Note: Descriptions are shown in the official language in which they were submitted.
9~
Thi9 inv0ntion r~latQs to new compositio2ls of matter
suitab~e for use a~: lubricant additives J and to m~thod~ for
their preparati~n.. More pax~icularly, i~ relate~ to ~ulfuriz~d
compc>sition~ prepared by re~c:ting~ at about 100-25QC., sulfur
with a mixt~lre comprising (A) 100 part~ by wei-3ht of at 1~3a~t
on~ fatlty ac~id e3ter, (B) about P-50 parts by weight of at
least one fatty acid, and (~) about 25~400 parts by weight of
~- a~ l~ast one aliphatic olefin containing about 8-36 ~arbon
atoms .
Sulfuriæed ~perm oil ha~ long been used a~ a l~ibrican~
additive, parti~ularly to improve extrerne presæure propertie~
while providirlg exs:ellent ~lip~ and ~ome degree of rust
inhibition in mator oil~, gear lubric~nts~ cutting and rolling
oil~ owev~r, the United State~ Govexnme~3t has r~cently
. taken a~tion to preverlt the killing of w~ale~s, ~rom which ~perm
oil is obtained, to avoid their beconnin~ extinct~ The only
~our~e o~ ~perm oil ha3 the~efore "dried up" and it ha~ become
nece~ary to find substitutes fcsr the sulfurized derivative
~hereof, whic~ can b~ cheaply and e~Eficiently produaed and
which provide the same advantageous properties to lubri~:ant~.
A prin~:ipal ob~ect o:~ the present invention, therefore,
3 i8 to provide a method for producing useful lubricant
additive~ .
A ~u~ther ob~ect i~ to produce sulfurized lubricant
additives whic~h improve extreme presslLre propertie~.
Still arlother object i5 to produ~e composi~ions which
may be sub~tituted for suluri2ed ~perm oil as lubricant
ad~itives, and which provide l:he same properties as the ~perm
oil derivative.
-- 1 --
?~
:,~'' . , . -
~, f $f / ~ f~
other ob~ect~ will in par~ be obvious and will in
par~ appear hereina~ r.
As previously describedg th~ method of ~hi~ înren~ion
comprise~ the reaction of sul*ur with a mixture of three
xeagent~., Reagent A is at least c3ale fatty acid ester~ ~he
term " fatty acid" as ~a~ed har6~in refers to acids which may
be obtained :by hydroly~is of a rlaturally occurring ~egetable
or animal f~at or oil ~. The~e are u~ ally in ~he C16 ~20range
and include palmitic at:id, ~tearic acid, oleic acid, linoleic:
10 acid a~ad the liXe.
Fatty ac:id esters w~ich are use:Eul as Reagent A are
primarily tho~e ~ith aliphatic alcohol~ cluding monohydric
alcohols sue:h a~ methanol~ ethanol, n-propanolJ isopropanolg
the butanol~, et~g and p~yh~dric alcohols including e~hylene ~:
glycol, propylene glycol, trime hylene glycol, neopelltyl glycol,
glys:erol and the like. Particularly preferred axe the ~atty
oil~, that i8 9 naturally occur~ing esters o~ glycerol with the
above-noted long c:hain carboxylic acids, and ~ynthetic es er~ of
8i~ ar structure. Still more preferred are fatty oil derived
20 ~rom un~a~urated acids, e~peaially oleic and linoleic, includin
~uch naturally oc~urring aninE~l and vegetable oils as lard oil,
peanut oil, cottonseed oil, soybean oil, corn oil, and the li~e.
Reagent B is at least one fatty acid as de~cribed
Te. It is u~ually an un3aturated fatty ac:id ~uch as oleic
o~ linoleic acid, and may be a mixture o~E acids such as i~
obtained ~rom tall oil or by the hydrolysi~ of peanut oilt
soybean oil or the likeO The a~ount o~ Reage~t B is about
2-50 partæ by weight p~r 100 part~ of reag2nt A. Reagen~ ~3
-- 2 --
~',
z~
ha~; the impor~ant function that it improves the "slip", rust
inhibi~ing and extreme pres~ure propertie~ of lub:ricants
containing the ~;ulfurized compt~sitions oi~ thi~ invention, and
so it~ pre~er~ce (pr~3f~rably in the amowlt o~ about 2-8 parts
by weight) is h~g~ly advantageous.
~ eage~t C i-~ at lea~t one Cg-36 aliphatic olefin.
About 25-400 parts, u~ually a~out 25-75 parts, of re~en'c C
are present per 100 parts of reagent A. Terminal olefins,
or a-ol~ins, are ~ ferred~ e~pecially tho~e in C12-20 range.
10 Mixture~ of these ole~ins are ~ommerc~ ally availa}~le and ~;uch
mix~ures ar0 contem~late~ ~or u~ in th ~ invent;ion.
In addit~n to the al~ove-deseribed reagents, the
rea~:tio~ mixture may cc~ntain other materialæ. The3e m~y
include, for example, sulfurization promoter~, typi~ally
; pho~phoru~-containi~g reagent~ su~h as phosphorou~ a~id
ester~ (e.g., triphsnyl phosphite), and ~urface active agent3
3 such as le~i~hin.
~he method of this invention compri~es the r~action o~E
a mixture of the above-noted reagents with sulfur at a
, 20 tamperatur~ of about 1~0-250C., usually about 150-210C.
~he weight ~atio of the co~ination o~ reagents A, B and C
to sul~ between about 5:1 and 15:1, generally between
about 5 :1 and 10 ~
he ~ulfurization reaction is e~fected by merely heating
the reagent~ at ~he ~emperature indicat~3d a:bove, usually with
e:eficien~ agita~ion and in an inert a1:mo~phere (e.g., nit~ogen)
i
I~ a~y o~ the reagent~, e~pecially xeagent C, are appreciably
volatile at the reaction t:e~nperature, ~he reaction vessel may be
sealed and maintained under pre~slare~ It i5 reS~uently
30 advanta~geou~ to add the ~ulfur ...
3-
portionwise to the mixture of th~ other reagents. I~lhlle it
is usually preferred that the reac-tion rnixture consist
entirely of the r~agents previously described, the r~action
; Illay al90 be effected in the presence o~ an inert solvent
(e.g., an alcohol, ether, ester, aliphatic hydrocarbon~
halogenated aromatic h~drocarbon or the like) which is
.. .
liquid within the temperature range employed. When the
reaction temperature is relatively high, e.g. J about 200C.,
there may be some evolution of sul~ur ~rom the product
which is avoided i~ a lower reaction temperature (eOg.,
about 150-170~C.) is used. However, the reaction sometimes
:: ~
requires a longer tim~-at lower temperatures and an adequate
sulfur content is usually obtained when the temperature is
at the high end of the recited range.
Following the reaction, insoluble by-products ma~
be removed by filtration, usually at an elevated temperature
(about 80-120C~). The ~iltrate is the desired sulfuri~ed
product,
In general~ products prepared as described above
and containing about 8-13~ (by weight) sulfur are pre~erred
for the purposes of this invention. It may sometimes be
desirable, however~ to employ products containing more
sulfur, typically about 13-16~ by weight. Also, it has
been found that a product having improved solubility in
bright stocks may be obtained by preparing B high~sulfur
product of this type and diluting the sa~e with a fatty
; oil such as lard oil to obtain a product having a lower
sulfur content.
The method o~ this invention is illustrated by the
followlng examples. All parts are by weight.
~4~ _
. .
d L~
~'
Examp]e 1
A rnix~ure of 60 parts of cor~nercial Cls-20
a-olefins and 100 parts o~ lard oil is heated to 160C.,
under nitrogen~ and 1~ parts o~ sulfur is addedO The mixture
is heatecl at 1.65-200C, and an additional 6. 5 parts of
sulfur is added Heating is continu~d ~or 4 hours, after
which the mixture is cooled to 100C. and filtered to
yield the desired product which contains 9.o% sul~ur.
~i' , ' ' ~ "'' .
E_~
lo To a mixture Or 100 parts of soybean oil and 50
; parts of 1 hexadecene at 165C. J under nitrogenS is added
~ o~er 20 minutes, with stirring, 20.6 parts o~ sul~ur. An
J exothermic reaction occurs which causes the temperature to
i rise to 200C. It is he&ted at 175-200C. ~or 6 hours,
jl 15 cooled to llOi~C. and filtered to yield the desired product
, ' ' , ' .
~ which contains ll.li~ sulfur.
,. : -
Example ~i
mixture of 100 parts of soybean oil and 50
. . .
parts of commercial Cl6 ~-olefins is heated to 175C.
20~ under nitrogen and 17.4 parts of sul~ur is added gradually,
1. , . : .
~ ~ whereupon an exothermic reaction causes the temperature to
. . . .
~ ; rise to 205C. The mixture is heated at 188-200C for
3~ five hours, allowed to cool gradually to 90C. and filtered
~ to yield the desired product containing 10.13i~ sulfur.
¦~ 25 Example 4
~ Following the procedure of Example 3, a sulfurized
', . .
product is prepared from 100 par~s of soy~ean ail, 50 parts
of commercial Cl5-l8 ~-olefins and 17.4 parts of sulfur.
It contains 10.1~ sulfur.
, .
. ~, .
_5_ ^
Exa~
Follo~ling the procedure of Example ~, a product
containing 10.~3~ sulfur is obtained by the reac~ion of lO0
.
par~s of soybean oil, 50 parts of commercial C 15-20 a-olefins
and 17.9 parts of sulfur.
Exarnple 6 ~:
, Following the procedure of Example 3, a product
; containing 9.69~ sulfur is obtained ~rom lO0 parts of soy~
bean oil, 100 parts of cornmercial C22 -28 ~-ole~ins and 23.2 :
parts of sulfur.
~Example 7 .
Following the procedure of Example 3, a produc~
containing 10,16% sulfur is obtained from 100 parts of
~ cottonseed oil, 33.3 parts of commercial Cl5-20 a-olefins
;1 15 and 15. 6 parts of sulfur,-
i
~. .
Following the procedure of Example 3, a product
~i containing 8.81~ sulfur is obtained from lO0 parts of a
triglyceride having an iodine number of 85-95, 25 parts of
2n co~ erclal C15-18 ~-olefins and 14.5 parts of sulfur,
A mixture of 100 parts of soybean oil, 50 parts -~
of commercial C15-18 a-olefins, 1.17 part of triphenyl phos
phite and 17.4 parts of sulfur is heated for 16 hours at
145-165C~ under nitrogen~ It is then cooled to room
temperature, reheated to 100C. and filtered ~ith the
addition of a filter aid rnaterial. The filtered product - -
contains 10,13~ sulfur.
:~
} . .
'i ~ . .
Ii ~6~ :
;;ZZ6
J~xamr~ Lo
_.
1~ miY~l;ure of :100 parts of soybean oil, ~. 7 par~;s
of tall oil acid and 45.3 par~s of commerc~al ~15-18
~-olefins is heated to ]65~C. under nitrogen, and 17~4 parts
of suli`ur is added. The terr,pera~iure of the mixture rises
to 191C. It is maintained at 165~200C ~or 7 hours and is
then cooled to 90C. and filtered. The product con~ains
10. 13% sulfur.
E xample 11
Following the procedure of Example lOg a product
containing 10. ~9~ sulfur is obtained from 100 parts of soy-
bean oil, 4 parts of tall oil acid, 46.3 parts of comrr.ercial
C 15 -l8 ~ -ole~ins and 20. 6 parts of sulfur
Exarl~p le 12
.
Following the procedure of Example 10, a product
containing 10. 6% sulfur is obtairied from 100 parts of soy-
bean oil, 5.25 parts of tall oil acid, ~4.8 parts OI
commercial Cls-l8 c~-olefins and 17. 4 parts o~ sulfur.
~Example_1~
- 20 Following the procedure of Example 10, a product
containing 10.~% sulfur is obtained from 100 par-ts of peanut
oil, 5O 25 parts of tall oil acid, 45 parts of comrQercia
C 15 -18 t~ -olefins and 170 5 parts of sulfur.
Example 14
Following the procedure o~ 13xample 10, a product
containing 12. 41~ sulfur is obtained frorn 100 parts of
soybean oil, 5O35 parts of tall oii acid, L16.3 parts of
cornrnercial Cl5-la c~-olefins and 26.8 parts o~ suliur.
2~`~
~,xc~t~ 15
Following the procedure o~ Example 10, a product ~.
contairling 9.98$ sul~ur is obtained ~rom 100 parts of scy-
~ bean oil, 4.11 parts of tall oil acid~ ~408 par-~s o~ a
:~ 5 mixture of C12-16 fractions from ~he polymerization of iso~
butene, and 20.o parts of sul~ur.
- :
E ~
A product containing 1~.7~ sulfur is obtained ~rorn
~, .
100 parts of soybean oil, 5.~ parts of ~all oil acid, 46.2
. ;
; 10 parts of commercial C15~18 ~-olefins, 1 5 parts of triphenyl
. phosphite and 2~ parts o~ sul~ur ~ollowing the procedure o~
Example 10 except that a temperature range of 135 165C. is
. employed,
, . . .
~ Example 17
.i : 15 Following the procedure of Example 10, a product
:1 containing 9.54~ sulrur is obtained from 100 parts of soybean
. oi], 5.53 parts of tall oil acid, 50.2 parts o~ comrlercial
15 -18 ~ -olefins, ~.18 parts of lecithin and 180 4 parts of
., .
~ : . . sulfur..
',1
,i .
l: 20 ~ . . , :~:
A product is prepared from 100 parts o~ soybean
. oi], 5.4 par~s o* tal1 oil acid, 46.3 parts of col~ercial - :.
. C 15 -18 a-ole~in and 2~.8 parts of sulfur, following the
i , .
procedure of ~xample 10 except that the temperature is
155~203C and the product is filtered at 110C. It
.
~ contains 14.45~ sulfurO
t. "'
Exarnple 19
. A product containing 13,5~ sulfur is prepared : .-
J '
,r~ -r~ '
~ ~,
according -to the method o~` ~xample 18. To 25~ parts of th:is
product is added ~8,~ par~s of lard oil. The resulting
composi~ion, which has il~lproved solubili~y ~n bright stocks,
contains 10~ sulfur.
The composi.tions Or this invention can be employed
in a variety of lubri.cating composi.t,ions based on diverse
oils o~ lubricating viscosity, including naturàl and syn-
thetic lubricating oils and mixtures thereof. The lubrica-
ting compositions contemplated include p~incipally crank-
case lubricating oils ~or spark-ignited and compression-
igni~ed internal combustion engines including automobile
and truck engines, two-cycle engine lubr:icants, aviation
piston engines, marine and railroad diesel engines~ and
the li~e. However, automatic transmission ~luids, trans-
axle lubricants, gear lubricants, metal-working lubricants,
hydraulic fluids~ and other lubricating oil and grease
:i .
compositions can benefit rrom ~he incorpora~ion of the
present ~Y~bf~
Natural oils include animal oils and vegetable
Z 20 oils (e.gO, castor oil, lard oil) as well as solvent-re~ined
or acid-re~ined mineral lubricating oils o~ the paraf~inic,
naphthenic, or mixed paraf~inic-naphthenic types. Oils of
` lubricating viscosity derived fro~n coal or shale are also
use~ul base oils. Synthetic lubricating oils include hydro-
carbon oils and halo~substituted hydrocarbon oils such as
polymerized and interpolymerized olefins (e.g., polybutylenes,
- polypropylenes, propylene-isobutylene copolymers, chlorinated
polybu~ylene.s~ etc,); alkylbenzenes (e~g., dodecylbenzenes,
tetradecylbenzenes,dinonylbenzenes, di-(2-ethylhexyl)
benzenes, etc.); polyphenyls (e.g., biphenyls, terphenyls,
,
_9_ _
.
,. - . ~ .. .
.. . . ~ , .
~tc.); and the like. ~lkylerle oxide po]y~ers and :Lnter-
polymers and derivatives ther~o~ where the terminal hydroxyl
groups have been rnodi~i.ed by est~ ication, etherif`ication,
etc., constitute another class Or known synthetic ]ubrica~ing
oils. These are exemplified by ~he oils prepared through
polymerization of ethylene oxide or propylene oxide, the
alkyl and aryl ethers of these polyoxyalkylene polymers
(e.g., methylpolyisopropylene glycol ether having an average
- rnolecular ~eight of lO00, diphenyl ether of polyethylene
glycol having a molecular weight of 500-lO00, diethyl ether
o~ polypropylene glycol having a molecular weight of 1000-
1500, etc.) or mono- and polycarboxylic esters thereof, for
example, the acetic acid esters, mixed C3-C8 fatty acid
esters, or the C130xo acid diester of tetraethylene glycol.
Another suitable class o~ synthetic lubricating oi]s comprises
the esters of dicarboxylic acids (e~g., phthalic acid,
succinic acid, maleic acid~ azelaic acid, suberic acid,
sebacic acid, fumaric acid, adipic acid, linoleic acid
! ~ dimer, etc~) with a variety of alcohols (e.g., butyl
3 20 alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
,
alcohol, pentaerythritol, etc.). Specific exarnples of
t these eeters~include dibutyl adipate, di(2-ethylhexyl)
sebacate, di-n~hexyl fumarate, dioctyl sebacate, diisooctyl
azelateS diisodecyl azelate~ dioctyl phthala~e, didecyl
phthalate, dieicosyl sebacate, the 2-ethylhexyl diester o~
.~ . .. . .
linoleic acid dimer, ~he complex ester formed by reacting
one mole of sebacic acid with t~lo moles of tetraethylene
~3 glycol and t~o mol~s of 2-ethylhexanoic acid, and the like.
Silicon-based oils such as ~he polyalkyl-, polyaryl~
~0 polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils
. 1
' ' ~ I
-10~
comE)rise anoth~r us~ru:L class o:~ synl;hel;ic lubricants ~e.g.,
tetraet~ly~. si~.icate, tetrai.soprcpyl sili.cate~ tetra~(2-
~thylhexyl) si.licake, tetra~ -me~hyl~2-tetraethyl) silica~e~
tetra-(p-tert-butylpheny~) silica~e, hexyl-(4~methyl-2-
pentoxy)-disiloxane, poly(methyl~-siloxanes~ poly(methyl~
; phenyl~si].oxanes~ etc.). Other synthetic lubricating oils
include liquid esters o~ phosphorus-containing acids (e.gO,
tricresyl phosphate, trioctyl phosphate, diethyl ester o~
decane phosphonic acid, etc~), polymeric tetrahydro~urans,
10 and the like,
: In general, about 0.05-2~.0 parts (by weight) of
the composition o~ this invention is dissolved in 100 parts
of oil to produce a satisfactory lubricant. The invention
also contemplates the use of other additives in combination
15 with the products o~ this invention. Such additives include,
for example, detergents and dispersants o~ the ash~conta:ining
or ashless type, oxidation inhibiting agents, pour point
depress mg ag~nts, auxiliary extreme pressure agents, color
. stabillzers and anti-~oam agents.
- The ash-containing detergents are exernplified by
j oil~soluble neutral and basic sal~s of alkali or alkaline~
eaxth metal~ with sulfonic acids, carboxylic acids, or
`$;~ organic phosphorus acids characterized by at least one :
,~ ~ direct carbon-to-phosphorus linkage such as those prepared :
` ; 25~ b~ the treatment of an olefi.n polymer (e.g~, polyisobutene -
jA'I' ` having a ~nolecular weight o~ 1000) wi~h a phosphorizing
agent such as phosphorus trichloride, phosphorus heptasul-
~ide, phosphorus pentasulfide, phosphorus trichloride and
sulfur, ~Ihite phosphorus and a sulfur halide, or phosphoro~
~ thioic chloride. The most cortL~only used salts of such acids ~
~, . .
,.
. ~, ' - .
,. ' ' .
`
~r~ oSe Or sod1um, po~ssium, li~hium, calcium~ m~gneslum,
strontiuln and barium.
The tcrm "b~sic salt" is used to designate metal
salts wherein the metal is present in stoi.chiometrlcally
larger amounts than the organic acid radical. The cor~nonly
employed methods for preparing the basic salts involve
hea~ing a mineral oil solution of an acid with a stoichio- !
metric excess of a metal neutralizing agent such as the metal
oxide3 hydroxide, carbonate, bicarbonate, or sulfide at a
-temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid
the incorporation of a large excess o~ metal likewise is
known. Examples o~ compounds use~ul as the promoter include
phenolic substances such as phenol, naphthol, alkylphenol, 'l
thiophenol, sulfurized alkylphenol, and condensation products ~ -
o~ ~ormaldehyde with a phenolic substance; alcohols such
as methanol, 2-propanol, octyl alcohol, cellosalve, carbitol,
ethylene glycol, stearyl alcohol, and cyclohexyl alcohol;
and amines such as aniline, phenylenediamine, phenothiazine,
phenyl-~-naphthylamine, and dodecylamine. A particularly
e~ective method ~or preparing the basic salts comprises
mi~ing an acid with an excess o~ a basic alkaline earth
, .. . . ~ .
metal neutralizing agent, a phenolic promoter compound, and ~ -
a small amount o~ water and carbonating the mixture at an ` ~-
?5 elevated temperature such as 60-200C.
AshIess detergents and dispersants are illustrated `~ ~
by the interpolymers o~ an oil-solubilizing monomer, e.g.~ ~`
decyl methacrylate, vinyl decyl ether, or high molecular
weight olefin, with a monomer containing polar substituents,
e.g., aminoalkyl acrylate or poly-(oxye~hylene)-substitU~ed
'
: ''~ ' ' , ,~ ~
-12-
.. . . .. .. .. .. . ... .. .
J/~
~cryla~e; ~he a~lirle S~l~S, ~mid~s, an~ im~ s of' oi].-
solubl~ monocarboxylic or dica.rbo~ylic acids such as s~earic
acid, oleic acid, tall oil acid, and high molecula~ wei~ht
~ .
- alkyl or alkenyl-substituted SUCCi.lliC acid, ~specially
us~ful as ashless detergents are the acylated polyamines and
similar nitrogen compounds containing at least about 54
carbon atoms as described in U.S. patent 3,272,71l6; reaction
products of such compounds with other reagents i~cluding
boron compounds, phosphorus compounds, epoxides, aldeh~des,
lO organic acids and the like; and esters of hydroc3rbon~
substituted succinic acids as described in U.S. patent
81,022.
Auxiliary extreme pressure agents and cor.rosion-
~,
inhibiting and oxidation-inhibiting a~ents are exemplified
by chlorinated aliphatic hydrocarbons such as chlorinated
,~ wax; .organic sulfides and polysul~ides such as benzyl
disul~ide~. bis(chlorobenzyl) disulfide, dibutyl tetrasul~ide~
sul~urized methyl ester o~ oleic acid, sulfurized alkyl- :
. phenol, sul~urlzed dipentene) and sulfurized terpene;
: 20 phosphosulfurized hydrocarbons such as ~he reaction product
o~ a phosphorus sul~ide with turpentine or methyl oleate;
I phosphorus esters including principally dihydrocarbon and ` :
trih~drocarbon phosphites such as dibutyl phosphite~
diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl
25 ~ phosphite,: dipentyl phenyl phosphite, tridecyl phosphite~
~ ~ distearyl phosphite, dimethyl ~aphthyl phosphite, oleyl .
~ ~ 4-pentylphenyl phosphite, polypropylene (molecular weight
500)-substituted phenyl phosphite, diisobutyl-substituted
phenyl phosphite; metal thiocarbarnates~ such as ~inc
dioctyldithiocarbamatc~ and bariurn heptylphenyl dithio- :.
- ~'
.~ ~
, . ,. ~'
-13 .
.. ... .
"
.... ... .... ,, . . . .
~ ~ .
carbamat~; Group II m~l;al phosphorodithi o~e~ ~uch as zinc
dicyclohexylphosphorod.ithio~te~ zinc dioctylp~?osphoro~
dithioa~e~ bar.ium di(hept~lphenyl) phosphorodithioate,
.~ cadmiurn dinonylphosphorodithioate, and the zinc salt of a
.` 5 phosphorodithioic acid produced by the reaction o~ phosphorus
.. . .
1 pentasulfide with an equimolar mixtUre of isopropy] alcohol
:, . . . ~~ ~nd n-hexyl alcohol.
.; It is possible to form the lubrican~s o~ this
,...................... . .
'2 invention by dissolving the various additives, or oil
,.. .
solutions thereof~ directly in a mineral oil. ~iIo~ever,
.' . it is generall~ more convenient and is pre~erred to prepare
additive concentrates containing two or more Or the desired -~
~ .
additives, and to dissolve these concentrates in the mirleral
oil to rorm the ~inal lubricating composition~
Typical lubricating compositions according to this .
.,, , ~,. :~ invention are listed în Tables I~III. All amounts listed,.
except those ~or mineral oil, are exclusive of oil present
i;; as~diluen~
:j .
i .: : ,,
.
~ , , - ~ :
lj
',
1 : , . .
'
! ! ~
~ 14- - ~
L~ I I I . I I Lt`,
~ cr~
. ~ .
L~ I I I I L~ I
~ I
.,'
:'~
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F~ ~ ~
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. ¢
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. .
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- . ~ ~ ' . - :
:,, ~ . ~ ~ ~ ~ ~ ~
--' X X X X ~ X
. . . ~ " . '
O O . O O O O O
: . a) ~o ~ o o ~o ~o
.: ~ h S-~ h h S~
~15 -
, . '
.i, .; ~"; . ; .- . . , . , - . . .
., . . , . - , , ~ . . . .. . - . .
~, ~ C~ U ` O
~l ~ o o o o l o
::
~ o o
'' a
h ~\ O o o ~- CU
," ~ t~ ~ C~l ~ O
I t~ o o o I O ~:
,.~ . : :
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. . I U~ t~ I I o o o , ~ o : '
, ' ~ I ~ I I ,'.. .
: :
;11 H¦ ....~ .
,~ ~ : . . . ~ .
r} . . - ' . ~
: ~ ' ' ;: ~ '.
:~ . Q. O o
~' . O S I
:,l . E-l . ~ O ~rl ~ t~ ,
~'~ ~ '~ ~ I ~ h
O O ~ d' ~ ~
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h ~ O~
;~ . . . ~.D ~ 5~ N
Iï ~ . , ~ ~ S~ O N ~, ~rl " 1 r
. C~ l O 5~rl O 5
,~ . O O ~ ~1 P, ~ 5
3~: :: ~ ~1 ~ ~ ~ ~ ~~ :>, ~ ~ ~ ~ ~rl 5~ o
CC ¢ ~ h~ ~ P a) ~
u~ O V. ~ 51 ~ I
rl rl q~ 1 0 I t~ J ~ rl ~ O
~1 ~ O O O O ~1 ~rl O Ci~ tB I O N
:~ ` ~ ~rl al ~rl r1 N 113 1 +~ O I ~ O
, ~ ~ ~ O ~ ~ h ,~:: ~ O ~ ~13 r~ O
~- : h 5~ V ~ C~
, ~ o ~ ~ ~ O ~ ~Q ~ a) q~ :" s~
O O O ~ r~ ;
~rl ~rl S~ h S~
~ ~ t U~ O U~ U~
,t
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In tne lubI:icating composi(;ions l:lsl;ed abo~re,
the su:l.furi7.ed co~positions of this inventlon provicle the
~,roperi;ies previously im.pa:rted by slllI'urized sperm oil.
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