LU82565A1 - LUBRICANT SYSTEM FOR THE HOT FORMING OF METALS - Google Patents

Description

rm »1 Troisdorf, June 28, 1979 OZ: 79 036 (2964) DYNAMIT NOBEL AKTIENGESELLSCHAFT Troisdorf, district of Cologne 5 I Lubricant system for the hot forming of metals; i .j The invention relates to a modification of the lubricant <i 10 system for the hot forming of metals according to the main [patent (DE-OS 27 00 04Ό.4). The modification of the lubricant system made possible by the invention enables an improved adaptation of the lubricant system to the different circumstances, which are due to the great variety of the technologies used , the deformation processes, but also caused by different I * production devices in one and the same processing operation or by the auxiliary devices connected to the actual deformation process.

> - ISo e.g. shown that · in a few cases the use of the lubricant systems formulated according to the main patent (DE-OS 27 00 040) is their I 25, the actual task, namely an adequate lubrication! - 2 - bzw. tion or separating effect between the tools used and the materials to be deformed, meet excellently, but because of their high emulsion stability, difficulties arise in the preparation 5 of the used, possibly diluted with cooling water emulsion. These difficulties are due to the fact that the stability of the emulsion itself, but also that of the highly diluted emulsion that arises when the tools are cooled with large amounts of cooling water, is so great that, in some cases, preparation provided Î des from the deformation process Sewage one | '. Separation of the existing lubricant residues is difficult. In these cases, the task arises of modifying the lubricant system in such a way that, while maintaining or improving the lubricating and separating action and the other advantages given in the main patent (DE-OS 27 00 040), it is easier to separate the lubricant components from the waste water becomes.

20 This object is achieved according to the invention in that a lubricant system is provided which, in addition to the contents of fatty acid monodiglyceride diethoxylates and / or fatty acid ethoxylates according to the main patent (DE-OS 27 00 040), contains fatty acid * 25 esters of polyols with 2 has up to 6 methylol groups in the molecule, the methylol groups being on quaternary carbon atoms, in an amount up to five times the content of fatty acid monodiglyceride ethoxylates and / or fatty acid ethoxylates.

30 The amount of active ingredients in the lubrication system, i.e. the atoxylates of fatty acid partial glycerides and / or of fatty acids and the polyol ester should not exceed 5 to 50% by weight of the total mixture.

The fatty acid esters of polyols with 2 to 6 ethylol-35 groups on a quaternary carbon atom are also called [7 - $ - "* 1 as fatty acid polyester", since several fatty acid residues are contained in the molecule and are bound to the methylol groups The polyols mentioned with 2 "to 6 methyl groups on one or more quaternary carbon 5 atoms have a branched molecular structure with at least five carbon atoms, the number of carbon atoms being unlimited, especially since conienation products are also limited two or more such polyols, such as dipentaerythritol or tripentaerythritol, may be present Ί0, some of which are used in the preparation of the polyols; 0 arise. Heopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol are preferred as polyols.

The methylol groups are wholly or very preferably largely esterified with fatty acids. In other words, these are polyol esters, the methylol groups of which are largely provided with fatty acid residues and, to a lesser extent, have free methylol groups.

: * 4 yyy It should largely mean that the degree of esterification should be high I, so that the hydroxyl number of the ester is low 120. Preference is given to polyol esters which have a hydroxyl number below 50 owing to an incomplete esterification with fatty acids.

I As the dead acid component of the polyol esters I 25 essentially the same fatty acids as those in the '* fatty acid monodiglyceride ethoxylates or the like. Fatty acid ethoxy Iates are present, i.e. fatty acids with 12 to 22 carbons! Substance atoms such as lauric, kyristic, palmitic, stearic, ipalmitoleic, oleic, linoleic, linolenic, arachidonic, erucic-5 ° acid or mixtures of these fatty acids, preferably

Mixtures of the fatty acid with 16 to 22 carbon atoms. Fatty acid mixtures based on natural raw materials such as e.g. Palm oil, peanut oil, cottonseed oil, soybean oil, sunflower oil, rapeseed oil. 55 Use oil, lard, beef tallow, whale oil, herring oil, V * / - 4 - Γ 1.

The fatty acid mixtures on which the fatty acid monodiglyceride ethoxylates and / or fatty acid ethoxylates or fatty acid polyol esters are based can be the same or different. For example, a fatty acid monodiglyceride ethoxylate based on lard can be combined with a fatty acid polyol ester based on peanut oil; all conceivable combinations of fatty acid mixtures are possible both for the fatty acid monodiglyceride ethoxylates and / or fatty acid ethoxylates and for the fatty acid polyol esters, provided that only the chain length of the fatty acid or mixtures used is between 12 and 22 carbon atoms. For economic reasons 15, however, the same fatty acid mixture will generally be used for the ethoxylene oxide component as for the polyol ester component.

The lubricant system 20 according to the invention is produced by stirring the fatty acid monodiglyceride and / or fatty acid ethoxylates and fatty acid polyol esters into water. Since the emulsion is formed spontaneously, further measures such as e.g. Be homogenized apart from '25.

* ψ

It has been found that the lubricant system according to the invention has a viscosity between 5000 and 40,000 cP, preferably between 15,000 and 50,000 cP, measured under 30 the conditions specified in the main patent, namely at -1 a shear rate of 2.64 cm and one Must have a temperature of 30 ° C. Lubricant compositions of less than 5000 cP and more than 40 000 cP, even if they contain ethoxylates and polyol esters with a corresponding or similar composition according to the invention -35, r ί '_______— I P-5-! 1 are not suitable for solving the task. · Lubricants with viscosities below 5,000 cP show insufficient adhesion on damp metal surfaces and are therefore not suitable for practical use. An upper limit of the viscosity range of the lubricant system according to the invention is given, on the other hand, by the fact that the conveying and application of the aqueous dispersion or emulsion are carried out using the usual operational facilities such as e.g. Pumps, nozzles and the like. Guaranteed i 10 must be. In addition, viscosities over 40,000 j cP are undesirable because of the difficulties! result in the even application of the lubricating film.

It was found that with increasing proportions of polyol esters according to the invention in the formulation, the Ί viscosity of the emulsion obtained decreased. Such

However, emulsions can easily meet the || Are used if only the viscosity values within | 20 half of the range of 5,000 to 40,000 lj cP according to the invention, preferably between Λ *? 000 and 50,000 cP.

«I

(On the other hand, by using this effect there is an additional possibility, such emulsions, which with viscosity values close to 40,000 cP are just one value

E

’25 in the area according to the invention and are therefore basically usable as lubricant systems according to the invention, but during transport through the cable

systems and when spraying due to the high viscosity require a higher expenditure on equipment, or li 50 even those whose viscosity value is above 40 000 I.

I · cP would be, by adding small amounts of polyol- | to modify esters in such a way that the viscosity values decrease accordingly and can, for example, be brought into the preferred range of 15,000 to 50,000 cps 55.

I / - 6 - Ί It has also been found that such lubricant systems, particularly those with high contents! Polyol esters according to the invention would have too low a viscosity, for example less than 5,000 5 cP, and could therefore no longer be used on wet metal surfaces due to a lack of adhesion, by adding small amounts of thickeners such as e.g. of cellulose ethers, alginates, carrageenans, polyacrylates etc. or inorganic thickeners such as bentonites, highly disperse silica or the like. can be converted into a formulation according to the invention with sufficient viscosity and good adhesion. For this purpose, the use of cellulose ethers, in particular the use of methyl ^ 5 celluloses, is preferred. The use of a combination of methyl hydroxyethyl celluloses of the highly etherified type with the same type of methyl celluloses is particularly preferred. The methyl-hydroxy-ethyl cellulose - particularly advantageous is the use of a type with a high viscosity level, since only minimal additional amounts are then required - to roughly adjust the required viscosity, while using a methyl cellulose low viscosity level at the same time so much thickening material can be introduced that the required adhesion and good film-forming ability is achieved. By suitably selecting the concentrations of the cellulose ethers, all of the viscosity levels according to the invention can be set without problems.

$ 0 The amount of thickener should not exceed 5% by weight of the ready-to-use emulsion; Amounts of 0.01 to 3 »5% by weight are preferred.

It was also found that the use of EP additives / / Γ - ν - 1 (extreme pressure additives) can be advantageous in the case of particularly difficult lubrication and separation problems. Deformation processes that are connected with high real speeds between the tool and the rolling piece often result in the formation of particularly strong wear zones, since cold welding occurs in these areas when the lubricating film is torn off. In these balls it is possible to use EP additives, e.g. create a pressure-resistant lubricating film through chemical reaction with the metal to achieve an additional lubricating effect, which can significantly reduce wear. Preferred is the use of EP additives of the long-chain phosphoric acid ester type, which are available, for example, under the brand name Gafen (manufacturer: GAF Germany) and / or I 15 of sulfur compounds, in particular of the type of poly-I sulfides such as e.g. Di-tertiary nonyl polysulfide, di-tertiary I doedecyl polysulfide, which are known as high-pressure additives for I drilling oils. Other EP additives are, for example, chlorinated paraffins, thiophosphoric acid esters, sulfur-20 or sulfur-chlorinated sperm oil, etc. For the Einar-! Processing the EPP additives the same rules apply as I have given for the additional use of the fatty acid polyol ester. The viscosity of the formulation is generally also reduced by the EP additives, so that the cellulose described '* ether must be provided for adjusting the viscosity.

The EP additives can be present in the ready-to-use emulsion in amounts of 0.01 to 10% by weight, preferably 0.1 to 6.0% by weight.

I50 The lubricant system of the invention exhibits excellent and even better adhesion to moist metal surfaces than the main patent and can therefore, although dispersible or emulsifiable in water,

Apply water-cooled rollers to a particularly even lubricating film.

: '-δη The lubricant residues that may become hot during the application, e.g. by spraying on the rolling stands and fittings during operational use, can be removed completely and easily, for example by rinsing with a 5 powerful water jet.

It is a particular advantage of the lubricant systems with contents of fatty acid polyesters, especially with high proportions of fatty acid polyester esters, that the lubricant-containing waste water can easily be e.g. by clarification in sedimentation tanks, filtering through gravel filters and similar measures, largely freed of lubricant residues and re-use e.g. can be supplied as cooling water. It has an advantageous effect that the emulsion, which is very stable when used as a lubricant, is rapidly degradable when cleaning the waste water and the degradability given by the composition of the lubricant is not impeded by remaining in the emulsified form.

20th

The lubricant system according to the invention finds a preferred use in the hot rolling of steel profiles.

This shows a uniform formation of the lubricating film, good adhesion to the W salts and a sufficient lubricating and separating effect.

f j The lubricant system i according to the invention is described in more detail in the following examples.

35 30 "'V * l I 1 Examples 1 to 19

In Examples 1 to 8, an active ingredient system consisting of 20% by weight of a fatty acid ethoxylate (based on rapeseed oil fatty acid with approx. 20% erucic acid content) with 3 koles of ethylene-5 oxide per mole of fatty acid (FEO) and 80% by weight of a tri -methylolpropanesters based on the same fatty acid with a hydroxyl number of 30 (TMP ester).

In Examples 9 to 11, the proportions of FEO to TMP ester are 20%, in Examples 12 to 19 the Anteile0 proportions are 22%. The active ingredient systems were processed into emulsions with a total lubricant content of 25% by weight.

j | · Example of FEO / TMP-EP additive cellulose ether viscosity | 15 esters MCa ^ MHEC5 · ^

No._%% Type% _% _ cP

; 1 22.5 2.5 DM 400? ^ - 1.0 7800! 2 22.5 2.5 IM 400 1.1 _ 5500 | 3 22.5 2.5 DM 400 1.3 - 7200 | 20 4 22.5 2.5 LM 400 1.6 - 9100! 5 22.5 2.5 LM 400 1.8 - 14800 \ δ 22.5 2.5 LM 400 2.0 - 22250 j 7 22.5 2.5 LB 400d ^ 1 0.2 5800 l 8 22.5 2.5 LB 400 1.25 0.38 9200 • 25 9 20 5 LB 400 1 - 6500; - '10 ’20 5 LB 400 1 0.1 7800 5 11 20 5 LB 400 1 0.3 12400 - 12 22 3 TNPS 2 - 6550'! 13 22 3 TNPS 0.8 0.6 5390 30 14 22 3 TNPS 0.8 0.8, 12450 \. 15 22 3 TNPS 0.8 1 19650 16 22 3 TNPS 1 0.6 9170 17 22 3 TNPS 1 0.8 15730 18 22 3 TNPS 1.5 0.5 14420 I 35 19 22 3 TNPS 2 0.5 24900 ' / -10 - γ / r 1a) highly etherified methyl cellulose, viscosity grade

1500 cP

h) highly etherified methyl hydroxyethyl cellulose, viscosity level 30,000 cP

3-c) long-chain phosphoric acid ester (Gafen IM 400 :) »partly neutralized with triethanolamine d) long-chain phosphoric acid ester with free acid contents (Gafen LB 400) e) di-tertiary nonyl polysulfide (manufacturer: Société ΊΟ nationale des Pétroles d ' Aquitaine)

Examples 20 to 24

The following formulations were made from a fatty acid. ethoxylate (FEO; based on beet oil fatty acid, 3 moles of ethylene--5 oxide) and a trimethylolpropane ester (TMP; based on beet oil fatty acid, hydroxyl number 30).

| Example FEO TMP EP additive cellulose ether water Visco- I -MC MHEC sity 20 Hr. TI. TI. TI. Type TI. TI. TI. cP! 20 20 20 3 TEES 0.65 0.20 57 10480 | 21 25 25 3 TEES 0.65 0.20 47 24 900! 22 24 6 3 TEES 1.7 0.30 67 38000 23 32 8 3 TEPS 1.0 0.50 57 7860 25 24 40 10 3 TEPS 1.0 0.50 47 27500 v Ψ

Examples 25 to 34

The following products were produced from the fatty acid mixtures A or B of the composition below: 3 ° MDEO = monodiglyceride ethoxylate (based on fatty acid A, containing 42% monoglyceride and 49% diglyceride before ethoxylation, ethoxylated with 4 moles of xylene oxide per mole of hydroxyl- 35 group) I -! t

A

S ^ r - ———- «.............." - '' "" i '“11" 11 FEOB = fatty acid ethoxylate (based on the fatty acid mixture B, with 3 holes of ethylene oxide) TMPB = trimethylolpropane ester (based on the fatty acid mixture B, with hydroxyl number 25)

‘Fatty acid mixture A fatty acid mixture B

Palmitic acid 29% ok

Stearic acid 12% 4% ^ oleic acid 49% JO%,

Linoleic acid 6% 20%

Linolenic acid 1% 5% I erucic acid - 19%? Pest: other fatty acids with 12 to 22 i 1 r 1 J carbon atoms i I.

; The products were processed into the following formulations tet: I 20 î Example HDEO FEOB ΤΓ1ΡΒ EP additive water viscosity

ί No. 0) 1. TI. TI. TI. Type TI. ',' CP

1 25 12 12 9 0 - - 67 20 970 26 10.5 10.5 9 3 TNPS 67 10 460 3 * 25 27 12.5 12.5 10.5 3 TNPS 61.5 24 900 Î 28 14 14 12 3 TNPS 57 27520 29 12 12 16 3 TNPS 57 20970 30 24 6 3 TNPS 67 10800 31 24 - 16 3 TNPS 57 6500 30 i *, / L.

j i I 33 - 12 - Γ

Example 52

Example 21 is repeated, but with the fatty acid ethoxylate based on the same proportions of the C "jg" bis. ^ Q fatty acids with 4 hol ethylene oxide and the polyol esters ^ a) with up to C2Q fatty acids up to a hydroxyl number of 10 esterified ITeopentylglycol b) was a, similarly esterified pentaerythritol. Pie Yiskosity was in the range of 25000 cP.

10 15 20 ’25 30 35 Dr.La/Be

Claims (6)

1 1- Lubricant off system for V / arm deformation of metals, consisting of an aqueous dispersion or emulsion of fatty acid monodiglyceride ethoxylates and / or fatty 5-acid ethoxylates, with a content of fatty acid monodiglyceride ethoxylates and / or fatty acid ethoxylates from 5 to 60 wt .-%, the fatty acid monoglyceride ethoxylates 2 to 6 moles of alkylene oxide per mole of hydroyl groups present or the fatty acid ethoxylates 2 to 6 Contain 110 moles of alkylene oxide per mole of fatty acid ethoxylate and the aqueous dispersion or emulsion has a viscosity between 5000 and 40,000 cP, with a shear rate of 2.64 cnF and a temperature of 30 ° C, | according to main patent 27 00 040, characterized in that 1. the lubricant system has an additional content of • fatty acid esters of polyols with 2 to 6 methylol groups bound to quaternary Ί carbon atoms per molecule in an amount up to five times the content of fatty acid monodiglyceride ethoxylates and / or fatty acid - I has 20 ethoxylates. j; i 2. Lubricant system according to claim 1, characterized in that the fatty acid polyol esters of I fatty acids with 12 to 22 carbon atoms, preferably 25, based on fatty acid mixtures with a predominant proportion of fatty acids with 16 to 22 carbon atoms atoms, are. 3. Lubricant system according to one of claims 1 or 2; 50 characterized by an additional content of thickeners, preferably of the type of highly etherified methyl celluloses and / or highly etherified methyl hydroxyethyl celluloses, up to an amount of i 5 wt .-%, based on the ready-to-use emulsion. I 35 / ^ -1 —— »——— · 1 '' Γ" '* "* .......... f -..... Ί i" ........ .. 1 - 2 - 1 ι \. SqhmierstoffSystem according to at least one of claims 1, 2 or 3 »characterized by an additional content of EP additives, preferably of the type of long-chain phosphoric acid esters and / or polysulfides, 5 pis in an amount of 10% by weight, based on the ready-to-use emulsion. \ λ k UAfi '/ / / \ j “V; 10 - ~ - i i! Ί5 ί 20 25 i ψ 3 ° 35 Dr.La/Be