DE905303C - Oils for metal processing - Google Patents

Description

Metalworking oils It has been found that. Oils or Aqueous oil emulsions with a (content of sulfamidocarboxylic acids, the at least contain an aliphatic radical with at least 6 carbon atoms, or their water-soluble salts and, if appropriate, solubilizers or dispersants can be used with advantage when machining metals. One goes by higher-boiling synthetic hydrocarbon oils, mineral oils, synthetic ester oils or similar connections. As sulfamidomono- or dicarboxylic acids, the at least Containing an aliphatic radical with at least 6 carbon atoms are preferred Compounds chosen by the implementation of higher molecular weight sulfamides in Giegenwart can be prepared from alkalis with Hb.logencarbonsäuren, for example Dodecane sulfamidoacetic acid, hexadecane sulfamidopropionic acid. Can with advantage Compounds are also used which, according to German patent specification 761 o7z by implementing such sulfamides, which by simultaneous treatment of saturated aliphatic hydrocarbons with sulfur dioxide and chlorine and implementation of the resulting compounds with ammonia or primary amines are obtained with Halocarboxylic acids are formed.

Also suitable are sulfamidocarboxylic acids, which can be prepared by reacting higher molecular weight sulfamides with formaldehyde or formaldehyde-providing compounds and salts of aminocarboxylic acids, for example octodecane sulfamidomethylaminoacetic acid. Here too, according to German patent specification 751 132 , one can start from sulfamides which are produced by means of sulfur dioxide and chlorine.

The sulfamidocarboxylic acids mentioned are expedient with the oils mixed and, if appropriate, some or all of the carboxylic acids in the mixtures with ammonia or organic bases or with alkalis or mixtures of these basic compounds neutralized. You can also use some of the carboxylic acids first or completely neutralize with the bases mentioned and these products with the oils Mix.

Dispersants can also be used; like higher molecular sulfone or carboxylic acids or their salts, or reaction compounds of ethylene oxide with higher molecular oxy- od; Compounds containing amino groups are also used whereby the effect can be increased or adjusted in some cases can.

Small amounts of water or other solubilizers can also be added to the mixtures of oils, sulfamidocarboxylic acids and optionally dispersants for homogenization. As such, z. B. called: Dekaliydronaplithalin, Terpenkohleniv asserstoffe. Terpene alcohols, relatively high molecular weight aliphatic or aromatic A lkohole, cycloaliphatic alcohols, glycol ethers, phenols, ketones, or aliphatic carboxylic acids. In some cases, the addition of urea also proves to be advantageous.

The above-described - # lkvlsulfamidocarbonsäuren and their water-soluble Salts have an excellent emulsifying effect and for the present purpose also offer very good protection against corrosion. They are capable of oily hydrocarbons to be solved hydrotopically in considerable quantities. In metal processing they are for can already be used as a lubricant and lubricant. _From the mixtures of oils, den: alkylsulfamidocarboxylic acids and optionally other dispersants and solubilizers, long-lasting emulsions can be produced by adding water, for all types of mechanical metalworking, e.g. B. for cutting, turning, Drilling, milling, can be used. Also the: emulsions generally have no corrosive effect on metals. The emulsions can, if desired other anti-corrosive agents, such as B. nitrite, are added.

The French patent 849,393 describes soluble oils which consist of or contain the saponification products of the products formed by the action of chlorine and sulfur dioxide on hydrocarbons. The compounds are soluble salts of: alkylsulfonic acids, which can be used as emulsifiers for oils per se, but which have the unpleasant tendency that they corrode metals if the oil emulsions produced with their help are not at least soda-alkaline are. Such settings are not permitted for many branches of metalworking. This way of working would also be cumbersome.

French patent specification 866 256 describes the use of aliphatic Sulphamides as fat and, (lubricants, among others also in metalworking. These sulfamides are insoluble in water and are intended to replace mineral oils. As emulsifiers they cannot be used for olemulsions. Example i 149 g one more Sulfamidce-asigsäure @ mixture containing some water (acid number q: 7.7), prepared by treating a hydrogenated hydrocarbon fraction from carbon dioxide reduction with boiling limits of 2o to 32o ° with chlorine and sulfur dioxide, up to about half is converted into sulfochlorides, implementation of the. Aliphatic from approximately equal parts Sulphochlorides and aliphatic hydrocarbons consisting of a mixture with ammonia into the corresponding sulfamide mixture and further conversion with chloroacetic acid, are mixed with 29! 8 g of a spindle oil with a viscosity of .4 to 61 ° 'Engler at 20 ° mixed and slowly stirring the mixture with the solution of 6.8 g calcined Soda in .0o water added. After the carbon dioxide development has ended. lie q_5q.g of a clear oil.

Pouring this oil into water immediately creates an extremely finely divided oil-in-water emulsioni. which can be used particularly advantageously as drilling oil. It shows no corrosive effect on cast iron. Example 2 A similarly usable mixture is obtained as follows: 35009 of the sulfamidoacetic acid mixture described in Example 1 are neutralized with a solution of 160 g of calcined soda in 800 g of water. iThe solution obtained is largely evaporated. The mixture thus obtained is mixed with 80 g of paraffin oil. Slight warming can accelerate the solution. A clear oil is obtained. Stirring in water, especially well and slightly warmed up water, can produce stable oil-in-water mixtures. Example 3 64.99 of a sulfamidoesisetic acid mixture containing about 50% aliphatic hydrocarbons according to Example i are mixed with 29g of a condensation product prepared by reacting a propylene polymer containing essentially} dodecylienes with phenol and further reacting the resulting dodecylphenols with about 6 to 7 moles of ethylene oxide, mixed and stirred into the mixture 4.5 g of water and i, q: g of ammonia (25% aig). 100 g of a: bare oil are obtained. 25 g of the oily product are mixed with 75 g of a mineral oil from 6 to K `E'ngler at 20 °. resulting in a clear liquid. Stirring water gives a stable emulsion which can be used as a coolant in the metal sawmill.

Example q.

Suction hexadecanesulfonamidopropionic acid, made by reaction of hexadecyl bromide with sodium sulfite, conversion of the sodium hexadecyl sulfonate formed in hexadecyl sulfochloride, reaction with ammonia and conversion of the hexadecyl sulfamide with α-chloropropionic acid, with 150 g of a mineral oil with a viscosity of 5 to 7 "Engler at 2d ° ', and the mixture is stirred with 10.6 g sodium hydroxide solution (4o%) offset :. A clear mixture is created. In this mixture you can Stir in about 5 g of water without any cloudiness. When pouring a product prepared in this way in water immediately becomes a very fine one. distributed stable emulsion, which is suitable, for example, for cutting threads. example 5 6o g of a sulfamidodicarboxylic acid, prepared by reacting the Sulfamidoacetic acid containing hydrocarbons described in Example i with chloroacetic acid in the presence of alkali and a mixture of the sulfamidodiacetic acid formed with approximately the same volume of methanol, with the sulfami, dodiacetic acid in solution go and! the hydrocarbon separates, separating the two layers and A: distilling the methanol, mixed with 340 g of a light spindle oil, and with: ii, 5g sodium hydroxide solution (40% aig) adjusted to be weakly acidic. Be in the mix Stir in about 5 to 10 g of water. A clear oil is obtained, which becomes clear when poured ini water to form a stable emulsion, which can be used as drilling oil can.

Example 6 of post-hydrogenated, predominantly paraffinic ingredients containing diesel oil with boiling limits 215 to 35o ° is mixed with sulfur dioxide and chlorine treated under irradiation with short-wave light until it is about half from sulfochlorides and the other half from unchanged hydrocarbons consists. This mixture is converted into the corresponding sulfamides and these with ammonia with! Chloracetic acid converted into a mixture in the presence of alkali, which z. B. has the following composition: 90 / a water, 32% alkylsulfamidoacetic acids, i5% unchanged alkyl sulfamides, 4.41 / o hydrocarbons.

The acidic oil is exactly neutralized with 40% sodium hydroxide solution. Man receives a Ü1, which when diluted with water becomes clear to very slightly opalescent Solutions results even though they contain about 60% neutral oils. These solutions are ideally suited for machining, in particular for turning, milling, broaching and grinding work, and are able to produce drilling oil emulsions or run to completely replace mineral oils or vegetable oils. The presence of the Water-insoluble alkyl sulfamides are found to be advantageous in many cases.

The connections are characterized by an extraordinary anti-corrosion effect the end. Their excellent emulsifying effect extends over a large p $ range. In neutral solutions, they are also used for a wide variety of machining processes Can be used with particular success in light metals. Example 7 A reaction product obtained by the action of chlorine and sulfur dioxide with exposure to short-wave Light on a post-hydrogenated hydrocarbon mixture. the pressureless carbon dioxide reduction with the boiling limits 23o to 32o '°' and in which about half of the hydrocarbons are sulfochlorinated, treatment with ammonia results in the corresponding mixture of sulfamides and hydrocarbons and by subsequent reaction with n-butyrolactone converted to a reaction mixture, which consists of alkylsulfami-d @ abutyric acids, somewhat unchanged alkyl sulfamides and hydrocarbons; consists.

So parts by weight of this reaction mixture become 150 parts by weight a spindle oil raffinate (viscosity 5 to 7 ° 'Ehgler at 20 °') mixed, the mixture neutralized with q: & / o sodium hydroxide solution. You get a clear one. oil, which provides stable emulsions when water is stirred in. These can be used as drilling oil emulsions use. Example 8 The Alkylsulfamidoessi: gsäuren prepared according to Example i are extracted from the added hydrocarbons by extraction with aqueous acetone freed. So parts by weight of these hydrocarbon-free ': Al'kylsulfami-do> acetic saunas are with so parts by weight of a spindle oil raffinate from 5 to 8t ° 'Engler 2o ° 'mixed and the mixture neutralized with cyclohexylamine or with Triethandlamin. When diluted with water, the oils obtained give stable emulsions which are outstandingly useful as drilling oil and grinding emulsions. Example 9, a Mixture of alkyl sulfamides and hydrocarbons produced by partial Sulfochlorination of a. post-hydrogenated light spindle oil (viscosity approx. 2 to 5 '°' Engler at 20 °) and subsequent reaction with ammonia, becomes with, acrylonitrile brought to implementation, containing the resulting alkylsulfamidopropionitrile The mixture is saponified in a known manner and the resulting mixture of alkylsulfamidopropionic acids neutralized with alkalis or ammonia or organic bases. The aqueous; Sulfamidocarbon Acids containing solutions are advantageous as cooling and lubricating liquids in the machining of metals can be used.

For example fo with the action of carbon dioxide and hydrogen Olefins or the hydrogenation of carbon monoxide results in higher molecular weight alcohols next to aliphatic hydrocarbons. These alcohols can via their halides, Sulphites and sulphohalogenides converted into alkylsulphamidocarboxylic acids or their salts be, which n ;; ch more or less, large amounts of aliphatic hydrocarbons contain. The aqueous solutions of such products can replace the previously common oils or oil emulsions are used in metalworking, with In addition to the anti-rust effect, the excellent emulsifying effect of the sulfamidocarboxylic acids comes into play. Example ii In the sulfochlorination of saturated aliphatic Hydrocarbons under exposure to photoactive rays are formed when using molar amounts of chlorine and sulfur dioxide a reaction product of approximately the following composition: 2o to 25% hydrocarbons, 2o to 25%, polysulfochloride (mostly disulfochloride), 6o. up to 50% Moriosulfochloride. When treating with ammonia and the rest Reaction with chloroacetic acid gives a mixture of sulfamidiomono- and diacetic acids and hydrocarbon egg. By adding alkali hydroxides, alkali carbonates, ammonia or organic (bases are adjusted to p $ -Wiert 6 to 8.5. The resulting "mixture When diluted with water, it provides clear solutions which are advantageous in metalworking Find use. Example 12 Hydrocarbon-free Alkylsulfamidoes, s.igsäuren, as obtained in Example 9, mixed with approximately the same amount a spindle oil (viscosity 5 to 7 '°' Ehgler at 2o °). Then -will go through Elrwarm neutralized with calcined soda. A clear oil is obtained, which when diluted it results in clear to slightly opalescent solutions that are used as drilling oil should find. Example 13 foo parts by weight of the mixture described in example i from alkylsulfamidoacetic acid: and hydrocarbons are neutralized with sodium hydroxide solution; 5 parts by weight of sodium chromate are added to the mixture. 15 (parts by weight this mixture is diluted with fooo, parts by weight of water, one being weak .opalisating solution is created. This solution can e.g. B. as cutting fluid for the metal-cutting deformation of aluminum and aluminum alloys applied in Sverden. Depending on the requirements, the solution can, for example, by adding sodium dichromate can be adjusted slightly acidic, neutral or alkaline. Example 14 75 parts by weight .the sodium salts of the sodium salts described in Example i, which still contain about 5 01o water Alkylsulfamidoessigsäuren are with 25 parts by weight of the reaction product of about 6 moles of ethylene oxide mixed with i M01 isododecylpheuene. You get a bare one Oil which, when diluted with water, gives almost clear solutions. D: e dilutions can be used with particular advantage in drilling, cutting and similar metalworking use. Corrosion does not occur. Example 15 "You get a very good one Drilling grease of a firm consistency, if one uses 15 parts by weight of the sodium salt of a Alkyl, sulfomethylamidoacetic acid; produced analogously to the process of the example i, mixed with 85 parts by weight of mineral oil. When diluting such drilling grease arise stable ewulsions; which show no rust on cast iron. Example 16 foo parts by weight a Allcylsulfamid'oessigsäuregemisches prepared according to Example i are with gaseous methylamine neutralized and with! io, parts by weight of the methylamine salt of coconut fatty acids blended. The mixture dissolves opal in water and can mixed with. heavy spindle oils used in various metalworking operations are ". Example 17 foo, tGo weight parts Getansulfami, doacetic acid, with sodium hydroxide solution neutralized with 2o parts by weight of an oxäthylierternD "icycloh: exylamine (ioMoll ethylene oxide) and 2 parts by weight of cyclohexanol added. In a mixture with Spindle oil i: i you get an oil that can be found in very dilute emulsions Suitable for grinding and turning special steels and their emulsions when cutting greatly increase the stability of the tools.

Claims (1)

PATENT CLAIM: Use of oils or aqueous oil emulsions with a content of sulfamidocarboxylic acids, which have at least "one aliphatic radical containing at least 6 carbon atoms, or their water-soluble salts and optionally solubilizers or dispersants during processing of metals. Attracted publications ": French patent specifications No. 849 393, 866: 256.