SU1313854A1 - Method for producing mixture of 2-oxo-2,3-dihydro-4,6-bis-(3ъdiethylaminomethylene-4ъ-oxyphenyl)-1,3,5-triazine and 2,4,6-tris-(3ъ-diethylaminomethylene-4ъ-oxyphenyl)-1,3,5-triazine - Google Patents

Abstract

The invention relates to triazines, in particular the preparation of a mixture containing 2-oxo-2,3-dihydro-4,6-bis-

Description

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The invention relates to a derivative of 1,3,5-triazine, namely to a process for the preparation of a mixture containing 20 ± 2% 2-oxo-2,3-dihydro-4,6-bis (3-diethylaminomethylene-4-oxyphenyl) -1 , 3,5-triazine and 80 ± 2% 2,4,6-tris- (3-diethylaminomethylene-4-oxyphenyl) -1, 3,5-triazine, which can be used as a hardener for epoxy-idiene resins in the preparation of rigid panoepoxides

The aim of the invention is to develop a method for producing a mixture of 1,3,5-triazine derivatives, which can be used as a curing agent for epoxy-diane resins in the preparation of rigid penoepoxides, which have advantages in physicomechanical properties as compared with those of peno-epoxides, for curing which a known hardener eutectic mixture of polyfunctional aromatic amides (ES-1).

The invention is illustrated by the following examples.

Example 1. Preparation of a mixture of 2-OXO-2, 3-dihydro-4,6-bis- (4-hydroxyphenyl) -1,3,5-triazine and 2,4,6-tris- (4-hydroxyphenyl) -1,3,5-triazine.

To a suspension of 71 g (0.53 mol) of anhydrous aluminum chloride in 200 ml of carbon tetrachloride, stirring at a temperature of 5t1 ° C, 32 g (0.173 mol) of cyanuric chloride are added in small portions, then a solution of 50 g (0.52 mol) of phenol in 150 ml of carbon tetrachloride. The reaction mixture was stirred for another 2 hours at the same temperature, the temperature was raised to 50 ° C, and stirring was continued for another 2.5 hours until the end of the intense evolution of hydrogen chloride. To decompose the resulting reaction complex, the reaction product is poured onto a mixture of 500 g of ice and 100 g of concentrated hydrochloric acid, the precipitated precipitate is filtered and subjected to distillation with steam. The residue is crushed, dried to constant weight, and 33 g (55.7%) of a powdery, yellow substance with m.p. 205-208 S.

The resulting material is extracted with boiling toluene (2 5 50 ml) and the residue is dissolved in dioxane. The dioxane solution is passed through a column.

filled with alumina II degree of activity.

The combined toluene extract is evaporated to half the volume, cooled, the precipitated crystals are filtered off, evaporated at 50 ° / 10 mm to constant weight, and 7.3 g (22%) of 2-OXO-2, 3-dihydro-4, 6-bis are obtained - (4-hydroxyphenyl) -, 3,5-triazine in the form of a light yellow powder with so pl. 153-155 ° C.

Mol mass 281 (mass spectrometrically.). i

those on the Silufol plates, eluent dioxane: octane (5: 1), and the iodine vapor prod uct (, 81).

Found.%: C 63.84; H 4.2; N 15.14.

C, 5H ,, N, 0 ,.

Calculated,%: C 64.05; H 3.91; N 14.95.

IR spectrum, -i, cm: 3380 br. Wed (HE); 1610 ate (); 1605, 1595, 1545, 1505, 1380 p. (, - res. and cyanurate: cycle); 1450 cf. (isocyanurate cycle); 815 (p-pos.).

PMR spectrum, O, ppm: 8.35 sq., 6.95 d., 6.83 d (CgH); 2.15 s. (HE). The dioxane solution passed through the column is stirred into 500 ml of water with stirring, the precipitated flakes are filtered, washed with water and dried at 100 ° C to a constant weight. 25.5 g (78%) of 2,4,6-tris- (4-hydroxyphenyl) -, 3,5-triazine are obtained in a dark yellow powder with m.p. 278-280 s.

Mol mass 357 (mass spectrometrically).

those on the Silufol plates, eluent dioxane: octane (5: 1), and the iodine vapor prod uct (, 79).

Found,%: C 70.83; N.

4.0;

12.03.

C, H, HaOZ, Calculated, 11.76.

C, 70.58; H 4.20;

IR spectrum, 3340 W.S. (HE); 1595, 1540, 1500, 1380 s., Def. and cyanurate cycle); 820 (p-position).

PMR spectrum, S, MD: 8.14 d., 6.83 d. (SbN); 3.28 s. (HE). The conditions and results of examples 2-9 are presented in table. one.

It should be noted that the target mixture is obtained only when the ratio of cyanuric chloride: phenol: aluminum hlrris31313854

thy equal to 1: 3.0 - 3.2: 3.0 - 3.2 (mol)

respectively. A decrease and increase in the ratio leads to the contamination of the target mixture with the initial cyanuric chloride or the tar products, which does not allow using the mixture obtained in Examples 4, 5 as the initial mixture for further transformations by the Mannich reaction. Replacing the carbon tetrachloride solvent with others (see examples 6-9), as well as changing the temperature-time intervals of the reaction (below O and above, below 4 and above 6 hours), also does not result in the desired mixture.

PRI me R 10. Obtaining a mixture of 2-oxo-2,3-dihydro-4,6-bis- (3-di-ethyl-aminomethylene-4-oxyphenyl) -1,3, 5-triazine and 2 , 4,6-tris- (3-diethylaminomethylene-4-hydroxyphenyl) -1,3,5-triazine (SPT).

To a mixture of 10 g (0.03 mol) consisting of 2.2 g (0.00783 mol) 2-oxo-2, 3-dihydro-4,6-bis- (4-oxyphenyl) -1.3, 5-triazine and 7.8 g (0.02185 mol) 2,4,6-tris- (4-oxyphenyl) -1,3,5-triazine, 6.57 g (0.09 mol) of diethylamine and 7.3 ml of a 37% aqueous formalin solution (which is 0.09 mol of pure formaldehyde) and heated under reflux in a water bath for 5 hours at 75 ° C. The reaction mixture is then poured into a porcelain dish and evaporated in a boiling water bath. The residue is triturated with petroleum ether (3 x 30 ml) to remove the starting material and dried at 40 ° C to constant weight. 14.6 g (85%) PTS are obtained in the form of a viscous cherry-colored oil.

Chromatography on a column filled with alumina of the II degree of activity of a dioxane solution of PTS with subsequent elution with dioxane and water showed that the resulting mixture consists of two adducts: 22% - 2-oxo-2, 3-dihydro-4,6- bis- (3-diethylamino-methylene-4-oxyphenyl) -, 3,5-triazine (1) and 78% - 2,4,6-tris- (3-diethyl-aminomethylene-4-oxyphenyl) -, 3, 5-triazine (II). I is a viscous cherry-colored oil; II is a burgundy crystalline substance with m.p., 92-94 cmol. mass 1: found 465 (by cryoscopy in dioxane), calculated 45

Found,%: C 66.1; H 7.5; N 15.26.

five

h o -5

,, N, 0,

C, 66.51; H 7.31;

Calculated% N 15.52.

IR spectrum I, 3600-3020 w.s. (HE); 2935 cf., 2885, 2863 ate. (CH .. and); 1720 cf. (); 1620-1580 br. p., 1500 sr. (and - sopr.). 1135 s., 1080-1050 br. Wed, (t, amine); 883 cf., 840, 770, 720, 580 ate. (1,2,4 - bzl.).

found

II

605, computed: C, 70.7; H 7.5;

Mol weight leno 612.

Found,% N 14.0.

with; bN48 it is calculated,%: C 70,58; H 7.84; N 13.72.

IR spectrum 11 ,, 3600 - 3020 br. with. (HE); 2930, 2855 el, 0 (CH and); 1600 s., 1505 sr., 1470 s. () and -sopr.); 1380s (cyanurate cycle); 1160-1170 BW 1060 cf. (tert, amine); 860, 755 ate, 733 cf., 580 ate (1,2,4 - bzl.).

 and measures 11-18 are presented in table. 2

This mixture (SPT) was tested as an epoxy resin hardener (ED-6).

Prepared compositions of the following compositions:

The compositions are prepared by mechanically mixing the epoxy resin and hardener at 20 ° C for 15 minutes, poured into special teflon molds of standard sizes and cured at 230 ° C for 3 hours. The curing process is accompanied by the decomposition of the hardener to form rigid foam epoxides. The resulting samples of the penoepoxides are cooled to 20 ° C, removed from the molds, and the softening temperature, specific toughness and static bending strength are determined (in accordance with GOST 4670-77 and 15065-69).

The original compositions are cast into aluminum molds with a diameter of 5.5 cm, cured in the indicated mode, and dielectric indices are determined.

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formed penoepoxides (according to GOST 22372-77).

The data of physicomechanical tests of a mixture of PTS as a hardener of epoxy resins to obtain rigid penoepoxides in comparison with the known technical solution are given in Table. 3

As can be seen from the data table. 3, the use of a mixture of PTS as an epoxy dopant resin breaker in the preparation of rigid foam epoxides has the following advantages over the known ones.

,one . Improving the physicomechanical properties of hardened foam epoxides:

increase in strength under static bending (53-72 instead of 35 kg / cm);

increase beats impact strength (1, 4 kg cm / cm instead of 1.2 kg cm / cm);

softening temperature increase (300-320 instead of 120 ° С).

2. Reducing the number of hardeners by 4-5 times (15-20 wt.% Instead of 80 wt.%)

3. Exclusion of the composition of the catalyst and equalizer, which excludes the possibility of premature curing.

4. The elimination of the need to use an autoclave, increased pressure, the additional use of freon and nitrogen as blowing agents, which simplifies the technology for the production of foam epoxides,

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At the same time, solidified commission has similar dielectric properties with a known composition.

5 Thus, the proposed method allows to obtain a mixture that can be used as a curing agent for epoxy diane resins in the preparation of rigid penospoxides with improved properties.

Claims (1)

Claims. The method of obtaining a mixture of 2-oxo-2,315 dihydro-4,6-bis- (3-diethylaminomethylene-4-oxyphenyl) -, 3,5-triazine and 2,4,6-tris (3-diethylaminomethylene-4-hydroxyphenyl ) -1,3,5-triazine, characterized in that the cyanurchloid REED is reacted with phenol and aluminum chloride, at a molar ratio of reagents of 1: 3.0 - 3.2: 3.0-3.2, respectively, in carbon tetrachloride at a temperature of 0-10 C, the resulting mixture containing 20 ± 2% 2-oxo-2,3-dihydro-4,6-bis- (4-oxyphenyl) -1,3,5-triazine and 80 ± 2% 2,4,6-tris- (4-oxyphenyl) -, 3,5-triazine, are treated 30 diethylamine and formalin, with a molar ratio of the mixture, diethylamine and formalin 1: 3.0-3.2: 3.0-3.2, respectively, at a temperature of 70-85, followed by evaporation of the reaction 35 mass and treatment of the residue with petroleum ether. Table 1 1313854 8 Continued table. one table 2 65 85 70 50 2.5 6.0 7.0 1.0 1.0 1.0 1.0. 18 85 2.0 1.0  In examples 13, 18, the resulting mixture contains up to 7-10% of tar tar by-products, the structure of which could not be established, and their presence makes it impossible to use the mixtures as curing agents due to the decrease in the physicomechanical properties of epoxy composites. According to examples 14, 17, the resulting mixture due to low conversion due to the lack of diethylamine and formalin contains up to 14% of the initial mixture of triazine-containing di- and triphenols, and its presence makes it impossible to use the resulting mixtures as an epoxy curing agent. 2.5 3.2 3.0 3.8 2.0 56.0 (target mixture is not received) 80.0 75.6 70.0 (target mix is not obtained) 55.0 (target mix not obtained) We offer) Epoxy-cleavage ED-6 Table 3 310 53 1.25 1.17 5-10- The hardener is a mixture of 2-oxo-2, 3-dihydro-4,6-bis- (3-diethylamino-methyl, 4-hydroxyphenyl) -1,3,5-triazine and 2,4,6-tris - (3-diethylaminomethlen-A-hydroxyphenyl-1,3,5-triazine (CPT) Q .  . H CHiNlCjH 13 Edb ED-6 CH NlCiHs j 85 15 83 17 100 80 , 3 h 0.45 315 63 1,31,37 6-10- 320 72 1,41,32 6-U- 0.2 .t20 35 1,21,35 6-TO-