Note: Descriptions are shown in the official language in which they were submitted.
Case EI-6349+
2~7~131
ORGANIC PHOSPHATES AND THEIR USE_AS WEAR INHIBITORS
This inven~ion relates to novel organic phosphate ester
combinations and their preparation, combinations which are
particularly useful as wear inhibitors in fuels, lubricants
and functional fluids.
A need exists for ashless (i.e., metal-free) wear inhi-
bitors for use in lubricating oils and oil-based functional
fluids subjected to high temperatures during actual service
conditions.
This need is particularly acute in the case of syn-
thetic diester-based lubricants for use as gas turbine
lubricants. A need also exists for ashless wear inhibitors
for use in middle distillate fuels such as diesel fuels, jet
fuels and turbine fuels.
This invention provides, in one of its embodiments, a
combination of aryl phosphates deemed suitable for use in
fulfilling the aforesaid needs. The combination is composed
of (i) at least one fuel- and/or oil-soluble aryl phosphate
of the formula
(RO)3P~
wherein each R is, independently, phenyl or an alkyl-substi-
tuted phenyl group; and (ii) at least one fuel- and/or oil-
soluble aryl polyphosphate of the formula
O O
ll ll
RO-[-P-O-Ar-~-] n P ( OR; z
OR
wherein each R is, independently, phenyl or an alkyl-
substituted phenyl group, Ar is m-phenylene or an alkyl-
substituted m-phenylene group, and n is a wh~le or number
from 1 to 4; said combination containing from 2 to 30% by
weight of component (i). When the above formula represents
a mixture of the depicted polyphosphates, n is a whole or
fractional number from 1 to 4, as n represents the average
composition of the mixture.
Among the advantages of these combinations is the
ease with which they can be formed pursuant to another em-
bodiment of this invention. In particular, the foregoing
Case EI-6349~
2~7~13~
-- 2
combinations can be formed by a process which comprises (a)
reacting from about 1.9 to about 2.1 equlvalents of phenol
and/or alkyl-substituted phenol with one equivalent of phos-
phoryl trihalide in the presence of a Lewis acid catalyst,
and (b) reacting the intermediate product formed in (a) with
from about 0.9 to about 1.1 equivalents of resorcinol and/or
alkyl-substituted resorcinol per equivalent of phosphoryl
trihalide employed in (a) again in the presence of a Lewis
acid catalyst. Although other modes of addition can be
used, it is preferable in (a) to add the phenol and/or al-
kyl-substituted phenol to the phosphoryl trihalide, and in
(b) to add the resorcinol and/or alkyl-substituted resorci-
nol to the intermediate product formed in (a). Non-limiting
examples of suitable Lewis acid catalysts include AlCl3,
AlBr3, FeCl3, FeBr3, BCl3, PCls, and MgCl2. In an alternate
process, the Lewis acid catalyst is replaced by a stoichio-
metric amount of a hydrogen halide acceptor and a solvent is
used. In step (a) a solution of phenol and/or an alkyl-sub-
stituted phenol and hydrogen halide acceptor is added to a
solution of the phosphoryl trihalide, and in step (b) a so-
lution of resorcinol and/or an alkyl-substituted resorcinol
and hydrogen halide acceptor is added to the intermediate
product formed in step (a).
In still another embodiment, the foregoing combina-
tions are ~oxmed by a process which comprises (a) reacting
from about 0.9 to about l.1 equivalents of resorcinol and/or
alkyl-substituted res~rcinol with one equivalent of phospho-
ryl trihalide in the presence of a Lewis acid catalyst, and
(b) reacting the intermediate product formed in (a) with
from about 1.9 to about 2.1 equivalents of phenol and/or
alkyl-substituted phenol per equivalent of phosphoryl tri-
halide employed in (a) again in the presence of a Lewis acid
catalyst. Although other modes of addition can be used, it
is preferable in (a) and in (b) to add the resorcinolic and
the phenolic reactants to the phosphoryl trihalide and to
the reaction mixture formed in (a), respectively. In an
alternate process, the Lewis acid catalyst is replaced by a
stoichiometric amount of a hydrogen halide acceptor and a
Case EI-6349+
~ 3 ~ 2~70131
solvent is used. In step (a) a solution of resorcinol and/
or an alkyl-substituted resorcinol and hydrogen halide ac-
ceptor is added to a solution of the phosphoryl trihalide,
and in step (b) a solution of phenol and/or an alkyl-substi-
tuted phenol and hydrogen halide acceptor is added to theintermediate product for~ed in step (a).
In each of the above processes, it is preferred to
employ the reactants in proportions such that there are at
least 3.1 equivalents of ar-hydroxy groups (phenolic reac-
tant plus resorcinolic reactant) per equivalent of phosphor-
yl trihalide used.
Lubricant compositions which comprisa a major pro-
portion of oil of lubricating viscosity -- preferably a
diester-based lubricating oil, i.e., a lubricating oil
composed predominantly or entirely of one or more diester
lubricating oils -- containing and a minor wear-inhibiting
amount of a combination of phosphate esters (i) and ~ii) as
described hereinabove, form the subject of another embodi-
ment of this invention.
Another embodiment is middle distillate fuel compo-
sitions which comprise a major proportion of a hydrocarbon-
aceous middle distillate fuel and a minor wear-inhibiting
amount of a combination of phosphate esters (i) and (ii) as
described hereinabove.
In the various embodiments referred to above, most
preferably each R is phenyl and Ar is m-phenylene. Like-
wise, it is preferred that at least 50% by weight of the
aryl polyphosphate correspond~ to the above formula of com-
ponent (ii) wherein n is 1. Particularly preferred are (1)
compositions wherein each R is phenyl and at least 50% by
weight of the aryl polyphosphate is m-phenylenebis(diphenyl
phosphate), and (2) compositions wherein at least 60~ by
weight of the combination of phosphate esters is a combi-
nation of m-phenylenebis(diphenyl phosphate) and triphenyl
phosphate in a weight ratio of 1 to 35 parts o~ m-phenylene-
bis(diphenyl phosphate) per each part by weight of triphenyl
phosphate.
The above and other embodiments of this invention
Case EI-6349~ 207~131
will be still further apparent from the ensuing description
and appended claims.
In forming the combination of aryl phosphates, use
can be made of phenol and/or one or more alkyl phenols which
contain from 1 to 5 alkyl groups on the ring. Each such
alkyl group can contain up to about 18 carbon atoms with the
proviso that the alkyl substituent(s) should not sterically
hinder the hydroxyl group to such an extent that the substi-
tuted phenol is incapable of reacting with the phosphoryl
trihalide. Examples of suitable alkyl phenols include o-,
m~ and/or p-cresol; 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, and/or
3,5-xylenol; o-, m-, and p-ethylphenol; p-tert-butylphenol;
p-tert-amylphenol; p-(1,1,3,3-tetramethylbutyl)phenol; p-
nonylphenol; p-decylphenol; 2,4,5-trimethylphenol; 2,3,4,5-
tetramethylphenol; pentamethylphenol, etc. Cycloalkylphe-
nols such as p-cyclohexylphenol can also be used. Mixtures
of two or more different phenols are also suitable.
The phosphoryl trihalide used in forming the phos-
phate combinations is preferably phosphoryl trichloride, but
other halides such as the tribromide can be used.
Resorcinol is the preferred dihydroxybenzene reac-
tant used in forming the phosphate combinations. However
alkyl-substituted resorcinols can be used again with the
proviso that the compounds are not so sterically hindered as
to be unable to undergo reaction on both hydroxyl groups
with the intermediate formed from the reaction between the
monohydric phenol and phosphoryl trihalide.
A few examples of alkyl-substituted resorcinols that
can be used include 5-alkyl-1,3-dihydroxybenzenes where the
alkyl group has 1 to about 18 carbon atoms; 2-methyl 1,3-di-
hydroxylbenzene;4-methyl-1,3-dihydroxylbenzene;4,5-dimeth-
yl-1,3-dihydroxybenzene; and the like.
The reactions of (a) and (b) above are usually con-
ducted at temperatures in the range of absut 30C to about
200C. It is desirable and most economical to conduct these
reactions without a solvent and in the presence of a ~ataly-
tic amount of a Lewis acid. However, a suitable inert liq-
uid solvent such as toluene, xylene, aromatic naphtha, or
Case EI-6349-~ 2070131
the like can be used.
The amount of catalyst used is typically between 0.1
wt % and 10 wt % based upon the amount of phosphoryl triha-
lide. More preferred is 0.5 wt % to 5.0 wt % and most pre-
ferred is 0.75 wt % to 2.00 wt ~.
In place of the Lewis acid catalyst, an at least
stoichiometric amount of a hydrogen halide acceptor can be
used. Hydrogen halide acceptors which are preferably used
in the reactions of (a) and (b) above are typified by
tertiary amines such as pyridine, pyrimidine, pyrazine,
triethylamine, tributylamine, and triphenylamine. Other
known hydrogen halide acceptors are usable, however. It is
most desirable to use an inert solvent for the reactions
involving hydrogen halide acceptors in order to facilitate
handling of the solid hydrohalide by~product. Suitable
solvents are toluene, xylene, aromatic naphtha, or the like.
The following examples illustrate various phosphate
combinations of this invention, and methods which can be
used for their synthesis.
EXAMPLE 1
A 912.87 g (9.70 mole) portion of phenol (Aldrich,
redistilled) and a 766.65 g (5.00 mole) portion of POC13
(Aldrich, 99%) were weighed into a dry, four-necked 5-L
flask in a glove box. The flask was then set up in a hood
with a mechanical paddle stirrer, a thermometer, a glycol-
cooled Friedrich condenser, an oil bath, and a rubber septum
addition port. Exit gases from the condenser were passed
through a trap and into an aqueous NaOH scrubber solution
located on a balance. A slow nitrogen purge was maintained
into the contents of the flask by a Teflon tube inserted
through the rubber septum addition port.
The brownish-gold solution was warmed to 33C by the oil
bath, and 15.42 g (2.01 wt % based on POCl3) of AlCl3
(Aldrich) catalyst was cautiously added. The solution was
slowly heated to 116C over a seven hour period while 344.9
g of HC1 (97.5~ of theory) collected in the exit gas
scrubber. The solution was then cooled to room temperature,
Case EI-6349+ 2fJ70131
-- 6
and a 291.79 g (2.65 mole) portion of resorcinol (Aldrich,
recrystallized~ was added (in a ylove box). The reddish-
purple mixture was then slowly heated to 170C over a five
and one-half hour period while 172.1 g of HCl (89.1% of
theory) collected in the scrubber.
The viscous golden-yellow crude product was
dissolved in toluene t2544.5 g), and the solution was shaken
with 10 wt % aqueous NaOH (2x1000 g) and then tap water
(3x1000 g) to obtain 3840.4 g of cloudy colorless organic
phase. The solution was then dried over 125 g of anhydrous
MgS04. The liquid was decanted from the drying agent and
passed through a bed (28 mm O.D. by 364 mm length) of 101.0
g activated silica gel (Aldrich, 70~230 mesh, 500 M2~g, wet
packed using toluene). The eluate was then stripped on a
15 rotary evaporator (95C/0.1 torr) to obtain 1242.7 g (87.2~
yield) of a slightly hazy, pale yellow fluid. This liquid
was pumped through a 10-micron Teflon membrane filter to
obtain 1227.67 g of a clear pale yellow product, properties
of which are summarized in Table I hereinafter.
EXAMPLE 2
A 77.24 g (0.5037 mol~) portion of POCl3 (Aldrich)
and 148.6 g toluene were weighed into a 1-L four-necked
flask in a glove box. The flask was set-up in a hood and
equipped with a paddle stirrer, thermometer, 500-mL addition
funnel, and a glycol-cooled Friedrich condenser attached to
a nitrogen bubbler. The flask was cooled with an ice bath
while a solution of 90.07 g (0.957 mole) phenol (Aldrich,
redistilled), 99.64 g (0.986 mole) triethylamine (TEA,
Aldrich), and 101.94 g toluene was added from the additional
funnel in 2.5 hr at 3-15C. After stirring for 15 minutes
at 7-15C, a hot (70-90C) clear blue solution of 30.51 g
(0.277 mole) resorcinol (Aldrich, recrystallized~ in 118.19
g (1.170 mole) TEA was pressured into the reaction flask
through a stainless steel transfer needle from a capped
bottle in 13 minutes at 15-29C. The reaction mixture was
stirred for 2.2 hr at 23-32C, and then 202.7 g of 5 wt ~
aqueous HCl was added follow d by 39.6 g concentrated
hydrochloric acid. The mixture was transferred to a
Case EI-6349~ 2070131
separatory funnel, and the lower hazy yellow aqueous layer
(514.8 g, pH 1-2) was removed. After washing with water
(3x225 g), the cloudy organic phase (513.6 g) was dried over
10.1 g anhydrous magnesium sulfate. Upon standing for 16
hr, the addition of 6.8 g of activated silica gel (Aldrich,
70-230 mesh, 500 m2/g) immediately reduced the color of the
yellow liquid. The mixture was gravity filtered through
paper, and the pale-yellow filtrate as stripped on a rotary
evaporator (100C/1 torr) to obtain 131.3 g (92% yield) of
hazy light-yellow fluid. A clear liquid was obtained after
pumping the product through a 10-micron membrane filter.
Table I, presented hereinafter, summarizes the properties of
this product.
EXAMPLE 3
This experiment was conducted as described in Exam-
ple 1. A 184.46 g (1.960 mole) portion of phenol was com-
bined with 153.33 g (1.000 mole) of POCl3 in a 500-mL four
necked-flask. The pale-yellow solution was warmed to 38C,
and 3.075 g (2.0 wt ~ based on POCl3) of MgCl2 was added, the
pale-orange solution was then 510wly heated with an electric
mantle for 8.0 hr to a final temperature of 150C. The cau-
stic scrubber for the exit gases from the reaction increased
ih weight by 65.1 g (91% theory for HCl). The reaction
flask was transferred to a glove box where 57.26 g (0.520
mole) of white resorcinol (Aldrich, recrystalliz~d) was
added. The mixture was then slowly heated over three and
one-half hours to a final temperature of 140C with the
subsequent incr~ase in the exit gas scrubber weight of 32.7
g (86.2% of theory for HCl). The dark brown viscous liquid
(287.33 g) was dissolved in 557.29 g toluene and washed in
a 2-L ssparatory funnel with 5.2 wt % aqueous NaOH (2x250
g~. The organic phase was then washed with tap water (3x275
g) until the recovered aqueous phase reached a pH of 7. The
cloudy organic phase was dried over anhydrous magnesium
sulfate (30.46 g). The mixture was then gravity filtered
through paper, and the clear, nearly colorless filtrate was
stripped of solvent on a rotary evaporator (0.1 torr/90~C)
to obtain 202.2 g (70.8~ yield) of a slightly hazy pale-
Case EI-6349+ - 8 - 2070131
yellow fluid. The liquid was pumped through a 10-micron
Teflon membrane filter to obtain 193.36 g of a clear pale-
yellow product. Properties of this sample are summarized in
Table I below.
EXAMPLE 4
A 376.44 g (4.00 mole) portion of phenol is combined
with 306.66 g (2.00 mole) of POCl3 in a l-L four necked flask
in a glove box. The light-orange solution is warmed to 40OC
and 2.993 g (1.0 wt % based on POCl3) of pyridine (Baker) is
added. The solution is heated with an electric mantle until
gas evolution stops (llo0 hr/145C). The exit gas scrubber
shows a weight increase of 139.8 g (95.9~ of theory for
HCl).
A 114.51 g (1.04 mole) portion of resorcinol is
added to the light-yellow reaction mixture in a glove box.
The solution is heated to 30~C and 3.062 g (1.0 wt % based
on POCl3) of magnesium chloride is added. The rusty-brown
solution is heated until gas evolution stops (7.0 hr/149C).
The subsequent increase in the exit gas scrubber is 64.0 g
(84% of theory for HCl). The light-yellow viscous liquid is
dissolved in 1070 g toluene. The solution is washed in a 4-L
separatory funnel with dilute (2.8 wt %) aqueous NaOH (2x290
g) and then water (3x400 g). The cloudy organic phase is
gravity filtered through paper to obtain a clear colorless
filtrate. The filtrate is stripped on the rotary evaporator
(0.1 torr/95C) to obtain 484.8 g ~84.4~ yield) of pale
yellow cloudy liquid~ The li~uid is pumped through a 10-
micron Teflon membrane filter to obtain 472.5 g of clear
product. Properties of this sample are given in Table I.
EXAMPLE 5
A 188.56 g (2.00 moles) portion of phenol (Aldrich,
redistilled) was combined with 153.35 (1.00 mole) of POCl3
(Aldrich) in a 500-mL four-necked flask. The clear light-
brown solution was warmed to 35C, and 3.039 g (1.98 wt %
based on POCl3) of aluminum chloride (Aldrich) was a~ded. A
small exotherm increased the temperature to 42C as HCl
evolution began. The clear red solution was then slowly
heated with an electric mantle for 5 hours to a final tem-
Case EI-6349~ 2 ~ 7 ~
_ 9
perature of 109~C. The caustic scrubber for the exit gases
from the reaction increased in weight by 70.4 g (96.5% of
theory for HCl). The reaction flask was transferred to a
glove box where 55.04 g (0.500 mole) of resorcinol (Aldrich,
recrystallized) was added. The mixture was then slowly
heated over 7 hours to a final temperature of 158C with the
subsequent increase in the exit gas scrubber weight of 33.8
g (92.7% of theory for HCl). The light-orange viscous
liguid (289.0 g) was dissolved in 467.8 g toluene and washed
in a 2-L separatory funnel with 10 wt % aqueous NaOH (2x200
g). The cloudy organic phase was then washed with tap water
(4x200g) until the recovered aqueous phase reached a pH of
6.5. The cloudy organic phase was dried over anhydrous mag-
nesium sulfate (11.5 g). The mixture was then gravity fil-
tered through paper, and the clear, nearly colorless fil-
trate was stripped of solvent on a rotary evaporator (0.1
torr/90C) to obtain 252.7 g (87.9~ yield) of a slightly
hazy pale-yellow fluid. The liquid was pumped through a 10-
micron Teflon membrane filter to obtain 241.6 of clear pale-
yellow product. The properties of this product aresummarized in Table I.
case EI-6349+ 2070131
-- 10 --
T~BLE I
Properties ~ x. 1 IEX. 2 ¦EX. 3 ¦EX. 4 ¦EX. 5
. ~ I _
¦Composition (HPLC wt%) .
l Triphenyl phospha-te 12.6 2.3 11.0 11.9 14.7 11
¦ Diphosphate _ 57.278.1 66.0 65.8 63.~ Il
IAPHA Color50-60 300150 60 60 1¦
¦Viscosity ae 25-C, cp 425_ 551 397 326 3~5
¦ Density at 25'C, g/mL 1.293 1.297 1.292 1.288 1.288 ~¦
Acid Number, mg KOH/g 0 17 0.98 0.46 0.75 0 09
I _
o L Ionic Cl, ppm _~ _0 5 _12 _ 1.5 < 1.0
EXAMPLE 6
This experiment was carried out as described in Ex-
ample 1. A 384.6 g ~1.75 mole) portion of nonylphenol wascombined with 137.94 g (0.8996 mole~ POCl3 in a 1-L four-
necked flask. A 2.78 g (0.0208 mole) portion of AlCl3 was
added to the mixture at 29 D C, and the mixture was heated to
118C over 3 hr. After cooling to room temperature, a 52.5
g (0.477 mole) portion of resorcinol was added to the reac-
tion mixture. The reaction was completed by heating to
170C in 2.5 hr. After cooling to 45C, toluene (433.4 g)
was added, and the solution was washed with 10 wt % aqueous
NaOH (200 g) and twice with water. To obtain good phase
separation for the last wash, the pH had to be adjusted to
10 with addition of aqueous NaOH. The organic phase was
dried over anhydrous MgSO4 (25.7 g), gravity filtered through
paper, and the filtrate stripped on a ro~ary evaporator (0.1
torr/100~C) to obtain 458.0 g (96.1% yield) of pale-yellow0 oil. Properties are summarized in Table II below.
EXAMPLE 7
Example 6 was repeated replacing the nonylphenol
with a mixture of phenol (91.30 g, 0.970 mole) and
nonylphenol ~213.75 g, 0.970 mole). A 153.3~ g (1.00 mole)
portion of POCl3, 58.36 g (0.530 mole) resorcinol and 3.130
g (0.023 mole) AlCl3 were used. The pale-yellow liquid
Case EI-6349+ 2 0 7 01 31
-- 11 --
product weighed 379.3 (93.1 % yield). Table II sets forth
physical properties of this product.
EXAMPLE 8
A 55.1 g (0.50 mole) portion of resorcinol (MCB,
recrystallized, 99.93 area % by GC) was weighed into a dry
four-necked l-L flask in a glove box. The flask was then
set-up in a hood with a mechanical paddle stirrer, a
thermometer, a rubber septum addition port, and a Friedrich
water condenser. Exit gases from the condenser were passed
through a dry glass trap and into an aqueous NaOH scrubber
solution located on a balance. A slow nitrogen flow was
maintained on the exit gas line during the reaction to
prevent back-up of the scrubber solution.
A 153.3 g (1.00 mole, 93 ml) portion of POC13
(Aldrich, 99~) was added to the flask by nitrogen pressure
from a septum capped bottle using a stainless steel transfer
needle. The easily stirred slurry was heated to 113C with
less than 0.3 g of HCl being collected in the exit gas
scrubber. After cooling to 40C, a 1.493 g (0.0112 mole)
portion of anhydrous AlCl3 (Aldrich) catalyst was added to
the purple-brown liquid. The sol~ltion was slowly heated to
110~C in 90 minutes while 37.5 g of HCl collected in the
exit gas scrubber. The yellow-brown mixture was cooled to
63C and a 194.2 g (2.064 mole) portion of phenol (Aldrich,
redistilled) was added in 15 min. The solution was heated
to 155C in 2 hr while an additional 66.0 g (94.6% of theory
for HCl~ of HCl was collected in the scrubber. Addition of
another 0 93 g (0.0070 mole) AlCl3 at 120-129C did not cause
release of additional HCl.
The viscous yellow-brown crude product (293.4 g) was
dissolved in toluene (446.7 g), and the solution was washed
with 5 wt % aqueous NaOH (3x200 g) and water (2x230 g).
The cloudy pale-yellow organic phase (722.2 g) was
dried over 15.17 g of anhydrous magnesium sulfate. The
mixture was gravity filtered through paper (What~an 2V), and
the clear filtrate was stripped on a rotary ~vaporator
(95C/0.1 torr) to obtain 260.1 g (90.5~ yield) of a
slightly hazy, viscous, light-yellow liquid. The liquid was
Case EI-6349+ 2070131
- 12 -
pumped through a 10 micron Teflon membrane filter to remove
the hazy appearance. Properties of this product are
summarized in Table II below.
EXAMPLE 9
Example 8 was repeated using the same reagents but
with a higher level of resorcinol. Phosphoryl chloride
(153.5 g, 1.001 mole) was added to resorcinol (66.15 g,
0.6008 mole) at 25C in 5 minutes. The temperature dropped
to 20C, and there was no evidence of HCl evolution from the
easily stirred slurry. A 1.561 g (0.0117 mole) portion of
anhydrous AlC13 was added, and the mixture was warmed gently
with an electric mantle. At 30C, HCl evolution began
slowly and nearly all solids had dissolved in the red-brown
liquid. Gas evolution continued at 60-80C for 1 hr. A
weight increase of 44.0 g was recorded for the exit gas
scrubber, and the solution color changed to yellow-brown.
Liquid phenol (193.2 g, 2.053 mole) was then added 5 minutes
at 70-77C. The mixture was held at 72-78C for 2.5 hr
during which the scrubber weight increase rose to 99.0 g
(90% of theory for HCl). The solution was then heated to
122C in 2 hr with the scrubber weight gain reaching a
constant value of 103.5 g ~94.5% of theory). The clear
orange liquid was sparged with nitrogen overnight at ambient
temperature. A solution of the crude product (299.5 g) in
toluene (449.4 g) was washed with 10 wt ~ aqueous NaO~
(4x200 g) and then deionized water (3x300 g) to obtain 697.9
g of a cloudy colorless organic phase. The solution was
dried over 16.3 anhydrous MgSO4, gravity filtered through
paper, and stripped on a rotary evaporator to obtain 238.1
g (84.8~ yield) of a slightly hazy, nearly colorless viscous
liquid. The liquid was pumped through a 10 micron Teflon
membrane filter to remove the hazy appearance.
Properties of the products formed in Examples 6-9
are summarized in Table II.
Case EI-6349+ 2~70~31
- 13 -
TABLE II
Propertles ¦ Ex. 6 j Ex. ' ¦ Ex. 8 ¦ Ex. 9
, _ __ ; . - ~r~-
¦Composition (HPLC wt~)
Triphenyl phosphate __ __ 1 17.4 9.2
Diphosphate __ __ 24.6 22.4
APHA Color __ __ 100 100-200
. . . _ .
Viscosity at 25-C, cp 111,40010,350 488 1270
Density at 25'C, g/mL 1.051 1.129 1.296 1.312
Acid Number, mg KOH/g O.10 O.07 O.41 O.07
Ionlc Cl, ppm ........ ~.1, 27~ 330< 40 ~ 97
The excellent thermal stability of the products of
this invention was illustrated by a series of thermogravi-
metric analyses in which weight loss of various phosphorus-
containing materials was determined in the range of up to
600C. Subjected to this test were the phosphate combina-
tion produced as in Example 1 and the phosphate combination
produced as in Example 6. For comparative purposes TGA
analyses were also conducted on samples of tri~n-octyl
phosphate (TOP), tricresyl phosphate (TCP~, tri-n-butoxy-
ethyl phosphate (TBEP), and cresyl diphenyl phosphate (CDP).
The results of these determinations are summarized in the
following table:
Case EI-6349~ 2 0 ~ O 131
14 -
TABLE III - TGA. % LOSS
TemPerature, C
Phosphorus
Compound _ 100200 300 350400 500 600
Example 1 0.01.315.8 39.0 77.8 97.4 98.8
Example 6 0.00.6 4.8 8.420.281.5 --
Example 7 0.00.6 4.3 -- 23.992.9 --
TOP 0.0 3.398.3 -- 98.7 -- -~
TCP 0.0 1.276.3 -- 99.1 -- --
TBEP 0.5 2.496.5 -- 97.1 -- --
CDP 0.0 1.488.0 -- 99.5 99.6 --
The antiwear properties of the phosphate combina-
tions of this invention, are illustrated by the results
obtained in a series of standard tests known as the ball on
cylinder lubricity evaluation test. The test procedure is
ASTM D 5001-90. In these tests scar diameter measurements
are taken, and thus the smaller the scar diameter, the more
e~fective the additive composition as regards wear inhi-
bition. For convenience, the results are herein expressed
in numerical values representing the scar diameter in milli-
~eters multiplied by 100.
In a first series of tests the aryl phosphate combi-
nation formed as in Example S was blended into a commer-
cially-available jet fuel at a concentration of 25 pounds
per thousand barrels (ptb). This blended fuel was stored at
77F under ambient liyht conditions for two months prior to
conducting the lubricity test, to be sure that the fuel com-
position had good storage stability. The clear base fuel in
this test showed a scar diameter of 67 whereas the fuel con-
taining the phosphate combination of this invention exhibit-
ed a scar diameter of 44.
In another such test the base fuel had a scar dia-
meter of 60 whereas the presence therein of 80 parts per
million (ppm) of a combination formed as in Example 4
Case EI 6349+ 2070131
- 15 -
reduced the scar diameter to 40.
Another series of such lubricity tests were conduc-
ted wherein the base fuel was a commercial JP-4 jet fuel.
This fuel as received gave a scar diameter of 60. The pre-
sence in the fuel of an aryl phosphate combination producedas in Example 5 at the level of 25 ptb gave a scar diameter
of 46. It is interesting to note that the presence in the
same base fuel of comparable concentrations of tricresyl
phosphate, trioctyl phosphate, and tributoxyethyl phosphate
gave, respectively, scar diameters of 80, 80 and 83.
When the lubricity test was applied to a series of
fuels based on a low sulfur grade of commercially-available
diesel fuel, the following results were obtained:
Fuel composition Scar diameter
15 Base fuel 65
Base fuel + 25 ptb combination per Example 5 47
Base fuel + 25 ptb tricresyl phosphate 64
Base fuel + 25 ptb trioctyl phosphate 65
Base fuel + 25 ptb tributoxyethyl phosphate 66
Another series of lubricity tests was carried out
using commercially-available jet fuel. The test results are
tabulated below.
Fuel composition Scax diameter
Base fuel 68
25 Base fuel ~ 25 ptb combination per Example 5 56
Base fuel ~ 25 ptb tricresyl phosphate 67
Base fuel + 25 ptb trioctyl pho~phate 68
Base fuel + 25 ptb tributoxyethyl phosphate 72
A group of tests were conducted in which two dif-
ferent aryl phosphate combinations were blended into a com-
mercially-available jet fuel at several different concen-
tration levels. One such additive combination was produced
as in Example 5 and thus, referring to the formulas given
above, R was phenyl and Ar was m-phenylene. In the other
Case EI-6349+ 2 0 7 01 31
such additive combination, R was nonylphenyl and Ar was m-
phenylene. The results of these tests are presented below
wherein "Combination A" refers to the combination wherein R
was phenyl, and "Combination B" refers to the combination
wherein R was nonylphenyl:
Fuel composition Scar diameter
Base fuel 73
Base fuel + 80 ppm Combination A 39
Base fuel ~ 40 ppm Combination A 56
10 Base fuel ~ 20 ppm Combination A67
Base fuel + 10 ppm Combination A 69
Base fuel + 80 ppm Combination B 68
Base fuel + 40 ppm Combination B 67
Base fuel + 20 ppm Combination B 68
15 Rase fuel + 10 ppm Combination B Ç8
The phosphate combinations of this invention can be
used as antiwear agents in any middle distillate fuel suit-
able for use in the operation of a jet engine, a gas turbine
engine or a diesel engine. Such fuels are predominantly hy-
drocarbonaceous in composition and are typically character-
ized by boiling ~n the range of about 130C to about 400~C.
It is to be noted that the term "middle distillate fuel" is
not intended to be restricted to straight-run distillate
fractions. These middle distillate fuels or fuel oils can
comprise straight run distillate fuel oils, catalytically or
thermally cracked ~including hydrocracked) distillate fuel
oils, or mixtures of straight run distillate fuel oils,
naphthas and like stock6, with cracksd distillate stocks.
Moreover, such fuel oils can be treated in accordance with
well known operations such as acid or caustic treatment,
hydrogenation, solvent refining, clay treatment, and the
like. The base fuels thus include diesel fuels, kerosenes,
jet fuels, gas oils, cycle oils etc. While derived princi-
pally from petroleum, the fuels can be derived at least in
part from shale, tar sands, coal, lignite, biomass, and si-
milar sources. The fuels can contain suitable oxygenated
blending components, such as alcohols, ethers, etc, includ-
Case EI-6349+ 207~3~
- 17 -
ing in situ produced oxygenates.
In general, the compositions of this invention are
employed in the base fuel in an amount at least sufficient
to inhibit wear between contacting metal surfaces.
Ordinarily, such amounts will fall within the range of from
about 0.005 to about 5 percent by weight of the base fuel,
and more typically within the range of from about 0.05 to
about 2 percent by weight based on the weight of the base
fuel.
Various additional additives may be used in the
fuels of this invention. These include antioxidants,
conductivity improvers (also known as static dissipator
additives), metal deactivators, icing inhibitor additives,
cetane improvers, combustion improvers (including smoke
suppressants), detergent/dispersant additives, induction
system cleanliness agents, corrosion inhibitors, demulsi-
fying agents, top cylinder lubricants, dyes, and the like.
Of the antioxidants, use of phenolic antioxidants is
preferred, although other fuel-soluble antioxidants are
available and can be used. Other suitable types of anti-
oxidants include amine antioxidants, phosphite esters,
sulfur-containing antioxidants, and other similar sub-
stances. Amounts of antioxidant in the range of about 1 to
about 10 pound~ per thousand barrels are typical. However,
greater or lesser amounts can be used whenever deemed
necessary or desirable.
Various conductivity improvers suitable for use in
the fuels of this invention are available in the market-
place. These include ASA-3 marketed by Royal Lubricants
Co., and Stadis 450 marketed by E. I. duPont de Nemours Co.
Typically, conductivity improvers are additives that can be
dissolYed in the fuel in the amount necessary to increase
the fuel conductivity to within a suitable range, such as
between about 50 and about 600 pS/m as determined by ASTM D-
2624. For further detail concerning conductivity improverswhich can be utilized, see U.S. Pat. Nos. 3,449,097; 3,455,-
665; 3,578,421; 3,652,238; 3,676,647; 3,674,450; 3,784,362;
3,917,466; 4,029,480; 4,113,443; 4,252,542; 4,25~,087;
Case EI-6349+ 207~131
- 18 -
4,333,741; 4,356,002 and 4,416,668.
Metal deactivators which can be used in the fuels of
this invention include N,N'-disalicylidene-1,2-propanedia-
mine, N,N'-disalicylidene-1,2-cyclohexanediamille, N,N'-
disalicylidene-1,2-ethanediamine, N,N"-disalicylidene-N'-
methyl-dipropylenetriamine. 8-hydroxyquinoline, ethylene
diaminetetracarboxylic acid, acetylacetone, octylacetoace-
tate, and like substances. Thiadiazoles such as HITEC~ 314
additive (Ethyl Petroleum Additivas, Inc.; Ethyl Petroleum
Additives, Ltd.; Ethyl Canada Ltd.; Ethyl S. A.) can also be
used for this purposeO Amounts of up to about 2 pounds of
metal deactivator per thousand barrels are ordinarily suffi-
cient, but higher concentrations can be used whenever neces-
sary or desirable.
Icing inhibitor additives that can be used include,
for example, alcohols, glycols, monocarboxylic acid esters
of polyoxyalkylene glycols, and nitroketonized amides.
Amounts of up to about 50 pounds per thousand barrels are
usually sufficient.
Detergent/dispersant additives which are suitable
for use in the fuels of this invention include amides and
imides especially succinimides (e.g., U.S. Pat. Nos.
3,471,458; 3,655,351; 4,596,663; and 4,744,798); mono- and
polycarboxylic acid esters especially succinic acid esters
25 (e.g., U.S. Pat~ Nos. 3,639,242; 3~708,522; and 4,596,663);
carbamates (e.g., U.S. Pat. No. 3,652,240); hydrocarbyl
polyamines (e.g., U.S. Pak. Nos. 3,753,670 and 3,756,793);
and hydrocarbyl polyether polyamines (e.g., U.S. Pat. No.
4,778,481).
As used herein the term "fuel-soluble" means that
the composition in the particular base fuel employed dis-
solves at 25C to at least the minimum concentration herein
specified.
The above phosphate combinations can be used as
antiwear agents in any of a variety of oils of lubricating
viscosity. Preferably they are used in a base oil composed
by volume of at least 50% and up to and including 100% of
one or more mineral oils, or at least 50% and up to and
Case EI 6349~ 2070131
-- 19 --
including 100% of one or more synthetic ester oils.
The concentrations of the phosphate combinations in
the base oils are minor wear-inhibiting amounts. These
amounts will of course vary depending upon such factors as
the type of base oil employed, the type of service to be
encountered, and the amount of wear protection desired. In
general, however, amounts in the range of about 0.005 to
about 10 weight percent based on the total weight of the
finished lubricant will usually be sufficient. Preferred
amounts are in the range of about 0.25 to about 5 weight
percent again based on the total weight of the finished
lubricant. The phosphate combinations can be included in
additive concentrates of the type used in formulating fin-
ished lubricants tsuch as crankcase motor oils for gasoline
engines, crankcase motor oils for diesel engines, gear oils,
tractor oils, etc.) and functional fluids (such as transmis-
sion fluids, hydraulic fluids, cutting and machining oils,
etc.).
Further embodiments of this invention are additive
concentrates and lubricant or functional fluid compositions
containing particular combinations of one or more additive
components (hereinafter described) together with a phosphate
combination employed pursuant to this invention. For con-
venience, these. are referred to hereinbelow as Emhodiments
A, B, C, D, and E.
Embodiment A
One such embodiment is an oil of lubricating visco-
sity or an additive concentrate for use in oil of lubricat-
ing viscosity containing at least the following components:
30 1) one or more oil-soluble zinc hydrocarbyl dithiophos-
phates; and
2) an aryl phosphate ester combination composed of (i)
at least one oil-soluble aryl phosphate of the
formula
(RO)3PO
wherein each R is, independently, phenyl or an alkyl-substi-
tuted phenyl group or an alkenyl-substituted phenyl group;
and (ii) at least one oil-soluble aryl polyphosphate of the
Case EI-6349+ 2070131
- 20 -
formula
O O
Il 11
RO-[-P-O-Ar-O-]n~P(OR)2
OR
wherein each R is, indspendently, phenyl or an alkyl-
substituted phenyl group or an alkenyl-substituted phenyl
group, Ar is m-phenylene or an alkyl-substituted m-phenylene
group, and n is a whole or fractional number from 1 to 4;
said combination containing from 2 to 30% by weight of com-
ponent (i). The relative proportions of these components is
preferably such that the weight ratio of phosphorus in 1) to
total phosphorus in 2) is in the range of from about 0.001:1
to about 100:1. These combinations serve to inhibit wear;
to inhibit deposit, varnish and/or sludge formation and/or
deposition; and to protect the lubricant or functional fluid
composition from premature oxidative degradation, e~pecially
at elevated temperatures. The quantity of these components
1) and 2) added to the base oil of lubricating viscosity is
a minor wear-inhibiting amount, and is usually such that the
total concentration of phosphorus provided by components 1)
and 2) tproportioned as just described) falls in the range
of about 0.005 to about S percent by weight of the total
composition.
Embodiment B
Another embodiment of this invention is an oil of lu-
bricating viscosity or an additive concentrate for use in
oil of lubrisating viscosity containing at least the follow-
ing components:
1) an aryl phosphate ester co~bination composed of (i) at
least one oil-soluble aryl phosphate of the formula
(RO)3po
wherein each R is, independently, phenyl or an alkyl-
substituted phenyl group or an alkenyl-substituted phenyl
group; and (ii) at least one oil-soluble aryl polyphosphate
of the formula
Case EI-6349-t 2~7~3~
- 21 -
O O
Il 11
RO- [ -P-O-Ar -O- ] n~P ( OR ) 2
OR
wherein each R is, independently, phenyl or an alkyl-
substituted phenyl ~roup or an alkenyl-substituted phenyl
group, Ar is m-phenylene or an alkyl-substituted m-phenylene
group, and n is a whole or fractional number from 1 to 4;
said combination containing from 2 to 30% by weight of com-
ponent (i); and
2) one or more oil-soluble ashless dispersants containing
basic nitrogen, preferably a succinimide sr succinic
ester-amide.
The relative proportions of these components is preferably
such that the weight ratio of component 1) to component 2)
is in the range of from about 0.001:1 to about 100:1. These
combinations serve to inhibit deposit, varnish and/or sludge
formation and/or deposition; and to protect the lubricant or
functional fluid composition from premature oxidative degra-
dation, especially at elevated temperatures. The quantity
of these components 1) and 2) added to the base oil of lu-
bricating viscosity is a minor wear-inhibiting amount, and
is usually such that the total concentration of components
2) and 3) (proportioned as just described) falls in the
range of about 0.005 to about 20 percent by weight of the
total composition.
Any of a variety of ashless dispersants can be
utili~ed as component 3) of the compositions of this inven-
tion. These include the ~ollowing types:
Type A - Carbox~lic Ashless Dispersants. These are
reaction products of an acylating agent such as a monocar-
boxylic acid, dicarboxylic acid, polycarboxylic acid, or
derivatives thereof with compollnds which contain amine and/
or hydroxyl groups (and optionally, other groups such as
mercapto groups, etc.). These products, herein referred to
as carboxylic ashless dispersants, are described in many
patents, including British patent specification No.
1,306,529 and the following ~. S. Patents: 3,163,603;
Case EI-634s+ 20701~1
- 22 -
3,184,474; 3,215,707; 3,219,666; 3,271,310; 3,272,746;
3,281,357; 3,306,908; 3,311,558; 3,316,177; 3,340,281;
3,341,542; 3,346,493; 3,381,022; 3,399,141; 3,415,750;
3,433,744; 3,444,170; 3,448,048; 3,448,049; 3,451,933;
3,454,607; 3,467,668; 3,522,179; 3,541,012; 3,542,678;
3,574,101; 3,576,743; 3,630,904; 3,632,510; 3,632,511;
3,697,428; 3,725,441; 3,868,330; 3,948,800; 4,234,435; and
Re 26,433.
Type B - Hvdrocarbyl Polyamine Dispersants. This
category of ashless dispersants which can be used as
component 3) is likewise well known to those skill~d in the
art and fully described in the literature. The hydrocarbyl
polyamine dispersants are generally produced by reacting an
aliphatic or alicyclic halide (or mixture thereof) contain-
ing an average of at least about 40 carbon atoms with one ormore amines, preferably polyalkylene polyamines. Examples
of such hydrocarbyl polyamine dispersants are described in
U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804;
3,671,511; 3,821,302; 3,394,57~; and in European Patent
Publication No. 382,405.
Type C - Mannich polyamine dispersants. This category
of ashless dispersant which can be utilized is comprised of
reaction products of an alkyl phenol, with one or more ali-
phatic aldehydes containing from 1 to about 7 carbon atoms
(especially formaldehyde and derivatives thereof), and poly-
amines (especially polyalkylene polyamines of the type de-
scribed hereinabove). Examples of these Mannich polyamine
dispersants are described in the following U.S. Patents:
2,459,112; 2,962,442; 2,984,550; 3,036,003; 3,166,516;
3,236,770; 3,368,972; 3,413,347; 3,442,808; 3,~48,047;
3,454,497; 3,459,661; 3,493,520; 3,539,633; 3,558,743;
3,5~36,629; 3,591,598; 3,600,372; 3,634,515; 3,649,229;
3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725,480;
3,726,882; 3,73~,357; 3,751,365; 3,756,953; 3,793,202;
3,798,165; 3,798,247; 3,803,039; 3,872,019; 3,980,569; and
4,011,380.
Type D - Polymeric polyamine dispersants. Also suit-
able for use of the compositions of this invention are poly-
2~70~3~
Case EI-6349~ -
- 23 -
mers containing basic amine groups and oil solubilizing
groups (for exampl~, pendant alkyl groups having at least
about 8 carbon atoms). Such polymeric dispersants are here-
in referred to as polymeric polyamine dispersants. Such ma-
terials include, but are not limited to, interpolymers ofdecyl methacrylate, vinyl decyl ether or a relatively high
molecular weight olefin with aminoalkyl acrylates and ami-
noalkyl acrylamides. Examples of polymeric polyamine dis-
persants are set forth in the following patents: U.S. Pat.
lo Nos. 3,329,658; 3,449,250; 3,493,520i 3,519,565; 3,666,730;
3,687,849; 3,702,300.
Type E - Post-treated basic nitroaen-containinq and/or
hydroxyl-containinq ashless dispersants. As is well known
in the art, any of the ashless dispersants referred to above
as types A-D can be subjected to post-treatment with one or
more suitable reagents such as urea, thiourea, carbon disul-
fide, aldehydes, ketones, carboxylic acids, anhydrides of
low molecular weight dibasic acids, boron compounds, ni-
triles, epoxides, phosphorus compounds, and the like. Such
post-treated ashless dispersants can be used. Preferably,
the post-treated dispersant contains residual basic nitro-
gen. Examples of post-treatment procedures and post-treated
ashless dispersants are set forth in the following U.S.
Patents: U.S. Pat. Nos. 3,036,003; 3,087,936; 3,200,107;
3,216,936; 3,254,025; 3,256,185; 3,278,550; 3,281,428;
3,282,955; 3,312,~19; 3,366,569; 3,367,943; 3,373,111;
3,403,102; 3,44~,808; 3,455,~31; 3,455,832; 3,493,520;
3,502,677; 3,513,093; 3,533,945; 3,539,633; 3,573,010;
3,579,450; 3,591,598; 3,600,372; 3,639,242; 3,6~9,~29;
3,649,659; 3,658,B36; 3,697,574; 3,702,757; 3,703,536;
3,704,308; 3,708,522; 4,025,445; 4,857,214; and 4~971,598.
Mannich-based derivatives of hydroxyaryl succinimides
that have been post-treated with C5-C9 lactones such as ~-
caprolactone and optionally with other post-treating agents
as described for example in U.S. Pat. No. 4,971,711 can also
be utilized in the practice of this invention. Preferably,
such post-trea~ed Mannich based derivatives of hydroxyaryl
succinimides contain basic nitrsgen. The disclosures of
Case EI-6349+ 2 ~ 7 ~
- 24 -
U.S. Pat. No. 4,971,711, as well as related U.S. Pat. Nos.
4,820,432; 4,828,742; 4,866,135; 4,866,139; 4,866,140;
4,866,141; 4,866,142; 4,906,394; and 4,913,830 are refer to
additional suitable basic nitrogen-containing ashless dis-
persants which may be utilized.
One preferred category of post-treated ashless dis-
persants is comprised of basic nitrogen-containing and/or
hydroxyl group-containing ashless dispersants which have
been heated with (i) a phosphorus compound such that they
contain phosphorus, or (ii) a boron compound such that they
contain boron, or preferably (iii) a phosphorus compound and
a boron compound such that they contain boron and phospho-
rus. Such post-treated ashless dispersants preferably con-
tain residual basic nitrogen. Examples of such dispersants
and methods for their production are described in U.S. Pat.
Nos. 3,087,936; 3,254,025; 3,184,411; 3,185,645; 3,235,497,
3,265,618; 3,281,428; 3,338,832; 3,2~2,955; 3,284,410;
3,324,032; 3,325,567; 3,403,102; 3,344,069; 3,502,677;
3,513,093; 3,511,780; 3,533,9~5; 3,623,985; 3,718,663;
3,865,740; 3,'~50,341; 3,991,056; 4,097,389; 4,234,435;
4,338,205; 4,428,849; 4,554,086; 4,615,826; ~,648,9~0;
4,7~7,971; 4,634,543; 4,857,214; and 4,873,004.
Embodiment C
Still another embodiment of this invention is an oil of
lubricating viscosity or an additive concentrate for use in
oil of lubricating viscosity containing at least the follow-
ing components:
1) one or more oil-soluble zinc hydrocarbyl
dithiophosphates;
2) an aryl phosphate ester combination of the type
described hereinabove; and
3) one or more oil-soluble ashless dispersants containing
basic nitrogen, preferably a succinimide or succinic
ester-amide.
The relative proportions of these components is preferably
such that the weight ratio of phosphorus in 1) to total
phosphorus in 2) is in the range of from about 0.001:1 to
about 100:1, and such that the weight ratio of component 2)
207~
Case EI-634s+
- 25 -
to component 3~ is in the range of from about 0.001:1 to
about 100:1. These combinations serve to inhibit wear; to
inhibit deposit, varnish and/or sludge formation and/or
deposition; and to protect the lubricant or functional fluid
composition from premature oxidative degradation, especially
at elevated temperatures. The quantity of these components
1), 2) and 3) (proportioned as above) added to the base oil
of lubricating viscosity is a minor wear-inhibiting amount,
and is usually such that the total concentration of
phosphorus provided by components 1) and 2) falls in the
range of about 0.005 to about 5 percent by weight of the
total composition.
Embodiment D
Yet another embodiment of this invention is an oil of
lubricating viscosity or an additive concentrate for use in
oil of lubricating viscosity containing at least the follow-
ing components:
1) one or more oil-soluble sulfur-containing antiwear
and/or extreme pressure agents; and
2) an aryl phosphate ester combination of the type
described hereinabove; and
3) optionally, one or more oil-soluble ashless dispersants
containing basic nitrogen, preferably a succinimide or
succinic ester-a~ide; and
4) optionally, one or more oil~soluble zinc hydrocarbyl
dithiophosphates.
It will be noted that in these compositions there are at
least two required components, d~signated 1) and 2). This
embodiment also includes two three-component mixtures, the
first composed of the components designated as 1), 2) and 3)
and the second composed o~ the components designated as l),
2) and 4). And additionally this e~bodiment comprises the
f~ur-componen~ combinations composed of the components
designated as l), 2), 3) and 4). In these various combina-
tions the relative proportions of these components is pre-
ferably such that the weight ratio of sulfur in l) to total
phosphorus in 2) i5 in the range of from about 0.01:1 to
about 100:1; such that when component 3) is employed, the
Case EI-6343+ 2070131
- 26 -
weight ratio of component 2) to component 3) is in the range
o' from about 0.001:1 to about 100:1; and such that when
component 4) is employed, the weight ratio of total phos-
phorus in component 2) to phosphorus in component 4) is in
the range of from about 0.01:1 to about lOoO:l. These
combinations serve to inhibit wear; to inhibit deposit,
varnish and/or sludge formation and/or deposition; and to
protect the lubricant or functional fluid composition from
premature oxidative degradation, especially at elevated
temperatures. The quantity of these components 1) and 2)
added to the base oil of lubricating vis~osity is a minor
wear-inhibiting amount, and preferably is such that the
total concentration of sulfur and phosphorus provided by
components 1) and 2) respectively, (proportioned as de-
scribed above) falls in the range of about 0.005 to about 20percent by weight of the total composition. When component
3) is used --with or without component 4) -- the quantity of
component 3) added to the base oil of lubricating viscosity
is a minor dispersant amount, and is usually such as to
maintain the proportions given above. Similarly, when com-
ponent 4) -- with or without component 3) - is used, the
quantity of component 4) added to the base oil of lubricat-
ing viscosity is a minor wear-inhibiting amount, and is
usually such as to mai~tain the proportions given abova.
Various types of sulfur-containing antiwear and/or ex-
treme pressure agents can be used in the practice of Embodi-
ment D.
When including component 3) in the practice of Embodi-
ment D, use can be made of any of the ashless dispersants
referred to hereinabove with reference to Embodiment B.
When including component 4) in the practice of ~mbodiment ~,
u~e can be made of any of the zinc hydrocarbyl dithiophos-
phates referred to hereinabove with refPrence to Embodiment
A.
Embodiment E
A still further embodiment of this invention is an oil
of lubricating viscosity or an additive concentrate for use
in oil of lubricating viscosity containing at least the
2~7~
Case EI-6349~
- 27 -
following components:
1) at least one oil-soluble amine salt of at least one
dihydrocarbyl ester of a thiophosphoric acid; and
2) an aryl phosphate ester combination of the type
described hereinabove; and
3) optionally, one or more oil-soluble ashless dispersants
containing basic nitrogen, preferably a succinimide or
succinic ester-amide; and
4) optionally, one or more oil-soluble sulfur-
containing antiwear and/or extreme pressure
agents.
It will be noted that in these compositions there are at
least two required components, designated 1) and 2). This
embodin~ent also includes two three-component mixtures, the
first composed of the components designated as 1), 2) and 3)
and the second composed of the components designated as 1),
2) and 4). And additionally this embodiment comprises the
four-component combinations composed of the components de-
signated as 1), 2), 3) and 4). In these various combina-
: 20 tions the relative proportions of these components is pre-
ferably such that the weight ratio of phosphorus in 1) to
total phosphorus in 2) is in the range of from about 0.001:1
to about 100:1; such that when component 3) is employed, the
weight ratio of component 2) to component 3) is in the range
o~ from about 0.001:1 ~o about ~00:1; and such that when
component 4) is employed, the weight ratio of total phos-
phorus in component 2) to sulfur in component 4) is in the
range of from about 0.01:1 to abDut 100:1. These combina-
tions serve to inhibit wear; to inhibit deposit, varnish
and/or sludge formation and/or deposition; and to protect
the lubricant or functional fluid composition from premature
oxidative degradation, especially at elevated temperatures.
The quantity of these components 1) and 2) added to the base
oil of lubricating viscosity should be such that the total
concentration of phosphorus provided by components 1) and 2)
(proportioned as described above) falls in the range of
about 0.005 to about 5 percent by weight of the total com-
position. When component 3) is used, the quantity thereof
2~0131
Case EI-6349~
- 28 -
added to the base oil of lubricating viscosity is a minor
dispersant amount, and is usually within the proportions
given above. Similarly, when component 4) is used, the
quantity thereof added to the base oil of lubricating visco-
sity is a minor wear-inhibiting amount, and is usually
within the proportions given above.
The amine salts of dihydrocarbyl esters of thiophos-
phoric acids employed as component designated 1) in Em-
bodiment E are comprised of the oil-soluble amine salts
(preferably the aliphatic monoamine salts) of one or more
dihydrocarbyl esters of a thiophosphoric acid, which esters
can be derived from a tetrathiophosphoric acid, a trithio-
phosphoric acid, a dithiophosphoric acid, or a monothio-
phosphoric acid, or a mixture of any two or more of the
foregoing. The amine salts of dihydrocarbyl esters of a
dithiophosphoric acid are preferred, and the amine salts of
dihydrocarbyl esters of a monothiophosphoric acid are
particularly preferred.
Methods for the synthesis of such amine salts are well
known to those of skill in the art, and are reported in the
literature. For example, see PCT Published International
Application WO 87/07~38, published 17 December 1987.
When including compon~nt 3) in the practice of E~bodi-
ment E, use can be made of any of the ashless dispersants
referred to hereinabove with reference to Embodiment B.
When including component 4) in the practice of Embodiment E,
use can be made of any of the sulfur-containing ~ntiwear
and/or extreme pressure agents referred to hereinabove with
reference to Embodiment D.
The effectiveness of the phosphate combinations of this
invention in oils of lubricating viscosity was illustrated
by means of ~-ball wear tests conducted using a mineral oil
based hydraulic fluid containing 200-300 ppm of phosphorus
as a phosphate combination of this invention. The tests
35 were conducted at 130F for 60 minutes while operating the
4 ball machine at 1800 rpm with a 40 kg load. In duplicate
determinations a blend containing approximately 300 ppm of
phosphorus as the phosphate co~bination gave wear scar dia-
Case EI-6349~ ~07~131
- 29 -
meters of 0o58 and o.68 mm. Duplicate determinations with
a blend containing approximately 200 ppm of phosphorus as
the phosphate combination resulted in scars of 0.61 and 0.57
mm. The scars produced by the base oil were 0.90 and 0.95
mm in diameter.
The compositions of this invention are also useful as
flame retardants for polymers such as polystyrene, poly-
phenylene oxide, blends of poly(2,6-dimethylphenylene oxide)
and rubber-modified polystyrene, polyethylene, polypropy-
lene, and the like.
This invention is susceptible of considerable variation
in its practice. Thus this invention is not intended to be
limited by the specific exempli~ications set forth herein-
above. Rather, what is intended to be covered is within the
spirit and scope of the appended claims.
