RU2187504C2 - 1,3,5-triazine quaternary trimethylammonium salt as intermediate compound in synthesis of modifying agent-cohardening agent of epoxyoligomers in composites of anhydride hardening - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: invention relates to 1,3,5-triazine quaternary ammonium salt of the formula (I)

Description

который является активным полу продуктом синтеза (синтоном) модификатора-соотвердителя эпоксидных олигомеров 2-аллиламино-4,6 -бис(этоксикарбоксилатометиламино)-1,3,5-триазина формулы:

Известны триметиламмонийные соли производных сим-триазина, содержащие алкиламинные заместители в положениях 4,6-триазинового цикла, такие, как N(СН₃)₂ и N(C₂H₅)₂, которые применяются в качестве промежуточных соединений в реакциях циклизации при получении бициклических аннелирлованных производных сим-триазина [см. В.В. Довлатян, К.А. Элиазян, А.В. Довлатян. Перегруппировки в ряду галогеналкокси (амино)-симм-триазинов. - ХГС. 1977, 7, с. 989-992] . Применение таких солей в качестве синтонов в синтезе модификаторов-соотвердителей эпоксидных олигомеров - неизвестно.The invention relates to the field of organic chemistry, specifically to a new derivative of sim-triazine: 2-trimethylammonium chloride-4,6-bis (ethoxycarboxylatomethylamino) -1,3,5-triazine (TAXT) of the formula:

which is the active semi-product of the synthesis (synthon) of the hardener modifier-epoxy oligomers of 2-allylamino-4,6-bis (ethoxycarboxylatomethylamino) -1,3,5-triazine of the formula:

Trimethylammonium salts of sim triazine derivatives are known containing alkylamine substituents at the positions of the 4,6-triazine ring, such as N (CH ₃ ) ₂ and N (C ₂ H ₅ ) ₂ , which are used as intermediates in cyclization reactions upon receipt bicyclic annelated derivatives of sim-triazine [see V.V. Dovlatyan, K.A. Eliazyan, A.V. Dovlatyan. Rearrangements in the series of haloalkoxy (amino) -sym-triazines. - CHC. 1977, 7, p. 989-992]. The use of such salts as synthons in the synthesis of epoxy oligomer hardener modifiers is not known.

Also known are 2-diethylamino-4,6-bis [ethoxycarboxylato (4'-phenoxy)] - triazine (DECT) and its use as a modifier for epoxy anhydride curing compositions. DECT is obtained by the reaction of 2-diethylamino-4,6-bis (p-carboxyphenoxy) -sim triazine acid chloride with absolute ethanol in a solution in benzene, in the presence of triethylamine, as an acceptor of hydrogen chloride, at an equimolar ratio of the starting materials. The introduction of DECT into the composition in an amount of 10 wt.% At 90 ^o C allows to obtain cured composites with heat resistance in air of 285 ^o C, heat resistance according to Vika - 110 ^o C, specific impact strength of 4.5 kJ / m ² , with a compressive strength of 100 MPa and Barkul hardness of 28 barg, water absorption of 0.12 wt.% And a gel yield of 93.8 wt.% [See VK. Pyzhov, V.N. Zapishny, A.A. Balyan, G.M. Poghosyan. Synthesis of some esters and amides of 2-substituted 4,6-bis (p-carboxyphenoxy) -symmetriazines. LTS, 1981, 10, p. 1406-1411 and E.A. Hakobyan, V.K. Pyzhov, V.N. Zapishny G.M. Poghosyan. The esters of sim-triazine-containing carboxylic acids are modifiers of epoxy resin. - Plast.massa, 1983, 10, p. 57]. The disadvantages of using DECT are the high temperature of combining it with an epoxy oligomer (90 ^o C), which impairs the manufacturability of use, its inability to act as a hardener modifier (as evidenced by the low gelation efficiency and relatively high water absorption), as well as the insufficient efficiency of increasing heat and heat resistance, specific toughness, Barkul hardness and compressive strength of cured composites (analogue in structure and application).

 The technical solution to the problem is to improve the manufacturability of use, increase heat and heat resistance, specific impact strength, Barkul hardness, compressive strength and gel yield of cured epoxy composites, as well as reduce gelation time, water absorption and the temperature of combining epoxy anhydride curing compositions.

используют как промежуточное соединение для синтеза эффективного модификатора-соотвердителя эпоксидных композиций ангидридного отверждения.The task is achieved in that the newly synthesized 2-trimethyl-ammonium chloride-4,6-bis (ethoxycarboxylatomethylamino) -1,3.5-triazine (TAXT) of the formula:

used as an intermediate for the synthesis of an effective modifier-hardener of epoxy anhydride curing compositions.

 The novelty of the claimed proposal is seen in the fact that the use of 2-trimethylammonium chloride-4,6-bis (ethoxycarboxylatomethylamino) -1,3.5-triazine as an active synton allows us to synthesize an effective modifier-hardener of epoxy oligomers and to obtain anhydride cured composites, characterized by increased heat and heat resistance , specific impact strength, Barkul hardness, compressive strength and higher gel yield of cured epoxy composites, as well as low gel formation time, water ogloscheniem and temperature combination with an epoxy resin.

In this case, cyanuric chloride, a technical product, is purified by double crystallization from carbon tetrachloride (mp. 146 ^{° C.} ). Amino acetic acid ethyl ester is prepared according to the well-known Fischer method by reacting amino acetic acid hydrochloride with an excess of ethyl alcohol and subsequent dehydrochlorination using dry ammonia [see E. Fisher. Ber., 1901, Bd. 34, S. 433]. Before use, triethylamine is dried over sodium hydroxide and distilled with an effective reflux condenser (mp. 89-90 ^o C). An analogue in the structure and use of DECT is obtained by the known method by the interaction of 2-diethylamino-4,6-bis (4'-carboxyphenoxy) -sim triazine acid chloride with ethanol in the presence of triethylamine, an acceptor of hydrogen chloride [see VK. Pyzhov, V.N. Zaplichny, A.A. Balyan, G.M. Poghosyan. Synthesis of some esters and amides of 2-substituted 4,6-bis (p-carboxyphenoxy) -symmetriazines. HCG, 1981, 10, p. 1406-1411].

 Specific examples of the preparation of the proposed quaternary ammonium salt of 1,3.5-triazine as an intermediate in the synthesis of epoxy oligomer hardener modifier are presented below.

Example 1. 2-Trimethylammonium chloride-4,6-bis (ethoxycarboxylatomethylamino) -1,3,5-triazine (TAXT). To a solution of 4.62 g (24 mmol) of 2,4,6-trichloro-1,3,5-triazine (cyanuric chloride) in 20 ml of absolute benzene at a temperature of 5 ± 1 ^o C with a stirring slowly add dropwise a mixture of 5 g (48 mmol) of ethyl aminoacetic acid ester (glycine ethyl ester) and 4.96 g (49 mmol) of freshly distilled triethylamine in 5 ml of abs. benzene and stirring is continued for 1 h at the same temperature, 1 h at 25-30 ^o C and another 1 h at 35-40 ^o C. The precipitate formed is filtered off, the filtrate is evaporated to dryness in a vacuum of a water-jet pump, and the dry residue is washed with water (3 • 50 ml) and dried. 6.1 g (71%) of 2-chloro-4,6-bis (ethoxycarboxy-latomethylamino) -1,3,5-triazine (CET) are obtained in the form of a white fine crystalline powder with mp. 178-179 ^o C.

Found,%: C 41.71; H 5.19; N, 22.18; Cl 12.05; C ₁₁ H ₁₆ N ₅ ClO ₄ .

 Calculated,%: C 41.58; H 5.08; N, 22.04; Cl 11.15.

IR, γ, cm ^-1 : 3250, 3180 _sr. (NH); 1740 _s. (C = O); 1575, 1540, _{c., Cp.,} (C = C and C = N-res.); 1240 _cp . (CN); 1190, 1130 _sr (C-O-C).

PMR spectrum, δ, ppm: 8.10 _br.s. (2H, -NH); 4.05 ... 4.20 _m . (4H, -OCH ₂ ); 3.85 ... 4.0 _m. (4H, -NCH ₂ ); 1.20 ... 1.30 _m. (6H, -CH ₃ ).

 Like ion 317 (mass spectroscopic).

Through a solution of 5 g (16 mmol) of the obtained CET in 30 ml of abs. benzene with stirring and a temperature of 10 ± 1 ^o With in a stream of nitrogen dry trimethylamine is bubbled. Saturation with trimethylamine was continued for 1 hour and the reaction mixture was left at 20 ^{° C.} for 12 hours. A rich precipitate was formed, filtered off, washed with abs. benzene (3 • 25 ml) and dried in a vacuum desiccator to constant weight. 5.81 g (98%) of 2-trimethylammonium chloride-4,6-bis (ethoxycarboxylatomethylamino) -1,3.5-triazine (TAHT) is obtained in the form of a white fine crystalline powder with mp. 180-180.5 ^o C.

Found,%: C 44.73; H, 6.81; N, 22.40; Cl 9.53. C ₁₄ H ₂₅ N ₆ ClO ₄ .

 Calculated,%: C 44.59; H, 6.69; N, 22.30; Cl 9.40.

IR, γ, cm ^-1 : 3435, 3225 _cf. (NH); 1730 _s (C = O); 1590, 1560, 1510 _s. , _cf. (C = C and C = N-res.); 1190, 1150 _cf. (C-O-C).

1 H-NMR spectrum, δ, ppm: 8.12 _{br s} (2H, NH); 4.08 ... 4.23 _m . (4H, OCH ₂ ); 3.87 ... 4.01 _m. (4H, NCH ₂ ); 3.20 _m. (9H, N (CH ₃ ) ₃ ); 1.22 ... 1.31 _m. (6H, -CH ₃ ).

Example 2. Carried out under conditions similar to example 1, from 5 g (16 mmol) of chemotherapy in 35 ml of abs. benzene, with the only difference being that the bubbling of dry trimethylamine is continued for 1.5 hours at 5 ± 1 ^{° C.} , then the reaction mixture is kept at 18 ^{° C. for} another 15 hours to give 5.87 g (99%) of 2-trimethylammonium chloride 4,6-bis (ethoxycarboxylato-methylamino) -1,3.5-triazine (TAXT) in the form of a white fine crystalline powder with mp 180-180.5 ^o C.

Found%: C 44.73; H, 6.81; N, 22.40; Cl 9.53. C ₁₄ H ₂₅ N ₆ ClO ₄ .

 Calculated,%: C 44.59; H, 6.69; N, 22.30; Cl 9.40.

IR, γ, cm ^-1 : 3435, 3225 _cf. (NH); 1730 _s (CO); 1590, 1560, 1510 _s , _cf. (C = C and C = N-res.); l190, 1150 _cp. (COC).

PMR spectrum, δ, ppm: 8.12 _br.s. (2H, NH); 4.08 ... 4.23 _m. (4H, OCH ₂ ); 3.87 ... 4.01 _m. (4H, NCH ₂ ); 3.20 _m. (9H, N (CH ₃ ) ₃ ); 1.22 ... 1.31 _m. (6H, -CH ₃ ).

 The obtained quaternary ammonium triazine-containing salt of TAXT is an effective intermediate (synthon) suitable for the synthesis of a more active, in comparison with the known, modifier-hardener of epoxy oligomers. Examples of obtaining a hardener modifier based on the proposed synton are presented below.

Example 3. 2-Allylamino-4,6-bis (ethoxycarboxylatomethylamino) -1,3,5-triazine (AEKT). To a solution of 5 g (13 mmol) of 2-trimethylammonium chloride-4,6-bis (ethoxycarboxylatomethylamino) -1,3.5-triazine (TAXT) in 35 ml of acetonitrile, a solution of a mixture of freshly distilled and dried is slowly added with stirring at a temperature of 5 ± 1 ^o С 0.75 g (13 mmol) of allylamine and 1.32 g (13 mmol) of triethylamine in 5 ml of acetonitrile. The mixture is stirred for another 1 hour at the same temperature, 8 hours at 20 ± 1 ^o C and evaporated in water-jet vacuum to 1/3 of the original volume. The residue is diluted with 40 ml of water, the precipitate is filtered off, washed with water (4 • 25 ml) and dried. 3.3 g (73%) of 2-allylamino-4,6-bis (ethoxycarboxylatomethylamino) -1,3,5-triazine (AEKT) are obtained in the form of a white crystalline powder with a melting point of 78-79 ^o C.

Found,%: C 49.81; H, 6.69; N, 24.93. C ₁₄ H ₂₂ N ₆ O ₄ . Calculated,%: C 49.69; H 6.55; N, 24.84.

IR, γ, cm ^-1 : 3330, 3220 _sr. (NH); 1710 _s. (C = O); 1640 _cf. (C = C); 1600 _ff., 1565 _p. (C = C and C = N-res.); 1180, 1140 _cf. (C-O-C).

J=17, 42 и 13); 4,0...4,15_м. (4Н, NH

); 3,75...4,0м (6Н,

); 1,15...1,30_м. (6Н, СН₃).PMR spectrum, δ, ppm: 6.70 _br.s. (3H, NH); 5.75 ... 5.90 _m. (1H, CH); 4.95 ... 5.15 _dd (2H, CH ₂ CH =

J = 17, 42 and 13); 4.0 ... 4.15 _m . (4H, NH

); 3.75 ... 4.0m (6H,

); 1.15 ... 1.30 _m. (6H, CH ₃ ).

 Like ion 338 (mass spectroscopic).

Example 4. Carried out under conditions analogous to example 3, from 5 g (13 mmol) of 2-trimethylammonium chloride-4,6-bis (ethoxycarboxylatomethylamino) -1,3,5-triazine (TAXT) in 35 ml of acetonitrile and a mixture of 0.75 g (13 mmol) of allylamine and 1.32 g (13 mmol) of triethylamine in 5 ml of acetonitrile, with the only difference being that the amine mixture was added at 10 ± 1 ^o C, and the reaction mixture was stirred for another 1.5 hours at this temperature and 10 hours at 20 ± 1 ^o C and get 3.6 g (79.6%) of 2-allylamino-4,6-bis (ethoxycarboxylatomethylamino) -1,3,5-triazine (AEKT) in the form of a white crystalline powder with mp . 78-79 ^o C.

Found,%: C 49.81; H, 6.69; N, 24.93. C ₁₄ H ₂₂ N ₆ O ₄ . Calculated,%: C 49.69; H 6.55; N, 24.84.

IR, γ, cm ^-1 : 3330, 3220 _cp. (NH); 1710 _s. (C = O); 1640 _cf. (C = C); 1b00 _words , 1565 _c. (C = C and C = N-match); 1180, 1140 _cf. (SOS).

J=17, 42 и 13); 4,0...4,15_м. (4Н, NH

); 3,75...4,0_м. (6Н,

); 1,15...1,30_м. (6H, СН₃).1 H-NMR spectrum, δ, ppm: 6.70 _{br s} (3H, NH); 5.75 ... 5.90 _m . (1H, CH); 4.95 ... 5.15 _dd (2H, CH ₂ (CH)

J = 17, 42 and 13); 4.0 ... 4.15 _m. (4H, NH

); 3.75 ... 4.0 _m. (6H,

); 1.15 ... 1.30 _m. (6H, CH ₃ ).

 Like ion 338 (mass spectroscopic).

 Specific examples of the use of AECT, obtained on the basis of the proposed intermediate, as an epoxy oligomer hardener modifier to increase heat and heat resistance, specific toughness, Barkul hardness, compressive strength and gel yield of cured epoxy composites, and also reduce gelation time, water absorption and combination temperatures are presented in tables 1, 2 (examples 5-11; see the end of the description).

In this case, the starting epoxy compositions are prepared on the basis of the ED-20 epoxy oligomer freshly recrystallized from CCl ₄ phthalic anhydride, the well-known DECT modifier and obtained on the basis of the proposed intermediate product - AECT modifier-hardener, in exact accordance with the known method [see E. A. Hakobyan, V.K. Pyzhov, V.N. Zapishny G.M. Poghosyan. The esters of sim-triazine-containing carbolic acids are modifiers of epoxidic resins. - Plast. masses, 1983, 10, p. 57]. The curing conditions of epoxy compositions are similar to the same method. The gel yield is determined by boiling a portion of the cured composite in acetone in a Soxhlet apparatus for 12 hours. The gelation time and water absorption are determined in accordance with the known method [see L. S. Kalinina, M.A. Motorina, N.I. Nikitina et al. Analysis of condensation polymers. M .: Chemistry. 1984. - 296 p.].

As can be seen from the data in table 1, the use of the proposed AEKT hardener modifier in comparison with the well-known DECT makes it possible to reduce the temperature of its combination with the epoxy oligomer by 37 ^° C (53 instead of 90 ^° C), which simplifies the technology for preparing the initial composition.

The same table shows that the use of AEKT in the epoxy composition can reduce the gelation time at 65, 75 and 95 ^o C to 47-124 min, 34-90 min and 7-32 min, respectively, instead of 2500-760 min in the case of control and 1300-380 min in the case of using the known DECT modifier, which indicates that the proposed AECT, in contrast to the known DECT, is also an effective hardener of epoxy anhydride curing compositions.

 The effectiveness of AEKT as a hardener is also confirmed by the data in Table 2. From examples 5-11 of this table it can be seen that the use of AEKT allows to increase the gel yield in the cured composition in comparison with the control by 8.6-11.8%, while the use of the known DECT modifier increases this indicator by only 7.8 % (94.6-97.2% instead of 86.0%).

 From the data of table 2, examples 5-11 it is also seen that the proposed AECT is a more effective modifier of epoxy oligomers in comparison with the known.

Thus, the use of AEKT allows one to obtain cured epoxy compositions, whose Vic and 44–57 and 60–75 ^° C heat resistance respectively exceed that in comparison with the control, while the use of the well-known DECT modifier allows increasing these indicators only by 39 and 50 ^o C, respectively (115-128 ^o C and 295-310 ^o C, respectively, instead of 71 ^o C and 235 ^o C, respectively).

The specific toughness of the composition cured using AEKT increases by 0.8-2.6 kJ / m ² in comparison with the control, while the use of the known DECT modifier increases this indicator by only 0.5 kJ / m ² ( 4,8-6,6 kJ / m ² instead of 4.0 kJ / m ^2).

 The compressive strength of the composition cured using AEKT increases by 28-48 MPa in comparison with the control, while the use of the known DECT increases this indicator by only 8 MPa (120-140 MPa instead of 92 MPa).

 The Barkul hardness of the composition cured using AEKT increases by 4-15 bark compared to the control, while the use of the known DECT increases this indicator by only 3 bark (29-40 bark instead of 25 bark).

 Water absorption of the composition cured using AEKT is reduced by 30-70.9% in comparison with the control, while the use of the known DECT does not affect this indicator at all (0.035-0.084 wt.% Instead of 0.12 wt.% )

 Thus, the use of the proposed quaternary ammonium salt of 1,3.5-triazine as an intermediate in the synthesis of modifier-hardener allows you to get a modifier-hardener, the use of which in the composition of epoxy compositions provides, in comparison with the known, lower temperature combination, which improves processability, and in cured composites it reduces water absorption and increases gel yield, increases heat and heat resistance, specific impact strength, hardness and compressive strength.

Claims (1)

Quaternary trimethylammonium salt of 1,3,5-triazine of the formula

as an intermediate in the synthesis of a hardener modifier of epoxy oligomers in anhydride curing compositions.

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