DE2700040A1 - LUBRICANT SYSTEM FOR HOT FORMING OF METALS - Google Patents

Description

Trolydorf, don? 0. Vg? .. 1976
ο · j

OZ: 77001 (26üB) 2 7Q00 AO j

DYHAIlIT ITOBLL AKT * 317GSSELLiJCHAFT
Troisdorf, district Cologne

Lubricant system for the Viarrcverfornmnc of metals

The invention relates to a Sehmierstoffsyütcra for the V / arrrvor-

forming of metals. In particular, the? Invention on!

water-containing, environmentally friendly Schmior.v.toff rr / s1 erne, which are designed for non-cutting metalworking such as, \ 'alsen or drawing and which provide sufficient lubrication or tronnecting?
between the tools used and the materials to be processed.

The previously known lubricant oysters based on tar or mino-4 ral oil have disadvantages. The otändi ^ o KHJilun ^ the V / merkzeure
with water - in the case of V / arrc rolling mills with large V.'assernienr.en - lets crack products and undecomposed raw oil fractions in

enter the cooling water circuit. The separation: the biological I

Substances which are difficult to degrade and which would impose an unreasonable burden on the wastewater cause considerable accounts and a ^! affects the economy of the process?;. I.

Products containing tar and tainoral oil decompose thermally
Due to high temperatures the V, ^f proceeds tue kt with the formation of star3; cr ^r .; uul: ·· and soot clouds, the removal of which is necessary for reasons of the workplacejh;> T.ieno it; t, v;? c; eb '; nrall! -; with er)) '1> au: · _-: i.! :: ·· ' ■ -

tionon connected int.

609

BATH ORIGINAL
COPY

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j Lubricant residues cover the i armature; n and scaffolding in the form of a thin film, which is only difficult to be removed. Smooth objects coated with oil can

j disrupt operations and cause accidents by slipping or slipping.

The invention is therefore based on the object of a lubricant : for hot forming of metals, especially for hot ! rolling of steel, to provide that the disadvantages of the known

avoids th lubricants based on mineral oil, the more j
a problem-free application with the usual fittings, pumps,

, Nozzles etc. allows a good film formation on the used Tools and shows excellent adhesion after application to damp metal surfaces, even then jwhen the tools are cooled by running water.

^; This object is achieved according to the invention in that a lubricant system is provided which consists of an aqueous dispersion or emulsion with contents of 5 to 60% by weight of fatty acid monodiglyceride ethoxylates and / or fatty acid ethoxylates,

! where the fatty acid monodiglyceride ethoxylates 2 to 6 mol, preferably

3 to 5 moles of alkylene oxide per mole of hydroxyl groups present and the fatty acid ethoxylates 2 to 6 mol, preferably 2.5 to

! ■ ι

'A mole, contain alkylene oxide per mole of fatty acid ethoxylate and the ί ^! aqueous dispersion or emulsion a viscosity between 5000 ^! _; and hO having 000 cP at a shear rate of 2.64 cm ^"1 and a temperature of 30 ⁰ C.

The reaction products with ethylene oxide are preferred as ethoxylates or, if given, understood as propylene oxide.

! Fatty acid ethoxylates and fatty acid partial glyceride ethoxylates are

80982? / 0489

known and are resp. . Fatty acid partial glycerides with ethylene oxide or g £ f. Propylene oxide j, whereby alkoxy chains bonded predominantly on one side to the OH groups of the fatty acids or the partial glycerides which end with Η atoms.

Mixtures of fatty acid monodiglyceride ethoxylates with fatty acid ethoxylates, in particular those with at least 10, are preferred As a rule, at least 20 Gev /.- Jü one?; r of the two components;

However, mixtures of the fatty acid monodiglyceride ethoxylates are also possible with each other and possibly a mixture of fatty acid ethers

i oxylates among themselves.

As monodiglycerides, such mixtures become free of triglycerides or understood with reduced levels of triglycerides,

! their content of mono- and diglycerides usually not of ! 30 to 100% by weight, preferably 55 to 90% by weight, deviates. the

j Fatty acid residues of the partial glycerides or fatty acids can become saturated or be unsaturated; Residues of hydroxy fatty acids should

; len not be included.

Admittedly, lubricants with levels of fatty acids have already been used.

¹ ethoxylates proposed in DT-OS 2 446 319, but is there

I with a different task a soluble in water _; '' Lubricant manufactured that diluted with water real trans-

j forms parente or seiai-transparent solutions.

i The lubricant solution according to DT-OS 2446319 are disadvantages ¹ part because of their low viscosity and thus low adhesion to the tool. These lubricants are washed off by VZeri :: ..: ^{1 ;;. '::: - j cooled with running water and therefore become theirs}

ORIGINAL INSPECTED

ic

Unsuitable lubrication.

Another disadvantage of the lubricants of DT-OS 2 446 319 is the laborious production from three components, namely (A.)
water-soluble substances with a longer alkoxy chain, (B) oil-soluble substances with a shorter alkoxy chain, and (G) a surface-active substance.

According to what has been said, the object of the present invention could not be achieved by DT-OS 2,446,319.

The suspension or emulsion preferably contains 10 to 40
of the ethoxylates, with increasing contents of the ethoxylates increasing the viscosity and thus there is a possibility of adjusting the viscosity. A second possibility of adjusting the viscosity is through the length of the alkoxy chain, with longer alkoxy chains reducing the viscosity in numerous cases. from
However, another influence on the viscosity is the degree of distribution of the sthoxylates in the aqueous phase of the dispersion or
Emulsion, · the chain length of the fatty acids and the content of mono- or diglycerides in the partial glycerides, so that the viscosity of the aqueous dispersion can be determined from the chemical analysis of certain ethoxylation products of partial glycerides or fatty acids! cannot be predicted with sufficient accuracy. i It is therefore intended to achieve the desired specific viscosity of a!

certain product, if necessary after measuring the viscosity of the batches, by simply mixing dispersions with higher and _;

Einausteilen dispersions with lower viscosities which is intended for the respective \ use viscosity.

8098/0489 ---

Preferred degrees of ethoxylation are photonic acid monodiglyceride ethoxylates between 3 and 5 moles of ethylene oxide per hydroxyl group of partial glycerides, in the case of fatty acid ethoxylates between 2.5 and 4 moles of ethylene oxide per mole of fatty acid. '

The dispersions or emulsions have the considerable advantage that they form spontaneously. It was found that the aqueous dispersion or emulsion of fatty acid monodiglyceride ethoxylates with a degree of ethoxylation of less than 2 moles of ethylene oxide per mole of hydroxyl groups and / or fatty acid ethoxylates with less than 2 moles of ethylene oxide per mole of fatty acid give adequate adhesion to moist metal surfaces such as water-cooled rollers However, the build-up of a uniform lubricating film is not guaranteed. An especially smooth or heavily loaded with water points there is a tearing of the film, resulting ultimately in increased wear of the W _e rkzeugs results. Aqueous dispersions or emulsions of fatty acid monodiglyceride and / or fatty acid ethoxylates with a degree of ethoxylation of more than 6 moles of ethylene oxide per mole of hydroxyl group or fatty acid, on the other hand, show poor adhesion to damp metal surfaces, so that a reliable application of the lubricating film, for example by spraying onto rotating, water-sprayed ones Rolling, is not possible as the lubricating film is quickly washed out.

It has also been found that the lubricant system according to the invention a viscosity between 5000 and 40,000 oP, preferably between 150,000 and 30,000 cP, measured under the specified

80982fV0A89 ORIGINAL INSPECTED

conditions.

The required viscosity measurements were made with the rotary Rotovisko viscometer from Gebr. Haake. It the temperature-controlled Couette device MV II P in combination: used with the measuring head 500, which by a special shape for the investigation of dispersions or emulsions suitable is. Details can be found in the company publication "Rotovisko, Description and Instructions for Use!", Printed publication 105/16, as well as the article by W. Heinz, Rheology and Rheometry with Rotational Viscometer ^ 2nd Edition, Springer-Verlag, Berlin, refer to.

The viscosity ranges mentioned above were found at a shear rate of 2.64 cm "and a temperature of 30 ⁰ C. lubricant compositions 5000 and about 40000 cP, even if ethoxylates are contained therein with corresponding or similar substances according to the invention composition, are not to solve the problem. Lubricants with viscosities below 5000 cP show inadequate adhesion to moist metal surfaces and can therefore not be used in practice or emulsion must be guaranteed with the usual operational equipment such as pumps, nozzles, etc. In addition, viscosities over 40,000 cP are also undesirable because difficulties arise in the uniform application of the lubricating film.

80982 ^ / 0489

The lubricant system according to the invention also shows what is known as a plastic viscosity behavior. Associated with this is the presence of a flow limit, which is given the value 50 dyn.cm "(

according to the relaxation method after 30 seconds of relaxation time). Corresponding to this behavior, a decrease in viscosity with increasing shear rate is observed. Thus, according to the invention lubricant system viscosity values between 100 and 500 results in the OP "at a shear rate of 428 cm ~ and a temperature of 30 ⁰ C.

The viscosity range according to the invention can be set by varying the concentration of the fatty acid monodiglyceride and / or fatty acid ethoxylates. Thus, dispersions or emulsions with a higher ethoxylate content generally have a higher viscosity and vice versa. However, the desired viscosity of the aq membered dispersions or emulsions can also be brought about by mixing for example two Äthoxylierungsprodukten, one of which results in a single component in the corresponding dispersion or emulsion, a low and the other used as a single component a high viscosity. The fatty acid residues of the ethoxylates used in the Sohmierstoffsystera according to the invention are derived from fatty acids with 12 to 22 carbon atoms such as lauric, myristic, palmitic, stearic, j palmitoleic, oleic, linoleic, linolenic, arachidonic, erucic acid or J of mixtures of these fatty acids, preferably mixtures of the |

Fatty acids with 16 to 22 carbon atoms. I.

The production of the ethoxylates can be particularly advantageous on the basis of natural raw materials such as palm oil, peanut oil, full-tree!

eaat oil, soybean oil, sunflower oil, linseed oil, rapeseed oil, j . 8 0 9 8 ΤψΙ 04 8 9 --- -

Lard, beef tallow, whale oil, herring oil. the Fatty acid monodiglyceride ethoxylates can be prepared by "known methods, for example by transesterification of those mentioned above Fats or oils with glycerine or by esterification of the fatty acids obtained by splitting fats with glycerine and then Ethoxylation with the specified amounts of ethylene oxide. The fatty acid ethoxylates can e.g. lenoxid to the fatty acids obtainable by splitting fats or by esterifying fatty acids with polyethylene glycols corresponding chain length can be produced.

The lubricant system according to the invention is produced by stirring the fatty acid monodiglyceride and / or fatty acid ethoxylates into water. Because the dispersion or emulsion formed spontaneously after the ethoxylates have been distributed in the aqueous phase, further measures such as homogenization can be dispensed with will. The aqueous dispersions or emulsions obtained in this way can be used immediately after production, but can also, since they have good stability, essentially unchanged over a longer period of time, e.g. over several weeks. In the latter case, it is advisable to add one of the usual preservatives to a prevent microbial decomposition. Furthermore, given

if other additives such as anti-corrosion agents, steam J

phase inhibitors, antioxidants and the like in small amounts j incorporate into the lubricant system according to the invention. ;

In the case of using fatty acid ethoxylates without any

Addition of fatty acidTnonodiglYQeridäthpxylntQn 1.Pt it is two- fold, I

- 270004Q

ΛΑ

a small amount of a sodium or potassium salt of a fatty acid with 12 to 22 carbon atoms to be used in the preparation of the corresponding dispersions or emulsions. Through this the formation of the dispersion or emulsion is facilitated and the application of the lubricating film is more even. The lubricant system according to the invention meets requirements which for reasons of environmental protection is increasingly being put to the use of auxiliary materials in the industrial sector Need to become. Thus, a reduction can be achieved solely by using, for example, a 25 # dispersion or emulsion according to the invention of organic material compared to the use of mineral oil-based lubricating systems achieve.

The lubricant system according to the invention is readily biodegradable, so that residues that get into the wastewater are only a low burden. Since, for example, in the case of V / arm rolling of steel, the greatest T _e ü of the organic material burns after the water has evaporated when it emerges from the nip, the proportions to be taken into account are extremely low. When using the S invention hmierstoffsystems _c is compared with the behavior of mineral oil containing substances a considerable reduction of soot and fumes recorded. An unpleasant odor, as is the case with the use of mineral oil

abundant systems through the formation of foul-smelling cracked products! occurs when using the lubricant according to the invention; systems not observed.

The lubricant system according to the invention shows an excellent

8098 2 *? / (H89

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adhered to moist metal surfaces and can therefore be applied to water-cooled surfaces, although they are dispersible or emulsifiable in water Apply rollers, forming an even film of lubricant. On the other hand, lubricant residues, which may occur during application, e.g. by spraying, on the roll stands and fittings during operational use have precipitated, for example by rinsing with a powerful jet of water in a simple manner and completely easily remove.

The lubricant system according to FIG of the invention in the hot rolling of steel profiles. It shows a uniform formation of the lubricating film, a good one Adhesion on the rollers and a sufficient lubricating and separating effect.

The lubricant system according to the invention is described in more detail in the following examples. Percentages refer to unless otherwise stated, to percentages by weight. The OH number is the hydroxyl number, the acid number is the acid number and the JZ the iodine color number, the latter understood as a measure of double bonds, its determination according to DGF standard methods (Deutsche Gesellschaft for fat science) Department D-IV 2b (61) or C-IV Aa (52).

ΤΤΓ9 Έ7φ / ü A 8 9

2700Q40

Comparative example 1

25 parts of a fatty acid monodiglyceride ethoxylate (made from partial glyceride with 46 % mono- and 10% diglycerides) based on

55 ° / ° caprylic acid (Cg)

40 io capric acid (G _{1 Q} )

as well as lower proportions of caproic and lauric acid

with 4 moles of ethylene oxide per mole of hydroxyl groups of the partial glyceride The mixture was mixed with 75 parts of water. The mixture had a viscosity which was considerably below the value of 5000 cP and no longer with the above-mentioned measuring arrangement could be determined exactly. The mixture showed an unsatisfactory one Adhesion to damp metal surfaces.

Yerglelchabeispjel 2

25 parts of a fatty acid monodiglyceride ethoxylate (42% mono- and Ml # diglycerides) based on a fatty acid mixture obtained from Schv / einschmalz with 1.9 mol of ethylene oxide per mol of hydroxyl groups present was dispersed in 75 parts of water. The mixture had a viscosity of 7200 cP, measured at a shear gradient of 2.64 cm and a temperature of 30 C. Although the test showed sufficient adhesion to moist metal surfaces, the applied lubricating film was non-uniform and tended to Tear off.

Comparative example 3 '

25 parts of a fatty acid monodiglyceride ethoxylate (42 # mono- and Mff $ £ diglycerides) on the basis of the description in Verglexchr-.bcjrriiel 2

80982W0 4 09

fatty acid mixture used rc ^; ; s with 6.25 moles of ethylene oxide per mole of hydroxyl group v / uroien mixed with 75 parts of water. The mixture had a viscosity of 4B00 cP, measured under the conditions given above, and gave a thin, very poorly adhering lubricating film.

example 1

25 parts of a fatty acid monodiglyceride "ihoxylate (42 llono- and 48 μl diglycerides) based on a fatty acid mixture obtained from lard and containing 4 mol of ethylene oxide per hydroxyl group were dispersed in 75 parts of water. An opaque emulsion with a viscosity of 13,000 cP was obtained. The emulsion showed excellent adhesion to moist metal surfaces and formed a cohesive, stable protective film.

Example 2

25 parts of a fatty acid ethoxylate based on a rapeseed oil fatty acid with 3 mol of ethylene oxide per liter of fatty acid were dispersed in 75 parts of water. The aqueous dispersion had a viscosity of 6500 cP 'and showed both sufficient adhesion] as film-forming behavior. "]

Examples 3 to 5

Mixtures of the fatty acid ethoxylate mentioned in Example 2, Kaliuip.oleat and V.'asr.er manufactured. Since there was - · .'.- end Preserve viscosities.

8 0 9 8 2f / 0 A 8 9

INSPECTED

27O00A0

Parts of fatty acid ethoxylate 30th 35 40 Share potassium olate 1 1 1 Share V.'asser 69 64 59 Viscosity cP 15700 '16400 28800

Adhesion and film bond of the blends were good.

6 am 11

Parts of a mixture of a) 48 parts of a fatty acid monodiglyceride ethoxylate (40 % mono- and 50 # diglycerides) based on a fatty acid mixture

27 # P8lmitic acid

12 5 & stearic acid

48 # oleic acid

8 % linoleic acid

as well as small amounts of lauric ··, myristic acid and

higher fatty acids

with a degree of ethoxylation of 4 moles of ethylene oxide per mole of hydroxyl group and b) 52 parts of a fatty acid ethoxylate based on a fatty acid mixture

12 # palmitic acid 3 % stearic acid

26 % oleic acid

18 i> Linoleic Acid 6 $> Linolenic Acid

21 % erucic acid

BO 9 8 2V- / 04 89 ~

as well as small amounts of lauric acid, myristic acid and higher Fatty acids

with a degree of ethoxylation of 3 moles of ethylene oxide per mole of fatty acid was mixed with 75 parts v / ater. The emulsion obtained in this way had a viscosity of 14,500 cP and adhered excellently on damp metal surfaces and formed a coherent lubricating film.

The 20-year dispersion of the same fatty acid monodiglyceride ethoxylate / fatty acid ethoxylate mixture had a viscosity of 5900 cP, the 30 # dispersion of 1200DcP, the 40 # dispersion of 22,300 cps.

The 25 # dispersion of a) 20 parts of the monodiglyceride ethoxylate mentioned and b) Θ0 parts of the fatty acid ethoxylate mentioned gave a viscosity of 10,500 cP.

The 25 #ige dispersion of a) 70 parts of said llonodiglyceridäthoxylats and b) 30 parts of said Fettsäureäthoxylats gave a viscosity of 500 cP 2h.

Examples 12-18

From a fatty acid monodiglyceride ethoxylate (36 $ mono- and 54 % diglycerides) based on a fatty acid mixture

Jf stexaric acid
J ^ Ö5e5ore
2 ' L-nolic acid

Everyone 4 i "lauric acid Mole »R
Myristic acid and 27000A0 Mixtures Fatty acid- ti 100 Vv Ü k viscosity
Dispersion
-1
2.64 cm »89 dei
bed as well as minor Ant ( Mole 3 # myristic acid Hydroxyl group high fatty acids represents. The 25% dispersions obtained from the mixtures IU 80 7000 with 4 moles of ethylene oxide per and a fatty acid ethoxylate 19 # palmitic acid showed the following values: 60 9000 the end 2 j £ stearic acid based on a fatty acid mixture Mixing ratio
Fat monodiglyoeride
ethoxylate 50 19500 31 io oleic acid 0 40 22000 $ 8 linoleic acid 20th 20th 29000 23? Δ erucic acid 40 0 22500 50 9 8 2 22500 60 80 * 25 weight & length
. Shear rate
-1
428 cm 100 140 150 260 280 340 as well as small proportions ? 9Ί Fatty acids 200; with 3 moles of ethylene oxide per of intermediate fractions and higher Fatty acid were

1*

Example 19

23 parts of a monoester obtained by esterification of 1.1 mol
Triethylene glycol (OHZ 7AO) with 1 mol of a fatty acid mixture obtained from rapeseed oil (SZ 190, JZ 115) was mixed with 2 parts of potassium oleate with heating. The one from it
25% emulsion obtained showed a viscosity of 21,000 cP. Adhesion and film formation were good.

Dr La/Hs,

80 9 8 2JP / 0 A 8 9

Claims (1)

failure: 1. Lubricant system for the V.'arriverformur _H '; of metals, consisting of an aqueous dispersion b: -: v, ·. Emulsion of fatty acid monodiglyceride ethoxylates and / or fatty acid ethoxylates, with a content of fatty acid monodiglyceride rithoxylates and / or fatty acid ethoxylates of 5 to 60 wt i Fatty acid monoglyceride ethoxylates 2 to 6 mol, preferably 3 to 5 moles, alkylene oxide per mole of hydroxyl groups present j and the fatty acid ethoxylates 2 to 6 mol, preferably 2.5 to 3 l 4 Hol, alkylene oxide per mole of fatty acid ethoxylate contain and aqueous Dispersion or emulsion has a viscosity between 5000 and ; 40,000 cP, with a shear gradient of 2.64 cm and a temperature of 30 ^° C. 2. Lubricant system according to claim 1, consisting of one aqueous dispersion or emulsion of fatty acid monodiglyceride and / or fatty acid ethoxylates based on fatty acids with 12 to 22 carbon atoms, preferably based on fatty acid mixtures with a predominant proportion of fatty acids 16 to 22 carbon atoms. 3. Lubricant system according to claim 1, characterized by j Fatty acid monodiglyceride ethoxylates with 3 to 5 moles of ethylene oxide per mole of hydroxyl group of the partial glycerides. 80982-70489 ORIGINAL INSPECTED L \. Lubricant system according to claim 1, characterized by fatty acid ethoxylates with 2, f; up to k Hol ethylene oxide per i: ol fatty acid. '5. Lubricant system according to claim 1, characterized by Dispersions or emulsions with a small amount of fatty acid. monodiglyceridate oxylates and / or fatty acid ethoxylates from 10 to L \ 0 wt. 6. Lubricant system, characterized by viscosities of 100,000 to 30,000 cP at a shear rate of 2.64 cm at 30 ° C. Troisdorf, December 30, 1976
OZ 77001 Dr.La/Hs. 9.9.8 gr / ο «β 9 COPy