NO171280B - Smoerefettblanding og fremgangsmaate for fremstilling av denne - Google Patents

Smoerefettblanding og fremgangsmaate for fremstilling av denne Download PDF

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Publication number
NO171280B
NO171280B NO865244A NO865244A NO171280B NO 171280 B NO171280 B NO 171280B NO 865244 A NO865244 A NO 865244A NO 865244 A NO865244 A NO 865244A NO 171280 B NO171280 B NO 171280B
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Norway
Prior art keywords
mixture
weight
fatty acid
alkyl salicylate
base fluid
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NO865244A
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English (en)
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NO171280C (no
NO865244L (no
NO865244D0 (no
Inventor
Alexander Colquhoun B Macphail
Henry Rutherford
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Shell Int Research
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Publication of NO865244D0 publication Critical patent/NO865244D0/no
Publication of NO865244L publication Critical patent/NO865244L/no
Publication of NO171280B publication Critical patent/NO171280B/no
Publication of NO171280C publication Critical patent/NO171280C/no

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    • C10N2010/00—Metal present as such or in compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14

Description

Denne oppfinnelse angår en smørefettblanding og en fremgangsmåte for fremstilling av denne.
Smørefettblandinger benyttes vanligvis på steder hvor det er tilstede vann i små eller i vesentlige mengder. Selv om blandingene gir smøring, kan de svikte med hensyn- til å beskytte metalldelene som de er i kontakt med, mot rustdannelse. Det er behov for smørefettblandinger som både gir utmerket smøring og som hindrer rustdannelse. For å oppnå dette er det blitt foreslått å tilsette rusthindrende additiver til smørefettblandingen. Særlig effektivt i denne hen-seende er natriumnitritt. Selv om denne forbindelse bidrar i en viss utstrekning til blandingens stabilitet overfor oxydasjon, innlemmes det i tillegg et antioxydasjonsmiddel. Egnede og effektive antioxydasjonsmidler er aminer og produk-ter avledet fra aminer. Imidlertid er det kjent at en kombinasjon av nitritter og aminer kan danne nitrosaminer, av hvilke enkelte antaes å være kreftfremkallende. Dette problem erkjen-nes av fagfolk på området, og det er blitt gjort anstrengel-ser for å hindre dannelse av nitrosaminer. Eksempelvis angis det i US patentskrift nr. 4 200 542 at inhibering av dannelse av nitrosamin kan oppnåes ved at det til smørefettblandingen tilsettes en kombinasjon av et ascorbat eller iso-ascorbat med a-tocoferol. Selv om denne kombinasjon påståes å være effektiv, er det klart at bare smørefettblandinger som ikke inneholder nitritter og/eller aminderivater, på den beste måte kan løse problemet med nitrosamindannelse.
Det har nu overraskende vist seg at når kalsiumalkylsalicylat settes til en smørefettblanding, får denne utmerkede rusthindrende egenskaper, slik at tilsetning av natriumnitritt ikke lenger er nødvendig. Imidlertid vil smørefettblan-dingens dryppepunkt, dvs. den temperatur ved hvilken smøre-fettblandingen går over fra en halvfast fase til væskefase, senkes gjennom tilsetningen av kalsiumalkylsalicylat. Det har nu overraskende vist seg at smørefettblandinger som inneholder en kombinasjon av kalsiumalkylsalicylat og magnesiumalkylsalicylat, oppviser utmerkede rusthindrende egenskaper og dessuten tilfredsstillende dryppepunkt.
Med foreliggende oppfinnelse tilveiebringes det såle-des en smørefettblanding inneholdende et basisfluidum og et fortykningsmiddel og et alkylsalicylat av et jordalkalimetall. Smørefettblandingen er særpreget ved at den inneholder kalsiumalkylsalicylat i en mengde på 0,1-10 vekt% og magnesiumalkylsalicylat i en mengde på 0,05-5 vekt%, beregnet på blandingens totalvekt. Smørefettblandingen ifølge oppfinnelsen har ikke bare utmerkede rusthindrende egenskaper og tilfredsstillende dryppepunkt men oppviser også vannutlutningsegen-skaper som er bedre enn for natriumnitrittholdige smørefett-blandinger.
Basisfluidumet kan være et hvilket som helst smøremid-del som er kjent i faget. Slike smøremidler innbefatter mineralske hydrocarbonoljer, syntetiske hydrocarbonoljer, poly-merforbindelser såsom polyolefiner og polyglycoler, estere såsom dialkylsebacat, polysiloxaner, fenoxyfenylethere og andre smøremidler, og blandinger derav. Foretrukne smøremid-ler er mineralske og syntetiske hydrocarbonoljer. Disse oljer kan være blitt underkastet visse behandlinger, spesielt hydro-behandling. Det er hensiktsmessig at viskositeten av smøre-midlet er mellom 2 og 60 rnrn^/s ved 100°C, fortrinnsvis mellom 3 og 50 mm 2 /s ved denne temperatur.
Fortykningsmidlet kan velges blant en lang rekke forbindelser som innbefatter substituerte ureaforbindelser, fthalocyaniner og leirmaterialer som er modifisert ved behand-ling med et overflateaktivt middel, hvilke leirmaterialer kan være valgt blant f.eks. montmorillonitter, spesielt bento-nitt eller attapulgitt, zeolitter og andre naturlig forekommende komplekse uorganiske silicater. Fortrinnsvis velges fortykningsmidlet blant alkalimetall- og jordalkalimetall-salter av fettsyrer med 9-30 carbonatomer. Metallsaltene som benyttes i såpen, er fortrinnsvis lithium- og/eller kal-siumsalter. Når alkalimetall- eller jordalkalimetallsaltene benyttes sammen, er det hensiktsmessig at vektforholdet mellom alkalimetall og jordalkalimetall er fra 1:2 til 20:1. Egnede fettsyrer er stearinsyre, hydroxystearinsyre, olje-syre, palmitinsyre, myristinsyre og hydrogenerte naturlig forekommende oljefettsyrer, spesielt hydrogenert beverolje-fettsyre. Disse såper kan anvendes i kombinasjon med et al-kalimetallsalt, spesielt et lithiumsalt, valgt blant de alka-limetallsaltene av alifatiske £4.12"dicarboxylsyrer, alkali-metallsaltene av aromatiske hydroxycarboxylsyrer og alkali-metallsaltene av borsyrer, såsom lithiummetaborat, lithium-tetraborat, lithiumperborat eller monolithiumsaltet av ortho-borsyre eller med fosfat-, fosfitt- eller thiofosfatestere.
Alkylsalicylatene kan være nøytrale kalsium- og magne-siumsalter. Fortrinnsvis er minst ett av alkylsalicylatene overalkaliserte. Særlig foretrukket er det tilfelle hvor begge alkylsalicylater er overalkaliserte. Fremstillingen av overalkaliserte metallalkylsalicylater er kjent i faget.
En velegnet metode er beskrevet i britisk patentsøknad nr.
2 097 417. De overalkaliserte metallalkylsalicylater er vanligvis komplekser av metallhydroxydet og/eller -carbonatet og alkylsalicylat. Graden av overalkalisering uttrykkes som basisitetsindeksen (BI), som er definert som ekvivalentforhol-det mellom metall og alkylsalicylsyre. Kalsiumalkylsalicylatet har hensiktsmessig en basisitetsindeks på fra 1 til 15, fortrinnsvis på fra 2 til 10, og magnesiumalkylsalicylatet har hensiktsmessig en basisitetsindeks på fra 1 til 15, fortrinnsvis på fra 2 til 8. Fordelen med å benytte overalkaliserte alkylsalicylater ligger i at de kan nøytralisere sure forbindelser som kan dannes når smørefettblandingen er i bruk, slik at korrosjonsangrep på metalldeler av disse sure forbindelser hindres.
Lengden av alkylkjeden i alkylsalicylatet spiller
en viktig rolle for å oppnå jevn fordeling av alkylsalicylatet i smørefettblandingen. Vanligvis kan kjedelengden variere mellom 5 og 50 carbonatomer, fortrinnsvis mellom 10 og 35 carbonatomer. Kjedene kan være forgrenede, men det er hensiktsmessig at de er lineære. Mengden av kalsiumalkylsalicylat er fortrinnsvis mellom 0,1 og 10 vekt%, spesielt mellom 0,5 og 5 vekt%, og mengden av magnesiumalkylsalicylat er hensiktsmessig fra 0,05 til 5 vekt%, spesielt fra 0,1 til 3 vekt%, idet alle prosentangivelser er regnet på basis av blandingens totalvekt.
Smørefettblandingen beskrevet ovenfor kan ytterligere inneholde flere andre forbindelser og additiver. Disse innbefatter alkoholer såsom glycol, glycerol, trimethylolpropan, pentaerythritol, linfrøolje eller beverolje, slitasjehindrende additiver og additiver som beskytter mot ekstreme trykk, såsom trifenylfosforthionat, sinkdialkyldithiofosfat, bly-nafthenat eller sulfuriserte fettoljer; antioxydasjonsmidler såsom diarylaminer, f.eks. difenylaminer, fenyl-nafthylami-ner eller alkylerte derivater derav, og andre konvensjonelle additiver.
Med oppfinnelsen tilveiebringes det også en fremgangsmåte for fremstilling av den nye smørefettblanding, kjen-netegnet ved at kalsiumalkylsalicylat i en mengde på 0,1-10 vekt% beregnet på blandingens totalvekt og magnesiumalkylsalicylat i en mengde på 0,05-5 vekt% beregnet på blandingens totalvekt blandes med en blanding inneholdende en fettsyresåpe og et basisfluidum. Et egnet basisfluidum kan f.eks. være mineralsk basisolje. Alkylsalicylatene blir med fordel blandes med den dannede blanding av såpen og basisfluidumet. Ved en foretrukken utførelsesform blir blandingen inneholdende fettsyresåpen og basisfluidumet fremstilt ved: (i) innlemmelse av fettsyren(e) i basisfluidumet og nøytralisering av den resulterende blanding med alkalimetall-og/eller jordalkalimetallforbindelser, eller (ii) separat fremstilling av fettsyresåpen og innlemmelse av den i basisfluidumet, eller (iii) forsåpning av en ester fra hvilken fettsyren skal oppnås, i nærvær av alkalimetall- eller jordalkalimetallforbindelser og basisfluidum ved forhøyet temperatur, f.eks. ved 120-250°C, avvanning av den oppnådde blanding, tilsetning av ytterligere mengder basisfluidum til den avvannede blanding og avkjøling av det oppnådde smørefett. Metallalkylsalicylatene blir hensiktsmessig blandet med smøre-fettblandingen under kjøletrinnet. Fremstillingen kan utførse satsvis eller kontinuerlig.
Oppfinnelsen illustreres i de følgende eksempler.
Eksempel 1
For å vise virkningen av kalsium- og magnesiumalkyl-salicylater på en smørefettblandings dryppepunkt og rusthindrende egenskaper ble det fremstilt et antall smørefett med varierende mengder kalsiumalkylsalicylat og magnesiumalkylsalicylat.
Den basis-smørefettblanding som ble testet, inneholdt 11,0 vekt% av lithium- og kalsiumsaltene av hydrogenert beveroljefettsyre med et vektforhold Li:Ca på
6; 4,5 vekt% av en blanding av konvensjonelt antioxy-das j onsmiddel , korrosjonshindrende additiv, additiv for å beskytte mot ekstremt trykk og slitasjehindrende additiv; og 84,5 vekt% mineralsk hydrocarbonolje med en kinematisk viskositet på 100 mm^/s ved 40°C og en viskositetsindeks på 90 (svarende til en kinematisk viskositet på 10,2 mm<2>/s ved 100°C).
Til denne basis-smørefettblanding ble det tilsatt overalkalisert kalsium-C^^g-alkylsalicylat (Ca-AS) med en BI på 3,0 og overalkalisert magnesium-C14_1g-alkylsalicylat (Mg-AS) med en BI på 7,5 i mengder som angitt i tabell I. Vektprosentmengdene er beregnet på vekten av basis-smøre-fettblandingen.
Blandingene ble underkastet en dryppepunkttest (IP 132) og en antirust-test (IP 200, under anvendelse av salt-vann). Graderingen ved den sistnevnte test strekker seg fra 0 (= ingen rust) til 5 (= rustarealer som dekker mer enn 10% av overflaten). Resultatene er oppført i tabell I.
Av resultatene vil det sees at Ca-AS forbedrer de rusthindrende egenskaper i betydelig grad, og at den samtidige tilsetning av Mg-AS effektiv motvirker den nedsettelse av dryppepunktet som forårsakes av tilsetningen av Ca-AS.
Eksempel 2
I dette eksempel sammenlignes smørefettblandinger
som inneholder natriumnitritt, Ca-AS og Mg-AS.
Smørefettblanding 6 inneholder
11,0 vekt% hydrogenert beveroljefettsyre 1,6 vekt% lithiumhydroxyd-monohydrat
2,0 vekt% natriumnitritt
5,3 vekt% av en konvensjonell blanding som skal hindre oxydasjon, gi beskyttelse ved ekstreme trykk og hindre slitasje. 80,1 vekt% av hydrocarbonoljen benyttet i eksempel 1.
Smørefettblanding 7 inneholder
12,0 vekt% hydrogenert beveroljefettsyre 1,5 vekt% lithiumhydroxyd-monohydrat
0,2 vekt% kalsiumhydroxyd
4,3 vekt% av en konvensjonell blanding som skal hindre oxydasjon, gi beskyttelse ved ekstreme trykk og hindre slitasje.
3,0 vekt% av det Ca-AS som ble benyttet i eksempel 1
1,0 vekt% av det Mg-AS som ble benyttet i eksempel 1 78,0 vekt% av hydrocarbonoljen benyttet i eksempel 1.
Flere egenskaper ved blandingene ble bestemt. Disse er angitt i tabell II.
Av de ovenstående resultater fremgår det at smørefett-blandingen ifølge oppfinnelsen har egenskaper som tilsvarer eller er bedre enn egenskapene av den tidligere kjente smøre-fettblanding. Spesielt er vannresistensen forbedret betydelig.

Claims (9)

1. Smørefettblanding, inneholdende et basisfluidum og et fortykningsmiddel og et alkylsalicylat av et jordalkalimetall, karakterisert ved at den inneholder kalsiumalkylsalicylat i en mengde på 0,1-10 vekt% og magnesiumalkylsalicylat i en mengde på 0,05-5 vekt%, beregnet på blandingens totalvekt.
2. Smørefettblanding ifølge krav 1, karakterisert ved at fortykningsmidlet er en alkalimetall- eller jordalkalimetallsåpe av en fettsyre med 9-30 carbonatomer pr. molekyl.
3. Smørefettblanding ifølge krav 2, karakterisert ved at den benyttede fettsyre er hydrogenert beveroljefettsyre.
4. Smørefettblanding ifølge krav 2 eller 3, karakterisert ved at metallene er lithium og/eller kalsium.
5. Smørefettblanding ifølge krav 1-4, karakterisert ved at kalsiumalkylsalicylatet har en basisitetsindeks på 1-15 og at magnesiumalkylsalicylatet har en basisitetsindeks på 1-15.
6. Smørefettblanding ifølge krav 1-5, karakterisert ved at metallalkylsalicylatene har en alkylgruppe med 5-50 carbonatomer.
7. Smørefettblanding ifølge krav 1-6, karakterisert ved at mengden av kalsiumalkylsalicylat er 0,5-5 vekt%, og at mengden av magnesiumalkylsalicylat er 0,1-3 vekt%, beregnet på blandingens totalvekt.
8. Fremgangsmåte for fremstilling av en smørefettblan-ding ifølge krav 1-7, karakterisert ved at kalsiumalkylsalicylat i en mengde på 0,1-10 vekt% beregnet på blandingens totalvekt og magnesiumalkylsalicylat i en mengde på 0,05-5 vekt% beregnet på blandingens totalvekt blandes med en blanding inneholdende en fettsyresåpe og et basisfluidum.
9. Fremgangsmåte ifølge krav 8, karakterisert ved at det som blanding inneholdende en fettsyresåpe og et basisfluidum anvendes én som er blitt fremstilt ved: (i) innlemmelse av fettsyren(e) i basisfluidumet og nøytralisering av den resulterende blanding med alkalimetall-og/eller jordalkalimetallforbindelser, eller (ii) separat fremstilling av fettsyresåpen og innlemmelse av den i basisfluidumet, eller (iii) forsåpning av en ester fra hvilken fettsyren skal oppnåns, i nærvær av alkalimetall- eller jord-alkalimetallf orbindelser og basisfluidum ved forhøyet temperatur, avvanning av den oppnådde blanding, tilsetning av ytterligere mengder basisfluidum til den avvannede blanding og av-kjøling av det oppnådde smørefett.
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EP0227182A3 (en) 1988-08-10
ZA869614B (en) 1987-06-22
HK54892A (en) 1992-07-30
DE3677479D1 (de) 1991-03-14
AU589478B2 (en) 1989-10-12
EP0227182B1 (en) 1991-02-06
TR24450A (tr) 1991-10-10
US4719023A (en) 1988-01-12
FI82068B (fi) 1990-09-28
GB8531626D0 (en) 1986-02-05
ATE60793T1 (de) 1991-02-15
IE59508B1 (en) 1994-03-09
NO171280C (no) 1993-02-17
BR8606359A (pt) 1987-10-13
NO865244L (no) 1987-06-24
EP0227182A2 (en) 1987-07-01
AU6683886A (en) 1987-06-25
CA1283399C (en) 1991-04-23
MY100718A (en) 1991-01-31
SG29492G (en) 1992-05-15
DK621786A (da) 1987-06-24
IE863373L (en) 1987-06-23
FI82068C (fi) 1991-01-10
DK169747B1 (da) 1995-02-13
FI865261A (fi) 1987-06-24
FI865261A0 (fi) 1986-12-22
NO865244D0 (no) 1986-12-22
NZ218745A (en) 1989-01-27
AR245491A1 (es) 1994-01-31
DK621786D0 (da) 1986-12-22

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