DE4300552A1 - Use of water insol. di:alkyl ether(s) of poly:hydric alcohol(s) - Google Patents

Abstract

Use of at least substantially water insol. dialkyl ethers of natural or synthetic mono- and/or polyhydric alcohols, the ethers being liquid at working temps., as the oil phase in agents for treating metal surfaces and in cooling lubricants is claimed. Also claimed is an agent comprising (a) the above ethers; (b) corrosion inhibitors, and (c) emulsifiers.Carboxylic acids of formula R1-COOH (I) are used as corrosion inhibitors. In (I), R1 = aliphatic, opt. branched 5-23C hydrocarbyl and 0 or 1-5 double bonds, or R2-Ph-COCH=CH (where R2 = opt. branched 8-18C alkyl, and Ph = phenyl).

Description

Field of the invention

The invention relates to means for the shaping Metallbe processing containing dialkyl ethers and the use of Dialkyl ethers as an oil body for the preparation of agents for the shaping metalworking.

State of the art

In the shaping of metals become auxiliary means that essentially the friction between Tool and workpiece reduce the heat generated lead and remove the metal abrasion or chips. in the Meaning of the invention are under the term "shaping Me tallbearbeitung "non-cutting forming processes such as rolling, cold extrusion molding, deep drawing and wire and tube drawing as well Machining processes such as cutting, drilling, turning, milling understanding, grinding, honing or lapping. The cleaning and degreasing and the corrosion protection of Metalloberflä This is one of the overarching notions of metal treatment and is not the subject of this patent application.  

An overview of the forming metalworking pro tesse and the tools usually used for this purpose is for example Ullmann's Encyclopaedia of Industrial Chemistry, 5th Ed., Vol. A15, 479-486. The spotting of the forms of submission of eligible aid Tel ranges from oils to oil-in-water emulsions up to towards aqueous solutions. Usually, the basic fluids oil or water - other components such as For example, viscosity regulators, defoamers or Korro tion inhibitors added. Especially with oil-based systems are also lubricants, for example so-called "EP additives", common. For the formation of emulsions In general, the use of emulsifiers is required; in In many cases, the funds are also stabilized by biocides Siert.

The oil components used today are preferably paraffin or mineral oils used. In addition, so-called synthetic lubricants ("synthetic oils") as in For example, polyolefins into consideration. By selecting the Oils and their mixtures according to properties such as polarity or viscosity, metal working agents can be formu ling the technical requirements for the under meet a wide range of applications.

Because metalworking tools sooner or later about Kläran have to reach the surface waters, high levels of demands on their ecological compatibility the. Particular attention is paid to means that are considered Oil body mineral and therefore biologically "hard" carrier oils contain. In this context, for example, in the  EP-A2 0 512 501 acetals as substitutes for mineral oils beaten, whose industrial production, however can only be done with considerable technical effort.

The object of the invention was therefore to provide funds for the to develop shaping processing of metals that are free are of the disadvantages described.

Description of the invention

The invention relates to compositions for the shaping Me metal-working containing dialkyl ethers of the formula (I)

R ¹ -OR ² (I)

in which R ¹ and R ² independently of one another represent aliphatic, linear or branched hydrocarbon radicals having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds.

It has been found that dialkyl ethers are an excellent oil represent basis for metalworking tools. The invention further includes the surprising finding that the Dialkyl ethers friction between tool and workpiece be especially effective and rapid heat dissipation ensure sport. The easy biodegradability of As oil body functioning dialkyl ethers also provides the ge desired improved environmental compatibility of the invention safe means.  

oil body

For the purposes of the invention, dialkyl ethers are used as oil bodies set. These are known substances that are after the relevant procedure of preparative organic Chemistry can be obtained. Process for their manufacture ment, for example by condensation of fatty alcohols in Presence of p-toluenesulfonic acid are, for example, from Soc. Soc. Chiz. France, 333 (1949), DE-A1 40 39 950 (Hoechst) and DE-A1 41 03 489 (Henkel) known. Regarding the Prior art is further to the HP-A1 0 170 076 (BASF) referred to in the use of dialkyl ethers as a carrier for heat liquids is proposed. From the US 4,844,534 (Esso) are known lubricants which are dialkyl ethers contain. According to the teaching of DE-A1 41 16 406 (Henkel) kom Dialkyl ethers also as components of low-foaming Rei into consideration.

From an application point of view, symmetrical dialkyl ethers are preferred as oil bodies for metalworking agents having 6 to 12 or 16 to 18 carbon atoms in the alkyl radicals. A particularly good lubricity have dialkyl ethers of the formula (I), in which R ¹ and R ^{2 are} octyl and / or 2-ethylhexyl radicals or stearyl and / or Isostea rylreste. The dialkyl ethers which are particularly preferred according to the invention are thus di-n-octyl ether, di-2-ethylhexyl ether, di-stearyl ether and di-isostearyl ether.

Metalworking fluids

The agents according to the invention can be the dialkyl ethers in Men 1 to 100 wt .-% - based on the means - enthal They can be used as pure oils or as oil-in-water emulsions be formulated. The preferred aqueous products make concentrates with a water content of 5 to 25 Wt .-%, if necessary by the user on site on a Application concentration can be diluted. In the ge The forms of preparation according to the invention can be mentioned for example, as rolling, thermoforming or cutting oils, as well be used as grinding, honing or lapping oils. For span offending edits, for example, from the Kon Centraten 1 to 10, preferably 2 to 6 wt .-% emulsions manufactured.

From the prior art are for certain rolling processes (DE-AI 38 35 460, FR-B 2 101 197) and for the Tiefziehver (US 5,020,350) special cooling lubricant technologies known to work with mixed O / W systems, without the two phases forming an emulsion. The two Rather, phases are fed separately, at the site of the users mechanically mixed by a mixing system and in this Mixture applied to the workpiece. The from the workpiece running mixture separates spontaneously in a short time, so that the two phases prepared separately and the respective Supply containers can be supplied. Also for this special embodiment come the agents according to the invention into consideration.  

Depending on the requirement profile and area of application, he can inventive agents further typical ingredients in Amounts from 1 to 75, preferably 20 to 70 wt .-% - related on the funds - included. Typical examples are Korro anionic inhibitors, emulsifiers, lubricants, pH regulators, Dyes, biocides, solubilizers, anti-fog additives, Anti-aging agents and defoamers. Exemplary For this purpose, the following additive classes are explained in more detail:

corrosion inhibitors

The corrosion inhibitors are, for example, carboxylic acids of formula (11),

R ³ -COOH (II)

in the R ^{3 is} an aliphatic, linear or branched hydrocarbon radical having 5 to 23 carbon atoms and 0 or 1 to 5 double bonds or an R ⁴ -Ph-COCH = CH group, wherein R ^{4 is} a linear or branched alkyl radical having 8 to 18 carbon atoms and Ph represents a phenyl group.

Typical examples are the fatty acids caproic acid, capryl acid, capric acid, isononanoic acid, lauric acid, myristic acid palmitic acid, palmitoleic acid, stearic acid, isostearin acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, Arachidonic acid, behenic acid, erucic acid and clupanodonic acid as well as their technical mixtures, as for example in the pressure splitting of natural fats and oils are incurred.  

Preference is given to using carboxylic acids of the formula (II) in which R ^{3 represents} alkyl radicals having 5 to 17 carbon atoms.

Examples of substituted carboxylic acids are in the group of alkylbenzoylacrylic acids. Especially preferred is the use of 3- (p-dodecylbenzoyl) acrylic acid.

The said free acids can also be used as alkali, Alkaline earth, ammonium, alkylammonium and / or zinc salts be set.

Another group of corrosion inhibitors is anionic surfactants of the petroleum sulfonate type. in this connection are sulfoxidation products of paraffinfrak with an average of 6 to 30, especially 10 to 20 Carbon atoms. The petroleum sulfonates can also be used as se be understood as secondary alkanesulfonates, where as counterions Alkali or alkaline earth metals, ammonium or alkylammonium in To consider. Preferably, the petroleum sulfonates are in Form of their sodium or calcium salts used.

Another group of corrosion inhibitors are sulfones tion products of unsaturated fatty acid glyceride esters of the formula (III), so-called "sulfotriglycerides" or "sulfoils" in Be costume,

in which R ⁵ CO for an unsaturated acyl radical having 16 to 24 carbon atoms and 1 to 5 double bonds and R ⁶ CO and R ⁷ CO independently represent acyl radicals having 6 to 24 carbon atoms and 0 or 1 to 5 double bonds.

Sulfotriglycerides are known substances, the example example by addition of sulfur trioxide or chlorosulfone acid to unsaturated triglycerides, in particular rapeseed oil or Sunflower oil can be obtained. In this context be to the published patent applications DE-A1 39 36 001 and DE-A1 41 18 955 of the applicant, in which the preparation and the corrosion inhibiting and self-emulsifying egg properties of the sulfotriglycerides are described. For the purpose of the agent according to the invention is preferably sulphonated Rapeseed oil in the form of sodium, calcium, ammonium or Al kylammoniumsalzes used.

As corrosion inhibitors also come - also individually or in combination - alkanolamines and their salts, in particular carboxylic acid salts, sulfonates, organic boron compounds, in particular boric acid esters, fatty acid amides, aminodicarbon acids, dimer fatty acids, phosphoric acid esters, thiophenic acid esters, dialkyldithiophosphates, mono- and dialkylarylsulfones te, benzotriazoles and polyisobutenic acid derivatives which partially also have emulsifying properties, in  Consideration. The agents according to the invention can corrosi onsinhibitoren in amounts of 1 to 80, preferably 2 to 50 Wt .-% - based on the funds - included.

emulsifiers

For ready-to-use rolling oil emulsions, where by coalescence the emulsion is a continuous lubricating film on the rolling stock is to be formed, the oil content after dilution of Concentrates usually of the order of less than 10, preferably 1 to 3 wt .-%. To optimize the Lubricating effect, it is advantageous if the oil droplets of the Emulsions are as large as possible (about 2 to 5 microns) and have a narrow band size distribution. For cooling lubricant materials for machining, however, is of of particular importance that the emulsions over a longer Period are stable. In contrast, rolling oil emulsions also metastable, d. H. they are allowed to move with the times demix if the components are easily re-emulsifiable and the original drop size sets again. All these properties and requirements can be passed through optionally include emulsifiers to be used, so that the selection of this active component a special Bedeu is due.

Suitable emulsifiers are adducts of ethylene and / or or propylene oxide on compounds with acidic hydrogenato men or fatty acid esters into consideration. Below are at For example, alkoxylation products of fatty alcohols, alkyl phenols, fatty acids, fatty amines, fatty acid methyl esters and  To understand sorbitan esters, according to the known procedures of the prior art can be obtained.

Typical examples are addition products of average Lich 1 to 20, preferably 2 to 10 moles of ethylene oxide and 0 or 1 to 5 moles of propylene oxide to fatty alcohols having 6 to 22 carbon atoms, alkylphenols having 4 to 12 Kohlenstoffato men in the alkyl radical and fatty acids, fatty amines and fatty acid esters with in each case 6 to 22 carbon atoms in the fat residue. Addition products of 2 to 10 moles of ethylene oxide with lauryl or C _12/14 coconut fatty alcohol (conventional or narrowed homolog distribution), octylphenol, lauric or C _12/14 coconut fatty acid, laurylamine, coconut fatty acid methyl ester and / or sorbitan monolaurate are particularly preferred ,

Other suitable nonionic emulsifiers may be used in the Group of sugar esters and / or alkyl polyglucosides found become.

Especially for coolants used in machining be used, come in addition to the nonionic mentioned Emulsifiers also anionic surfactants such as Sei Fen, sulfonates and alkyl phosphates into consideration. Typical case games for this group of compounds make alkaline soaps of fatty acids, naphthenes, alkylarylsulfonates, alkanesul fonates, alkylbenzenesulfonates, alkylsulfates and alkylethersul The agents according to the invention can be the emulsifiers in amounts of 1 to 80, preferably 2 to 50 wt .-% - bezo to the funds.  

lubricants

As lubricating additives can at low cost tions to the lubricating effect in addition to the corrosion inhibitor known fatty acids fatty acid esters ("fatty oils"), syn thetic esters or metal soaps are used. For hö here, it is more advantageous to use so-called "EP Additives ", examples being organic Chlorine compounds, such as chlorinated paraffins, chlorinated fatty oils, sulfochlorinated fatty oils or sulfur-containing compounds, such as sulphurised fatty oils, organic mono- and disulphides or sulfurized polybutenes and phosphorus compounds of the type of phosphoric esters or dialkyldithiophos phosphates. The agents according to the invention can be the lubricants in amounts of 1 to 80, preferably 2 to 50 wt .-% - bezo to the funds.

solubilizers

In order to obtain homogeneous solutions or stable emulsions solubilizers or "stabilizers" are occasionally required. Typical examples of these are C ₁ -C ₄ -alcohols, glycols or glycol ethers. The agents according to the invention may contain the solubilizers in amounts of from 1 to 50, preferably from 2 to 25,% by weight, based on the compositions.

Industrial Applicability

The agents according to the invention reduce the friction between Tool and workpiece, ensure a rapid Wärmeabt ransport, metal abrasion and chips continue to rinse and are good biodegradable. A special advantage over the Prior art is in the hitherto unknown choice of readily biodegradable dialkyl ethers as an oil base for these funds.

Another object of the invention therefore relates to the Ver Use of dialkyl ethers of the formula (I) as an oil body in the Production of means for cutting or machining shaping metalworking, for example rolling, drawing Cutting, drilling, turning, milling, grinding, honing or lapping oils and cooling lubricants, in which they are available in quantities of 1 to 100, preferably 5 to 95 wt .-% - based on the means - may be included.

The following examples are intended to form the subject of the invention explain it in more detail without restricting it to it.  

Examples Examples 1 to 4, Comparative Example VI

The surface pressure of mineral oils was investigated with the Friction Scales according to Reichert (Sommer and Runge, Ber lin). Here, the specific surface pressure (out expresses in bar or% -rel to the standard), at which the Lubricating effect collapses. A high value of specifi In this context, surface pressure means one good lubricating effect of the liquids.

Substances used:

I: di-n-octyl ether
II: di-2-ethylhexyl ether
III: di-stearyl ether
IV: di-isostearyl ether

As standard, according to 100% -rel, diesel oil was used det. The results are summarized in Tab. 1.  

Table 1

Specific surface pressure (SFP)

Examples 5 to 7, Comparative Examples V2 and V3

There were water-miscible coolant concentrates (for Composition cf. Tab. 2). For this purpose, 1/3 was the provided amount of oil together with tall oil fatty acid and a Solubilizers presented in a kettle and stirred. so indicated remotely, salicylic acid was then metered. To the mixture was then aqueous with constant stirring Added potassium hydroxide solution at such a rate give that the temperature was between 50 and 70 ° C. to Finally, the mixture was stirred for a further 60 minutes until a clear solution was obtained. After that, the was Bende amount of the oil body and the remaining ingredients added to the formulation and stirred for a further 60 min.  

Table 2

Composition of coolant concentrates

Percentage as weight%

The efficiency of the coolant concentrates was on the basis of their corrosion-inhibiting action according to DIN 51 360, part 2 tested by pouring castings on filter paper with the Emulsions were wetted. After 2 hours, the rust formation evaluated according to the comparison scale according to DIN 51 360, Part 2. Corrosion degree 0 means no corrosion. In Tab. 3 is the minimum concentration of coolant concentrates specified, which is required to 0 degree of corrosion to reach.  

Table 3

Corrosion inhibiting effect

Example 8, Comparative Example V4

It became a rolling or cutting oil of the following composition prepared by stirring the components:

base oil 50% by weight C _16/18 fatty acid TXP ester 30% by weight Sulfurized sperm oil 12% by weight Sulfurized Diisobutene 5% by weight Zinkdiethyldithiophosphat 3% by weight

The base oil was di-n-octyl ether (Example 8) or a naph thenisches mineral oil (Pionier® 4556, Hansen and Rosen Thal, Hamburg / FRG). Checking the lubrication effect was performed according to ASTM D 2625-83, method B, according to Falex Pin and Vee Block method. After that, the burden and the moment or break of the pin is determined. It was with the standardized FP machine worked, where  initially set to 2224 N load, the moment read and read again after 5 minutes. From the next Bela level (see Table 4), the burden was changed in each case and the moment registered immediately as well as after 1 minute.

Table 4

Lubricating effect after the FP

Claims (5)

1. Composition for shaping metalworking containing dialkyl ethers of the formula (I) R ¹ -OR ² (I) in the R ¹ and R ² independently of one another for aliphatic, linear or branched hydrocarbon radicals having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds are available. 2. Composition according to claim 1, characterized in that they contain symmetrical dialkyl ethers of the formula (I) in which R ¹ and R ^{2 are} linear or branched alkyl radicals having 6 to 12 carbon atoms. 3. Composition according to claim I, characterized in that they contain symmetrical dialkyl ethers of the formula (I) in which R ¹ and R ^{2 are} linear or branched alkyl radicals having 16 to 18 carbon atoms. 4. Composition according to claims 1 to 3, characterized net that they dialkyl ethers in amounts of 1 to 100 Wt .-% - based on the funds - included. 5. Use of dialkyl ethers of the formula (I) as an oil body for the production of means for forming metal processing.