DE887096C - Process for the production of lubricating greases - Google Patents

Description

Process for the production of lubricating greases Lubricating greases are commonly used composed of soaps and hydrocarbon oils, in particular mineral oil fractions, The general procedure here is to mix soap-forming ingredients with suitable ones Hydrocarbon oil fractions mixed and, the mass of a saponification with alkalis or subject to alkaline earths. Vegetable ingredients are mainly used as soap-forming ingredients or animal fats or the corresponding fatty acids or montan wax or the acids contained therein or tallül in question; one can also use synthetically produced ones Use fatty acids as they are obtained by the oxidation of high molecular weight aliphatic hydrocarbons, such as paraffin, can be obtained in the liquid phase, both the so-called Soap fatty acids, i.e. the acids that have a molecular weight and constitution roughly correspond to the fatty acids commonly used in the manufacture of soaps, as well as the so-called tail fatty acids, d. H. : dne higher molecular weight and accordingly high-boiling fatty acids which either immediately or after refining, z. B. by exudation or by dissolving from organic solvents, such as Butanone, can be applied.

The properties of the lubricating greases depend on the type of soap-forming Components and the hydrocarbon oils and their proportions as on the type of base used for saponification. Good lubricating greases should be homogeneous and even when it cools down as well as both effects of pressure remain and do not separate any oil even after prolonged storage .. In general, will more or less high dropping points are also required. In many cases it does also check the water resistance of the greases. Obtained by saponification with baking soda Fats generally show fairly high dropping points, but typically they are not water-resistant, while fats produced by saponification with lime are water-resistant but have rather low dropping points, well below those of their respective counterparts Soda fats lie. Attempts to hit the dropping point in making lime fats by using baking soda did not lead to success, since the fats obtained in this way easily separate 01. In the manufacture of lubricating greases it also shows that with the same approaches by slight changes in the Working conditions Products with completely different properties can be obtained. What this is due to has not yet been fully clarified.

Elsewhere it has already been suggested the properties of Lubricating greases. to be improved by adding additives in addition to the soap-forming acids of other organic carboxylic or sulfonic acids. As such are suitable especially those involved in the oxidation of paraffin and similar hydrocarbons so-called first-run fatty acids obtained, also aliphatic unsaturated monocarboxylic acids with up to 1a ,, preferably with q. to ia carbon atoms or aliphatic acids With up to 10 carbon atoms, in whose molecule there is also a hydrocarbon residue and the carboxyl group at least one substituent, for example an amino, keto or an oxy group or a halogen atom or also a further carboxyl group is; there are also aromatic or heterocyclic carboxylic or stulphonic acids in question. By using these substances, the dropping point of the fats becomes essential increased, but so far it has not been possible to use the additives mentioned: the Significantly affect water resistance.

It has now been found that one can obtain lubricating greases with very special properties obtained when mixtures of hydrocarbon channels, soap-forming constituents and acidic additives of the type mentioned above with saponifying V bonds of the alkali and / or alkaline earth metals, optionally together with compounds of other metals, heated, taking care that at least part of the saponifying agent with the acidic additive a heavy in water Forms soluble or insoluble salt and regulates the temperature so that the water largely or completely removed from the mass, the respective dropping point of the Mass as soon as fat has formed but is not reached. Using one. A large number of saponifying agents should also be used next to each other, that the saponifying agent, which is poorly soluble or with the acidic additive is able to form insoluble salt, not later than the saponifying agent, that is either before or together with this, that with the acidic additive is added - results in a slightly water-soluble salt.

For: the process can use any hydrocarbon oils of character the lubricating oils are used. You can, for example, from mineral oils, shale oils or tars or synthetic, e.g. B. by polymerization of gaseous or liquid Olefins.

Not only those mentioned in the introduction are used as soap-forming agents natural and synthetic fatty acids or their saponifiable derivatives, that is z. B. vegetable - or animal fats or montan wax or tall oil or the .by Soap fatty acids and tail fatty acids obtained from paraffin oxidation or their Raffiin @ ate, but also other substances in question whose salts are soap-like in character have, -in particular those with a longer aliphatic carbon chain, for example the sulfochlorination of higher molecular weight aliphatic hydrocarbons and Hydrolysis of the sulfochlorides formed or obtained aliphatic sulfonic acids the alkylsulfamido fatty acids derived from these, e.g. B. Alkylsulfami, doacetic acids. What has been said above applies to the acidic additives.

One can, the process with one or more saponifying agents carry out. At least one of these agents must be a compound of an alkali or alkaline earth metal. In particular, saponifying compounds are used for this purpose of sodium, potassium, lithium, magnesium, calcium and barium in question, in particular .the oxides, hydroxides and carbonates of these metals. You can also go to Saponification; suitable compounds of other metals, e.g. B. those of aluminum, Use zinc or lead. If a single saponifying agent is used, it must it forms a salt with the acidic additive that is difficult to dissolve or insoluble in water. In many cases, the alkaline earth metal compounds are particularly suitable for this Lime and barite. But you can also use these sparingly soluble salts-forming bases as well Use bases which, with the acidic additives, are more readily water-soluble salts form. Such compounds include sodium, potassium, and lithium, for example in question. In this case, as already mentioned, it is important to ensure that the one that is difficult to dissolve or insoluble salt-forming base either before or simultaneously with the base, which forms a more soluble salt, is added, but in no case after this.

The saponification takes place with heating, with the reaction participants introduced and possibly the water formed during saponification or must be removed completely. During the saponification, a Mass, which, as samples taken show, even in the cold is liquid. The water can flow out of it at first without any special precautionary measures removed. After some of the water is removed, fat build-up occurs a, d. H. a removed sample forms one more or less when it cools down solid mass with which in the usual way: a dropping point determination can be carried out is; : the height of the drop point depends on the water content of the mass. Of this At this point in time or, better still, some time before, the water must be very careful and slowly removed. For this purpose the temperature must always be so low be kept that they are noticeable, expediently at least 3 to io P, below, the respective dropping point of the mass. When all the water is removed from the mass in some cases they can be brought to temperatures above their dropping point warm, but this is not necessary and therefore generally not recommended, especially since a discoloration occurs with such a relatively high level of heating that makes the product unsightly.

The proportions of the individual components of the grease can fluctuate within fairly wide limits. For example, you can process mixtures, the 3.5 to: 2j50 / 0, preferably about 100/0 or more, of the soap-forming ingredients (calculated as free acid). The amount of acidic additives is about 5 to 40%, preferably 10 to 300/0, of the soap-forming ingredients.

The procedure can be carried out in a number of ways. For the production a pure lime fat, for example, a mixture of hydrocarbon oil, a soap-forming acid and an acidic additive, e.g. B. Be.nzoic acid heat about 70 °, at this temperature the amount required for saponification add slaked lime or milk of lime or calcium carbonate, then add the mass Stir at about 75 to 80 ° until all the water has been driven out, and that Then let the fat cool down. If you want to make a mixed soda lime fat, so one can add to the mixture: of hydrocarbon oil, soap-forming acids and z. B. Benzoic acid at about 7o ° the desired amount of slaked lime o, d. ,, - l. and at the same time or afterwards at the same temperature that for the rest of the time Add the saponification required amount of caustic soda or sodium carbonate to the mass then stir at g.o ° and as the water is removed, the temperature. Increase to 12o ° or more. It may then be advisable to continue stirring, until the mass has cooled to about 6o to 7o °, and then without stirring to ordinary To cool down temperature.

The greases made in the manner indicated are perfect evenly and show if only the content of soap-forming ingredients and is sufficiently high in acidic additives, no tendency to separate oil. she have high drop points and are sufficiently waterproof and can therefore be used for the can be used for a wide variety of purposes. The following B.eispi@el.en specified parts are parts by weight.

Example 1 86.4 parts of a mineral oil are used in a stirred kettle with a viscosity of 2 ° E at 2o ° and the pour point -6o ° 'with 10 parts of a fatty acid mixture obtained by paraffin oxidation and having about 14 to 18 carbon atoms and the saponification number are mixed together and heated to 70 ° with stirring. Be on it . Introduced 1.5 parts of benzoic acid into the mixture. Now the mixture is with 0.68 parts of slaked lime, slurried in 1.7 parts of water, and then with q-, 15 Parts of sodium hydroxide solution (36 # 'o / aig) are added and the mixture is stirred at 70 ° for 1/2 hour. On that the temperature is slowly increased to go °. After stirring for one hour at go ° shows a sample that grease has already formed; the sample shows a- Drop point of i.oi5 °. The temperature is then increased to g5 ° and the cooking time continued for i hour. Another sample then shows a water content of i ° / o; the fat now has a much higher consistency. After six hours further stirring at g5 ° the fat becomes thin and long-grained; the dropping point is now increased to i7, oP. The temperature is then increased to 120 °. After two hours Stirring at this temperature, the mass is largely anhydrous and has a dropping point of 221 °. It is drained after the scrambled eggs. The fat is pliable and consistent and largely water-resistant. It is a good cold-resistant lubricating grease. Will not proceed in the manner indicated, but the temperature, like this it is common with soda fats to bring it to over iao ° at the beginning, where the dropping point is the mass itself is not yet 100 ° due to the higher water content, so no lubricating grease can be produced, but the mass breaks down into its constituent parts (Soap, 01 and benzoate).

If, on the other hand, the caustic soda is added before the lime, a fat is obtained which has only low water resistance the pour point - 7a ° 'with 13 parts of a synthetic fatty acid mixture purified by dissolving with butanone from the paraffin oxidation with 14 to 18 carbon atoms and the saponification number 21.0, added and mixed with 1.5 parts of benzoic acid after heating to 70 °. After the fatty acid and benzoic acid have dissolved in the oil, 10.4 parts of barium hydroxide, dissolved in: 2ioi parts of water, are slowly added with stirring. In the course of: 2 hours, the bulk of the water is first evaporated rapidly at 115 and 120 ° and the mass is cooled to 85 ° as soon as there is a decrease in foam formation. After stirring for two hours at 85 °, a sample shows that fat is starting to form, ie a uniform mass is present which becomes consistent when it cools; it shows a dropping point of 95 °. After another half an hour, the drop point has risen to 105 '. The temperature is now increased to 95 °, and at this temperature the mass is kept under constant monitoring of the dropping point, which is constantly increasing. As soon as a drop point of 1300 ° is reached, the temperature is increased to 12o) °. When the dropping point has risen to 1 (750, the mixture is allowed to cool. The fat obtained in this way is pliable; has a consistency of 24 ° ASTM and can be stored for several days in warm water of 510 ° for several days without even changing superficially Excellent as a cold-resistant ball: ager fat usable.

If the production does not proceed as indicated, but the temperature is left at 120 ° after the fat formation has started, the fat breaks down into its components during production or it separates into an oil and soap layer after cooling. Example 3 In a stirred tank, 24.2 parts of a mineral oil with a viscosity of 5 ° E at 50 ° with 4.5 parts of what is known as a tail fatty acid obtained from paraffin oxidation, from which the low molecular weight, branched and oxyacids are washed out with Ethylene chloride were removed, and o, 24 parts of benzoic acid heated to 6o °; After a homogeneous solution has formed, 0.35 parts of calcium hydroxide are slurried in 1.6 parts of water at the temperature mentioned and 0.8 parts of 36% sodium hydroxide solution are saponified. Shortly after the saponification, the contents of the kettle become thick. The temperature is now slowly increased to 85 °. After 1 hour, the dropping point of the mass at which fat has since started to form is 106 °. The temperature is kept at 85o, well below the dropping point, for the purpose of good oil binding and to achieve a better bandage and to avoid pilling. This has risen to 135 ° after 1 hour. After another hour at 85 ° a drop point of 160 ° is reached and the fat is drained off. The fat is good what, serviceable.

Will not proceed in the manner specified, but also after the start the fat formation when measuring a drop point of 10> 6 ° the temperature above Leave 1o6 °, so the fat separates after completion or before the Hauptmerige, of the oil it contains.

Claims (1)

PATENT CLAIM: Process for the production of lubricating greases by Heat. of mixtures of hydrocarbon oils, soap-forming components and non-soap-forming organic acidic additives, especially organic ones Acids, with saponifying compounds of alkali and / or alkaline earth metals, possibly together with compounds of other metals, characterized in that that one uses such saponifying agents, at least a part of which with the acidic additives mentioned are a salt that is sparingly soluble or insoluble in water forms, from the: mass produced by saponification .the water largely or drives out completely at temperatures below the respective dropping point of the Mass, in the case of the use of several saponifying agents the with the acidic additive forming a sparingly soluble or insoluble salt Means no later than a saponifying agent that forms a more easily soluble salt, is added.