Note: Descriptions are shown in the official language in which they were submitted.
1~7g76
This invention relates to sulphurised products
having utility as lubricant ad~itives and lubricating
compositions containing them. The invention also relates
to a process for preparing sulphurised products, the
. .
products so prepared and lubricating compositions containing
such products.
Antioxidant additives used in lubricating oils,
particularly, but not exclusively, automotive lubricants,
require a combination of properties which is dif~icult
; 10 to meet in practice. Such additives must, of course,
impart a high degree of resistance to oxidation to the
~- lubricant, but in addition must be reasonably inexpensive,
must be compatible with various other additives commonly
used in lubricants, must have adequate thermal stability
and must satisfy various other criteria of suitability,
such as the ability to protect copper-lead bearings from
corrosion. Very many different types of antioxidants
have been proposed, and in some cases have been commercially
used on a comparatively small scale. However, for many
years the type of antioxidants which have been very widely
used as the most suitable general purpose antioxidants
for automotive and other lubricants are metal, particularly
zinc, salts of di-hydrocarbyl dithiophosphoric acids.
Ho-~!ever, the need for lubricant developments to
keep pace with engine developments has given rise recently -
to difficulties in the use of metal dithiophosphate salts
as antioxidant. The metal content of these additives is
a source of ash and there is a growing tendency for the
quality standards laid do~n by manufacturers and other
3o interested organisations to specify low-ash lubricant
formulations for modern engines. Attempts have been made
to develop dithiophosphate derivatives, which do not contain
2.
~ ~047476
. .
metal, in order to meet these requirements. However,
such developments have been forestalled, at least to some
extent, by yet another development in engine design,
namely the use of catalytic devices in engine exhausts
to minimise pollution caused by vehicle emissions. The
catalysts used in such devices are sensitive to phosphorus
compounds and can become poisoned and ineffective if exposed
,;
to s.uch compounds. Consequently, the need has arisen
G for antioxidants which do not contain metal or phosphorus,
and yet still meet all the requirements for antioxidants
formerly satisfied by the metal dithiophosphates.
We have now found certain sulphurised products
which are, at least in the preferred embodiments, very
effective antioxidants in lubricating compositions such
as crankcase lubricants. The sulphurised products are also
useful for other purposes, for example as load-carriers
in gear oil formulations.
Accordingly in one aspect of the present invention
there is provided a lubricating composition containing
a major amount of lubricating oil and a minor amount of
a ~ulphur containing additive wherein said additive is a
sulphur containing norbornenyl compound having the general
- formula:
~ R
(h~
R
wherein:
- ~047476
(a) each of R, R2 and R4 when taken singly is
a hydrogen atom, an alkyl group containing from
1 to about 15 carbon atoms, an aryl group
containing from 6 to about 15 carbon atoms or : .
a cycloalkyl group containing from 4 to about 10
carbon atoms;
(b) each of R1 and R3 when taken singly is a
hydrogen atom, an alkyl group containing from 1
. . .
to about 15 carbon atoms; an aryl group containing
-~ 10 from 6 to about 15 carbon atoms; a cycloalkyl group
.
~ containing from 4 to about 10 carbon atoms or
., .
an alkenyl group containing from 2 to about 10
carbon atoms or Rl and R3 taken together form
the group -CHY.CY=CY- in which Y is a hydrogen
atom or a methyl group or R1 together with R2
form an alkylidene group containing from 1 to ~-
about 6 carbon atoms; and -
(c) R5 is a hydrogen atom or an alkyl group
containing from 1 to about 15 carbon atoms; or, - : .
wherein said additive is the oil-soluble
.. . . . . .
. sulphur containing norbornenyl product resulting
from sulphurising a compound having the general -
: formula:
. R
~ 3 ~ ~O
wherein R, Rl, R2, R3, R and R5 are as hereinbefore
4.
- .
''
- 1047~76
defined at a temperature of up to 180 C., said
sulphurisation being carried out in the absence
of a solvent or in the presence of a non-polar
~; solvent.
The foregoing compcunds of formula (A) are known
compounds and are described in United States Patent
No. 3586700, which also describes the preparation of the
compounds by sulphurisation of norbornenyl compounds to
form the trithiolan derivatives depicted above. The
sulphurisation reaction of United States Patent No. 3586700
is carried out necessarily in tne presence of certain
highly polar organic solvents.
However, in a very important aspect of the present
invention there is prGvided a process for preparing an
oil-soluble, metal-free, phosphorus-free substance suitable
for use as a lubricant additive, which process comprises
sulphurising a compound having the general formula:-
R
(O
R Rl R2 R3 R4, and R5 are as hereinbefore
defined, at a tempera~lire of up to 180C., said sulpnurisation
being carried out in the absence of a solvent or in she
presence of a non-polar sovent, and thereafter removing
any oil-insoluble constituents from the resulting
~ulphurised product.
, .,. ,.1 .
~.
' ': ,
~047476
Examples of compounds which may ~e sulphurised
in the process of the present invention are norbornene,
5-vinylnor~ornene, dicyclopentadiene and methyl
cyclopentadiene dimer of which dicyclopentadiene and
methyl cyclopentadiene dimer are especially preferred.
If desired the process of the present invention
may be carried out in the presence of a catalyst of the
type common;y used in sulphurisation reactions, for
example tertiary amines such as triethylamine or pyridine,
secondary amines such as di-isopropylamine, di-butylamine,
and di-cyclohexylamine and primary amines such as cyclo- -
hexylamine and the~, ~-dimethyl tertiary alkyl primary
amines available commercially under such trade names as
:~ Primene JM-T and Primene 81-R. Other catalysts which may
be used include:-
2,5 - Dimercapto - 1,3,4,- thiadiazole
2,5 - Dimercapto 1,2,4- thiadiazole
2,5 - Bis(t-octyldithio) - 1,3,4- thiadiazole
Mercaptobenzothiazole
Sulphide ions, e.g. provided by sodium sulphide
- Alkanolamines
Diphenyl guanidine
- A Mixture o~ NaOH and mercaptobenzothiazole
peroxide such as the material marketed as ter~iary
butyl hydroperoxide consisting of about 70% of that
- peroxide together with about 30% di-t-butyl peroxide
Farti.^ular]y preferred catalysts are combinations
of an amine and a thiadiazole derivative.
m e amount of catalyst used is not critical, but
normally will be about 0.1 to 20%, for example, from 2 to 10%
more preferabiy 0.1 to 10% and most preferably 0.3 to 2%,
, . . , ,-
....
J
: ~047~'7~;
by weight based on the weight of the compound to be
sulphurised.
The process of the present invention may also be
carried out in the presence of a small amount, e.g. not
~ore than 25 molar percent based on the compound to be
sulphurised, of a solubilising agent. Examples of
solubilising agents which may be used are:-
Conjugated d -or poly-olefins such as alloocimene
(1,5-dimethyl-2,4,6-octatriene)
Non-conjugated di-or poiy olefins such as 1,5,9-
., .
cyclododecatriene and 1,s-cyclooctadiene
Dialkyl ma'eates, preferably containing from 1 to
12, more preferably 4 to 8, carbon atoms in each
alkyl group, e.g. dibutyl maleate
Alkenyl succinic acids or anhydrides thereof,
preferably containing 8 to 12 carbon atoms in the
alkenyl group, such as dodecenyl succinic acid
Alkyl mercaptans, preferably containing 8 to 12
,. . .
carbon atoms such as t-dodecyl mercaptan
Polyisobutenyl succinimides
Mercaptobenzothiazole
Benzothiazole disulphide
~- Alkenoic acids, preferably containing ~rom 8 to
18 carbon atoms such as oleic acid
Alkyl esters of alkenoic acids such as octyl
methacrylate
Ethoxylated amines such as the material available
comrr.e-cially lmde~ the trade name Ethomeen T15
Dimerised alkenoic acids, preferably containing from
18 to 36 carbon atoms
Dicyclopentadiene hydrate
Alkanols, such as isodecanol.
7~76
Such solubilising agents may assist in increasing
the proportion of oil-soluble constituents in the product
of the sulphurisation reaction and, when used, will normally
be present in an amount of 1 to 25, preferably 2 to 15, molar
percent. Within this range it is preferred to use as small
an amount of solubilising agent as possible consistent with
obtaining a reasonable amount of oil-soluble product (for
example not more than 25-30/o by weight, preferably less, of
the product should be oil-insoluble). The effectiveness of
the solubilising agent has been found to be dependent in
part on the proportion of sulphur used in the sulphurisation
reaction, effectiveness decreasing with increasir.g
proportions of sulphur used. Moreover, as exemplified -
hereinafter some solubilising agents are more effective
than others and solubilising agentssuch as alloocimene,
dibutyl maleate, dodecenyl succinic acid, t-dodecyl
B mercaptan, Ethomeen T15, oleic acid and mercaptobenzothiazole
are most preferred.
In the process of the present invention the sulphur
- 20 is preferably used in an amount of from 0.1 to 4 moles
per mole of compound to be sulphurised, with an amount cf
about 1 to 2 mcles per mole of compound to be sulphurised
; being most preferred. m e sulphurisation can be
conveniently carried out by merely mixing the reactants,
including any catalyst, and/or solub lising agent used,
and heating. Alternatively, the compound to be sulphurised
can be added to hot sulphur. However, when using a
rel~t,ively high amount of sulphur, i.e. an amount in the
upper end of the preferred range, it is preferred to add the
3 , sulphur in portions over an initial period to the compound
to be sulphurised maintained at the reaction temperature
and then to continue maintaining the reaction temperature
~rc~Jer~ark
8.
1047476
for a further period.
In general a reaction temperature of at least
60C. is preferred, with at least 90C. or 100C. being
; most preferred for providing the preferred sulphurised
materials as hereinbefore described. Also, a reaction
temperature no greater than 160C is preferred.
Sulphurisation is normally completed in from 0.5 to 24
hours depending on the reaction temperature. At the
optimum temperature of about 110C. to 140C. a reaction
time of about 2 hours is generally found to be most
satisfactory, the co-reactants either being mixed and heated
for 2 hours or the sulphur being added to the compound to
be sulphurised in portions over, for example 1 hour at
120C and thi~ temperature then being rnaintained for a
further hour.
The sulphurisation may, if desired, be carried
out in an inert atmosphere such as a nitrogen blanket.
The-pressure at which the sulphurisation is carried out
i8 not critical, but is preferably not reduced to a level
at which significant amounts of the compound being
sulphurised are lost from the reaction system by distillation.
Although it is preferred to carry out the ~-sulphurisation in the absence of a solvent .it is also
possible to carry out the reaction in the presence of a
non-polar solvent, examples of the latter being petroleium
ether, toluene, benzene,XYlene and mineral oil (especially
a mineral lubricating oil).
After comp~ef ' on of the sulphu isatior. any oi;-
insoluble constituent of the product may be remove~ by ~-
any convenient method using well known-techniques such as
solvent exbraction or dissolving in oil followed by filtration.
9.
.' . ''
~o474 ~6
However, if the reaction ;s carried out under careful
,
control at the optimum conditions the whole product is
frequently oil-soluble and removal of oil-insoluble
constituents is not necessary. Accordingly, reference
made herein and in the appended claims to removal of
oil-insoluble constituents is to be understood to mean,
unless the context denotes otherwise, removal of oil-
insoluble constituen~s if, and as, necessary.
- A preferred technique for removal of oil-insoluble
' 10 by products is to initially strip off excess olefin which
~; would otherwise solubilize the insoluble component and to
then add excess petroleUm ether to precipitate an
. insoluble phase which can be removed. The petroleum ether
is then stripped off co yield a~otallyoil-soluble product.
In a preferred embodiment of the invention
dicyclopentadiene is sulphurised using 2 moles of sulphur
per mole of dicyclopentadiene at a temperature of about
~- 120C using di-isopropylamine and 2,5- bis(t-octyl-dithio)-
1,3,4- thiadiazole as catalysts, and, optionally, one Or
the most preferred solubilisers listed above.
In a further aspect the present invention also
includes the oil-soluble, metal-free, phosphorus-free
products prepared by the process of the present invention.
It is to be understood that as with all chemical
substances purity, in an absolute sense, is impossible to
achieve and the sulphurised olefins of the present
invention may contain, as a result of contaminants present
in the starting materials, a trace of metal and'or pnosphorus.
However, such traces should be present in such minute
quantities as to be of no practical significance and it is
to be understood that the starting materials should not be
grossly contamin~ted with metal and/or phosphorus compounds.
10 .
1047476
, .
However, commercially available grades of starting
materials are normally completely adequate in this
respect and any contamination arising therefrom is far
. .
below any level of practical significance.
The products of the process of the present
invention preferably contain from about 15 to 40% by
weight of sulphur and reaction conditions and proportions
of co-reactants may be adjusted in order to vary the
sulphur content of the product. Further the products of
the process of the present invention are believed to
contain substantial amounts of the trithiolan derivatives
hereinbefore depicted in formula (A).
Preferably the lubricating compositions of the
present invention comprise from 0.1% to 10%,more preferably
0.25% to 5%, by weight of the oil-soluble, metal-free,
phosphorus-free products and/or compounds of foregoing
formula (A) and the Iubricating oil may be any of the
~ell known mineral or synthetic oils of appropriate
viscosity characteristics.
It will be understood that the lubricating
compositions of the present invention may also contain, if
desired, conventional lubricant additives such as ancillary
antioxidants and anti-wear additives (preferably ashless),
corrosion inhibitors, dispersants, particLlarly dispersants
f the succinimide type, detergents, thickeners, pour-point
depressants and viscosity index improvers. A particularly
useful additive to be used in conjunction with the additives
of the present invention is benzotriazole whic~ has been
found to reduce lacquer formation and improve the appearance
of bearings in test engines lubricated with compositions
of the present invention. The benzotriazole may, if desired,
,
11 . '
- .
i :~
~047476
be incorporated prior to the sulphurisation reaction
of the present invention or after sulphurisation but
either before or after the removal of any oil-insoluble
` constituents.
.
The additlves of the present invention may also
be conveniently prepared as a concentrate consisting of
a concentrated solution of a major amount of the
:
~- additives and a minor amount of mineral oil, or as an
.
additive package consisting of a concentrated solution
, 10 in mineral oil of a major amount of a combination of the
additives with one or more conventional additives. Such
concentrates and packages are frequently very convenient
~orms in which to handle and transport additives and are
diluted with further quantities of oil, and optionally
blended with further additives, before use.
Hence in accordance with another aspect of the
` invention there is provided a solution comprising a -
L major amount of one or more compounds having the formula
(A) or one or more of the oil-soluble metal free,
phosphorus-free products of the process of the invention
and a minor amount of a lubricating oil.One or more
conventional additives may be combined with the compounds
of formula (A) or the oil soluble, metal-free, phosphorus-
free products.
The present invention will now be illustrated
with reference to the following examples:-
EXAMPLE 1
A mixture of dicyclopentadiene (264g.;n 2.0m) and
triethylamine catalyst (13.2g) was added dropwise over a
period of one hour to sulphur (128g., 4.0m) maintained at
a temperature of about 140C. About half-way through this
.. . .
12
` ~047476
addition an exotherm to 155C. was noticed and this was
quickly controlled by air blast cooling and no further
problems were encountered during the remainder of the
addition. After completion of the ~ddition the resulting
reaction mixture was maintained at 140-145C. for a
further one hour, whereafter about 0.2g hydroquinone was
added to the resulting crude product.
me crude product was stripped under high vacuum
(0.2mm. Hg) to a base temperature of 160C. (internal
temperature 140C.) to yield 33.0g (8.4% by weight) of a
distillate (predominantly unreacted dicyclopentadiene).
:~,s
i The residue was placed in a 1 litre separating funnel
together with an amount of petroleum ether (B.Pt. 62-68C.)
7~ sufficient to substantially fill the funnel resulting in
15 a viscous, oily, petroleum ether-insoluble layer (yield
212.1g., 54.1% by weight) anl a petroleum ether layer.
The latte. was separated and the petroleum ether stripped
off to yield 149.2g. (38.2% by weight) of the final, oil-
soluble product containing 32.5% sulphur.
;; 20 EXAMPLE 2
Dicyclopentadiene (264g., 2.m) was added
dropwise over a period of 40 minutes to sulphur (64g.2.Om)
- at 145C. The resulting reaction mixture was maintained at
145C. for a further hour and about ~.2g. hydroquinone
added to the resulting crude product which was cooled and
then stripped under high vacuum to a base temperature of
140C. to yield 180g (55.0% by weight) of unreacted
dicyclopentadiene as distillate. The residue was wcrked
up in the same manner as in Example 1 to yield 66.3g.
(20.2% by weight) of soluble material containing 31.0%
sulphur and 18.9g (5.8% by weight) of oil insoluble product.
'
1047~76
EXAMPLE 3
Dicyclopentadiene ~64g., 2.0m), sulphur(64g.,
2.0m) and triethylamine catalyst (13.2g.) were mixed
- and heated to 145C. for 2 hours. The resulting crude
product was cooled slightly and about 0.2g hydroquinone
. added thereto. The crude product was then cooled and
worked up in the same manner as in Example 2 to yield
; 116.7g (35.6% by weight) distillate, 53.2g (16.2% by
weight) insoluble material and 155.0g (47.4% by weight)
oil-soluble product containing 27.7% sulphur.
EXAMPLE 4
..
Dicyclopentadiene ~238g., 1.8m) sulphur (64g.,
2.0m), triethylamine catalyst (14.2g.) and, as solubilising
agent, dibutyl maleate (45.6g 0.2m) were mixed and heated
to 140-150C. for 2 hours. Hydroquinone (about 0.2g) was
added to the crude product which was then stripped to
- 120C. at 0.2mm Hg. to yield 83g. (23.9% by weight)
distillate. The residue was worked up in the same manner
as in Example 1 to yield about lg. insoluble material
and 250.3g (72.0% by weight) oil-soluble product containing
24.7% sulphur.
EXAMPLE 5 T0 14
Further preparations were carried out in the -
mannér of Exa~ple 4 and details thereof are given in the
following Table 1.
EXAMPLE 15
.'~ mixture of dicyGlopentadiene (178g., 1;35m)
dibutyl maleate (34.2g., 0.15m.) and triethylamine (10.6g.)
was heated to 140C. and suiphur (72g., 2.25m) was added
thereto over a period of 50 minutes during which the
temperature was maintained at 140C. The temperature was
14.
- !
:
1~47~76 )t
maintain~d at 140C. for a further 70 minutes whereafter
0.2g. hydroquinone was added and the crude product stripped
to 150C. (140C. internal temperature) at O.lmm Hg. to
yield 57g. (20.1% by weight) distillate. The residue
was worked up in the same manner as in Example 1 to yield
32.6g. (11.5% by weight) insoluble material and 184.3g.
;, (64.8% by weight) oil-soluble product containing 28.4%
sulphur.
,; . .
EXAMPLE 16 to 30
- 10 ~urther preparations were carried out in the -
manner of Example 15 and details thereof are given in the
following Table 2.
EXAMPLE 31
Sulphur (144g. 4.5m.) was added incrementally
over a period of 1 hour to a mixture of dicyclopentadiene
(356g., 2.7m.) dibutyl maleate (68.4g., 0.3m.) triethylamine
(21.2g.) and 2,5-dimercapto -1,3,4- thiadiazole (4.2g.) at
a temperature of 160C. The reaction mixture was then
,' .
maintained at 160C. for a further hour, whereafter it
was stripped up to 110C. on a rotary evaporator under
.
water pump vacuum (about 30mm Hg) to yield 2g. of distillate
~excess dicyclopentadiene). The product was extracted
with three times its volume of petroleum ether (boiling
point 62-68C.) yielding 75.1g. (13.7%) of insoluble
material and petroleum ether stripped off the extract to
yield 472.3g. (83%) of soluble material containing 25.0%S.-
EXAMPLE 32 - -
Example 31 was repeated except in tha~ the reaction
temperature was kept at 90C. and extraction with petroleum
ether was nct carried out to yield 184g. (50.4%) excess
cyclorentadiene, no insoluble material and 386g. (68.o%)
soluble product containing 35.5%S.
15.
"
)47~76
EXAMPLE 33
, Example 32 was repeated, except in that the
.
,,
reaction temperature was kept at 120 C., to yield 120g
^ excess cyclopentadiene, no insoluble material and 455g.
t 5 (80%) soluble product containing 31.9%S.
EXAMPLE 34 to 42
Further preparations were carried out in the
manner of Example 33 and details thereof are given in the
, following Table 3.
EXAMPLE 43
Sulphur (172.8g., 5.4m.) was added incrementally
over 1' hours, at a temperature of 90 C., to a mixture
of dicyclopentadiene (356g., 2.7m.), dibutyl maleate
(68.4g., O. 3M. ) di-isopropylamine (5g.) and sodium sulphide
powder (5g.). The reaction mixture was then stirred for
a further 2 hours with the reaction temperature maintained
in the range of 85-90C. me resulting product was then
filtered and stripped to 120 C. under water pump vacuum
to yield 83g. distillate (excess dicyclopentadiene). The
;.20 stripped product (462g.) was not fully oil soluble and was
therefore boiled with 1~ litres petroreum ether to yield
350g. (59%) of soluble product containing 33.8%S.
EXAMPLE _44
Dic-lclopentadiene (356g., 2.7m), dibutyl maleate
(68.4g., 0.3m), diisopropylamine (4g) and 2,5-bis
(t-octyldithio) -1,3,4,-thiadiazole were dissolved in
toluene (500ml) and sulphur (172. 8g., 5.4m) added thereto
incrementally over 1 hour while maintaining a reaction
temperature of 120 C. The reaction mixture was then stirred
3 for a further 1 hour at 120 C. and vacuum stripped (removing
toluene at 100 C. and excess dicyclopentadiene at 120C.)
16.
~4747~
to yield 461g. (76.7%) soluble product containing 34.1%S,
EXAMPLE 45
Example 44 was repeated using 500 ml petroleum
ether (boillng point 80-100C.) in place of the toluene.
- 5 The reaction temperature was maintained in the range of
100-110C. throughout due to the volatility of the solvent.
In this way was obtained 469.9g. (78.2%) of soluble product
containing 36.2%S.
EXAMPLE 46
Dicyclopentadiene (178g. 1.35m), dibutyl maleate
(34.2g., 0.15m), di-isopropylamine (2g.) and 2,5-bis
(octyldithio) -1,3,4-thiadiazole (2g) were dissolved in
200g. of high viscosity index 100 Solvent Neutral mineral
oil. Sulphur (86.4g., 2.7m) was added incrementally over
1 hour at 110-120C. and the reaction ~emperature maintained
at 120C. for a further 1 hour. The product was vacuum
stripped and filtered to yield 461g. (92.4%) of oil
soluble product containing 19.0%S.
EXAMPLE 47
Dicyclopentadiene (178g., 1.35m), dibutyl maleate
(34.2g., 0.15m) di-isopropylamine (2g) were dissolved in
250ml toluene. Sulphur (129.6g. 4.05m) was added thereto
over ~ hour at 110-120C. and the resulr,ing mixture
stirred for a further 1~ hours at 120CC. After vacuum
?5 stripping and filtration 300g (88%) of product containing
39.9%S was obtained. This gave a hazy solution in mineral
oil indicating the presence of a very low level of insoluble
material.
EXAMPLE 48
3C Example 44 was repeated except in that 172.8g.
(5.4m) sulphur was used and a reaction temperature of 110C.
17-
:::
~;
104747
: was used. There was obtained 191.4g. (49.9%) soluble
. product and 138.6g (36.1%) insoluble product. -
3: EXAMPLE 49
~$ 5-Vinylnorbornene (84g. 0.7m), di-isopropylamine
(4.0g.) and 2,5-bis (t-octyldithio) -1,3,4,-thiadiazole
:,:
(o.8g.) were mixed, heated to 130C. and sulphur (22.4g.,
-` 0.7m) added thereto portionwise over 1 hour. The -
temperature was maintained at 130C. for a further 1 hour
and the reaction mixture was stripped to 100C. at O.lmm
Hg. to remove 20.8g. (19.6%) unreacted 5-vinylnorbornene.
The product was extracted with 250ml petroleum ether
(boiling point 62-68C.) and filtered to remove a small
` quantity of insoluble material. The petroleum ether was
i stripped frotn the extract to yield 51g (48%) of soluble
~- 15 product
, . . .
,..:
~- In some of the foregoing examples (1 to 5, 9
11 and 18) a small quantity of hydroquinone was added to
the crude product of the sulphurisation reaction since it
was thought that the reaction proceeded by a free
radical mechanism and that continuation of a free radical
reaction during working up of the crude product could lead
to some degradation. The hydroquinone was therefore used ~-
to suppress free radical reaction. However, subsequent
.,, ~.
experiences ~ndicated that the use of hydroquinone did
not materially improve the additive preparation.
Various products of the foregoing examples were
s
tested to determine their suitability as lubricant additives.
Petter WI Engine testr were carried out by the Institute
of Petroleum's method IP 176/69 using an ashless blend
consisting of a commercially available succinimide-type
dispersant, a secondary aromatic amine antioxidant and a
18.
~.V47~ :
combination of corrosion inhibitors together with 1.0%
by weight of the test additive all dissolved in a 500 l-
Solvent Neutral mineral oil. Bearing weight losses afte
a 36 houF test were measured and were as follows:
; Test AdditiveBearing Test Bearing [
~ Weight Additive Weight
Loss (mg) Loss (mg.)
1.
Product of Example 1 9 Product of EY.ample 15 12
" 3 17.4 " n - 16 -8
" " " 4 9 " " '' 19 8 ~-
" "' 5 75 ~ t n 21 3 ~-
" " " 6 8 22 -17 i
" " " 8 7 " " " 24 19 l~
11 5 " " " 30 9
- " " " 12 5 '' " " 37 13
i' " " 14 10
Extended WI tests were carried out for typical test
/ additives (in the same blends) by the same method except
_ that oil samples removed from time to time were not replaced.
19-
~04 ;~'76
:
. Bearing Weight Losses were as follows:-
" . .
Test Additive Bearing Weight Loss (mg.)
36 hours 72 hours 108 hours
Product of Example 29 10 19 28
" " " 30 22 28 51
.: " " " 42 10 17 20
In comparison a typical fully-formulated
.; commercially available lOW/50 oil containing a zinc dialkyl
:.
dithiophosphate as antioxidant, a succinimide-type
dispersant, a metal sulphonate detergent, a polymethacrylate
viscosity index improver and a combination of corrosion
inhibitors gave bearing weight losses in this test of 15mg,
27mg and 68mg at 36,72 and 108 hours respectively.
; 15 Load carrying properties were determined using
the Timken OK load test according to the IP240/69T method
(except in that results are quoted in lbs.) The test blends
con8isted of test additive diæsolved in 150 Solvent Neutral
mineral oil, the former being in amount to provide 0.3% by
weight sulphur in the test blend and the results were as
follows:-
Test Additive ~i~kln OK Load (lbs)
None (h~se oil only) 12
Product o~ Example 5 ~ 30
/ " " " 6 ~5-
" ,. ~ 8
20.
-
~ 7~6
:
: , ,
. ll " 19 45
~` " " " 23 40
" " " 33 40
.
. .
.,~ , .
In comparison commercially available zinc dialkyl
dithiophosphates usually give Timken OK loads of 35-40 lbs
in this test.
.,, :, . .
Rotary Bomb TestScarried out by the IP229/68T
.. 5 method on blends consisting of 2.0% by weight test additive
dissolved in 500 Solvent Neutral mineral oil gave the
following induction periods:-
. ' , .
Test Additive Induction Period (minutes)
i 10 None (base oil only) 35
Product of Example 5 99
" " " 11 178
49 150 - -
~ " " 1 190 (25 p.s.i. loss~
.. " " 19 216 (25 " "
. " " " 23 112 (25 " "
Copper strip tests were carried out by the ASTM
method except in that a temperature of 120C. was used. The
blends tested consiS~e~ of sufficient test additive to
provide a blend containing 0.15%S dissolved in a 500 Solvent
Neutral or a 150 Solven'c Neutral mineral oil. ASTM ratings
after 3 hours were as follows:-
21,
1~3~ 6
,
Test Additive RatingTest Additive Rating
.; , ~ , ~
None (bace oil only) 2bProduct of Example 18 2e
Produc~ of Exa~ple 1 2a 19 2e
" " " 4 2e " " " 21 1b
' " " " 5 2e " " ~ 22 2e
" " " 6 1b n ~ ~ 23 3b
" " " 8 1b " " " 24 1b
" " " 11 2e " " " 30 1b
" " " 12 2e " " " 33 1b
" " " 14 2b/c " " " 37 2c/3a
n n n 15 1b/3a 42 1b
" " " 16 3b " " " 49 2a
From the foregoing test results it can be seen
that the additives of the present invention impart
antioxidant properties (Rotary Bomb Test) and yet have a
low level of corrosiveness (Copper Strip Test) despite the
high sulphur content. Furthermore in the standard tests
the additives demonstrate load carrying abilities (~imken
OX load Test) and test engine performance (Peter WI Tests)
in fully formulated blends similar to those exhibited by the
zinc dialkyl dithiophosphateSnormally used in premium grade
-~ crank~se lubricants.
, 22,
~3~7~76
; The suitability of the additives of the present
invention for use in gear oil formulations was determined
- by use of the S.A.E. test~ in which two parallel shafts
are provided with interengaging surfaces lubricated with
. . .
the test blend and are driven at speeds in a ratio of
14.6:1. After a short running period the load on the
interengaging surface is incrementally increased until
scurfing occurs. With a blend consisting of an S.A.E.
90 base oil, 4.5% by weight of an additive in accordance
with the present invention (containing 30.3%S) and 0.5%
by weight di-isopropyl phosphite scuffing resulted at
2451b and 2301b (duplicate tests) at a drive shaft speed
of 1,000 r.p.m. Under the same condition a blend
consisting of the same base oil containing 4.5% by weight
sulphurised isobutylene (a commercially available gear oil
additive containing 45%S) and 0.5% by weight di-isopropyl
- phosphite resulting in scuffing at 2651b and 310 lb. Thus
, the blend containing the additive according to the present
invention produced similar test results even though the
sulphur content was substantially less than in the
comparison blend.
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