SU1121259A1 - Process for preparing triallylisocyanurate - Google Patents

Abstract

Process for the preparation of triallyl isocyanurate, starting from derivatives of s-triazine with a solvent and a catalyst comprising copper, under heating, followed vscheleniem title product of tlichayuschiySYa in that, in order to simplify the process is carried out isomerization trialliliianurata in toluene in the presence of copper as a catalyst and a reducing agent selected from the group comprising tin dichloride and iron dichloride, at 95-130 ° C and a molar ratio of triallyl cyanurate - toluene - reducing agent i is equal to 1: 1,3-4, -1: 0,39-0,8: 0,0013-0,0026, (A and isolation of the desired product is carried out by distillation in vacuo.

Description

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with the Inventions, refer to an improved method for the production of trial allysocyanurate (TAIC) used as a crosslinking agent in the manufacture of sealants and organic glasses. A known method for the preparation of TAIC, according to which TAIC is obtained by isomerization of triallyl cyanurate (TAC) in the presence of a metallic copper catalyst in an amount up to 20 May of the amount of TAC taken at 30 ° C, the process proceeds 5-25 hours depending on the catalyst concentration and temperature DJ "However, in the description of this method, neither the loading of the reagents, nor the instrumentation, the order of the synthesis, nor the yield of the finished product are indicated. Only the isomerization of TAC and TAZh1 is given. When playing this method, it turned out that the process is explosive in nature (the isomerization of TACs in TAIC takes 50 kcal / mol with heat, the final product is released, it is not possible to isolate and accumulate it. The closest in technical terms to the invention is a method for obtaining a TAIC by the interaction of allyl chloride with cyanuric acid in the presence of a catalyst — a system of one-chlorine copper — copper powder in an amount of 0.02–0.03 and 0.06-0.02 mol per 1 mole cyanuric acid, respectively, in an aqueous-alkaline medium at 50–65 ° C, followed by isolation of the target prod. The molar ratio of cyanuric acid: chloride; caustic soda: HgO is 1 b; 6:87. The process takes place in 0.5-2 hours. The product is isolated in the following way: at the end of the process, the reaction mass is filtered, settled and the oil layer is separated. The product is extracted from benzene from an aqueous solution. The extract is added to the oil layer and washed with 5% hydrochloric acid solution and then with water. The benzene is distilled off and the residue is distilled off by vacuum distillation. The yield of triallyl isocyanurate is 95% C2J. . The disadvantages of this method are the difficulties associated with the instrumentation of the process, as well as the multi-stage separation of the finished 592 product. In addition, a significant amount of waste is generated in this process: per 1 kg of the finished product 6.6 kg of water, 0.97 kg chloro-. allyl, 0.46 kg of sodium hydroxide, 0.74 kg of sodium chloride, and 0.84 kg of a 5% aqueous solution of hydrochloric acid. The total waste per 1 kg of product is 9.61 kg. In addition, the use of volatile low boiling allyl chloride significantly deteriorates the working conditions and requires the use of heat exchangers with efficient cooling, which is associated with significant energy costs. The purpose of the invention is to simplify the process of obtaining trial allysocyanurate. This goal is achieved in that according to the method for producing trisal isocyanurate, isomerization of tallyene is carried out in toluene in the presence of copper as a catalyst and reducing agent selected from the group consisting of dichloride dichloride and dichloride at 95-130 ° C and a mole ratio of triallyl cyanurate: toluene: copper: reducing agent, equal to 1: 1.3-4.1: 0.39-0.8:: 0, .0013-0.0026, followed by separation of the target product by vacuum distillation. The isomerization time is between 3 and 20 hours, depending on temperature, amount of catalyst, solvent and reducing agent. The yield of the target product is 92-95%. The starting compound TAC is an available reagent, the preparation method of which is based on. interaction of cyanuric chloride with allyl alcohol in the presence of Alkali as an acceptor of released hydrogen chloride SSC. The essential difference of this method consists in the preparation of TAL1 by isomerization of TAC in an environment of tolu ol in the presence of copper as a catalyst and a reducing agent selected from the group comprising tin dichloride, iron dichloride, at 95-130 C and molar ratio of TAC: toluene: copper: 1) recovery: ., equal to 1: 1.3-4.1: 0.39-0.8: 0.0013-0.0026, with distillation of the finished product by distillation in a vacuum.

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  The proposed method for producing TAI is simple to implement, comes from cheap and available raw materials, retains a high yield of the finished product of the required quality, is distinguished by the ease of separation of the target product and a small amount of waste (0.050, 09 kg per kg TAIO.

Example 1. 50 g (0.79 mol) of powdered copper 0.60 g (0.0026 mol) of SnCf 2H20 and 100 ml of a toluene TAC solution (249.46 g ( 1 mol) TAC in 400 ml (3.8 mol) of toluene). The reaction mixture is heated to 95-100 ° C. Then, for 3 hours, the remaining TAC solution is metered in and the mixture is held for 1 hour at 95-110 ° C. The reactor is cooled, and the Toluene solution is filtered. The solvent is distilled off and the residue in the amount of 245 g is subjected to distillation under vacuum. Vapor temperatures IZS-HO C / I 2594

2 mm Hg 237 g of chromatographically pure TAIC are obtained, yield 95%, nj 1.5115, -literary data. P25 1.5115 Cll. The amount of waste per 1 kg of the finished product at a yield of 95% is in the order of 0.05 kg, the IR spectra of the starting and final substances, and the chromatographic profiles are shown in FIG. 1 and 2.

Example 2. In a column with a height of 200 mm and a diameter of 10 mm load 20 g of copper shavings. The column is heated to and passed at a rate of 0.5 ml / min to 100 g of the solution, consisting of 66.5 g (0.27 mol) TAC, 33.5 g (0.36 mol) of toluene and 0.008 g (0 , 00003 mol) SnClj- 2H20. Toluene was distilled off from the resulting reaction mixture and the residue was distilled in vacuo. Get 57.2 g (90%) TAITS, p 1,5115, the amount of waste 0,087 kg per 1 kg TASH.

According to the methods of examples 1 and 2, the synthesis of TAIC was carried out, the data on which are given in the table.

Heritage Tables

The isomerization was carried out according to the procedure of Example 2. It can be seen from the above examples and the table that carrying out the process in toluene at a molar ratio of TA1I: toluene: copper: reducing agent is 1: 1.3-4.1: 0.39-0.8: 0.0013-0.0026 at 95-130 C. allows isomerization under controlled conditions and ensures creeping of the finished product with high yield. The use of toluene less than 1.3 mol leads to a bickered flow of the process, and the use of toluene in quantities greater than 4.1 mol (Example 13) leads to a decrease in the removal of the target product per unit volume of equipment. Conducting isomerization in the presence of copper in an amount less than 0.39 (Example 9) resulted in a significant increase in isomerization time.

a decrease in the yield of the target product, and in an amount greater than 0 $ 8 mol (Example 15) has almost no effect on the speed of the process, but also leads to some decrease in the yield

TAHIJ; .

Using a quantity of a reducing agent less than 0.0013 mol (example 7 and 16) also delays isomerization and reduces the yield of TAI-HI. but. an increase of more than 0.0026 mol (Example 17) does not affect the process time. Conducting isomerization without a reducing agent significantly increases the induction period of the process.

Thus, in Example 12 (for comparison) without a reducing agent, ceteris paribus, isomerization in 20 hours passed only 10%.

A decrease in the process temperature below 95 ° C (example 10 and 18) leads to

is 0.004 wt.%, 0. 02 wt.%. Conditions for analysis: DIP8 column of 4% XE-60 silicone on Chromosorb G carrier, metal column I in length, 2 m, internal diameter 3 km, nitrogen consumption 30 ml / min, consumption. hydrogen 26 ml / min. air consumption 500 ml / min, column thermostat temperature 170 ° C, evaporator temperature, sensitivity of the amplifier 200, sample volume 0.4 ml toluene solution or TAIC. Under these conditions, the holding time of TA1D 24 55, TAIC is 1405.

As can be seen from the above chromatograms (Fig. 2), there are no impurities in both the original TA1 ((Fig. 2-1) and the final TAIC (Fig. 2-2). There are only two peaks; TAC or TA1-Y and toluene, which serves as a solvent, a significant increase in time; -: isomerization, the upper temperature is limited to: the boiling point of the solution (np # ip 19). The IR spectra were taken on a UP-2O instrument in a solution of toluene, a layer of 0.06 mm , in the region of 600–3600, the completeness of isomerization was controlled by the disappearance of the bands 823, 1138, and 1565, caused by out-of-plane, deformed and valence numbers The appearance of the bands 768 and 1690 cC characteristic of the group of the isocyanate ring (Fig. 1-2). The purity of TAIf and ТЛ1-Щ were tested using the method developed by undertaking a PPM M-5927 method using PNH chromatography on a Tsvet-YuO instrument. Accuracy of the analysis of low-boiling impurities

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Claims (1)

METHOD FOR PRODUCING TRIALALLYZOCYANOURATE, starting from derivatives of sym triazine, using a solvent and a catalyst including copper, when heated, followed by isolation of the target product, which is characterized by the fact that, in order to simplify the process, isomerization of triallylpianurate in toluene medium in the presence of copper as a catalyst and a reducing agent selected from the group comprising tin dichloride and iron dichloride at 95-130 ° C and a molar ratio of triallyl cyanurate - toluene-copper - reducing agent equal to $ 1: 1.3-4.4: 0.39-0.8: 0.0013-0.0026, and the target product is isolated by distillation in vacuo. SU,. „1121259 1 1I2I The invention relates to an improved process for the production of triallyl isocyanurate (TAIC) used as a crosslinking agent in the production of sealants and organic glass. ‘ There is a known method for producing TAIC, according to which TAIC is obtained by isomerization of triallyl cyanurate (TAC) in the presence of a catalyst — metallic copper in an amount of up to 20 wt% of the amount taken of · TAC at 30–70 ° C. The process takes 5-25 hours, depending on the concentration of the catalyst and temperature 01 · 15 However, neither the reagent loading, nor the hardware design, nor the synthesis procedure, nor the yield of the finished product are indicated in the description of this method. Only fact ₂ θ of isomerization of TAC and TAIC is presented. When reproducing this method, it turned out that the process is | explosive (TAC 'isomerization in the TAIC takes place with the release of heat of ₂ 5 50 kcal / mol), the finished product is released, its isolation and accumulation is not possible. The closest in technical essence to the invention is a method of producing ~ 30% TAIC by reacting allyl chloride with cyanuric acid in the presence of a catalyst - system _d monochlorine copper - copper powder in an amount of 0.02-0.03 and 0.06 - 35 0.02 mol per 1 mol of cyanuric acid, respectively, in an aqueous alkaline medium at 50-65 ° C, followed by isolation of the target product. The molar ratio of cyanuric acid: 40-allyl chloride ·; caustic soda: H ₂ 0 is 1: 6: 6: 87. The process takes 0.52 hours. Isolation of the product is carried out · as follows: at the end of the process, the reaction mass is filtered, 45 are defended and the coat layer is separated. From the aqueous solution, the product is extracted with benzene. The extract is added to the oil layer and washed with a 5% hydrochloric acid solution and then with 50 water. Benzene was distilled off, and the residue was subjected to vacuum distillation. The yield of triallyl isocyanurate is 95% C2J. . . . · The disadvantages of the known method 55 are the difficulties associated with the hardware design of the process, as well as the multi-stage selection of the finished 259 2nd product. In addition, a significant amount of waste is generated in this process: 1 kg of the finished product 6.6 kg of water, 0.97 kg of chloride. go allyl, 0.46 kg of sodium hydroxide, 0.74 kg of sodium chloride and 0.84 kg of a 5% hydrochloric acid solution. The total amount of waste per 1 kg of product is 9.61 kg. In addition, the use of volatile low-boiling allyl chloride significantly worsens working conditions and requires the use of heat exchangers with efficient cooling, which is associated with significant energy costs.