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Патент USA US2403792

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Patented July 9, 1946
2,403,792
UNITED * STATES PATENT" OFFICE
2,403,792
DI-PHOSPHORUS ESTERS AND PROCESS ‘
OF MANUFACTURING
Ernest F. Engelke, Merchantville, N. J ., assignor
to Cities Service Oil Company, New York, N. Y.,
a corporation of Pennsylvania
No Drawing. Application March 28, 1942,
'
v
'
Serial No. 43.6,623
6 Claims.
1
-
.
.
(Cl. 260——461)
.
This invention relates to’ improved organic di
phosphorus esters and to the process for their
'2 f
.
organic diphosphorus esters vtogetherwith their
e?ectiveness‘ as?lm strength agents or extreme
pressure lubricants, may be illustrated by refer
ence to'the follo'wingspeci?e examples in which
di-phosphorus 5 the quantities of materials aregiven in parts by
manufacture. More particularly», the invention
relates to the manufacture of extreme pressure
lubricants
containing " organic
esters.
'
'
a
_
1
weight‘.
Many types of extreme pressure agents have
‘
'
‘
,
'
Example
p
.
.
5'
1
,
_ been used in lubricating'oils and greases and in
A‘ tetra-cresyl ‘di-phosphorusl'ester was. pre
most cases such agents are relatively unstable
and contain constituentswhich may react'with 10 pared from dirpara'cresyl phosphorus acid mono- >
chloride, (CH3.C6H4.O)2PC1, by‘ dissolving approx
the metal surfaces and induce excessive sludge
imately 56 ‘parts of the latter'in about 100 parts
formation. Reactions of this type materially
of xylol and heating the resultingv solution in a
change the lubricant and gradually deplete its
reaction vessel equipped with a reflux condenser.
effective constituents. '
'
'
'
The heating was carried out by the use of an’ oil
' 'The primary object of the present invention
bath and thetemperature gradually raised to 200°
is to provide an improved extreme pressure lubri- '
F., at which time ?ve parts of metallic sodium~
was added to the, solution in small portions 'at-a
eating agent which is relatively stable and which
is especially e?ective in the lubrication of hypoid
time. The reaction was rather violent and sodi
gears and‘ other mechanisms in which high pres
sures are
involved.
.
’
'
'
um chloride crystals were deposited on’ the sides
~
and bottom of the reaction vessel.
Another object of the inventionis to provide
improved organic di-p‘hosphoru's esters suitable
for use as ?lm strength agents.
tinued ‘for about one-half hour, and the reaction
I
mass then cooled and ?ltered to remove the, 'so'di-i
A further object of the invention is to provide
um chloride.
an improved process for the manufacture of di
phosphorus organic esters.
'
In accordance with the features of the present "
The ?lter cake was Washed with
hot xylol, and added to the ?ltrate whichwas
'
invention the improved di-phosphorus organic
When the
reaction was ‘complete, the heating was con
washed with water untilneutral‘, and then-sub
, jected to distillation for the removal of the xylol.
The ?nal stageof the distillation was‘ conducted
ata reduced pressure in order to insure substan
esters may be made from the ordinary mono or
di-organic phosphites, phosphates, or thiophos
phates, more particularly the acid halides suchv
as the monochlorides.‘ In general, the improved
process includes the steps of reacting the organic
tially. complete removal of the xylol.
>
'
The resulting di-phosphorus ester was a straw
yellow-colored oilylliquid at room temperature.
Its effectiveness as a ?lm strength agent was
phosphorus acid chloride with metallic sodium or
its equivalent, at temperatures of from about 150° 30 tested on the Timken testing machine using
blends of 30 SAE Pennsylvania lubricating oil .
to about 225° F., the temperature being adapted to
containing 0.5%, 1.0% and 1.5% of the agent.
effect elimination of the chlorine as sodium chlo
These blends ‘showed load-carrying capacities
ride and the direct combination of two molecules
of the acid chloride by a phosphorus-phosphorus
linkage.
'
The organic phosphorus esters used as starting
materials are preferably the mono- or dichlorides
of phosphorous acids, phosphoric acids, and thio
phosphoric acids, while the ?nal products may
be represented by the general formula:
40
respectively of 27,000; 30,800 and 32,000 lbs. per
square inch, ;while the lubricating oil alone car
ried only 15,750 lbs. per square inch. The use of
the above-mentioned ?lm strength agent in- the
. lubricating oil increased its pour'point by about
5° F. and increased the viscosity index ‘but made
very little change in the viscosity of the oil.
Example 2'
' A phenol thiophosphate,
(061150) 2SP-PS (00.11.).
-The compounds, in which the‘ phosphorus is
50 was prepared by reacting 62.5 parts of
linked to phosphorus with a double linkage, are
(C6H5Q)2PSC1
made from the dichlorides such for example as
dissolved in xylol, with sodium, 25% in excess
(RX) P012. In the above general formula, X
of that theoretically required to remove the chlo
stands for oxygen or sulfur, and the (RX) ‘groups 55 rine. The reaction was carried out substantially
represent ester groups directly attached to phos
in the‘ manner described in Example 1, but the
phorus through X. In the above formula'R rep
temperature rose to 240° to 250° F. after a por
resents aliphatic, aromatic, or aralkyl radicals,
either of Which-may be halogenated.
tion of the sodium had been added.
.
The ?nal reaction mixture was cooled to room
The method of manufacturing the improved 60 temperature, ‘filtered to remove the sodium chlo
2,403,792
3
4
It isIt'o be understood that while the invention
ride, and? then washed with water untiln'eutral'.
has been- described andv illustrated» in connection
The resulting washed ?ltrate was dried and then
distilled to remove the xylol. Portions of the
finished product were blended with 20 SAE Penn
with the use of the improved compounds as ex
treme pressure agents in lubricating oils, such
compounds aregsuitable for other purposes as for
example in the making of cutting oils, greases,
and for blending with fatty oils, synthetic oils
sylvania lubricating oil to make blends containe
ing 0.5%, 1.0% and 1.5%. These blends when
tested on the Timken testing machine showed
load-carrying capacities of‘2'7,900; 32,0G0'and‘ 29>,- ’
. and esters, to produce various types of lubricants.
‘ It‘ is to be further understood that the improved
800 lbs. per square inch; whereas the oil alone
had a load-carrying capacity of only 12,380’ lbs.
compounds may be used directly as lubricants.
Certain subject-matter originally claimed in
per square inch.
thisv application is now claimed in divisional ap
Example 3
A mixture of di-phosphorus esters containing
single and double linkages
plication Serial No. 469,125, ?led December 15,
I 42.
Having thus described the invention in its pre
vferred form, What is claimed as new is:
(CI-IsCsl-RD) SP=PS(O.C6H4.CI~I3)
'1. The process of manufacturing organic di
phosphorus esters comprising'the steps of re
V (CH3.C6H4.0) 2SP-—PS(O.CGI{4.CHS) a
acting an organic‘ phosphorus ester chloride in
vwas prepared. by reacting 130 parts of.‘ a mixture 20 which a hydrocarbon-oxy group and a chlorine
of thiophosphoric acid cresyl ester mono and di
atom are linked to a phosphorus atom with a
metal adapted to effect a Wurtz-Fittig reaction
chlorides with metallic sodium, 10% in excess oi‘
at a temperature‘ of from l50°jto 225° F., sepa
that theoretically required to remove the chlorine
rating the resulting‘ organic all-phosphorus ester
from the chlorides. The initial mixture was dis
.solvedinxylol and reacted with the‘ sodium under
the‘conditions described in Example No. 2. After
from the metal chloride formed in the reaction,
and‘ recovering the organic di-phosp'horus ester.
2. The process of‘ manufacturing organic di
‘the-r product was recovered and washed as in Ex
ample 2, portions of it were blended with 20‘ SAL‘.
spectively, of- 19,350; asses; and 24,390, while
pho-sphorus esters in which a phosphorus atom
is directly linked to a phosphorus atom, which
comprises dissolving an organic phosphorus hal
ide ester“ in which a hydrocarbon-0x3" group and
a; halogen atom are‘ linked to a phosphorus atom
theIPennsylvania lu' ricating oil alone had a load
in an inert solvent, heating thev resulting solu
Pennsylvania lubricating oil to produce blends
‘containing 0.5%, 1.0% and 1.5% of the mixture.
These’ blends showed load-carrying capacities re
carr'ying'capacity of only 12,350.
While in the'f-oregoing‘ examples ‘sodium was
35
used to effect the P-—P linkage, it is believed that
tion‘to a temperature of approximately‘ 200°‘ F.,
slowly adding metallic sodium to the‘ heated mix‘
ture until an excess has been added for the re
lithium, potassium and ?nely divided silver, cop
per and zinclmaybe employed at least in certain.
reactions, as is true in the warez-Fang synthesis.
Organic phosphorus chlorides were used in the
operations described in the examples primarily
moval‘ of halogen from said ester‘, removing the
resulting sodium halide, neutralizing the remain
ingr'eaction mixture, removing the solvent, and
40 recovering the dl-DhOSphOI‘Ll-s organic ester.
3. The process of making (ii-phosphorus esters,
for economic reasons, but it is possible to’ use
which comprises reacting an organic phosphorus
‘other organic phosphorus halogen compounds
ester chloride in which a hydrocarbon-oxy
‘especially the iodides and bromides. While it is
group and a chlorine atom are linked to a phos
believed that the reactions described in connec
phorus atom at a temperature of about 200° F.
tion with the foregoing examples proceed. mainly
with metallic sodium to thereby effect the re
to ‘produce the products indicated, it is possible
moval' of the chlorine from the ester and join the
that minor proportions of other materials are
formed, as for example, a compound in which two
phosphorus atoms are linked to a third may be -.
produced where mixtures of mono- and di-chlo'~
rides are used as starting materials.
'
The examples are given above for the purpose
of illustrating the invention, and it is to be un
derstood that R in the general formula may rep
resent an aromatic or aliphatic radical or com
pound and that either of these may be halogenat
ed or contain other elements such as oxygen or
phosphorus atom of one ester molecule with that
of another ester molecule to produce di-phospho
rus esters having an organo-oxy group attached
to each phosphorus atom, and separating the
resulting di-phosphorus ester from the resulting
sodium chloride.
4. The process of making a di-phosphorus
cresyl ester, which comprises reacting a cresyl
ester of phosphoruscontaining a chlorine atom
attached. to the phosphorus atom of the ester
with metallic sodium at a temperature of about
sulfur. , Where the ester chloride starting ma
200° F., thereby effecting the removal of chlo
60
terials contain aliphatic radicals as R the hydro
rine and the production of a (ii-phosphorus ester
carbon chain may be straight or branched.
in which a phosphorus‘ atom- is directly linked to
Where two (RX) groups are attached to a single
a phosphorus atom and in which a cresyl group
phosporus one R may be aliphatic and the other
is linked to each. phosphorus atom, and separat
aromatic. The di-phosphorus esters, in which
ing the resulting. (ii-phosphorus ester from the
65
phosphorus has a valence of 5, may be produced
sodium chlorideproduced in the reaction.
by oxidizing or sulfurizing the di-phosphorus es
_' 5. A (ii-phosphorus ester having thev formula
ters in which phosphorus has a valence of 3.
_(RO)2P—P(OR)2 in which R is a radica1 select
Such compounds of course may be produced, as
ed from the group consisting of alkyl, aryl and
shown in theexamples, by starting with the es
alkaryl radicals.
ter halide in which phosphorus has a valence‘ of
6. A tetra-cresyl (ii-phosphorus ester having
5, .as. for example (RO)2PXC1 or (RO)PXClz
the
formula: (CH3.C6H4.0) 2P—-P(O-C6H4.CH3) 2.
where X is oxygen or sulfur directly attached to
ERNEST F. ENGELKE.
phosphorus with a double bond.
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