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Патент USA US2404446

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Patented July 23, “1946
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UNITED ‘ STATES‘ PATENT - ;}oF'FlcE;f
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2,404,446
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LUBRICANT ADDITIVES AND PREPARATION
“_
V.
.
~>
THEREOF
' > ‘I-
.
p “Eugene
N. Y., Lieber,
and Aloysiuf's
WestNew
F. Cashman,
Brighton,Bayonne,
Staten‘Is'land;
N. J; I . '" t ‘ V
‘
assignors to Standard Oil ‘Development Com
‘ pany,a corporation (of Delaware '
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No Drawing. Application December 30, 1942,
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Serial No. 470,642
1 Claim.
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(01. zoo-"i251 ‘
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This invention relates to improved extreme
pressure additives for incorporation‘ in ‘mineral
andthen allowing the mixture to settle into two
layers, onethe extract phasejj (usually the upper
lubricating oils torprepare lubricants especially
adapted'for operationunder extreme pressure,
layer) andlthe'other thera?inate phase (usually
the'lower layer). Such a'batchextractionImay
such as involved in the operatidn'of‘hypoid gears
, behrepeated successivelyuntil, the desired jsep+
usedinmotor vehicles, etc.’
' aration has been made ‘bythevdesirediconstitul
7
‘
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It has been known for some time thatmineral
oils per se are not capable of. withstanding» the
ems having good 1 stability ‘and {good extreme
; pressure lubricating. ‘characteristics, which’ ‘gen
great pressures encountered between engaged
orally are "constituents having about 1_ to ‘10%: of
metal surfaces in various types of machines, etc., It) sulfur and about 30 to 40%‘ of 'chlorine,as1dis
such as hypoid gears; but that additives capable
ting-ui‘shedf'rom' the ‘undesirable fraction" which
of increasing their load carrying capacity to a
satisfactory degree can be‘ made by' making
generallylhas?such poor st'ability‘a's to ‘be actually
insolublein‘mineral “lubricatingoilsland which
petroleum‘v hydrocarbon derivatives containing
generally'ha's'rnore‘than v110% ofisulfvur. and’ less
both sulfur and a‘h'alogen'such‘as chlorine. Such 15 than 30%;o’f7chlorine. Thistype of extraction
additives may be made, for instance, as described
in U. S. Patent 2,124,598, by chlorinating a pe-'
troleum hydrocarbon fraction such. as kerosene
or paraffin wax and ‘reacting the resultant .chlo-
maybe illustrated by the usejof isopropylalcohol
I as the extracting‘ solvent, in which case ‘the 'de
sired constituents‘ are dissolved ‘preferentially in
the solvent and ‘therefore are contained vin_ the
rinated hydrocarbon product with alkaline poly- 20 extract ‘phase ‘while' the undesired constituents ‘ ‘
sul?de.
'Other related products are ’made ‘by
remain in the raftinate phase.
7
_ H ,
reacting a. chlorinated l kerosene ‘with ‘alkaline
Such solvent extraction may be carried "out
xanthates, alkaline-'thiocyan'ates, alkaline mereither by batch operation usingone or a plurality
captides, etc; ' Although ‘such extreme.‘ pressure
of successive batches‘ or stages, using eitherrrfresh
additives‘have in" general been quitesatisfactory, 25 or recycled’ solvent, or it maybe carried ‘outcom
it has been observed occasionally that ‘some of
tinuously; and it‘ may also be carried-out concur
these additiveshave ‘shown a'slig‘ht' tendency to-
rently or" rcountercurrently. " A preferred I pro
ward instability during: storagefapparently due
to" the presence therein‘f‘ofi constituents, which
cedure is continuous countercurrent solvent ex!
traction,_- illustrated by feeding a solvent such‘ as’
either are not as completely soluble 'or'r tend to .30 isopropyl alcoholiinto the base of-a vertical?tower
become insoluble and settle out'during‘ storage.
" and-feeding'the original or c-rudeiextremehpres- '
It ‘is one object of the present invention to '
prepare extreme pressure additives which are
sure additive (-which'lhas'a‘highergravity‘than
the alcohol) near the top thereofisozthat itzwill’
substantially free from any constituents which
descend while the alcohol is ascending-With’ the
are either insoluble or tend‘ to' become insoluble ',3 in result that, a‘ countercurrent contacting is 'car
during storage. Another objectvof the invention " riedout-continuously, the alcohol extract .phase
is to ‘improve the load carrying'capacity ‘of 'exbeing‘ removed icontinuously from the topof the '
trem‘e‘pressure additives;
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_
tower and the undesired insoluble ra?inate being
Broadly the invention T'coinprises re?ning‘ peremoved continuously at ‘the bottom of the tower.
troleum hydrocarbon derivatives which-‘contain vgm Another way of carrying out the inventionlis
both sulfur'and halogen by contacting them'with ’ to mix the crude extreme pressure additive with
a selective solvent havin'gfa preferential solvency
for relatively low-sulfur constituents as compared
a suitable solvent, heat- to the point of complete
solubilityi. or miscibility; ‘andv._;}thenf;either; ‘cool
to relatively highrsulfu’r constituents. ‘
and/or addl'a precipitating agent,or‘antiésolyent
‘
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The invention may be'carried' out‘ in a number ,45 to cause theyseparation into two‘ liquidphasesf '
The material to‘; be usediasj'jsolvent mayf‘be
of different-ways such. as by contacting the. or
iginal'extreme pressure additive, i. e.,lthe:' crude
selected from a wide ‘variety of ‘substances; {Ex
petroleum‘ hydrocarbon derivative fraction 1 con
ainples include the. lower alcoholsfsuchas iso-a
taining both sulfur and halogen, with‘ a; selec-
‘propyl alcohol, amylalcohol, butylv alcoholiethyl'y
?ve-‘solvent; preferablywith suitableVZ-agitation, Q9 alcohpl; letc.',‘iorfjvarious,othergtypes;prop ygen'
9,404,446
3
4
V
rial, referred to as crude extreme pressure agent
A, was contacted very vigorously with 1,000 cc.
of isopropyl alcohol (91% grade) in a separatory
funnel and the mixture settled at room tempera
containingaliphatic organic compounds, such as
ethers, e. g., di-ethyl ether, di-isopropyl ether,
etc., ketones, e.’ g., acetone, methyl isopropyl
ketone, methyl isobutyl ketone, etc., esters, e. g.,
ethyl acetate, isopropyl acetate, amyl acetate,
ture for 48 hours. The following separation was
effected.
methyl propionate, isopropyl butyrate, ethyl
valerate, etc., or organic acids, such as acetic
Extract phase (upper layer) =1,040 cc.
acid, chloracetic acid, propionic acid, etc. Other
Ra?inate phase (lower layer): 960 cc..s ’
substances known more or less as aclass-of selec
» The extract phase was-distilled in order to
' tive' solvents "having a preferential solvency for
remove the isopropyl alcohol, ‘taking off" the last ’
aromatic and, unsaturated hydrocarbons may be
used such asqphenol, liquid sulfur dioxide, aniline,
furfural, dichlor diethyl. ether, nitrobenzene, etc.‘
traces under high vacuum on‘a water bath. An
‘extract weighing ll2'grams was obtained. This,
willrtbe identi?edas “First extraction” product.‘
A still different type of solvent vwhich may be
7 The ra?inate phase obtained above was con
used comprises lique?ed normally gaseous'hy- _ .
tacted very vigorously with 1,000 cc. of 99% is0-‘ s‘
drocarbons such’; as butane, propane, ethane, etc,
In carrying out the solvent'extraction withfany
of the'various types of solvents mentioned ‘above,
propylyalcohol by contacting vigorously in a sep- 7
aratoryrfunnel and the mixture settled for 24
hoursat room temperature. The following sepa
instead of using a single solvent, two 'or‘ more ' 7
different solvents either within the same'class of to
substances or in different classes may be used.
Also, if desired, various substances, known‘v as
anti-solvents in the lubricating oil solventmex
traction art, may be used such as water, glycols,
liquid anhydrous ammonia, etc.; such materials
are preferablyused iri relatively _small amounts
ration was effected:
'
-Second extract phase (upper layer) =‘l,240 cc.
Second raf?nate phaseilower layer): 710cc.
The second extract phase was" distilled as before,
and
a‘ “Second extraction” product weighing 363
25
grams was
obtaine_d.~
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_
The “Second raf?nate” phase was contacted
vigorously again with ‘1,000 cc. of 99% isopropyl
to 'modify the solvency characteristics 'of one‘ ‘of
‘ the other .types 'o‘f'lsolvents‘ mentioned above.
alcohol as before. After settling for '72 hours at
A still 'further‘alt‘ernative procedurevis 'to dilute
’ the crude'extreme' pressure additive with a light’ 30 room temperature the following separations were '
hydrocarbon liquid, such. as'a re?ned‘ naphtha,‘
before contactingit with the, selective solvent. ' ‘
Third extract phase (upper layer), =l,220 cc.
obtained:
{After the extraction has been completed, the
solvent maybe removed from ‘the. solvent phase .
and this'may be done either after individual steps 35
.
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r“hird ra?inate phase; (lower layer) =
500 cc. 7
The third extract 'phase was distilled as before
to remove isopropyl alcohol and a “Third extrac
' in a prooess'involving'seve'ral‘stages,or'at'the ‘end.
, of a cumulative or-countercurrent operation.j
tion" product weighing 201 grams was obtained.
In‘ carrying out the invention the ‘proportions
The “Third ‘ra?inate” phase obtained above'was
of materials to be used will, ofjco'urse, vary within
, contacted vigorously again with 1,000 cc. of‘99%
a Wide range depending upon the nature ofpthe 40 isopropyl alcohol. vAfter settling for 24phours the
crude extremepressure ‘additive being‘treated, ,
following separation was obtained.
the, type of solvent, and anti-‘solvent (if any)
used, as'well as‘upon ‘the temperature and pres
Fourth extract phase (upper layer) ,='1,-l2’0 ‘cc.
Fourth raf?nate. phase (lowerlayer): ‘360cc.
sure conditions used and the degree of re?nement
desired; However, usually‘about 1A; to 10 parts
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45
The fourth extract phase was distilled'as‘ before
of solvent should be usedto one ‘part by volume
to remove isopropyl alcohol and a “Fourth extrac
.of crude extreme pressure additive, and generally
tion” product weighing l34'grams was obtained.
The fourth raf?nate phase which was becoming
quite viscous'was ‘given a j?nal extraction‘with
v1,500 cc. of 99% isopropyl alcohol as ‘before. The
I about 1 to 5 volumes ‘of-‘solvent to ‘one of extreme
,‘pressure additive will be found to give satisfac- I
.tory results} The temperature used maybe‘either
50
room temperature or ‘above or below room tem
perature,~and generally a ‘temperature between , '
room temperature and 250° F.‘ will be'satis'factory.
contacting was carried vout at 125°“ F.in‘ord'er to
aid handling because of’thei high viscosity'joffthe
raflinate phase at thisfpoint; After "settling for}?
days at room temperature; the'followingsepara
vThe pressure ‘may be, atmospheric or above or
.below atmospheric, a slight, superatmospheric 55
tion'was'obtained: ’ I
‘ pressure being, of course, necessary when using
volatile materials,’ such as lique?ed normally
gaseous ‘ hydrocarbons.
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The objects, advantages and details» of the in- V
,v,
'
Fifth extract phase
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layer)- ,=1,600 .cc.
Fifth ra?inate phase (lower layer)‘: 260cc,’
The ?fth _, ra?inate phase 'was‘found to be ex-i
vention will be better understood froma consid 60
‘ "Théf?fth' extract phaselwais ‘distilled, asib‘efore
eration' of the following specific examples which.
to‘ remove isopropyl alcohol and, a :,“Fifth extracé
areloffered by Way of illustration but withouti'the
tionf" product weighing 919 jg'ra‘rnjs‘was‘wobtained;
intention of limiting the invention speci?cally
tremely viscous.
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The *?fth ra?inate phase was. also subjected :lZQ
thereto.
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:EXAlVlIPLE?L ‘
“ 'A sample of commercial extreme pressure‘addi
' tive marketed under the trade‘name f‘Pa'rapoid
65 . distillation and 'a' ‘f?nal” ra?inate :product-weigh-j
i'ng 313, grams and consisting, of an‘extremely
viscous tar-like material .wasobtained, 5 ' "'
9‘? 7
The 'extract'products and thejj?nal railinate
'10,’.f‘rriade'by' chlorinating kerosene atatempera=
product were tested ‘for the followin' points?"
ture/of about 175°"F; to a ‘ chlorine fcontent'of
Solubility a 10% Catamaran’gramme
about 210 %.1chlorine, andreacting theresulting
chlorinated kerosene with sodium 'polysul?'de',jand
lalsojffouhdito contain 7.3 %, 'sul'furiand"l33'.0,%
' chlorine,lwasusedrasraw material according to
BrightlStock Analysis forg-sulfurandchlo ne ,
Extreme ipressureiproperties Pas;;-measured-; by
machine
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thisinvention. About 1;;200grams of ‘thisniate- 75 ' The "data “obtained ‘are summarixedi'i
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2,404,446.
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TABLE
1
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_
SolWm el'tm‘ction q; pampoz.d_ 10?
-
. EXAMPLE Noll-r1’
Per
t
. om
yield 1
Fraction
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v
, .Analysis
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j
7‘ Solubility characteristics :1; “‘
Exfrdm? .
pressure
‘
' Page“ Pegcfnt
Original unextracted extreme pressure agent A- ........ _ _
First extraction product ______________________ ._
. 9. 4
Second extraction product
; '
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7. 3. >1.9
23. 6
-> 33.0
35.0
properties 1
5% blend in Varsol
P510 °a§§§dB‘f‘s_
SAE No.8
‘Cloud and sediment___
Clear
Cloud and sediment.-.
Clear
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320
400
3. 2
35. 7
363
Third-extraction product"
16. 8
V 3.4.
38. 0
425
Fourth extraction product.
11. 2_
- 3. ‘3-
36. 0
390
5. 6‘
35. 5
Fifth extraction product.__
Rammm
.
___________ _.
____ __
-
‘
‘
823
> _ __
26. 2
17. 0
__.__do _______________ __
24. 4
398
Heavy tarry sediment. __________ ._
1 These are weight yields based on the original unextracted Parapoid-lo.
1 10% blend of particular fraction in Panhandle Bright Stock.
1 This test is described in the an. E.>Journal, volume 39,‘ pages 23 to 24 for the year 1936; ‘ a ‘ 1 >
It will be noted that all of the extracted phases
>
isopropyl alcohol were-placed in a glass ?ask or
have excellent solubility in both Varsol and Pan- 20 still, used 'afsreboilen. Heat was applied to the
handle Bright Stock as contrasted with the original unextracted extreme pressure» agent A.
reboiler and the alcohol was vaporized. The va~
pors were led through an'insulated vapor line to
“Varsol” is a re?ned varnolene ini the heavy . ~ a'watere'cooled condenser and condensed and led
naphtha boiling range. The data also bring out
through a long-stemmed funnel to the bottom of
the hitherto unknown fact that materials of the 25 the Parapoid1l0 in the‘extractor. The‘liquidal
Parapoid ‘type containing only relatively‘ small
cohol then percolated‘ upward through the ~oil
quantities of sulfur have even better extreme pres-'
sure properties, as measured by the, S. A. E. test~
ing machine, than the original unextracted mavterial. It was hitherto believed that in order ‘to 7m
and formed an extract phase ?oating ' above‘ the
ra?inate. The extract phase was siphoned con
tin'uously from the extractor through a linecon
taining a vapor trap to the reboiler. ‘In-the “re
function asan extreme pressure additive the ma-
boiler ' the ~ alcohol was ‘vaporized and 1' repeated
terial had to ‘have a, relatively high percentage
the cycle ‘while thel‘extract accumulated.
of sulfur in the molecule.
process-W'as-‘continued for-16 hours, at which time
a
‘
v
It is believed that the improvements in solu-
it appearedlto be‘fairly complete.
l
The
\
-
bility characteristics are due essentially to the 35 Extract-‘and ra?inate‘ were recovered by strip
removal of the heavy tarry material comprising
ping off the solvent under high vacuum over a
the“‘ra?inate.” It was found that this material
boiling water bath. “They are compared below‘
immediately precipitated not only from~Varsol
with the originalParapoid-JO.
‘
and Panhandle Bright‘Stock ‘but also ‘from less
highly re?ned petroleum oil fractions.
40
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I
‘Parapoid-IOH name marinate.
EXANIPLE 2 '
‘
742 grams of commercial Parapoid, referred to
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gins. retcovery ________________ _.',____'._.'___.
Per cent Sulfur“
6_ 5‘
_
‘
as crude extreme pressure agent ‘B, having the
er cen
__.__-_______ ._
£86
M
r
.‘5
' 32,0
I
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I
318
28.
13.
~21
INSl’ECTIONS ON {0% BLENDS IN ‘BANHANDLEV‘
BRIGHT STOCK
(7 S 84
=
-
Per cent c111orme_;__
following analyslsz
0
recovery"
.
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%
.
1
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V
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V
.ParaDoiddo’
‘Extract
‘ B’af?nate
was subjected to solvent fractionationbythe pro- 50 Soh‘1bimy{_.at ‘1o. Haze andshgh'té cléar and ?eavyéibud,
cedure of Example 1, except that 99 %. isopropyl
days.
sediment.
lagginnté I?) heavy?i'sed
H .
alcohol was used as solvent throughout.
1111811 .‘
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Copper strip at Slight stain_____ Slight stain. Heavy mm,
The data obtained are summarized in Table 2.
212° F.
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TABLE 2
Solvent extraction of Rarapoid-IO
;
EXAMPLE ,No. a
Analysis
'-
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7 ‘
Fraction
7
Extreme
-
-
Percent
-
Lyield!
-
Solubility
characteristics 10%
-
Percent
Percent
S
01
blend in Panhandle B. S.
“
ressure
p
.-
properties
.
1,“ ‘ I v
S_>A_,E_ A ~ ‘7 I v
number8 '
Original unextracted material... ________ ..
First extraction product ______ ..
11. 8
6 4
1 8
290
372
Second extraction product. _
Third extraction product_
Fourth extraction product
35.9
19. 6
7. 6
4 l
4 1
5 0
388
‘ 443
418
19. 7
16 0
Ra?inate ______________ __
.
34. 3 _.___d07 .................... __
25. 0
Precipitates out as a tar-..“ ____________ ._
1 These are weight yields based on the original uncxtracted Parapoid-IO.
9 10% blend of the particular fraction in Panhandle Bright Stock.
B This test is described in the S. A. E. Journal, volume 39, pages 23 to 24, [or the year 1936.
‘
.
As indicated above, even in this small-scale
laboratory continuous extraction, the extract was
EWLE 3
600 gms. of Parapoid-lO, containing 6.5% S
remarkably superior to the original crude extreme,
and 32% Cl, were placed in a tall vertical glass
pressure agent in regard to solubility and sta
cyllnder used as extractor and 1500 cc. of 98% 75 bility, while the ra?‘lnate'developed a heavy cloud
2,404,446’
and sediment in the solubility test and showed ' “were subjected to solvent fractionation by the
procedure of1Example 1, except that 91% iso
This type of continuous extraction'can' be fear-"f1, prqp'yl alcohol was used as solvent in the ?rst
ried outxon arcommercialr scale byusing a?large‘ "three extractions and 99% isopropyl alcohol in
vertical tower extractor, vwhich may contain _5':the"fourth' and ?fth. The data is summarize
excessive copper COI'I‘OSiOI'I.’
below-f
.
TABLE
v.
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'
Solvent .ertraction of Santapoid-A' '
,
’
Analysis
_
p
r_
Peréent
7
yield 1
Fraction
7
7
.
,
_
'
Perscent
sant?poid-A ____________________ -__;;_; ........ _.
9. 6
V
‘
p
,
;
2nd extraction product“...
'
16. 6
'
, 3rd; extraction product.
20. 4
116.0
4th extraction product.~__
. 42.3
‘5th extraction product-"
_
9. 0'
‘ -
Extreme
pressure
. properties
Percent, handle Bright Stock 2. S. A. E. No.
7: >31. 6
Oloudtandslight sedi-I _
men
7
~
tics 10% blend inPan-
‘
1st extraction product___'___
-'
_7S_olubihtycharacteris-
_
6. 7 , ,
33. f1
6. 9
35. 2
7.3V
.
.
340
-
.
Clearand no sediment;
'
380
do
365
'365
10. 57 v
365
‘11.9
_____do_..~. ____ _; _____ __
405 '
1‘These areweightkyields based on original unextracted Santapoid.
7 .
I. ..
; I
2710% by weight of'the particular fraction in Panhandle Bright Stock.
order'wto obtain better.v contacting 0f the up-goilng 25
7
i
’
, It is thus seen that by means Of the Present in- ‘
andrldown-going liquids, ,then feeding the crude
vention vit is possible to make extreme pressure
extreme ‘pressure agent into the-tower near the
additives which have a much better temperature
top thereof and feeding the alcohol in near the’
bottom of' the tower, continuously withdrawing
and storage stability, especially in the presence,
‘of metals, and also such pro-ducts having superior
the solvent extract phase at the top ‘and the ‘
extreme pressure lubricating characteristics, as
compared to the‘ originalor crude extreme pres
raf?nate at the bottom of thetower, continuously
’ passing the solvent'extract phase tpVa-reboiler or.
still from which the alcohol is continuously Va.
is withdrawn, the alcohol vapors being continu
ously'condensed‘ and recycled to the extraction
‘
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and spirit of the invention.
A commercial extreme pressure agent known ‘as
‘ Santapoid A gpreviously referred’ to above) is said 40
to be prepared as follows: 7
v
V ._
Isopropyl alcohol is heated with anhydrous so
dium hydroxide and then carbon disul?de jis
added to formiisopropyl xanthate.
i
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,
-
5
J
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ks
'7
'
“
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I
t
’
It is not intended thatthis invention be'limited
to the speci?crexam'ples which have been given" '
merely for the sake of illustration but only by
the appended claim in which it is intended to
claim all novelty inherent in the inventionas'
well as all-modi?cations coming within the scope
porized and 'fro-mjwhichthe solvent free extract
tower‘.
sure additives.
.
We claim:
'
1
' '
"
a
.
Process of preparing improved extreme pres;
sure lubricating agents, whichcomprises solvent
extracting a chlorinated para?in alkali poly
sul?de reaction product containing about’ 5 to
10% of sulphurand about 30 toT,4U% of chlorine
at about room temperature with isopropyl alco
hol of about 91% concentration, using about 1000
'
OaHr-ONa —|- CS2 —> CaH7-O-C-S-Na
Chlorinated ‘kerosene is then added in the.
proper _proportion and the mixture is re?uxed.
cc. of the alcohol per 1200 grams of material
Sodiumchloride 5 plits out and‘the‘Santapoid is 1 t
treated, separating the ra?inate phase from the
‘extract phase, subjecting the ra?inate phase to
formed.
three successive extractions at room tempera
,
ture with isopropyl alcoholof about 99% concene
tration,‘ using about the same volume of solvent
i a : ----.
_'
QaH7-—O—‘O—SENa + O1!—Ker0——(Cl)4'——-->
| _________ ...,
.
S
as in the ?rst extraction phase, extracting the
V
‘ 55 fourth raf?nate at about 125° F. with isopropyl
.
I
v
¢
7
,1
C aHr-O-C-S-Kero (O1)l
585 gms. of this commercial Santapoid-A hav
ing the following analysiszniu V J
% 's.=”9;6
% Cl-V=_'31‘.‘6~
:
‘alcohol of about 99%" concentration, and recov
eri'ngthe "solvent from each of the extract phases
and from the ?nal raf?nate phase.
EUGENE LIEBER.
'7 '
‘ALOYSIUS F. CASHMAN.
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