ml of N, N-dimethylformamide is heated to 353 K and 50 mg of tetrabutylammonium bisulfate and 14.8 g (0.09 mol) of 2-bromoethylallyl ether are added. The reaction is carried out for 12 hours at 353 K, while the reagents are thoroughly mixed. After this time, the solvent was removed from the reaction mixture under reduced pressure from the reaction medium, and the residue obtained was extracted with diethyl ether and washed with water. The ether extract was dried over anhydrous magnesium sulfate (MgSO4) and then the ether was removed under reduced pressure. The residue, 6.5 g, is a yellow, viscous liquid.

The efficiency of the process in terms of ICA is 56 mol%, the boiling point is 415K / 0.1 mmHg (bath temperature).

1

The product was analyzed by ¹³ C NMR, and ¹ H NMR. The results of the analyzes are as follows:

¹³ C NMR (CDCl 3) (d ppm); 42 (N-CH2); 66.2 (N-CH2-CH2); 71.7 (-CH2-CH = CH2); 117.3 (= CH2);

134.5 (-CH2 =); 149 (-C = O).

¹ HNMR (CDCl3) (d ppm); 5.8 (m, 1H); 5.2 (m, 2H); 4.1 (d 2H); 4.0 (t 2H); 3.7 (t 2H)

Claims (6)

Patent claims A method for producing an isocyanuric acid derivative, characterized in that the reaction of isocyanuric acid with 2-bromoethylallyl ether is carried out with a weight ratio of 1: 3, in a basic medium, in the presence of a solvent, in the presence of a phase transfer catalyst and in an inert gas atmosphere, the product from the reaction mixture is isolated by extraction with methylene chloride or diethyl ether, and washed with water and dried according to known methods. 2. The method according to claim 1, characterized in that the reaction is carried out at the temperature of 323-373 K under autogenous pressure. 3. A method according to claim 1, characterized in that N, N-dimethylformamide (DMF) is used as the solvent. 4. A method according to claim 1, characterized in that isocyanuric acid trisodium or trilithium salt is used in the reaction or generated in situ in the reaction medium. A method according to claim 1, characterized in that NaOH, LiH in N, N-dimethylformamide is used as the basic medium. A method according to claim 1, characterized in that the catalyst is Bu4N ⁺ HSO4 ^- or Bu4N ⁺ I ^- or [18] -corona-6 ether.