DE2042279A1 - Method of lubricating aluminum and aluminum alloys - Google Patents

Description

j:;. Dirt ... r: .V .. H.-J. WOLFP
' ¹ Ji ¹ V. ii ^: - Z CKH. L ". E! L

RA H K J- 'L -, - Ϊ AM MAl N - H OCHST

Laser ΙΓγ. 16 481

Chevron Research Company San Francisco, CaI., V.St.A.

Method of lubricating aluminum and aluminum alloys

The invention relates to the use of diols in lubricating the surface of aluminum or aluminum alloys during forming, machining, Tapping and drilling included, or in mechanical devices.

When rolling aluminum or aluminum alloys under Forming sheets or foils, lubricants are used to reduce the friction between the metal and the rollers and to achieve a good surface finish. The lubricants also serve as a heat transfer medium, to dissipate the heat generated in the rolls and in the metal during rolling.

The lubricants used in rolling aluminum are almost always mixtures of polar or "oily" Additives and a light mineral oil, a synthetic one Hydrocarbon oil, a petroleum distillate or water

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The additives in the rolling lubricants should oie lubricity improve the oil or water in order to reduce the friction when engaging between 7 / alze and metal, A reduction in friction enables a reduction the thickness of the metal to be rolled. The additives are also used because of their chemical or polar effect Reduction of the tendency of the metal to adhere to the surface of the roller during rolling.

Similar lubricants are used to lubricate aluminum parts used in Με machines, gears and other devices. Here the problems are particularly acute, and that The lack of a suitable aluminum lubricant has led to the development of machines with non-lined aluminum cylinders severely limited.

Machining aluminum also requires lubricants. The lack of suitable lubricants when drilling, tapping or other machining processes of aluminum shortens the useful Life of tools such as drills and thread cutting devices essential.

Long-chain monohydric alcohols are described as components of lubricants in U.S. Patents 2,193,631 and 2,350,570. According to U.S. Patent 2,962,401, an aluminum lubricant containing a saturated aliphatic alcohol having fewer than eight carbon atoms is used. U.S. Patent 3,124,531 discloses an aluminum lubricant containing polypropylene glycol. From Guminski et al. the use of 1.10 decanediol in an aluminum lubricant based on n-propanol is described in J. of the Inst, of Metals, Vol. 88, p. 481 (1959-1960).

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2U42279

In the inventive method sun! Serming of aluminum and ^ liuuiniumle.-ionen during cold working, machining or other mechanical processes, a lubricant is applied to the surface of the aluminum or the aluminum alloy, which contains a larger part of a 'Irafeerflussi ^ keit and a smaller part of a Ο ., - ΰ-τ-, diol contains, in de: i: the two hydroxyl groups bonded to cenachb ^ rte odec by a carbon atom separated ivar.lenstoffatome i = inö. The Trä ^ erflüssiirkeit k Λ'Λΐι an i-.iner löl _r a synthetic Aöhlenw ^r ater & tofföl? "One PeTroieu:; ic.estillat, a haioceuierter or oxygenated xvoiilemvasseretoff or" be .. "ater.

In the case of the diols used in accordance with the invention, it is a matter of course around C-iq-Cv diols with the following saturated or .atic unsaturated. Structure unit ent

OH OE

¹ "'■ t ι

ii) - σ - σ - σ-Ι I I

CK OH
III) 'C = as σ- or

IV)

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2U42279

The general formula of 'JDiol is

V) (R ¹ )

(H ⁶ )

in α er

1; The small letters a, Td and d to h mean G or 1 U2id At least 2 columns are 1;

1 6

>) R and R mean hydrogen or a carbon. _: ru; .pe with 1 to 28 carbon atoms and

3) K, R / R and i \ are Loijienv / asserstofi '^' groups having 1 ice 12, _vorzu: / else 1 to 6 carbon atoms _GV, and V / ei

> 4

i. and R or K and R combine to form a carbocyclic kin% - they together have 2 to 28 and preferably 4 to 20 carbon atoms. jjie G-esamtcnsphl ^r 3 XIIR. ^ CARBON fs tome is 4 to fc, preferably 5 to 7 and in particular 6.

.at d, n α-Liolen

f = 0; in the case of the .ΐ-jjiols, f = 1.

liie ivoi'iiensto J'atorne can en straight in the form of or versv / cif th sliphc-Nazi, cyclo ^ liphr: schematically, aryl or f: liphstisch cubstitui ^ rten jirylkonfi '_.urationen vorli · i on. -.enn f = C and b and dg both 1 and e and / or h = v. i ;; t, kernels R ^ and R ^;: u :: ·· .amen with ο en Ivchliriistoff f tomen, i ^j n (.it sit ^ g. cunden beef, a corhccyc] ischen (i.e. an alicyclic or f -romati ^ ciien) or a suDi-tituated curbocyclisc ^; ien η in * bil (ien. iüinlie ¹ · can, v.'ei.na, e and f respectively 1 and b and d jev.'eils ü are, R and R: -: uHiimiiien i .'- it the i \ oh c -nstoffatomen, ·? Η which are bound, a c i'bocyclischen or substituted car'bocyclishen j \ ing blink.

1 Π 9 B 1 Q / 2 0 1 b

BATH

_ 5 -

Preferred structures include

OH OH

1 I '

VI) R ¹ OH. - CH-R

OH

YII) R ¹ OH - CHj - CH - R ⁶

YIIl)

and

IX)

1) R, R and R have the meaning given above and

2) R ⁷ , R ⁸ , R ⁹ and R ¹⁰ [each denote hydrogen or a hydrocarbon radical having 1 to 24, preferably 4 to 20 carbon atoms.

The structure YI can be used as aliphatic.es a-diol, - the structure YII as an aliphatic ß-diol, the structure VIII as

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2 ί; 42 27 9

Catechin and the ütruk '.; Ur IX as mixed denotes v / earth.

.3When lubricating aluminum, it is important that materials cie adversely affect the aluminum surface, are not contained in the lubricant. The diols show accordingly. according to the invention no others Atoms as carbon, hydrogen and oxygen atoms on. Likewise, the carrier liquid should not contain any atoms other than carbon, hydrogen, oxygen and halogen atoms contain.

Moles which can be used for the purposes according to the invention are cc-diols (f = 0) and β-diols (f = 1), such as 1,2- and 1,3-C ₁₀ -C ₅₀ alkanediols and C- | o ~ ^C 3O Dihydroxyalkylbenzenes. Specific examples are 1,2-n-decanediol, 1,3-n-decanediol, 1,2-n-dodecanediol, 1,3-n-dodecanediol, 1,2-n-hexadecanediol, 1,3-n-hexadecanediol 1,2-n-eicosanediol, 1,3-n-eicosanediol, 4,5-n-hexadecanediol, 4,6-n-kexadecanediol, 1,2-dihydroxybenzene, 1,2-dihydroxynaphthalene, 1,2-dihydroxy -3-n-hexy! Benzene, 1,3-dihydroxy-5 ~: n-decyrbenzene, 4-ethyl-4- (3 ¹ , 4 '-dihydroxy) -pheny! Heptane, 1,4-dihexyl- 2,3 ~ dihydroxybenzene, 2- (1'-hydroxyethyl) -4- (1 ", 3", 5 ", 7" -tetramethyloctyl) phenol, 2- (1'-hydroxypropyl) -4- (1 ", 1 "-dipropylbutyl) phenol and 6,8,10,12-tetramethyldecane-1,2-diol.

A particularly preferred group of diols are terminal aliphatic ^ diols of the formula

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2 ü 4 2 2 7 9

OB ί

-Ο -

(κ ² ).

Οίι.ΟΗ

-I! ■ -

in aer R an aliphatic hydrocarbon group r.:It Represents 7 to 26 carbon atoms and the other o: lboles have the Jedeut-uni given above. Representative

~ 2 "* ■

Examples of these diols are those in whose R , Ϊ / and

R ^ all './ascstoff mean U2id a = 1 iet. bie -a ": ~ h hurry general formula

λ!)

R ¹ I

- ί

Ch, OH

-is is correct, if there is no longer a one-carbon atom between the carbon atoms in the kernel, rn. which the two hydroxyl groups -; - bunaen, ie in the above i'oriiiel V is f = O or 1. In the 3-di oils en sir.d äementscrecliend cie hydroxyl groups r: nv; eixesten separated from each other. 2s' .. "uröe found, ar.I Uiole, in which the hy5rox; en veiter v ^ no? -näor are removed, aie superior faithfulness. the erfincr.n .s _t: einä.i; do not own en liole. Vieiraehr have diols with v. ?. ^T - i "; he another, distant hydroxygruop'en the Li ^ s & chef th EINV ^r erti _he jiikonole which, as below ₆ ec isplays v; ith the erfindun ^ sgeitE-iei: α- and ß.. Dioleii v: eit unt;: rle _t : eii cind.

Das i) .iol mui: r;: indeeter.s 10 vnä \ ^r o:. '. "U ^ Bv; eise ι.: Ίηαεετ; εηε i2 Carbon txit!:; Iten. 3s ' .τιroe gefunänen, öi- .J- Uiols with less than 10 carbon atoms do not have the superior anti-wear and tear-resistant properties of the C ^ QCQ-Liole on iron. The diols with a lower carbon: fr: r.hl have etv / a the pale ones . not 0 ^ ₀ diols äquivi-i'jijt '- ociimiereigenschaften v / ie the monovalent C-jQ-OVQ alcohols Similarly ^ was efrmden, AEC, the diols ü with more eleven .. 30 Koi.lenstol'fatoraen the 0 - ^ are.

1 09 8-1 Π / 2.0 1

BAO ORiGtNAL

2U42279.

The Trägerflüseigkeit, which accounts for the greater proportion of the inventions ciungsgemäßen lubricant, a mineral oil, a hydrocarbon oil, a hydrocarbon distillate, a halo _r can: enierter / oxygenated hydrocarbon or l / ater be. Water v. Is preferred because of its high>. <Poor drainage ice l'rageriquid. When using as a carrier liquid, it is preferred to add a small amount, generally up to about 5 to 10 volumes, of an emulsifying agent to the water-diol mixture. The emulsifier can be ionic or non-ionic. Suitable emulsifiers are alkylaryl polyethoxy alcohols, sorbitan monooleate, polyethoxylated amines, amides or fatty acids, sugar esters, soaps and sulfonates.

As carrier liquids for the purposes according to the invention suitable oils are generally hydrocarbon oils, those by distillation, cracking, hydrogenation or similar Refining process are produced. You have typical Boiling points from 260 to 540 ° C and viscosities from 50 to 500 SSU at 38 ° C. Jiin typical example of a suitable Oil is a neutral hydrocarbon oil with a viscosity of 130 SbU at 38 ° 0. You can go to a smaller one Part itself contribute to the lubrication.

Halogenated ones are also suitable as carrier liquids and oxygenated hydrocarbons. They are particularly preferred as carrier liquids for the a-diols because the latter has.en-in these non-hydrocarbon liquids often a greater solubility than in ο en hydrocarbons off liquid en.

To the oxygenated hydrocarbon liquids that can be used according to the invention include carboxylic acid esters, alcohols, ketones, ethers and aldehydes. The similarly substituted hydrocarbons include haloalk.yl- and haloarylkoh-

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hydrocarbons. The liquid carriers can "have both substituents have, as in the case of a halogen ether. Typical spruce hydrocarbon liquids that can be used are Carbon tetrachloride, 1,1,1-trichloroethane, chloroform, Bromoform, 1,2-dichloroethane, chlorobenzene, ethanol, metha-. nol, isopropanol, allyl alcohol, benzyl alcohol, n-butyralehyde, Benzaldehyde, acetone, methyl ethyl ketone, 2-hexanone, Methyl isobutyl ketone, ethyl ether, n-propyl ether, ethylphenyl ether, 1,4-dioxane and propylene oxide.

The above materials are given as examples only. It can be any suitable hydrocarbon, halogenated Hydrocarbon or oxygenated hydrocarbon can be used by applying suitable emulsifying agents with the particular alpha or beta diol in question can be made mixable. In addition, the "carrier liquid" can be a mixture of two or more of the above Materials exist. All materials combined in this way should be mutually miscible or can be made miscible through the use of suitable emulsifying agents.

In the lubricant composition of the present invention, the diol makes up the minor portion. Typically, the diol constitutes no more than 30 vol. ^ Of the diol-carrier liquid mixture. Preferably the diol makes up no more than 15% by volume of the mixture, and more preferably no more than 10% by volume. The smallest diol concentration is 0.1 vol. $. In a preferred embodiment, the diol is first dispersed in a polyolefin, for example polybutene having a number average molecular weight of about 300 to 1000. The mixture is then emulsified in water. These materials are easily volatilized during the cooling following the cold rolling of the aluminum, leaving little surface residue on the aluminum. In general

109 8 10 / 201B

2U42279

- ίο -

mine is the volume ratio of di-oil to polyolefin 1: 1 "to 1:10. In a typical composition according to the invention are 90 vol.yj water, 2 vol .; ' Diol, 7.5 vol .; /: - Polybutene and 0.5 vol.; O contain non-ionic emulsifiers.

The lubricant composition of the invention may contain ^c mch conventional additives, for example! Rust inhibitors, oxidation inhibitors and lubricants. A typical lubricant is lard oil. These additives are normally present in an amount of from 5 to 25 percent by weight of the lubricant.

Table I illustrates the lubricating properties of the invention Diol lubricant. The data in this table were obtained in a "Falex machine" test. This test, in which a cylindrical steel shaft between and rotating in contact with two V-shaped aluminum blocks is known. The shaft is over a small shear bolt connected to an engine. The shaft and blocks are immersed in the lubricant to be tested. The blocks will increasingly loaded so that they are pressed against the shaft. The point at which the shaft meets the blocks sticks and shears the shear bolt is measured and the load in kg on the blocks at that point recorded as the failure load of the lubricant.

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Table I.

Diol

concentration in the lubricant, vol.> ö

As a liquid carrier liquid 1, 2-iiexadecanäiol
1, 2-üodecs.nüiol
1, 2- (G ₁ cC ₁₀ ) alkcinol mixture

1,3-Alketnäiol liigung? From C ₁ P ₅ -C ₁₈ olefins

hydrocarbon carrier fluid

si;: speed

1,2- (C _{1 K} -C ₁ ..) alkanediol-Hi-

1,2- (C ₁ -C ₁₆ ) Uic
schung

1,3-alkanediol mixture of

C-Ir-C ₁ Q olefins
Ί 5 Io

1,3-Alkanäiol-I-I-I-mixture for C ₁ CC ₁₈ olefins

2- (1'-Hydrοχy üthyl) -4-

(C ₁ (--C oQalkyl) -c- methylphenol-

Hi schung

2- (1'-hydroxyethyl) -4- (1 ", 3", 5 ", 7" -tetramexhTloctj ⁷ "!) Phenol

2 2

1 5 1

Falex failure load, kg

1 820 1 b20 1 385

820

1 135

1 27C 1 315 1 45P 1 540 1 250

It can be seen from the data in Table I that a large number of of α- and ß-diols: "for the purposes according to the invention is useful. The values obtained also show that one good lubrication is achieved regardless of whether the Lubricating liquid; - the time in which the diols are dispersed, aqueous or is not watery.

Table II illustrates the superiority of the alpha and beta diols to similar materials, such as diols, in which the hydroxyl groups are far apart, or

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monohydric alcohols. All in the table below materials listed were in an amount of 2 vol No aqueous lubricant available.

Table II

component Falex failure load stung, kg 1-Gctad.ecen 770 1-Gctadeca-nol 685 2-acetoyl-1-octadecanol 685 1,2-diacetoyloctadecane 770 1,2- (C ₁₅ -C ₁₀ ) alkanol mixture 1 385 1,3-Alkanäiol from G ^^ - G ^^ olefins > 1 820 1-eexadecanol 1 065 1,2-hexadecanediol > 1 820 1-dodecanol 770 1,2-dodecanediol > 1 820 1, 12-dodecanediol 685 3-Kyäroxymethyl-1 - Oente decanol 565 3-Hvdrox ' ^iT 3i _i bth "" l-1-rjent8cosanol 565

From the data in Table II it can be seen that the a- and ß-moles in their greasy properties of all others listed compounds are far superior to closely related compounds, such as diols, in which the hydroxyl groups continue are distant and include monohydric alcohols.

The diols used according to the invention have when they are used as Aluminum lubricants are used, also have excellent anti-wear properties. That they are the appropriate monohydric alcohols in this mind; ot far superior are shown in Table III. The values of this Table were modified in a "Falex iiaachinen"

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2 nights 4 2 2 7 9

Test received. In this modified test, a -constant Force exerted on the aluminum blocks. The steel shaft rotated a certain time between these blocks. After this time, the one rubbed off the blocks The amount of aluminum was determined and the aluminum loss recorded in mg.

Table III Concentration
tion in
Lubricant
tel, vol.; * aluminum
abrasion, mg component Aqueous carrier liquid IV) 71 1-dodecanol 2 20th 1,2-dodecanediol 2 76 1-hexadecanol 2 16 1,2-hexadecanediol IV) 90 1-octadecanol IV) 21st 1, 2 "- (C ₁ c-Ci ₈ ) alkanediol mixture Hydrocarbon carrier fluid
sweetness

2- (1'-hydroxyethyl) -4-

(O ₁ CT-G _9n -alkyl) -6-methylphenol-

Misdhoof

2- (i'-hydroxyethyl) -4- (T ", 3", 5 "^" - tetramethyloctylphenol

13 11

From the data of Table III that the a- and ß-diols char acteristics in their antiwear be seen, the related materials are far superior.

In another test, a lubricant for the processing of aluminum maechinelle was of 80 wt. $ 1,1,1-trichloroethane, 16 wt. # Speoköl, 4 wt. # 1,2- (C ₁₅ -CJ ₈₎ -Allcandiol- Mixture and a small addition of a G-eruchastof-

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-H-

fes made. This lubricant was made for thread cutting used by aluminum. It has been found that the life of the G-ev / inde cutter is more than ten times over the service life (i.e. the time until the thread cutter breaks) that one with the same Lubricant received, but in which no diol was included.

Some of the diols used according to the invention are commercially available available. In other cases they can be synthesized. Syntheses for typical α- and Ö-diols are given below described.

example 1

A mixture of 245 g (1 mole) of "ITedox 1518", a commercially available mixture of C ^ -C ^ q terminal epoxies, made from cracked wax olefins and sold by Ashland Oil and Refining Co., 90 g Mol) "Water and 2 g of concentrated sulfuric acid as catalyst were refluxed for 8 hours at 100 ° 0, washed acid-free and dried. The product consisted of a waxy white pesticide; P = 52 ° C, the 1,2- (C ₁₅ -C ₁₈ ) alkanediols.

Example 2

Following the procedure of Example 1 using 1,2-epoxydodecane, 1,2-dodecanediol was prepared} P = 53 ° C.

Example 3

Following the procedure of Example 1 using 1,2-epoxyhexadecane, 1,2-hexadecanediol was prepared! P = 49 ° C.

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Example 4

A solution of 270 g (1 ha) of a mixture of cracked C-io-CpQ wax olefins, 30 g (1 KoI) paraformaldehyde, 120%? (2 kol) of acetic acid and 30 g of sulfuric acid as catalyst ZA hours was heated to 100 to 120 C, then with dilute iiauB solution and '-, / ater washed. The crude esters obtained were reacted with KOE solution to form a mixture of _{1,3 (C 1} OC.-J ₀ ) alkanols.

From the ooigen versions shows that the α- and a-diols represent soga.r in very low concentrations superior aluminum lubricants and anti-wear additives. They have a higher load capacity and are able to reduce the aluminum wear and tear to a greater extent.

BAD ORIGINAL 1098 10/201 B

Claims (12)

Claims 1. Procedure for lubricating aluminum and aluminum alloys, characterized, that one on the surface of the aluminum or the Aluminiumlei-ierungen a lubricant made up of a major part of a carrier liquid and a minor part of a C-q-C ,, -. Diol brings its hydroxyl groups are bonded to adjacent carbon atoms or carbon atoms separated by a carbon atom. 2. Verfr.hran according to claim 1, characterized in that Diol has the general formula (R ¹ ) in the OH
I. (R ² ) - (R ³ ),
C.
(R ⁴ ) eJ (R ⁵ ) (R ⁶ ) 1) the letters a, b, d, e, f, g and h mean 0 or 1, v. ^r obei are at least two of the letters 1; 2) R and R ^ hydrogen or hydrocarbon groups represent having 1 to 28 carbon atoms and 3) .R ² , R, R ⁴ and R " ^{3 are} hydrogen or hydrocarbon groups with 1 to 12 carbon atoms, or if R and Ii or R and R together form a carbocyclic ring, they together have 2 to 28 carbon atoms. 3. The method according to claim 2, characterized in that a , R, R and R represent hydrogen or hydrocarbon groups with 1 to 6 carbon atoms. 109810/2015 2Ü42279 4. The method according to claim 2, characterized in that the G-) o " ^C 3O ^ ^{01 is an} aliphatic α-diol, an aliphatic β-diol OH or . ■ OH is, vroToei R ⁷ , R ⁸ , R ⁹ and R are hydrogen or a hydrocarbon group with 1 TdIs 24 carbon atoms. · 5. The method according to claim 1, characterized in that the Cio " ^C 3O ¹ ^ ^{01 is present in a Men} S ^{e of} °» ^{1 to 1} 5 Vol.96 of the lubricant. 6. The method according to claim 1, characterized in that the carrier liquid is water. 7. The method according to claim 1, characterized in that the carrier liquid is a halogenated or oxygenated Is hydrocarbon. 10 9810/2015 8. The method according to claim 7, characterized in that the halogenated hydrocarbon 1,1, 1-1'richloräthan is. 9. The method according to claim 1, characterized in that the carrier fluid from mixtures of 2 or more of the components: v / water, mineral oils, hydrocarbon oils, halogenated hydrocarbons and oxygenated hydrocarbons. 10. Composition for carrying out the method according to claim 1, characterized in that it contains a larger proportion of V / water and a small proportion of a C ₁₀ -CU ₀ diol. 11. Composition according to claim 10, characterized in that it also contains an emulsifying agent. 12. Composition according to claim 10, characterized in that that they a) water b) an aliphatic diol of the formula R ¹ I CHOH (CH ₂ ) - CH ₂ OH in which R is an aliphatic hydrocarbon group having 7 to 28 carbon atoms and f = 0 or 1, and c) contains an emulsifying agent. · ^. Composition for carrying out the procedure according to 1, characterized in that it 109810/2015 a) 1,1,1, -trichloroathane b) an aliphatic diol of the formula R ¹ 'CHOH (OH.,) - CH ₉ OH 1 '
in which R is an aliphatic hydrocarbon group with 7 ois 28 carbon tones and f = O or 1, and c) öpecköl contains. Ä For Chevron Research Company San Froiicisco, Gel, Y.St.A Lawyer 109810/2015