DE2504115A1 - LUBRICANT FOR METAL WORKING - Google Patents

Description

"Metalworking Lubricants"

Priority: February 4, 1974, V.St.A., No. 439 656 September 9, 1974, V.St.A., no.504 414

Metalworking processes such as rolling, forging, hot pressing, Punching, bending, embossing, drawing, cutting, punching or pressing are generally performed using a Lubricant carried out. Lubricants reduce the effort required to carry out the work, prevent the tools from seizing and reduce the amount of force the wear and tear on the molds and cutting inserts. In addition, they often impart anti-rust properties to the metal being processed.

Since the metals are usually chemically processed after machining Be subjected to further treatment, for example the application of coating solutions (conversion coating so-

509832/0935

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lutions), it is necessary to move the workpiece between the machining stages and to subject the chemical treatment to a purification stage. It. is therefore in addition to the above The mentioned properties are preferred that the lubricating oils used for metalworking with the help of ordinary cleaning processes are easy to remove from the metal surface.

The invention is based on the object of improved lubricants for metalworking, which have excellent lubricity and good extreme pressure properties, give the metal a corrosion resistance and represent a protection against wear of machining parts and the at the same time relatively easy to remove from the metal surface by cleaning after metalworking is finished are. This object is achieved by the invention.

The invention thus relates to that characterized in the claims Object.

The lubricants according to the invention for metalworking essentially consist of a mixture of three components. Component A is at least one oil with a lubricant viscosity. For the inventive lubricant both natural and synthetic oils are usable.

Examples of natural oils are animal and vegetable oils, such as castor oil and lard oil, as well as having liquid mineral oils Solvents or acids refined, paraffin-based,

509832/0935

Naphthenic or mixed paraffin-naphthenic mineral lubricating oils.

Oils with a lubricating viscosity from coal or oil shale can also be used. Further examples of oils which can be used according to the invention are hydrocarbon oils and halogen-substituted hydrocarbon oils, such as polymers and copolymers of olefins, e.g. B. polybutylenes, polypropylenes, propylene-isobutylene copolymers and chlorinated polybutylenes, poly (1-hexene), poly (1-octene) and poly (1-decene) and mixtures thereof, furthermore alkylbenzenes, eg. B, dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes and di- (2-ethylhexyl) -benzenes and polyphenyls, e.g. B. biphenyls, terphenyls and alkyl-substituted polyphenyls, alkyl-substituted diphenyl ethers and diphenyl sulfides and their derivatives, analogs and homologous compounds. Alkylene oxide polymers, their copolymers and derivatives in which the terminal hydroxyl groups are esterified or etherified represent a further class of known synthetic oils. For example, such oils consist of polymers of ethylene oxide or propylene oxide, alkyl or aryl ethers of these polyoxyalkylene polymers, e.g. B. methyl polyisopropylene glycol ether with an average molecular weight of 1000, diphenyl ether of polyethylene glycol with a molecular weight of 500 to 1000 and diethyl ether of polypropylene glycol with a molecular weight of 1000 to 1500, or mono- or polycarboxylic acid esters of these polymers, for example acetic acid esters, mixed C, - to Cg -Fatty acid esters or the C _i3 -oxo acid diesters of tetraethylene glycol. Another class L,

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Synthetic oils are the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl- and alkenyl-substituted succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid and dimeric linoleic acid, malonic acid, alkyl- and alkenyl-substituted malonic acids, such as butanol, hexonic acids with a wide variety of alcohols , DQdecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether and propylene glycol. Specific examples of these esters are dibutyl adipate, di- (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecy azelate, diisodecy azelate, dioctyl phthalate, didecyl phthalate, diicosyl sebacate and the dimeric acid sebacate of 1 Moles of sebacic acid with 2 moles of tetraethylene glycol and 2 moles * 2-ethylcaproic acid obtained ester mixture. Further examples of synthetic oils are the oils obtained by esterifying C ₅ bis (^ ,, - monocarboxylic acids with polyhydric alcohols and their ethers, for example neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

Examples of another class of synthetic oils are SiIi-

Poly ary! -., _ /
con oils, such as polyalkyl, / polyalkoxy or polyaryloxy oxanols and silicate oils. Specific examples are tetraethylsilicate, tetraisopropylsilicate, tetra- (2-ethylhexyl) -silicate, tetra- (4-methyl-2-ethylhexyl) -silicate, tetra- (p-tert-butylphenyl) -silicate, hexyl- (4-methyl) -2-pentoxy) -disiloxane, poly- (methyl) -siloxanes and poly- (methylphenyl) -siloxanes. Other synthetic oils are the liquid esters of phosphoric acids, such as tricresyl phosphate, trioctyl phosphate and diethyl decylphosphonate,

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as well as polymeric tetrahydrofurans. As component A of the invention Lubricants can be unrefined, refined and re-refined oils and their mixtures of the type described above can be used. Unrefined oils natural or of synthetic origin are used directly and without further purification. For example, issue a directly oil from oil shale originating from the retort furnace, a mineral oil obtained directly from petroleum distillation, or a An ester-based oil that goes directly to the esterification process taken and not subjected to further treatment are unrefined oils. Refined oils are similar Properties like the unrefined oils, with the exception that the former have undergone at least one purification stage to improve one or more properties. The cleaning takes place in a manner known per se, for example by solvent extraction, extraction with acids or bases, filtration or percolation. Re-refined oils can be obtained by processes that result in the refined oils, wherein oils already in use are refined. The oils obtained in this way are also called regenerated or reprocessed oils are known and are often obtained by means of processes aimed at removing used additives and oil decomposition products lead, additionally refined. Particularly preferred mixtures for component A in the lubricants according to the invention are mixtures of a common mineral oil and a mineral oil fraction, which usually consists of a bright stock, especially those mixtures in which the weight ratio of Brightstock to common mineral oil in a range of

L _J

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about 0.5: 1 to 5.0: 1. The use of such amounts Brightstock often improves the viscosity properties of the metalworking lubricant.

The component B used in the lubricant for metalworking according to the invention is at least one carboxylic acid or their derivative. Anhydrides and esters can be used as derivatives. The esters are preferably made from lower-alkyl-monohydroxy or polyhydroxy compounds, such as methanol, ethanol, 1-butanol, n-Hexanol, ethylene glycol or pentaerythritol, or made from epoxides such as ethylene or propylene oxide, wherein as lower-alkyl radicals those with a maximum of 7 carbon atoms come into question. The esters made from epoxides are understandably hydroxy esters. As derivatives neutral, acidic or basic salts, in which the same cations are used as in of component C described below, namely both the salts of the free acids and those of their hydroxyesters. The lithium salts are preferably used because of their anti-corrosive properties. Finally come as Derivatives amides and mixtures of amides and imides in question, "especially those which are derived from aliphatic amines and particularly preferably from lower aliphatic amines. Examples of preferably used amines are alkylene polyamines, in particular ethylene polyamines. The ones described above Derivatives can be prepared from the acids in a manner known per se, optionally in several stages.

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The free acids, their lithium salts and their anhydrides have been found to be the most useful B components. Preferably aliphatic carboxylic acids having at least 8 carbon atoms and their derivatives described above are used. Dibasic acids are particularly preferred, especially those Anhydrides of hydrocarbon-substituted succinic acids, such as that by the implementation described below of maleic acid or maleic anhydride with a hydrocarbon compound of at least 6, preferably about 6 to 75, especially about 10 to 20 carbon atoms produced anhydrides. The term "hydrocarbon compounds" denotes compounds with a predominantly hydrocarbon character. Examples of compounds of this type that are preferably used are:

1) hydrocarbons such as aliphatic, e.g. B. alkanes or Alkenes, alicyclic, e.g. B. cycloalkanes or cycloalkenes, aromatic, by aliphatic or alicyclic radicals' substituted aromatic and aliphatic and alicyclic hydrocarbons substituted by aromatic radicals. ·

2) Substituted with other than hydrocarbon radicals Hydrocarbons which, through their substitution, do not lose their predominant hydrocarbon character to have. Specific examples of usable substituents are Ilalogenatome, hydroxyl, ether, keto, carboxyl, Ester (especially lower-carbalkoxy ester), amide, nitro, cyano, sulfoxy and sulfone groups.

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3) Heterosiabstitaierte compounds χά uater which - maintaining the prevailing sole hydrogen character to otherwise composed of carbon atoms chain-B or rings of other atoms are contained as Kohlenstoffatoine "Specific examples of preferably used heteroatoms are Stick ~ cloth _# oxygen and sulfur"

In general, the hydrocarbon compounds contain a maximum of 3 substituents of heteroatoms on 10 carbon atoms ^. In the radial unit, there is at most one secondary substituent of heteroatcres.

■ Di.j; ί433Γ KerstilluRg der i ^ äsr- erfinfi'aagsgeHtäsSen lubricants e: isiiCiIt © K <an component B vsr: - / endeian K öaagsn are I ^ v; esentliohsn crsisäfc-äig.,
dsz G3S £ sitf _; Most of the CC-Bi.niingea is saturated _, and the hydrogen verjinäuisg.en should not contain any triple bonds and no side chains should contain 6 aliphatic carbon atoms. The 3ar Harstellang iron Komponsßte B of erfindungogemäBen Schmiersiittsl varwesilats ^ i ^ Solilessvfasseri3i.aaiaiigen erüs-i ^{_'; v} CK2 "igsweiee c ^ s ^ saturated Erdölr uäü 0l3finpoiynerisatea - iiisbasoadsre aws Oligoäneren JLefirjsa (forwards all ??? sadstlnäigew tlcaooIefiseKj 2 up at ^ wa 10 Zchleiistofmtosuea aeffcestellto Spsgislla examples fiir isävorzuft "total etate Kohlso.wa3Ssrstoff ~ ¥ erbiBiäi5agen conduct SiOH ¥ GJ5 Pöl ^ srisateii mm Xthylsn? Prcpea _f i-Baten., 2 ~ butene, i £ IBAT © e _f 3-ii * iten oösr l-öctsü eb, ifeiter-s examples are Gcpölymerisata of the above o-se ehr Lebeneu Olsfi-is yn with others

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polymerizable compounds with olefin character, such as styrene _f chloroprene, isoprene, p-methylstyrene and piperylene. In general, these copolymers should contain at least about 80 percent by weight, preferably at least about 95 percent by weight, of polymer units derived from the aliphatic monoolefins. Further examples of hydrocarbon compounds that can be used are mixtures of saturated aliphatic hydrocarbons, such as highly refined, high molecular weight white oils or synthetic alkanes. The hydrocarbon compound should optionally contain an activating polar radical which facilitates the reaction with the low molecular weight acid-yielding compound. Specific examples of activating radicals used are halogen atoms, preferably chlorine atoms, or sulfide, disulfide, nitro, mercapto, keto and aldehyde radicals.

As already stated above, component B is preferred by reacting maleic acid or maleic anhydride with the hydrocarbon compound, preferably a propylene oligomer. This reaction takes place by heating the two reactants to about 100 bis 200 C, optionally in the presence of an inert organic solvent. An excess of a liquid used Reactant can also be used as the reaction medium. Examples of further reactions necessary for the production of component B are the oxidation of a hydrocarbon-substituted 1,4-butanediol with potassium permanganate, Nitric acid or a similarly acting oxidizing agent,

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the ozonolysis of a hydrocarbon-substituted 1,5-diene, the preparation of a disubstituted organometallic derivative of a hydrocarbon-substituted 1,2-dihalide, which is then reacted with carbon dioxide, or the production and subsequent hydrolysis of a dinitrile. As well as the aforementioned reactions / as well as the resulting substituted succinic acids and their derivatives are already known.

Those in the lubricants for metal working according to the invention Component C used is a phosphoric acid salt of the general formula I. As already mentioned, the radicals

1 2

R and R represent hydrocarbon radicals. According to the invention, these are radicals which directly contact a carbon atom are connected to the remainder of the molecule and their hydrocarbon character, that of component B described above

1 2

speaks. The radicals R and R preferably and usually do not contain any triple unsaturated carbon bonds no olefin bonds. They contain a maximum of about 30, preferably a maximum of about 12 carbon atoms. Specific examples for preferred radicals are the methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, vinyl, decenyl, Cyclohexyl and phenyl groups and their isomers; Particularly

1 2 compounds are preferred in which the radicals R and R Represent alkyl radicals having 1 to 7 carbon atoms.

The compounds used as component C are salts of dialkylphosphoric acids or dialkylphosphinic acids and their

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Thio derivatives. Particularly preferred sxad salts of thiophosphorus acids, ie compounds. In -ikssten a ιιηά b each have the value 1, the radicals X ¹ and S js-ieils a Bauersteffatoäi.

3 4

and the radicals X and X each represent a -ohws ^ elatom becseiifceru The radical M can in these terms have the meaning described above or a given safailfe st'-bsiifeuierts jaamonium group (for example eir.wn, 'ißinsalsresti represent »■ Preferably the Remainder M ZLrik cäsr lead ^ in zinc, Furthermore, the invention can be used compounds, such as gr ^ iszlacli-Siigiisive substances O auxiliaries, such as residual or corrDS ^ nsv-rMttiutgSHdtteli; pressure additives as well as wear prevention agents, especially suitable protective pressures efelorierfce what

The proportions d ^ r axn ^ as & t ^ ten Eest

Lubricants for metalworking are relatively broad in the range "la general-öicen xs? Earth" about 10 to 40 parts by weight of the component Ά whom about Q _f 5 to .5

Parts by weight of component E per part by weight of C are used. Provided also sin chlorinated wax, so will usually be a proportion thrived te itsb 0.5 to parts by weight per GewichtsteiX c & x Soifisoaente C The total content of the components B \ C _f and ζζά

if chlorinated wax is present, gewötelich- ®ti

5 to 30 percent by weight of the singest Ge

the component Λ the rest. Concentration looks at it. The components B and ' C are preferably in the coraponerite &' -vlieh. However, stable dispersions or LÖ can also be used

509832 / ÜS35 ORIGINAL INSPECTED

TABEL

Parts by weight

Components AB CD E "F GHJ K

Mineral oil 75 _f 65 13.65 26.65 88.5 14.9 39.3 43.55 12.9 93.1 92.5

Brightstock mineral oil, - 62 45 - 64 28.8 32.1 58.9

Tetrapropeny! Succinic anhydride. 20 20 19 8 8 - 20

Polyisobutene- (mol, -wt.

about 1000) -substituted

Succinic anhydride - - - - - 18 - 19

^OT lithium salt of the polyiso-

^ buten- (MoL weight approx

O ₀ 1000) substituted

co succinic acid - - - - - - - - 4 4;

^ Zinc Salt of the Mixed £ J

ο isobutyl (65 mol%) - and

ca n-amyl '(35 mol%) - dithio- ■ ω phosphate 4.35 4.35 4.35 3.5 13.1 3.9 4.35 ~ - 3.5

Zinc salt of tetrapropeny 1-phenyl-di thiophosphate - - - '- -τ- - - - 2.9 -

Lead isooctyldithiophosphoric acid ester - - - - - - - 4.2 - -

Chlorinated wax

(approx. 42% chlorine content) - - 5 - - 10 - 5

L J

Solutions containing components A, B and C are used will.

In Table I are typical compositions of the invention Lubricants indicated.

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_J

According to the invention, the lubricants for processing all Metals are used, for example when machining ferrous metals, aluminum, copper, magnesium, titanium, zinc and manganese and their alloys and alloys which contain further elements, for example silicon. The invention Lubricants can be applied to the workpieces to be machined before or during machining in any suitable manner Form are applied. The workpieces can either completely or only partially with the inventive Lubricants are treated. For example, the lubricants can be applied by brushing or by spraying the workpieces are applied or the workpieces can be immersed in a Schmie.rölbad. Preferably at Process in which the metal is deformed at high speed , the lubricant is sprayed on or applied by means of a dipping process.

In a typical embodiment, the coating takes place of ferrous metal workpieces with the lubricants according to the invention before processing. For example, if the workpiece is to be pulled, it can be pulled through the The drawing nozzle can be provided with the lubricant. However, the lubricant can also be used during the entry of the workpiece be applied to the workpiece in the drawing nozzle, or applied to the drawing nozzle, in the latter case is transferred to the workpiece through contact. The use of lubricants for metalworking therefore includes all Types of metalworking in which the invention

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Lubricant in any form on the surface of the workpiece be applied.

A test is carried out to demonstrate the lubricant properties of the lubricants according to the invention. Here, a cold-rolled sheet steel (5.1 34.3 cm) is drawn between two drawing nozzles with an Instron Universal Tester, model TT-C. Before drawing, the edges of the metal strip are deburred and the sheet is steam degreased and dried with a clean cloth. The lubricant according to the invention is then applied to the metal sheet, after which it is clamped in the test device. The drawing nozzles are tightened with a torque wrench set to a torque of 5.53 kg «m. The metal sheet is then pulled 5.1 cm out of the drawing nozzle at a pulling speed of 12.70 cm / min. The force (or "load") required to pull the metal sheet out of the drawing nozzle is recorded on a recording strip. If "rattling" and irregular movements due to friction occur, the deviation from a uniform load is also noted on the recording strip. When comparing a number of different lubricants, the relevant tests are carried out on the same day with sheet metal made from the same steel strip. ' ,.

In Table II are the results from various lubricant tests summarized. The "load" fourths are measured after the 5.1 cm draw time. All tests were carried out at Rauin-

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temperature performed. The designation "comparison l" denotes a commercially available drawing fat consisting of a chlorinated wax, which is known as "T13-B" is offered. The designation "Comparison 2" denotes a rust-preventing drawing oil, which is available under the designation "Ferro Cote" is commercially available. The designation "Comparison 3" denotes successive treatments of the metal with the above-described drawing oil "Ferro Cote" and a drawing fat consisting of a fatty acid ester, which under the Designation "Quaker 693M" is commercially available

O TABLE II

test lubricant Load, kg Deviation from uniform load, kg 1 Comparison 1 510.7 18.2 C. 510.7 11.4 2 Comparison 2 794.5 '34.1 A. 874.0 0 3 Comparison 3 794.5 0 A. 828.6 0 4th A. 794.5 0 B. 499.4 0 G • 681.0 0 5 B. 612.9 0 C. 681.0 0

The high pressure properties of the lubricants are v / ground according to Test standard of. Society of Automotive Engineers (V.St.Α., SAE test) carried out. Here, 2 tapered roller domes located on shafts are placed against each other in a test lubricating oil bath moved with a relative speed of rotation of 500 rpm, wherein

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the gradual application of a load is automatic. The load at which scoring occurs gives the test result. The test results are summarized in Table III.

TABEL III Load, kg 7th
3
4th lubricant 66
46,
50, Comparison 1
B.
C.

The four-ball wear test is used to determine the wear-preventing properties of the lubricants according to the invention carried out according to test standard ASTM D 2266. A steel ball treated with the lubricant according to the invention is used here 1 hour at 1200 rpm against three other similar balls and rotated with a load of 40 kg at room temperature. The diameter of the notched scratch on the ball after it has been made Rotation is a measure of the wear and tear that were received Results are summarized in Table IV.

TABLE IV Lubricant scratch diameter, mm

A - 0.48

G * 0.48

To determine the washability of the inventive Steel sheets are coated with lubricants and then coated with a known, potassium hydroxide, sodium silicate

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cat and the sodium salt of cleaning agents containing ethylenediarainetraacetic acid. The cleaning takes place at about 70 ° C and a pressure of 0.7 at by spraying the metal surface for 1 minute with the cleaning agent. Of the Percentage of the removed plaque is measured. In addition, the extent of the foam formation and the "Ktfasserausausbildung" observed. The measurement results obtained in this way show a 100 percent removal for lubricants A and B. from the metal surfaces. Foaming or water interruptions are not observed.

The anti-corrosive properties of the invention Lubricants are measured by treating metal plates with the lubricants of the invention. These metal plates are then approx. with the side to which the lubricant was applied facing downwards A closed room heated to 60 C is hung about 15 to 21 cm above the surface of water. The plates remain in place during a certain period of time in this room, after which the rust content is determined. This measurement shows that one with the inventive lubricant A coated plate 66 hours shows no rust formation. After 96 hours the amount of rust is 10 percent.

From the above test results it can be seen that the erfindungsgercässer Lubricants with very many properties, all of which are important for metalworking, with known properties Lubricants are comparable.

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Claims (12)

- 19 patent claims C) at least one phosphoric acid salt of the general formula I. " ^A > PXM in the M a metal of the I. or II. main group of the period system, aluminum, tin, cobalt, lead, molybdenum, Represents manganese, nickel or an ammonium group, R and R each denote hydrocarbon radicals, the Re- 12 3 4 ^y ste X, X, X and X each represent an oxygen or sulfur atom and a and b each have the value O or 1 and optionally
υ) Auxiliary supplements. ■ 2. Lubricant according to claim 1, characterized in that component A is a mineral oil, component B is an aliphatic Carboxylic acid with 6 to 75 carbon atoms, whose anhydride or lithium salt is and in component C. 12th
the radicals R and R each be a hydrocarbon radical 1 2 3 k '■■■■ - interpret X and X oxygen atoms, X and X sulfur atoms and a and b have the value 1. B09832 / 093G 250A1 15 3. Lubricant according to claim 2, characterized in that 1 2 that in component C the radicals R and R each represent a lower alkyl radical and M is a zinc atom. 4. Lubricant according to claim 2, characterized in that component B is one with a hydrocarbon radical substituted succinic acid, the anhydride or lithium salt of which is. 5. Lubricant according to claim 4, characterized in that that component B is tetrapropenylsuccinic anhydride 12th and in component G the radicals R and R each represent lower alkyl radicals and M represents a zinc atom. 6. Lubricant according to claim 5 »characterized in that that component C is the zinc salt of the mixed isobutyl and n-amyl dithiophosphate. 7 »Lubricant according to claim 6, characterized in that that component D is a chlorinated wax, 8. Lubricant according to claim 4, characterized in that that the component. B the lithium salt of a polyisobutenyl succinic anhydride with a molecular weight of about 1000 represents the polyisobutene radical, in component C 1 2
the radicals R and R each represent a lower alkyl radical and M is a zinc atom, 509832/0935 9 · Lubricants after. Claim 8, characterized in that that component C is the zinc salt of the mixed isobutyl and is n-amyl dithiophosphate. 10. Use the lubricant after. Claims 1 to 9 metalworking " 509832/0935 ORIGINAL INSPECTED