RU2290425C1 - Super-concentrate used in preparing antifreezes and heat carrier - Google Patents

Abstract

FIELD: chemical technology.

SUBSTANCE: invention relates to materials used in preparing antifreezes and heat carriers. Antifreeze super-concentrate comprises the following components, wt.-%: mixture of at least one monocarboxylic acid, such as caproic, caprylic, 2-ethylhexanoic, benzenecarboxylic acid, and at least one dicarboxylic acid, such as butanedionic, hexanedionic, decanedionic, phthalic acid or their alkaline metal salts or alkanolamines, 0.05-60.0; tolyltriazole or benzotriazole or their mixtures taken in the equal amounts, 0.001-5.0; sodium molybdate, 0.005-5.0; caprolactam, 0.001-1.5; sodium polyacrylate, 0.001-3.0; monoalkylphosphoric acid salt of the general formula:

wherein R means hydrogen atom (H), C₁₆H₃₃ - C₁₈H₃₇; M means Na, K, -NH(CH₂CH₂OH)_n; n = 9-15, 0.3-0.5; frothing agent, 0.001-0.03; water, 5-15, and glycols, such as ethylene glycol, propylene glycol, polyglycols, the balance. Invention provides enhancing protective properties, stability in exploitation at high temperatures, resistance against hard water, providing compatibility with majority of commercial antifreezes and tosols. The proposed super-concentrate is used in preparing antifreezes designated for internal engine combustion systems and heat carriers used in heat-exchange devices.

EFFECT: improved and valuable technical properties of concentrate.

3 cl, 9 tbl, 26 ex

Description

The invention relates to the field of chemical technology, in particular, to antifreeze concentrates for the manufacture of coolants used in cooling systems of internal combustion engines of cars, and also as a coolant intended for use in heating and air conditioning systems of buildings

Known compositions of antifreeze concentrates (CS patent No. 226394, IPC 6, 23 F 11/10, 1985; YP patent 59157167, IPC 6, 09 K 3/00, 1984), which do not prevent the corrosion of ferrous metals. Antifreeze, made on the basis of a ferrous metal inhibitor (CS patent No. 213154, IPC 6, C 23 F 11/10, 1984), is aggressive towards brass.

A known glycol-based antifreeze concentrate (FR application No. 2489355, IPC 6, C 09 K 15/04, 1982). Although it prevents corrosion of ferrous and non-ferrous metals, the antifreeze obtained on its basis is unstable with respect to hard water.

Known corrosion inhibitors, which are a concentrate of antifreezes (RU patent No. 2046815, IPC 6, 09 K 5/00, 1995; RU patent 2050397, IPC 6, 09 5/00, 1995; RU patent No. 2095388, IPC 6 , С 09 К 5/00, 1997), which provide protection of ferrous and non-ferrous metals, but containing sodium tetraborate (borax), the presence of which can impair the protection of aluminum and its alloys under heating conditions.

Highly concentrated superconcentrate for the production of antifreezes and coolants (RU patent No. 2196797, IPC 7, С 09 К 5/00, 2001), on the basis of which antifreezes with improved anticorrosive properties are made, as in previous inventions, has a significant disadvantage in that it contains triethanolamine. It is believed that such compounds can break down at high temperatures and lead to the formation of high molecular weight carcinogenic compounds, such as nitrosoamines, which are toxicologically hazardous.

Similar disadvantages exclude the compositions of corrosion inhibitors for glycol-based antifreezes (RU patent No. 2104330, IPC 6, 09 K 5/00, 1999; RU patent No. 2143499 IPC 6, 09 K 5/00, 1999; RU patent No. 2125074, IPC 6, C 09 K 5/00, 1999). However, the presence of potassium phosphates in the compositions of these inventions reduces the stability of antifreeze during its operation, the reason for this is the formation of precipitation that interferes with the circulation of the coolant and thereby reduces heat transfer.

A phosphate-free corrosion inhibitor is known (US 5422026 MKI 6, C 09 K 5/00, 1995), which contains borax, nitrates and silicates, the presence of which is characterized by the precipitation of insoluble silicate modifications at high temperatures, which indicates the instability of antifreeze in general.

Known aqueous corrosion inhibitor (US patent No. 6228283, IPC 7, With 09 To 5/00, 2001), the composition of which is represented by stabilized silicate, however, the presence in it of alkali metal phosphates, nitrate and nitrite of alkali metals does not allow to recognize such antifreezes meet modern requirements presented to antifreezes.

A polyglycol-based coolant is known that contains mono- and dicarboxylic acids, alkali metal phosphate, sodium tetraborate and / or high-modulus liquid glass and / or trilon B and / or dextrin as anti-corrosion additives (Patent RF 2213119 C 7, C 09 K 5 / 00, 2003). The presence of such components reduces the stability of the coolant as a whole. It is known that the presence of borax contributes to increased corrosion of aluminum, alkali metal phosphate does not provide a long-term protective film on the metal surface, and the inclusion of high-modulus liquid glass (sodium silicate) helps to reduce the stability of antifreeze during storage and the formation of a gel-like precipitate in operating conditions at high temperatures.

According to modern requirements of car manufacturers (see Ford WSS-M97 B44 D Engineering Materials Specification), the presence of silicates, phosphates is limited to 0.001 wt.%, Borax - 0.0005 wt.%; according to the technical requirements of AvtoVAZ TTM 1.97.1172-2004, the presence of nitrate and nitrite is completely eliminated.

Known ethylene glycol-based antifreeze concentrate containing monocarboxylic acids of the following composition: alkali metal salt of 6.6 ', 6 "- (1,3,5-triazine-2,4,6-tril-triimino) -trihexanoic acid (0, 1-6.0 wt.%), Benzotriazole or tolyltriazole (0.02-2.0 wt.%), Magnesium nitrate (0.01-1.0 wt.%) (DE patent 19930682, IPC 7, C 09 By 5/00, 2001. However, the antifreeze obtained on the basis of this concentrate, despite the high anticorrosion properties, is not available for domestic production due to a shortage of raw materials of this composition and the undesirable presence of nitrate.

The closest in composition, properties and purpose to the claimed composition of antifreeze concentrates is an organic composition (RF patent 2249634, 04/10/2005) of the following composition, wt.%:

Antifreeze formulas with enhanced performance characteristics were further developed through the use of a selected combination of mono- and dicarboxylic acids and a number of other corrosion inhibitors. The composition of new modern antifreezes completely eliminates the presence of silicates, phosphates, nitrates and nitrites, amines, borates while maintaining high corrosion protection of metals, especially aluminum, steel, cast iron, solder, copper and brass.

The objective of the invention is to provide a composition of a superconcentrate for producing antifreeze with high protective properties that meets the modern requirements of automakers, which has increased stability during operation at high temperatures, miscibility with other antifreezes.

This goal is achieved in that a superconcentrate for the manufacture of glycol-based antifreeze and coolants containing, as an inhibitory composition, a carefully selected combination of mono- and dicarboxylic acids such as caproic, caprylic, 2-ethylhexanoic, benzenecarboxylic, butanedioic, hexanedioic, decanedioic, phthalic their alkali metal salts or alkanolamines, tolyltriazole or benzotriazole, or their mixture in equal proportions, sodium molybdate, additionally contains caprolactam, sodium polyacrylate I monoalkilfosfornoy acid salt, defoaming agent, water, and as the glycol - monoethylene glycol or propylene glycol or polyglycols with the following component ratio, wt.%:

A mixture of mono - and dicarboxylic acids or their alkaline salts metals or alkanolamines 0.05-60.0 Tolyltriazole or benzotriazole or their mixture in equal proportions 0.001-5.0 Sodium Molybdate 0.005-5.0 Caprolactam 0.001-1.5 Sodium Polyacrylate (Medium molecular weight 8000 g / mol) 0.001-3.0 Monoalkylphosphoric Acid Salt general formula:

,

,

Where

R is H; C ₁₆ H ₃₃ -C ₁₈ H ₃₇ ; M = Na, K, NH (CH ₂ CH ₂ OH) ₃ n = 9-15 0.3-0.5 Antifoam agent 0.001-0.03 Water 5.0-15.0 Monoethylene glycol, or propylene glycol, or polyglycols rest.

Moreover, as a specified anti-corrosion composition of mono- and dicarboxylic acids or their salts, their mixture can be used in the following ratio of components, wt.%: 0.01-10.0 caproic acid or its sodium, or potassium, or alkanolamine salt, or 0.01-10.0 caprylic acid or its sodium or potassium or alkanolamine salt, or 0.005-20.0 2-ethylhexanoic acid or its sodium or potassium or alkanolamine salt, or 0.01-10.0 benzene carboxylic acid or its sodium, or potassium, or alkanolamine salt, or 0.01-10.0 butanedi of acid, or its sodium, or potassium, or alkanolamine salt, or 0.01-10.0 hexanedioic acid, or its sodium, or potassium, or alkanolamine salt, or 0.01-10.0 decandionic acid, or its sodium, or potassium or alkanolamine salt, or 0.005-10.0 phthalic acid or its sodium, or potassium, or alkanolamine salt, or a mixture thereof in any combination.

As the alkanolamine salt of these acids, a salt of triethanolamine, or β, β ¹ -dihydroxy-N-methyldiethanolamine, or 2,2 ', 2 "-nitrilotriethanolamine, is used.

As an antifoam agent, Dow Silicone DSP emulsion or PMS-200 A liquid silicone polymer of various viscosities (OST 6-02-20-79) can be used.

The polyglycols used (TU 6-15-1761-94) are a by-product of the production of ethylene glycol and are an aqueous solution of a mixture of glycols with a mass fraction of 75-90%, which contains 60-80 wt.% Monoethylene glycol, 5-20 wt.% Diethylene glycol up to 5 wt.% triethylene glycol.

Comparative analysis with the prototype shows that this composition of the antifreeze superconcentrate differs from the known one by the introduction of new components: an anticorrosive composition containing free mono- and dicarboxylic acids or in the form of alkali metal salts or alkanolamines such as caproic, caprylic, 2-ethylhexanoic, benzenecarboxylic, butanedione , hexandionic, decandionic, phthalic in any combination thereof, caprolactam, sodium polyacrylate, antifoam. The composition of antifreeze superconcentrate is represented by readily available raw materials.

Thus, the claimed technical solution meets the criterion of novelty.

The use in this composition of new components in combination with the known and found ratio of all ingredients provides properties that are manifested only in the specified technical solution, namely:

- high anticorrosive properties of antifreeze or coolant obtained on its basis, relative to structural materials (copper, solder, brass, steel, cast iron, aluminum), including protection against cavitation and erosion (see tables 2 and 3);

- a high degree of preservation of the stability of antifreeze at high temperatures (see table 4);

- the stability of corrosion protection in harsh conditions when tested by the potentiostatic method (see table 5);

- compatibility with most trademarks of antifreeze and antifreeze (see table 6).

The proposed composition prevents mineral deposits in closed water systems, does not allow foaming, resistant to hard water.

When studying other technical solutions in this field of technology, signs that distinguish the claimed invention from the prototype were not identified, which ensures that this technical solution meets the criterion of significant differences.

A concentrate of this composition is prepared by sequential mixing of the components.

Example 1. In a container with a stirrer placed 5.0 g of water, 0.01 g of sodium molybdate, 0.001 g of benzotriazole, 0.001 g of caprolactam, 0.001 g of sodium polyacrylate, 71.976 g of ethylene glycol, 10.0 g of caproic acid sodium salt, 0.01 g of sodium salt of benzenecarboxylic acid, 10.0 g of butanedioic acid, 2.7 g of phthalic acid, 0.3 g of monoalkylphosphoric acid salt and 0.001 g of antifoam. The mixture is stirred at ambient temperature for 1 h until the components are completely dissolved.

Example 2. In a container with a stirrer, 7.5 g of water, 3.0 g of sodium molybdate, 1.2 g of tolyltriazole, 1.5 g of caprolactam, 0.05 g of sodium polyacrylate, 75.215 g of ethylene glycol, 0.7 g of potassium salt are placed caproic acid, 10.0 g of the potassium salt of caprylic acid, 0.5 g of the potassium salt of hexanedioic acid, 0.01 g of the potassium salt of butanedioic acid, 0.01 g of decandionic acid, 0.01 g of phthalic acid, 0.005 g of antifoam and 0, 3 g salt of monoalkylphosphoric acid. The mixture is stirred at ambient temperature for 1 h until the components are completely dissolved.

Examples 3 and 4 are carried out analogously to Example 2.

Example 5. 12.0 g of water, 3.0 g of sodium molybdate, 5.0 g of tolyltriazole, 0.5 g of caprolactam, 0.05 g of sodium polyacrylate, 58.275 g of ethylene glycol, 0.5 g of caproic acid are placed in a container with a stirrer , 0.01 g of caprylic acid, 20.0 g of triethanolamine salt of 2-ethylhexanoic acid, 0.01 g of sodium salt of benzenecarboxylic acid, 0.35 g of sodium salt of decanedioic acid, 0.3 g of salt of monoalkylphosphoric acid, 0.005 g of antifoam. The mixture is stirred as described in example 1.

Examples 6-22 are prepared analogously to Examples 1 and 2.

Example 23. In a container with a stirrer, 10.0 g of water, 3.0 g of sodium molybdate, 2.0 g of benzotriazole, 1.0 g of caprolactam, 0.05 g of sodium polyacrylate, 63.528 g of propylene glycol, 0.01 g of potassium salt are placed , caprylic acid, 20.0 g of 2,2 ', 2 "-nitrilotriethanolamine salt of 2-ethylhexanoic acid, 0.11 g of decanedioic acid, 0.3 g of monoalkylphosphoric acid salt, 0.002 g of antifoam. The mixture is stirred as described in example 1 .

Examples 24 to 25 are prepared analogously to Example 23.

The compositions of the antifreeze concentrate according to examples 1-25 and the prototype are shown in tables 1, 1A, 1B, 1B.

Samples of antifreeze are prepared from the antifreeze superconcentrate compositions shown in Tables 1-1b for corrosion testing on metals by diluting it with ethylene glycol or propylene glycol, or polyglycols in a ratio of 1: 4.

Antifreeze samples are subjected to corrosion tests in the form of their 50% solutions according to GOST 28084-90 for 336 hours at 88 ° ± 1 ° C with aeration by air.

Comparative results of corrosion tests are presented in table 2. The main physicochemical properties of the antifreeze superconcentrate and antifreeze obtained on its basis are presented in table 3.

Determination of storage stability at elevated temperatures of coolants obtained on the basis of antifreeze concentrate is carried out according to the methodology of AvtoVAZ Technical Requirements (TTM 1.97.1172-2004) and Ford Engineering Materials Specification (WSS-M97 B44-D). The coolant concentrate in an amount of 60 ml is placed in a thermostat in a hermetically sealed vessel and heated to 65 ± 2 ° C for 14 days. The presence of gelatinous sediment is monitored on days 2, 7, 10, 14. When sediment appears, the tests are terminated. In the absence of sediment, 30 ml of the test liquid is dissolved in the same amount of synthesized hard water containing 275 mg / dm ³ calcium chloride, 148 mg / dm ³ sodium sulfate, 165 mg / dm ³ sodium chloride, 138 mg / dm ³ sodium bicarbonate. The resulting solution was again placed in a thermostat at a temperature of 65 ± 2 ° C for the next 14 days, the presence of gelatinous precipitate was monitored on days 2, 7, 10 and 14. In the presence of sediment, the liquid is considered to have failed the test.

The results of tests for stability at high temperature are presented in table 4.

The stability of the effective protection of corrosion inhibitors of antifreeze obtained on the basis of superconcentrate was tested using a laboratory electrochemical potentiostatic method. According to generally accepted standard testing methods for automobile antifreezes BL 5-1 Ford Motor Company (galvanostatic method) and PCP method (cyclic polarization scanning method), the tests are carried out on an aluminum alloy in the form of a 30 vol.% Solution of antifreeze in corrosive water according to ASTM D 1384 containing 0.0028 M NaCl (165 mg / L), Cl ions ^- which are the main activator of aluminum corrosion. The effectiveness of the protective effect of corrosion inhibitors in the present invention was evaluated by the potentiostatic method of a 20 vol.% Antifreeze solution containing 0.01 M NaCl (585 mg / l), i.e. when creating more stringent testing conditions. Polarization curves were recorded on samples of aluminum alloy AB 00 (technically pure aluminum). The pitting potential E _pr , at which a passivating metal film breaks through, was determined by a sharp rise or by the appearance of stable current oscillations in the polarization curves. Comparative efficacy of inhibiting antifreeze compositions were determined from the values of E _s and baseline values protivopittingovogo? E = E _s -E _k, where E _k - stationary (first) potential, and also on the values of the current density I _a, according to the general corrosion rate. The higher the ΔE value, the more effectively this anti-freeze formulation prevents pitting corrosion. The higher the value of I _a , the faster corrosion occurs, the less effective this composition is to protect the metal. The results of the tests are presented in table 5.

The compatibility of the antifreeze obtained on the basis of the superconcentrate with other commercial antifreezes and antifreezes was checked according to the Ford WSS-M97B44-D Engineering Materials Specification (Section 3.4.2) and using the potentiostatic method. A 50 vol.% Solution of antifreeze according to the claimed composition, prepared by dilution with corrosive water according to ASTM D 1384, and a 50 vol.% Solution of a test concentrate of commercial antifreeze or antifreeze diluted with the same corrosive water are mixed in a volume ratio of 1: 1. Allow to stand for 24-48 hours at 20 ± 2 ° C in the complete absence of light. After a specified time, the presence of sediment is checked and tested for corrosion in compliance with weight loss. Additionally check the change in corrosion rate using the potentiostatic method. To remove the polarization curves, an antifreeze mixture is prepared in equal volume ratios according to the claimed composition, diluted 1: 1 with distilled water, and the tested commercial antifreeze or antifreeze with the addition of 585 mg / l NaCl. The test results are presented in table 6.

In addition, antifreeze samples prepared on the basis of a superconcentrate are tested for hardness in hard water according to GOST 28084-89. The criterion for the resistance of antifreeze to hard water is the absence of sediment and separation of the liquid phase. Determination of alkalinity reserve is carried out according to the method of ASTM D 1121. The hydrogen index (pH) is measured in 30% aqueous solutions of samples of superconcentrate according to the method of ASTM D 1287.

As can be seen from tables 1 and 2, the compositions 1-3, 5-7, 19-21, 23 have high anticorrosive properties. A decrease in the concentration of sodium molybdate below 0.01 wt.% Causes increased corrosion of steel (example 4), and an increase above 5.0 wt.% Does not increase the positive effect (example 8).

A decrease in the concentration of benzotriazole or tolyltriazole below 0.001 wt.%, I.e. practically their exclusion causes corrosion of copper and brass (example 9), and its increase above 5.0 wt.% does not lead to a positive effect (examples 10 and 22, respectively).

With a decrease in the salt content of monoalkylphosphoric acid below 0.3 wt.%, The protection of aluminum is significantly reduced (example 11), and an increase in its content above 0.5 wt.% Leads to the formation of an insoluble precipitate, as well as to a decrease in the protection of non-ferrous metals (example 12) .

A decrease in the concentration of caprolactam below 0.001 wt.%, Practically its exclusion, leads to a decrease in the corrosion resistance of non-ferrous metals (example 13), an increase in its content above 1.5 wt.% Sharply enhances the corrosion of all metals (example 14).

A decrease in the content of sodium polyacrylate below 0.001 wt.%, Practically its exclusion, leads to precipitation when mixed with hard water (example 15). The increase in its concentration above 3.0 wt.% Does not give a positive effect (example 16).

In the absence of an antifoam (Example 24), in the preparation of a superconcentrate, foaming is observed, with the introduction of an antifoam of more than 0.03 wt.%, A positive effect is not observed (Example 25).

A decrease in the concentration of a mixture of sodium or potassium or alkanolamine salts of caproic, caprylic, 2-ethylhexanoic, benzenecarboxylic, hexanedioic, butanedioic, decanedioic, phthalic acids below the lower limit causes increased corrosion of copper, solder, steel, cast iron, aluminum (example 17). An increase in the concentration of the mixture of these components above the upper limit leads to the formation of an insoluble precipitate in the form of a suspension, which sharply reduces the corrosion protection of all metals (example 18).

Dilution of the antifreeze superconcentrate with ethylene glycol or propylene glycol or a water-glycol mixture or polyglycols allows to obtain antifreeze and coolants with a given freezing temperature from minus 10 ° C to minus 65 ° C.

Thus, the use of new components in the composition of the antifreeze superconcentrate according to the invention in combination with the known ones and the found ratio of ingredients and the synergistic combination of mono- and dicarboxylic acids allows to obtain antifreezes and coolants that provide high and long-term corrosion protection with respect to structural materials of internal combustion engines or heat exchangers (copper, solder, brass, steel, cast iron, aluminum), protection against cavitation and erosion without the use of nitrites, stable to be hard water, storage stability at high temperatures, compatible with most commercial antifreezes and antifreeze.

Table 1 Name of components Superconcentrate Composition one 2 3 four 5 6 7 8 Content, wt.% 1. Caproic acid or its sodium or potassium or alkanolamine salt 10.0 0.7 0.01 10.0 0.5 0.01 10.0 - 2. Caprylic acid or its sodium or potassium or alkanolamine salt - 10.0 5.9 0.01 0.01 10.0 2.7 - 3,2-ethylhexanoic acid or its sodium or potassium or alkanolamine salt - - - - 20,0 10.0 0.005 0.005 4. Benzenecarboxylic acid or its sodium or potassium or alkanolamine salt 0.01 - 10.0 8.7 0.01 3.6 10.0 - 5. Hexanedioic acid or its sodium or potassium or alkanolamine salt - 0.5 10.0 10.0 - - - 0.01 6. Butanedioic acid or its sodium or potassium or alkanolamine salt 10.0 0.01 - 0.32 - - - - 7. Decandionic acid or its sodium or potassium or alkanolamine salt - 0.01 - 0.01 0.35 - - 10.0

Table 1 (continued) Name of components Superconcentrate Composition one 2 3 four 5 6 7 8 Content, wt.% 8. Phthalic acid or its sodium or potassium or alkanolamine salt 2.7 0.01 - - - - - 10.0 9. Tolyltriazole - 1,2 - 1,5 5,0 0.001 1,0 - 10. Benzotriazole 0.001 - 5,0 1,5 - - 1,0 0.5 11. Sodium molybdate 0.01 3.0 5,0 0.001 3.0 5,0 1,0 11.0 12. Caprolactam 0.001 1,5 0.15 0.2 0.5 0.2 0.2 0.2 13. Sodium polyacrylate 0.001 0.05 3.0 0.05 0.05 0.003 0.05 0.1 14. Salt of monoalkylphosphoric acid 0.3 0.3 - 0.5 0.3 0.5 0.5 0.2 15. Antifoam 0.001 0.005 0,03 0.005 0.005 0.003 0.003 0.003 16. Water 5,0 7.5 15.0 15.0 12.0 10.0 10.0 10.0 17. Ethylene glycol rest 18. Propylene glycol - - - - - - - - 19. Polyglycols - - - - - - - -

Table 1a Name of components Superconcentrate Composition 9 10 eleven 12 13 fourteen fifteen 16 17 Content, wt.% 1. Caproic acid or its sodium or potassium or alkanolamine salt 10.0 0.5 - 0.5 10.0 - 10.0 10.0 0.003 2. Caprylic acid or its sodium or potassium or alkanolamine salt 0.01 - - - - - 10.0 10.0 0.006 3. 2-ethylhexanoic acid or its sodium or potassium or alkanolamine salt - 3.0 0.005 20,0 0.5 10.0 - - 0.005 4. Benzenecarboxylic acid or its sodium or potassium or alkanolamine salt 0.01 - - 0.01 - - - - 0.001 5. Hexanedioic acid or its sodium or potassium or alkanolamine salt 9.5 0.5 0.01 - 5,0 0.02 0.01 0.001 6. Butanedioic acid or its sodium or potassium or alkanolamine salt - 20,0 10.0 - 7.8 0.01 0.01 0.01 0.008 7. Decandionic acid or its sodium or potassium or alkanolamine salt 0.01 0.01 0.35 0.01 0.5 0.01 - 0.5 0.001

Table 1a (continued) Name of components Superconcentrate Composition 9 10 eleven 12 13 fourteen fifteen 16 17 Content, wt.% 8. Phthalic acid or its sodium or potassium or alkanolamine salt - 7.0 - 0.25 - - - - 0.005 9. Tolyltriazole - 7.0 1,5 1,5 2.0 - - 2.0 2.0 10. Benzotriazole - - 1,5 1,5 - 2.0 2.0 - 2.0 11. Sodium molybdate 5,0 5,0 5,0 5,0 3.0 3.0 3.0 3.0 3.0 12. Caprolactam 0.5 0.5 0.5 0.5 - 2.0 0.2 0.2 1,5 13. Sodium polyacrylate 2.0 2.0 2.0 0.5 0.1 0.1 - 3,7 0.05 14. Salt of monoalkylphosphoric acid 0.3 0.3 0.01 0.65 0.3 0.3 0.3 0.2 0.5 15. Antifoam 0.001 0.001 0.002 0.002 0.002 0.003 0.001 0.001 0.005 16. Water 12.0 12.0 10.0 10.0 11.0 11.0 10.0 10.0 10.0 17. Ethylene glycol rest - 18. Propylene glycol - - - - - - - - - 19. Polyglycols - - - - - - - - rest

Table1b Name of components Superconcentrate Composition eighteen 19 twenty 21 22 23 24 25 Content, wt.% 1. Caproic acid or its sodium or potassium or alkanolamine salt 10.5 10.0 0.01 0.01 0.01 - 10.0 10.0 2. Caprylic acid or its sodium or potassium or alkanolamine salt 10,2 - - 0.01 0.01 0.01 - - 3. 2-ethylhexanoic acid or its sodium or potassium or alkanolamine salt 20.3 20,0 0.005 0.005 5,0 20,0 15.0 15.0 4. Benzenecarboxylic acid or its sodium or potassium or alkanolamine salt 10.8 5,0 0.01 0.01 - - 0.01 0.01 5. Hexanedioic acid or its sodium or potassium or alkanolamine salt 3.2 - - 0.01 - - - - 6. Butanedioic acid or its sodium or potassium or alkanolamine salt 2.7 9.6 0.02 0.01 10.0 - 0.01 0.01 7. Decandionic acid or its sodium or potassium or alkanolamine salt 8.5 10.0 - 0.01 - 0.11 - -

Table 1b (continued) Name of components Superconcentrate Composition eighteen 19 twenty 21 22 23 24 25 Content, wt.% 8. Phthalic acid or its sodium or potassium or alkanolamine salt 1.8 5,4 0.005 0.005 - - - - 9. Tolyltriazole 0.5 - 1,0 2.0 - - 1,2 1,2 10. Benzotriazole - 5,0 1,0 - 5.8 2.0 - - 11. Sodium molybdate 0.01 3.0 1,0 3.0 3.0 3.0 3.0 3.0 12. Caprolactam 0.05 0.5 0.2 1,0 1,5 1,0 0.5 0.5 13. Sodium polyacrylate 0,03 0.05 0.05 0.05 0.05 0.05 0.1 0.1 14. Salt of monoalkylphosphoric acid 0.3 0.3 0.3 0.5 0.5 0.3 0.5 0.3 15. Antifoam 0.002 0.003 0.003 0.001 0.002 0.002 - 0.05 16. Water 5,6 12.0 10.0 10.0 9.0 10.0 15.0 15.0 17. Ethylene glycol - rest - - - rest 18. Propylene glycol - - - - - rest - - 19. Polyglycols rest - - rest - - -

Table 1c Name of components Prototype Content, wt.% 1. Tolyltriazole 1.0-5.0 2. Benzotriazole 1.0-5.0 3. Sodium molybdate - 4. Caprolactam - 5. Sodium polyacrylate - 6. Monoalkylphosphoric acid salt - 7. Antifoam - 8. Undecylenic acid 5.0-15.0 9. A mixture of monocarboxylic acid (n-hexanoic, n-octanoic, nonanoic) and dicarboxylic acid (suberinic, sebacic) 40.0-70.0 10. Tricarboxyl derivative of 1,3,5-triazine 20,0-40,0 11. Water - 12. Ethylene glycol rest 13. Propylene glycol - 14. Polyglycols -

table 2
The results of corrosion tests of antifreeze obtained on the basis of antifreeze superconcentrate Structure Material copper solder brass steel cast iron aluminum weight loss, g / m ² · day one 0.01 0.06 0.02 0.02 0.02 0.02 2 0.01 0.09 0.01 0.01 0,03 0.02 3 0.02 0.11 0.01 0.01 0.01 0,03 four 0.05 0.10 0,03 0.20 0.04 0,03 5 0.01 0.05 0,03 0,03 0.01 0.01 6 0.02 0,07 0.02 0.01 0.02 0.02 7 0.01 0.08 0,03 0.02 0.02 0.01 8 0.04 0.08 0.04 0.04 0,03 0.02 9 0.21 0.10 0.17 0,03 0.02 0.02 10 0,03 0,07 0.05 0.01 0.02 0.01 eleven 0.05 0.08 0.05 0.04 0,03 0.16 12 0.17 0.23 0.15 0,03 0.02 0.02 13 0.18 0.25 0.19 0,03 0.01 0.01 fourteen 0.20 0.26 0.15 0.20 0.20 0.24 fifteen 0.05 0,07 0.04 0.10 0,03 0,03 16 0.08 0.10 0.06 0.02 0.04 0.05 17 0.20 0.33 0.05 0.25 0.18 0.23 eighteen 0.21 0.33 0.29 0.29 0.21 0.32 19 0,03 0.05 0,03 0.01 0.02 0.01 twenty 0.02 0.06 0.01 0.02 0.02 0.01 21 0.02 0,07 0,03 0.02 0.01 0.02 22 0,03 0.15 0,03 0.01 0.04 0.02 23 0.02 0,07 0,03 0.01 0.01 0.01 24 0.02 0.05 0.02 0.02 0,03 0,03

Table 2 (continued) Structure Material copper solder brass steel cast iron aluminum weight loss, g / m ² · day 25 0.02 0,03 0,03 0,03 0.02 0.01 Prototype, mg / pl-ku -0.4 -0.5 -0.2 -0.5 -0.4 GOST 28084-89, lg / m ² · day. 0.1 0.2 0.1 0.1 0.1 0.1

Table 3
Physico-chemical properties of antifreeze superconcentrate and antifreeze obtained on its basis
Tests were conducted according to GOST 28084-89 No. p / p The name of indicators Antifreeze Super Concentrate Antifreeze one Appearance Transparent colorless homogeneous liquid without mechanical impurities Transparent painted liquid without mechanical impurities 2 Density at 20 ° C, g / cm ³ 1,100-1,220 1,110-1,145 3 Hydrogen index (pH) at 20 ° С 7.5-9.5 when diluted with distilled water in a volume ratio of 1: 2 7.5-9.5 when diluted with distilled water in a volume ratio of 1: 1 four Alkalinity reserve, cm ³ 2.5-10.0 5 Hard water resistance No stratification and sediment

Table 4
The results of determining the stability of coolants obtained on the basis of antifreeze superconcentrate when heated
Tests were conducted according to the Specification of engineering materials Ford WSS-M97 B44 D (Clause 3.4.3.) And Technical requirements of AvtoVAZ TTM 1.97.1172-2004 (Clause 4.1) Composition of antifreeze superconcentrate Type of coolant after heating at 65 ± 2 ° C without dilution after dilution on day 2 on day 7 on day 10 on day 14 on day 2 on day 7 on day 10 on day 14 one no sediment no sediment 2 no sediment no sediment 3 no sediment no sediment 5 no sediment no sediment 6 no sediment no sediment 7 no sediment no sediment 19 no sediment no sediment twenty no sediment no sediment 21 no sediment no sediment 23 no sediment no sediment Composition 1 with the addition of 0.33 wt.% Sodium silicate, 2.1 wt.% Borax, 0.26 wt.% Sodium nitrite no sediment no sediment the presence of a gel-like precipitate - - - - -

Table 5
Test results of a 20 vol.% Antifreeze solution obtained on the basis of antifreeze superconcentrate using the potentiostatic method in the presence of 0.01 M NaCl (585 mg / l) Superconcentrate Composition Anti-pitting basis ΔЕ, mV Breakdown potential E _pr , mV The current density I _a , µA / cm ² one 687 470 6.6 2 840 356 7.1 3 697 298 6.9 5 827 377 5,6 6 856 345 7.5 7 635 305 6.8 19 760 399 5.9 twenty 689 357 6.5 21 743 400 5.5 23 854 389 7.3 traditional antifreeze 278 -243 12.3

Table 6
Super Concentrate Antifreeze Test Results for Compatibility with Commercial Coolants No. p / p The composition of the coolant The appearance of the coolant after testing for 48 hours at 20 ± 2 ° C Corrosion tests according to GOST 28084-89, weight loss, g / m ² · day Potentiostatic method on aluminum at 20 ± 2 ° С Material copper solder brass steel cast iron aluminum anti-pitting basis ΔЕ, mV current density, μA / cm ² one 50 vol.% Antifreeze solution according to the claimed composition (Composition 1) no sediment 0.01 0.06 0.02 0.02 0.02 0.02 1380 787 2 A mixture of a 50 vol.% Solution of antifreeze according to Composition 1 and commercial antifreeze in a volume ratio of 1: 1 no sediment 0,07 0.1 0.09 0.08 0.06 0.09 643 -44 3 A mixture of a 50 vol.% Solution of antifreeze according to Composition 1 and commercial antifreeze in a volume ratio of 1: 1 no sediment 0.05 0.08 0.08 0.05 0.06 0.08 1067 399 four 50 vol.% Commercial antifreeze with water 0.09 0.18 0.1 0.09 0.08 0.12 417 -418 5 50 vol.% Commercial antifreeze with water 0.06 0.09 0.09 0,07 0.08 0.09 520 52 6 Norm according to GOST 28084-90 - 0.1 0.1 0.1 0.1 0.1 0.1 - -

Claims (3)

1. A superconcentrate for the manufacture of glycol-based antifreezes and coolants, including monocarboxylic and dicarboxylic acids, tolyltriazole or benzotriazole or a mixture thereof in equal proportions, sodium molybdate and water, characterized in that it contains at least one monocarboxylic acid as anti-corrosion additives such as caproic, caprylic, 2-ethylhexanoic, benzenecarboxylic, and at least one dicarboxylic acid, such as butanedioic, hexanedioic, decanedioic, phthalic, or their alkaline salts metals or alkanolamines, and additionally contains caprolactam, sodium polyacrylate, monoalkylphosphoric acid salt, antifoam in the following ratio, wt.%: A mixture of mono - and dicarboxylic acids or their alkali metal salts or alkanolamines 0.05-60.0 Tolyltriazole or benzotriazole or their mixture in equal proportions 0.001-5.0 Sodium Molybdate 0.005-5.0 Caprolactam 0.001-1.5 Sodium Polyacrylate (average mol.m. 8000 g / mol) 0.001-3.0 Monoalkylphosphoric Acid Salt general formula

where R is H; C ₁₆ H ₃₃ -C ₁₈ H ₃₇ ; M = Na, K, NH (CH ₂ CH ₂ OH) ₃ , n = 9-15 0.3-0.5 Antifoam agent 0.001-0.03 Water 5.0-15.0 Glycols (ethylene glycol, propylene glycol, polyglycols) Rest 2. The antifreeze superconcentrate according to claim 1, characterized in that it contains a mixture of mono- and dicarboxylic acids, wt.%: 0.01-10.0 caproic acid or its sodium, or potassium, or alkanolamine salt, or 0.01 -10.0 caprylic acid or its sodium, or potassium or alkanolamine salt, or 0.005-20.0 2-ethylhexanoic acid or its sodium, or potassium or alkanolamine salt, or 0.01-10.0 benzenecarboxylic acid or its sodium, or potassium or alkanolamine salt, or 0.01-10.0 butanedioic acid or its sodium or potassium or alkanolamine with whether or 0.01-10.0 hexanedioic acid or its sodium, or potassium or alkanolamine salt, or 0.01-10.0 decanedic acid or its sodium, or potassium or alkanolamine salt, or 0.005-10.0 phthalic acid or its sodium, or potassium or alkanolamine salt, or a mixture thereof in any combination and in any ratio. 3. The antifreeze superconcentrate according to claim 1, characterized in that it contains a triethanolamine salt, or β, β ^1- dihydroxy-N-methyldiethanolamine, or 2,2 ', 2 "-nitrilotriethanolamine, as the alkanolamine salt of these acids.