DE1937722A1 - lubricant - Google Patents

Description

» Ι tt

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS, DIPL.-ING, GERHARD COLDEVVEY PATENT LAWYERS. "1» Q * 5 7 Π *)

8 MÖNCHEN 2 3 ■ S I EG ES S TR ASSE 26 · TELEFON 3480 67 ■ TELEG R AMM ADDRESS: INVEN T / MONCHEN

TELEX 'S 29

u.z. » P 6317 D (Pi / J / Hu) aft. JuXi 1969

SHELL INTERNATIONAL RESEARCH IiAATSCHAPPIJ NV The Hague, The Netherlands

lubricant Priority: July 26, 1968, Great Britain, No. 35734/68

Nan can compress air in a piston «* or a centrifugal compressor. During the compression process, the air is heated and this in turn heats the lubricating oil in the compressor, e.g. through direct contact with the oil. Because of this contact with air and heating, the lubricating oil must be opposite be resistant to degradation through chemical reactions »ZoBo must be able to withstand oxidation by the air, since rubber-like compounds can arise in the process, which in the lubricant = Oil-containing solids of all kinds, such as dust, can bind. Furthermore, the lubricating oil must not form any residues such as paint or hard carbon on the oil-wetted surfaces. she Resistance to oxidation and the formation of deposits depends on the type of oil used. the

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Lubricating oils must also be resistant to the smell

■■■■■ .. ■■ '■■ ..' ■ '■■ ■■.' ■■ ■■■■ '... ■' .- ■ ^-:.: ■ - * - ■ - ■■ ■■■ '. Sion formation with the water that comes into contact with the lubricating oil, eg «with the cooling water or the water contained in the air which is being compressed» If _;

If an emulsion is formed, the usefulness of the oil can reduced as lubricating oil and possibly hindered the oil circulation «Emulsions can also contain chemical, cause electrochemical or mechanical corrosion «The

Cylinder walls can be ZoB. attacked by drops of water

and salts dissolved in water can be transported through the lubrication system and attack metal parts.

The object of the invention is to provide a new lubricant for To make available that meets the aforementioned requirements.

The invention thus relates to a lubricant that thereby is characterized in that θβ a mineral smear oil as a base ·? component and

A) 0.001 to 5% by weight of at least one Bie- (alky! Hydroxyphenyl) alkane and / or at least one bis (amino- <= phenyl) alkanes and / or at least one 3ia- (alkylaminophenyl) alkane and / or at least one. Alkylphenols,. . ■■,

B) 0.001 to 0.1% by weight of at least one carbon dioxide-substituted beematic acid and / or at least one an anhydride a hydrocarbon-substituted one Succinic acid and / or at least one ester

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hydrocarbon-substituted succinic acid, and

C) 0.001 to 5% by weight? » at least one homopolymer

bift /

an ester of an acrylic acid with a 4 / 2Ό "carbon atom containing alkenol and / or at least one copolymer! - aate of various such esters, as well as optionally

D) contains up to 0.1% by weight of at least one organic tin compound «

The lubricant of the present invention does not tend to form hard carbon on oil-wetted parts. The cons? faced the formation of carbon is in presence an organic tin compound still increased, as after-. is described standing.

The lubricating oil, which serves as the basic component, can be produced by refining an aromatic-rich 'asphalt', naphthenic, paraffinic, or smokedbian crude oil. "Can proceed nation any suitable process stage for this purpose include, for example," The refinery distillation, chemical refining or LÖ8ungstaittelraffixation and dewaxing. A turbine mineral Bchaier oil is preferably used as the base component. Typical TiskösitÜtemrfce for such an oil are 32 to 120 cS (38 ⁰ C), and up to 35 (see Examples 5 and 6!) CS (99 ° C), Gagebenenfalia a mineral oil mixture is used. -

The ailment of the 25uä «takompc> neiite A) is preferably p-2 to 2 * 6 wt .- ^ _e A preferred ai8 ^ (a ^ lkylhyd * okyphenyl) ralkane

909885 / U82

is Bi8 ^ alkyihydroxyphenyl) methane. Dae phenyl) alkane can contain 1 to 8 alkyl groups. Preferably used compounds contain 2 to 6, in particular 4, alkyl radicals. The alkyl radicals of a molecule can be straight or different, as well as linear or branched. The preferred bis (alkylhydroxyphenyl) alkanes have at least one tertiary alkyl radical. Each alkyl radical can have 1 to 10 carbon atoms. The alkyl radicals preferably have 2 to 6 carbon atoms , in particular 4 carbon atoms. _v

Examples of bis (alkyl) suitable as additional component A)

·· I- ^; '■■ "* ^V':" "■ * / methane,

hydroxyphenyl) ^ alkanes are 3is- (3 ^ 5-dini »thjl-2-hyö2 ^ xyphefiyIJ- /

.-butyl-4-hydroxyphenyl) ^ - methane. ·., di-tert. ~ butyl-4 * -hydroxyphenyl-'methane, butyl-4 ° hydroxyphenyl) methane,
hydroxyphenyl) methane, bis ^ (J
hydroxyphenyl) «methane, Bi8- (3» 5 ^ di- »sec.« boetyl ~ 4-hydroxy «phenyl) methane _r bis (3-tert. -» butyl-5 "methyl-2-hydroxyphenyl) ~ methane, Bi8 «(3-tert-biityl-5-tert- _e- octyl-4-hydr4xyphenyl) -methane, ^ bis- (3 * tert." aiByl-5-ethyl "2-hyaroxypfeeiiyl methane, bis- {5 ₉ 5-di-tert-octy1-4-hydroxyphenyl) -methane, Bie- (3-tert-octyl ~ 5-ethyl-2 ^ hydroxyphenyl) -methaa, 2.2 = - bis ( 3-tert _β ~ butyl * 5-methyr = -2- ° hydroxyiE> henyl J ^ n-propan, 2 _f 2-bis- (3-tert. ^ 1> utyl ~ 5-methyl ^ 2-hydroxyphenyi> in ^ biitän and 1,1-Bi8- (3-tert-butyl-5-lBetlιyl * 2-kydroxypheIϊyl) «-isobutane. Preferably one uses bis- (3,5-di» tert * ~ buty1-4 «= - hydffoxyphenyl) methane, which is commercially available as a mixture with Hinderal oil.

9098SB7 1482

The preferred bis (alkylaminophenyl) · alkanes are the bis ^ ikylamino phenyl) - methane _β The bis (· alkylaminophenyl) - alkanes can have 1 to 8 alkyl =, preferably ack / they sit 2 to 6 alkyl _o Alkyl radicals of a molecule can be identical or different, as well as linear or branched. Each alkyl radical can have 1 to 10 carbon atoms. The alkyl radicals preferably have 2 to 6 carbon atoms, in particular 4 carbon atoms

Examples of bis- = (alkylaminophenyl) alkanes suitable as additional component A) are Bi8 ^ 4 "dimethylaminophenyl)" methane, bis- (4 <-diäthylaminophenyl) - »methane, bis ~ (4- = di-n <» propylamino = phenyl) "methane, bis -" (4 - = - di "n ^ butylaminophenyl) methane, bis" (4 "di-tert-butylaminophenyi) -" methane, Bi8 ^ (4-diainy! amino- , phenyl ) - =. methane and BiS '= - (4 «' dioctylaminophenyr) - 'methano Bia- (4-sec-butylaminophenyl) methane. which is commercially available as a mixture with mineral oil, is preferably used

The preferred bis (aminophenyl) alkanes are the bis (amino = phenyl) methanes.

The preferred alkylphenols have 1 to 5 alkyl rates » The alkyl radicals of a molecule can be the same or different, as well as being linear or branched ·, The preferred compounds have at least one tertiary alkyl radicalo Each alkyl radical can have 1 C 10 C atoms «, '

Examples of alkylphenols suitable as additional component A)

9098 85/1482

are 2,4 ~ dimethyl ~ 6 ~ * tert- _o ~ butylpbenol, 2,4 ~ 3 ~ imethyl-e-tert. -oetylphenol, 2y4 _t 6-Triiiethy! phenol, 2,4-Di-n- * l »iityl-6-tert. ~ · oetylphenol, 2,4 ^ 3) i-selc _< , -butyl ^: Β1-ΐβΓΦ» -Butyl-6-methylphenol,

phenol, 2 '4,6-Tri "tert-but3rlphenol, 2,4-Pi-tert = -> amyl-6-methylphenol and 2,6-di-amyl-shouldered" 4 ^a' methylphenol. 2,6 -]) i-tert. «- butyl-4- = methylphenol _i , which is commercially available, is preferably used. The lubricant of the invention can always contain at least one alkylphenol, ZoB. when the base oil of the lubricant already contains some amount of an alkyl phenol.

The proportion of the additional component * B) is preferably 0.02 up to 0.1

The A ^ Sjäsuclc "Kohlenwasseretoff ^w in" kohlenwaseerstoffi- ■:, * ■ substituted succinic acid, its anhydride or corresponding ester ", which represent the additional component B), refers here to a hydrocarbon-like radical. This radical can be a pure hydrocarbon radical or even suitable substituents as polar sect "z * B bear · halogen atoms or Hitro- ,, = aldehyde, ketone or .Äthergruppen. to ti doers the proportion of or Subs 10 ßew ο" 56, based on the j eweiligen entire Kohlenwaäieerstoffrest not exceed tibet ·

The additional component B) is preferably an alkyl or an alkyl Alkenyl succinic acid, its anhydride or a corresponding

90988571482

Ester ο bit alkyl or ~ Älkenylr-eete preferably Bernstein "acids have ^^ - mindeatens 1 -C £ _o-AtOiBe Particular preferred · are succinic acids, their Substitueiiten _β have 12 or 1§ carbon atoms In this case, the check alkenyl derived from tetrameric or pentameric propylene. The corresponding alkyl radical can be obtained from the alkenyl radical by hydrogenation. The anhydride can be an internal anhydride formed from a single molecule of the corresponding acid or an external anhydride formed from, for example, 2 molecules of the corresponding acid. The worshiper can be a full or rope ester and can be derived from a monohydric alcohol, such as methanol, ethanol or another alkanol, or from a polyhydric alcohol 10% drpj ^ l £ dolls. Particularly preferred are alkylene polyols, in particular alkylsglycols, such as ethylene, bioethylene, triethylene, fetraethylene, propylene, or dipropylene. Tripropylene glycol. Commercially available products and a mineral oil concentrate of a mixture of pentapropylene succinic acid and the honopropylene glycol ester of this succinic acid, a kineral oil concentrate of a mixture of fatty and pentapropylene succinic acid and a kineral oil concentrate of fetrapropylene succinic acid.

The additional component C) can be derived from acrylic acid. However, it is preferably derived from a dt -AllQrlacrylaäurs whose alkyl radical has 1 to 4 carbon atoms, and

909885 /

particular of methacrylic acid from «Preferably used aaa a copolymer of several acrylic acrylates The copoly- / uerieate from © at least one eater of metfeaeryl acid ait. an alkenol with 4 to H C atoms iind at least one Esters of methacrylic acid with an alkenol with 15 * to 20 C atoms are particularly preferably used · ser-like Copolymers are appropriate copolymers iron Ootyl>, Lauryl and cetyl methaorylate ■ · ■ The latter are available as MineraleoIimierullEionentrate erold. "

The proportion of the optional additional component B) fee is up to 0.1% by weight and preferably at least 0.001% by weight a tin atom carries at least one alkyl reet, and that. the other valences of the tin atom, unless a further tin atom are bonded, are linked with acylpoxyethylene with 9 to 21 carbon atoms each on "Beaonders be" ▼ orzugte alkyl groups are butyl groups> The bevoraugten Aoyl- oxy groups are Leisrpylgruppen _a Baispiele for ^ suitable organic tin compounds are fri-nb ^ ^ tyleinniÄurail · and di-n-oetylzinndiläurat. pi-n-butylzinaiailaiirat .ffird. befOJiSiagi and is Ιή: trade available «,. _; : - / ^; - ' .-.- ■'

The examples explain the invention · The Susatskomppn @ nt © n A 1, B 1, C 1 and D 1 siaci commercial products (A 1 ί bis- (3,5- '■■''- ■■■■ - V-. - §09885 / 1482 ■■; .. ". '.'-''. ■ -: /,

di ^ tert.-l (Utyl-4 ^ hydroxyphenyl) ° ßietiian in a mixture with mineral «· oil; Bi: Mineral oil concentrate of a mixture of pentapropylene succinic acid and its monopropylene glycol ester; CI: Mineral oil concentrate of a copolymer of petyl-, lauryl-

; and cetyl methacrylate D 1: di-'n-butylamine dilaurate)

Lubricant for a centrifugal compressor Components

Turbinenschmieröi _v

(Viscosity! 14 cS / 60 ° C) Additional component Al Additional component BT Additional component C 1

Shares, .45 98 .50 O .05 O .00 1

, 00

Properties of the lubricant: viscosity

.37.6 cS / 38 ° Qi 5.98 cS / 99 ° C " emulsion breaking Bteat J ASTM test B1401) 40» 37-3 (5) (oil-water-Bmulslon) (ZiBit in minutes) test for rust tendency fS salt water ! (ASgM «yrttfnorm D 665) rust tendency;. '■

Example 2 Lubricant for. a reciprocating compressor. ^

9 09885/14 8 2.

. ₁₀ - T937722

Components Shares,

Turbine lubricating oil (Viscosity: U cS / 60 ° C) Additional component A i Additional component B 1 Additional component dl

Properties of the lubricant: Enilion breakage test (ASTM test standard D 1401) 40-38-2 (5) (oil-water eoulsion) (time in minutes) Test for ro a ting of salt water] (ASTM test standard D 665) no tendency to rust

Lubricant for a reciprocating compressor: Components Shares,

Turbine Lube Oil -

(Viscosity! H eS / 60 ° e) 98.40

Additional discount at 0.50 Additional component B 1 0.05 Additional component 0 1 1.00 Additional component D 1 0.05

100.00

Properties of the lubricant: Emulsion broadening test (ASTH early standard D 1401) (Oil ^ water emulsion) (time in minutes)

-ti.

grflfting on Rostaeiipaaig . (ASfM-EralfnegB B 66 $)

no boet tendency.

Lubricant for a reciprocating compressor Components

fttrbineneehiaierttl (viscosity * 14 oS / 6O ° e) Ciis & tskeaponente A 1 gusatskoaponente B 1 Znsatsverbindungen C 1 S ^ satskosiponsate B 1 " parts"

Beer for one Components

(Sesiiseh from 40 Qew .- ^ «ines turbines ■ ehBlerule with an ¥ iskoeität 14 cS / 60 C and 60 few .- ^ one eohBierSle with a viscosity 39 eS / 6P ° C

Susat component A 1

Susatskoaponente Bt Sueatskomponente 6 1 Snsatskooponente S 1 0.50 0.05 0.40

100 * 00

Shares,

99.10

ο , 40 ο , 05 ο , 40 Q ^ OJS

-.12- ^; - ■. ■ '■ - ■■' ■ - -..- ■■■. ■ .-.: .- ■

Try to compare

The lubricants according to the invention of Examples 1, 2, 3 and 4 and the lubricants of Comparative _{Examples I, 9} II and III described below are compared with one another. The test methods used are an oxidation test (method B) and the hot plate test. Both test methods are described below.

The lubricant of Comparative Example I has the following Composition:

Components,. Shares,

Turbine grade oil

(Viscosity 14 cS / 60 ^w C) 99 # 5'5

Additional component B 1 .'-- O, Ö! L

Additional component C 1

Bas lubricant from Vergleiohsbeieplel II has the following composition! , '- .. ^; *. ^: .; - ■■;: ■ ■■ - · -. - ■; r _ '-; ■ ".; _: ': -. ;; ^: Components of shares ₉ ,

furbineneeiimierölv ■■ ';·'; \ λ. ^: _; ^; ""_; - ^: ■ ". '■ ^{; r} -" (viscosity 14 cS / 60 ° Cl 99.50

Additional component B 1 OVCK » Additional component! C 1.

Se D \ - . : ■■ /■.■■ ;; '_:;" Q

lOOjOO

9 098 85/148 2

The seizing agent of Comparative Example III has the following composition:

Beetandteile shares

98 4 pounds ο, 50 05

Turbine boiling oil (Viscosity: 41 oS / 60 ° G)

Additional component A1 Additional component B 1

129 * 92 »

In the oxidation test (method B), 5 g of the lubricant to be tested in an oxygen atmosphere exposed, the lubricant absorbing oxygen. The test is finished when 100 g of lubricant 1000 ml Have absorbed oxygen. The induction period is that Time interval at which the rate of oxygen absorption increases sharply.

In the hot plate test, 500 ml of the are allowed in each case testing lubricant for 20 hours at one speed " Density of 5 ml / Hin, over which polished before each test Surface of a rectangular, at an angle of 45 ° * inclined cast iron plate run. The surface will electrically heated to the required temperature. Afterwards, the residue that has formed on the surface is removed and weighed. The result of the meeting is determined by the Temperature shown at which 200 mg of residues were obtained will"

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Table I shows the results of the two tests. Table ^! Lubricant oxidation test (method B) Hejffelatten

Induction acid of the *)? Ön / onn period, test, hours ^{l C / ZQO} stdo

from

example 1 I. - «... example 2 II 48 example 3 III did -
ι example 4th 48 Comparison
example 16 N 18th H

68

248 248 282 286

24 28

261

259 80

♦) Time for the absorption of 1000 ml 0 _2/100 g lubricant.

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Claims (12)

a t e η t a η 8 ώ r ti @ h e 1.Lubricant, thereby g a k e, 's e i ehne t, it /. ■. ■ ''. that / a min © raleehmier81 as g _ae £ _s g> sagO and A) 0.001 to 5 §ew * - # of at least one bis (alky1-hydro2 ^ phenyl) alkane and / or at least one Bt8 ~ (aifiiaopbeEyI) «- alkaae and / or at least one Bi8 -> (alkylaminopli © siyl) -alkaii2i tsna / oSer minfieetens of an alkylphenol «- B) 0.001 to 0 _t 1 dew .- ^ at least one hydrocarbon-substituted amber fiber land / or at least one anhydride of a hydrocarbon-substituted succinic acid and / or the least one of a hydrocarbon-substituted amber mine "and C) 0.001 to 5 @ ew ·· »^ at least one Hoaopolymerie & ts an eater of an acrylic acid is a © 4 to 20 Alksnol containing C-AtOQe and / or at least of a copolymers of different Solher esters, as well as, if necessary D) at EU 0.1 6ew. * - 5b miKdeetens an organic Tin compound contains 2 · Abrasive agent according to claim 1, characterized in that it is t that the lubricating oil is a turbine mineral lubricant 1st. 90S885 / U82 3. Lubricant according to claim 1 or 2 ,. characterized g "" β k to se ie h net "that the Zueatskomponente A) a BiQ- (aikylhydroxyphenyl)» alkali, a yoreugsweiee di-tert-butyl-4-hydro ^ pfcan ^ 4. Lubricant according to claim 1 to 3 # characterized by k β η η a eich η et _r that the Ziasatskoctponente B) an alkyl or Älkenylbsrneteineäure, whose anhydride or an enteprechunder Beter iet. 5. 8ehmierid.ttel according to Änepröch 4 _f thereby g β; Ke η ä "->'■": make sure that the alkyl or alkali radicals of the all SiieatekOfBponente B) "tuιβΐΐtuierte HtutuiertHe acid" at least 12 C-Atoae, ^ orsugsweiee 12 or : ■. ■; , 15 C-Atoo * V 6. SehBiendttel according to claim 1 to f "thereby g β ken η se ich η et, that di." Additional component · C) cal from a & * -alkyl & oryl acid, its alkyl radical _:: "1 to ^; i" has carbon atoms, derives ·; /. - .:; ;.; ^; ; -:; 7 · Sehmiemittei * according to Anepruch 6, ded «rch g ö k β η η - - let ch η β t that the susate component 0) © ta 'Co -' polymerieat 'mimdestsns one. BsterS; the ll®thä © ryls.äiire bit eiaem: Alkenol ult-4 to 14 C * Atom # ii lait mind @ etens "an ester aeT'EethB. © ryl0 & uve \ mit'®inem klTumbi '. ■.' .. 15 to: 2.0.O ^ .fbiten \ _^iet: i- ^; V '".;"' --- ^r ' ^V .. ^: "..' ■ ' ^: ' ■ - ■■" - ^; ; -; ■; : Λ:: ^; _: ^ so 98 ^ a / 14 si -., '■■. ■ ■. ■ ".- .. 8. Lubricant according to claim?, Characterized ge ke η η - ζ β I η et that the additional component C) is a copolyoerisate of octyl, lauryl and oetyl methaorylate Lubricant according to claims 1 to 8, geke η η -zeichne t by a content of 0.001 to 0.1 Qew · ~ i> an organic tin compound (additional component D)) with at least one C-Sn bond in the molecule, in which at least one Tin atom carries at least one alkylreate, while the other valences of the tin atom, provided they are not bound to another tin atom, are linked to aoyloxy radicals each with 9 to 21 carbon atoms. 10, lubricant according to claim 9 »characterized in that the additional component S) a organic tin compound with a tin atom, whose alkyl radicals each have 5 to 12 carbon atoms » 11 "Lubricant" according to claim 9 or 10, characterized in that g e · = ■ k e η η ζ e ic h η e t that the additional component D) is an organic tin compound whose alkyl radicals Butyl groups and their acyloxy groups lauroyl groups are ·, ■. ' 12. Lubricant according to claim 11, characterized in that the additional component D) Di-n- 909885/1482 butyltin dilaurate fet 13 · Lubricant according to claims 1 to 12, characterized in that θβ 0 ₆ 2 to 2 wt. 5ε of the additional component A), 0.02 to 0.1 wt .- ^ of the additional component B), from 0.001 to 5% by weight of the additional component C) and from 0.001 to 0.1% by weight of the additional component D). 909885 / U82