RU2259391C1 - Emulsifier for preparation of water-miscible lubricating fluid - Google Patents

Abstract

FIELD: lubricants.

SUBSTANCE: emulsifier for lubricating fluids used in metal machining operations based on transformer oil base or transformer oil and including 9.0-10.0% oleic acid and 3.0-4.0% triethanolamine further contains 3.0-4.0% zinc dithiophosphate as anticorrosion additive and 3.0-4.0% bactericide additive, which is neutralized product of reaction of di- and trimethylthiourea mixture with disodium phosphate.

EFFECT: improved anticorrosion and bactericide properties of emulsifier and prolonged lifetime of water-miscible lubricating fluids.

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Description

The invention relates to the field of protection against biodefeat. It can be used in the machine-building industry, namely, in water-miscible cutting fluids (coolant) used in the machining of metals.

An effective method of combating corrosion of processed metals and machine tools communications, as well as with biodegradation of coolants used, is the use of emulsols with anticorrosive and bactericidal effects in their composition.

From (Fuel and lubricants. Product market: Catalog / Compilers. - M.: Mashinostroenie, 1994. P.107-115, Berdichevsky EG. Lubricant-cooling means for processing materials: Reference book. - M.: Mashinostroenie, 1984. S.74-85) it is known that for the preparation of coolant emulsols Akvol-15, Akvol-16, Akvol-18, SINKHO-6, MHO-67, Ukrinol-1, containing various improving additives in their composition, are widely used. At the same time, anticorrosion and bactericidal additives were introduced into IHP-45E emulsol, in which sodium nitrite plays the role of a corrosion inhibitor, and hexachlorophen acts as a bactericide (E.G. Berdichevsky. 82). In the composition of emulsol NL-205, sodium nitrite (0.5% wt.) And trisodium phosphate (0.5% wt.) Are used as an anticorrosive additive (Oils produced by enterprises of the USSR Ministry of Oil and Chemical Industry: edited by V.M. Shkolnikov, N .A. Kuznetsova. Directory-directory. - M .: TSNIITEneftekhim, 1986, p. 49)

Common features of the known technical solutions and the present invention is the use of bactericidal and anticorrosive additives as one of the components of the emulsols.

The main disadvantages of the known emulsifying compositions (emulsols) are the high cost, toxicity and lack of effectiveness of improving additives used in their preparation.

It was proposed (A. S. 43940 NRB. Publ. September 30, 88) to improve the anticorrosive properties of emulsols (emulsifying compositions) by introducing the following compounds into their composition: boron-containing ester of triethanolamine and / or ethylene glycol and fatty acids and the condensation product of sodium tetraborate decahydrate with ethylene glycol.

Common features of the known and proposed invention is the introduction of emulsol improving additives.

The disadvantages of the known technical solutions include the corrosion of emulsols and water-miscible coolant obtained on their basis, the loss of functional properties when stored in conditions with low temperatures.

B (Fuels and lubricants. Product market: Catalog / Compilers. - M.: Mashinostroenie, 1994. P.107-115. E.B. Berdichevsky. Lubricating and cooling agents for processing materials: Reference book. - M.: Mashinostroenie, 1984. P.74-85) it is indicated that the composition of emulsifying compositions, such as RIZOL, Carbamol-C1, emulsicide EGT, emulsicide ET-2, emulsol ET-2GHF, includes only bactericidal additives.

Common features of the known and proposed invention is the introduction of emulsol bactericidal additives.

The disadvantages of emulsifying compositions include the corrosion of emulsols and water-miscible coolant obtained on their basis, monofunctionality, toxicity and poor water solubility of the additive - hexachlorophene. The insolubility in water of such an additive as hexachlorophene creates difficulties when used in production.

The closest (prototype) to the proposed invention is emulsion SP-3, manufactured by the Orenburg NMZ in accordance with GOST 5702-75 (Oils produced by enterprises of the USSR Ministry of Oil and Oil Industry: edited by V. M. Shkolnikov, N. A. Kuznetsov. Directory. - M .: TsNIITEneftekhim, 1986, p. 48), which includes 82-85.5% of the mass. transformer oil (without additives), 4.5-6% of the mass. triethanolamine, 10-12% of the mass. oleic acid.

The disadvantages of the prototype are the corrosion of emulsols and water-miscible coolants obtained on their basis, significant biodegradability and a limited period (not long-term) of operation of the latter.

The objective of the invention is: to improve the anticorrosive and bactericidal properties of emulsol and, accordingly, water-miscible coolants obtained on their basis; expanding the range with improved anticorrosive and bactericidal properties of emulsols used for the preparation of water-miscible coolant; increase the service life of water-miscible coolant obtained on the basis of the proposed emulsol.

The technical result, the achievement of which is achieved by the implementation of the claimed invention, consists in improving the anticorrosive and bactericidal properties of emulsol and, accordingly, water-miscible coolants obtained on their basis, as well as in expanding the range of emulsols used for the preparation of water-miscible coolants.

The specified technical result is achieved due to the fact that the composition of emulsol, including oleic acid, triethanolamine, the base base of transformer oil or transformer oil, in the following ratio, wt.%:

oleic acid - 9.0-10.0; triethanolamine - 3.0-4.0; base base transformer oil or oil transformer - the rest

zinc dithiophosphate and a bactericidal additive are additionally introduced, which is the neutralized product of the interaction of a mixture of di- and trimethylolthiourea with disodium phosphate in the amount of 3.0-4.0 wt.% and 7.0-8.0 wt.%, respectively, based on 100 wt.% Of the above composition.

A comparative analysis of the prototype and the proposed invention shows that it is common to use oleic acid, triethanolamine and the base base of transformer oil or transformer oil in the composition of the emulsol.

The difference between the invention and the prototype is that the composition of emulsol containing, wt.%:

oleic acid - 9.0-10.0; triethanolamine - 3.0-4.0; base base transformer oil or oil transformer - the rest

additionally includes an anti-corrosion additive - zinc dithiophosphate and a bactericidal additive, which is a neutralized product of the interaction of a mixture of di- and trimethylolthiourea with disodium phosphate, in an amount of 3.0-4.0 wt.% and 7.0-8.0 wt.%, respectively, calculated on 100 wt.% the above composition.

Oleic acid and triethanolamine are components of an emulsifier (surfactant), which, when interacting with each other (during the production of emulsol) form an oleic acid triethanolamine ester of the following formula:

(C ₂ H ₄ OH) ₂ —N — C ₂ H ₄ OOC — C ₁₇ H ₃₃ ,

being an emulsifier. Transformer oil or the base base of transformer oil is a lubricating component of emulsol.

The possibility of implementing the invention, namely: obtaining a bactericidal additive and emulsol, using the latter in cutting fluids, as well as determining the bactericidal and anticorrosive properties of emulsol and coolant prepared on its basis, is shown in the following examples.

Example 1. Preparation of emulsol.

As a result of the implementation of the invention receive emulsol containing, wt.%:

oleic acid - 9.5; triethanolamine - 3.5; base base transformer oil or oil transformer - the rest,

which additionally includes an anti-corrosion additive - zinc dithiophosphate and a bactericidal additive, which is a neutralized product of the interaction of a mixture of di- and trimethylolthiourea with disodium phosphate, in an amount of 3.5 wt.% and 7.5 wt.%, respectively, based on 100 wt. .% of the above composition.

Below is a description of the ingredients used.

1. Technical triethanolamine (TU 6-02-916-79):

- Formula - C ₆ H ₁₅ O ₃ N;

- Molecular mass - 149.19;

Name of indicator Norm Brand a Brand b Brand B 1. Appearance Transparent liquid, opalescence is allowed, color from yellow to light brown Transparent liquid, opalescence allowed, brown Brown to Dark Brown Fluid 2. Density at 20 ° C, in the range, g / cm ³ 1,095-1,124 1,095-1,135 1,095-1,135 3. Fractional composition: at a residual pressure of (2.7 ± 0.2) kPa or (20 ± 1.5) mmHg distilled,%: a) at temperatures up to 170 ° C, no more 14.5 1 Not regulated b) at a temperature of 170 to 225 ° C, not less than 82.0 80.0 80.0 c) residue after distillation, not more than 3,5 6.0 20,0

2. Technical oleic acid (GOST 7580-91):

- Formula - C ₁₇ H ₃₃ COOH;

- Molecular mass - 282.198;

- Color number - not more than 70 mg of iodine;

- Mass fraction of fatty acids in anhydrous product - not less than 97.4%;

- Mass fraction of unsaponifiable and unsaponifiable substances - not more than 2.5%;

- Iodine number - 85-105 g of iodine / 100 g (for brand B14), 90-105 g of iodine / 100 g (for brand OM);

- Acid number - 185-200 mg KOH / g;

- The number of saponification - 185-200 mg KOH / g;

3. Transformer oil GK (TU 38. 1011025-85):

- Kinematic viscosity:

- at 50 ° C - not more than 9 mm ² / s;

- at minus 30 ° С - no more than 1200 mm ² / s;

- Acid number - not more than 0.01 mg KOH / g oil;

- The flash point, determined in a closed crucible - not lower than 135 ° C;

- pour point - not higher than minus 45 ° C;

- The color on the CNT colorimeter is not more than 1 unit. CNT;

- Stability against oxidation (at 150 ° C, 14 h, oxygen consumption 50 ml / min):

a) the mass of volatile low molecular weight acids is not more than 0.04 mg KOH / g,

b) the mass fraction of sediment is not more than 0.015%,

c) the acid number of the oxidized oil is not more than 0.1 mg KOH / g;

- The dielectric loss tangent at 90 ° С - not more than 0.5%;

- Density at 20 ° С - no more than 895 kg / m ³ .

4. Zinc dithiophosphate - additives DF-11 (TU 38 590 1254-90):

- Kinematic viscosity at 100 ° С - 5-10 mm / s;

- Mass fraction of zinc - 5.0-5.6%;

- Mass fraction of phosphorus - 4.4-4.9%;

- Degree of purity - not more than 185 mg per 100 g of additive;

- Corrosion of M-11 base oil according to TU 38 101523-80 with 1.2% DF-11 additive on a lead plate of grade C1 or C2 op GOST 3778-77 - not more than 5 g / m ² ;

- The flash point determined in an open crucible is not lower than 170 ° C;

- Color (at a dilution of 15:85) - not more than 3.5 units. CNT.

5. Germicidal supplement:

a white crystalline powder, readily soluble in water, insoluble in alcohols and hydrocarbons, has a melting range of 315-325 ° C and a bulk density of 0.45 g / cm ³ .

The method of obtaining emulsol is as follows.

1. The base base of transformer oil or transformer oil (half of the total amount of oil) is introduced into the contactor-mixer, then the whole amount of oleic acid is added to the oil with constant stirring. The mixture is stirred for one hour at a temperature not exceeding 25 ° C. Subsequent operations are carried out with constant stirring and at a temperature not exceeding 25 ° C.

2. The whole mixture of triethanolamine is gradually added in the resulting mixture in small portions (mixing lasts 2-3 hours). At this stage, the synthesis of an emulsifier - triethanolamine oleic acid soap proceeds.

3. Then enter the remaining amount of the base base of transformer oil or transformer oil, after which the resulting mixture is stirred for one hour.

4. The resulting solution of triethanolamine oleic acid soap in base oil (or transformer oil) is injected with the entire amount of anti-corrosion additive - zinc dithiophosphate, and then stirred for two hours.

5. After the zinc dithiophosphate is completely dissolved, a bactericidal additive is added to the mixture, the resulting mixture is stirred for one hour.

Example 2. Synthesis of a bactericidal additive.

A method of obtaining a bactericidal additive includes the following stages:

1) conduct the condensation of thiocarbamide and formaldehyde and get a mixture of di- and trimethylolthiocarbamide;

2) then carry out the phosphonylation of the reaction mixture with disodium phosphate;

3) at the end of phosphonylation, the resulting product mixture is neutralized;

4) the precipitate formed is filtered under vacuum and dried at room temperature.

A method of obtaining a bactericidal additive is as follows. 10 ml of a 70% (mass.) Solution of thiocarbamide and 20 ml of 37% (mass.) Formalin are charged into a reaction flask with a stirrer and reflux condenser, the mixture is heated to boiling and incubated for 40 minutes. After the specified time, the reaction mass is cooled to 40-45 ° C, after which 60 ml of a 50% (mass.) Solution of disodium phosphate salt heated to 20-30 ° C are introduced and incubated for 4 hours. Then the mixture is cooled, after which add 100 ml of a 15% (mass.) Aqueous solution of caustic soda.

The precipitated flocculent precipitate was filtered under vacuum and dried at room temperature to constant weight. The result is 50 grams of a product - a bactericidal supplement. The structure of the substance is not clearly established.

Example 3. Determination of the bactericidal properties of emulsol. The bactericidal properties of the emulsol obtained in Example 2, and used for the preparation of coolant, were studied according to the method described in (Lubricating and cooling technological means for metal cutting: Handbook / Under the general editorship of S. G. Entelis, E. M. Berliner. - 2nd ed., Revised and enlarged M: Mashinostroenie, 1995.496 s.). The experiments were carried out as follows. In one test tube, 9 ml of infected used coolant is placed, which is a 5% (w / w) aqueous emulsion of emulsol that does not contain a bactericidal additive. In a second test tube, 9 ml of used coolant, which is a 5% (mass.) Aqueous emulsion of emulsol containing a bactericidal additive, is placed. Then, 1.0 ml of indicator, 0.5% (mass.) Aqueous solution of 2,3,5-triphenyltetrazolium chloride (TTX), is added to both tubes. The contents of the tubes are thoroughly mixed, the tubes are placed in a thermostat and incubated at a temperature of 30 ± 5 ° C for the time necessary for the appearance of a characteristic color in the test coolant (1-5 days). Visually assess the presence and intensity of the color of the coolant and determine the microbiological damage score of the emulsion. As a result of the tests, it was found that after the test period the coolant prepared from emulsol without a bactericidal additive has a limit IV biodefeat score on a V-scale from 0 to IV, which indicates the unsuitability of the coolant for further operation. Coolant prepared from emulsol with the addition of a bactericidal additive has a score of 0-1, i.e. This coolant is suitable for operation for a long time.

Example 4. Determination of the anticorrosive properties of emulsol.

The anticorrosive properties of the coolant prepared from emulsol with the addition of zinc dithiophosphate were evaluated according to the method described in (Lubricant-cooling technological means for metal cutting: Handbook / Under the general editorship of S.G. Entelis, E.M. Berliner. - 2- ed., revised and enlarged M: Mashinostroenie, 1995. 496 pp. Dubrovsky Yu.S., Rumyantseva TA, Chugay GN Operational properties of water-miscible cutting lubricants. - K .: UkrNIINTI Gosplan of the Ukrainian SSR, 1991, issue 2 .64 p.). Research was carried out as follows. On a paper filter with a diameter of 50 mm, placed in a Petri dish, 2 ± 0.1 g of cast-iron shavings are uniformly applied with a spatula. 2 ml of fresh coolant, which is an aqueous 5% (mass.) Emulsion from emulsol, is taken into a pipette and the chips are uniformly wetted on the filter. The Petri dish is closed with a lid and incubated for 2 hours at room temperature, excluding direct sunlight. Then the filter is removed from the Petri dish, chips are removed, and the filter is dried at room temperature. After that, the corrosion score is assessed by the nature and number of spots on the filter or by their absence. The tests are carried out in parallel in two Petri dishes. Corrosion score is estimated for coolants prepared from emulsols containing and not containing an anti-corrosion additive (zinc dithiophosphate). As a result of the tests, it was found that the coolant prepared from emulsol without an anti-corrosion additive (zinc dithiophosphate) has a corrosion score of III (on a V-scale from 0 to IV points), which corresponds to a moderate degree of corrosion. Coolant prepared on the basis of emulsol with an anticorrosive additive (zinc dithiophosphate) has a score of 0, which corresponds to the absence of corrosion.

The presented examples convincingly show the possibility of implementing the invention and achieving the claimed technical result.

Claims (1)

Emulsol for the preparation of a water-miscible cutting fluid containing oleic acid, triethanolamine and a base base of transformer oil or transformer oil, characterized in that the composition of emulsol containing wt.%: Oleic acid 9.0-10.0 Triethanolamine 3.0-4.0 Transformer oil base or oil transformer Rest additionally contains an anti-corrosion additive - zinc dithiophosphate and a bactericidal additive, which is a neutralized product of the interaction of a mixture of di- and trimethylolthiourea with disodium phosphate, in the following ratio of components by weight, based on 100% by weight of the above composition:   Anticorrosive additive 3.0-4.0   Bactericidal supplement 7.0-8.0