Note: Descriptions are shown in the official language in which they were submitted.
~06Z696
~ s invention relates to lubricant additives, more
particu~arly to lubricant oil dispersants.
Amongstthe numerous types of additives used in blend-
ing lubricants, particularly but not exclusively auto-
motive lubricants, are;various surface active materials.For example dispersants, particularly ashless dispersants,
are incorporated in lubricants in order to disperse carbon
particles and other insoluble materials such as decom-
position products and fuel oxidation products in the oil
medium which is the major constituent of the lubricants.
The insoluble materials are thus suspended in the oil
medium and prevented from forming deposits which can de-
leteriously affect engine operation.
According to the present invention there is pro-
vided a lubricating oil dispersant containing a polyisobutyl
phenoxy substituted acetic amide, said dispersant being pre-
pared by the process comprising ti) reacting a polyisobutyl
substituted phenol wherein said polyisobutyl substituent
contains from 50 to 200 carbon atoms with a Cl_4 alkyl
chloroacetic ester to form an intermediate mlxture con-
- taining polyisobutylphenoxy-substituted acetic ester, and
(ii) reacting said intermediate mixture with an ethylene
polyamine without removing unreacted C50_200 polyisobutyl-
phenol to convert said acetic ester to carboxylic amide,
said dispersant having a high amide and low polyisobutyl-
phenol content.
The present invention also includes a lubricating
oil containing a dispersing amount of such a dispersant.
In our copending Patent Application No 193507
there is provided a compound which is a condensation product
of an alkyl-substituted phenol, preferably a p-alkyl-
substituted phenol, in which the alkyl substltuent contains
at least 8 carbon at~ms and at least one halogen substituted,
preferably ~-halogen substituted, aliphatic carboxylic acid
or ester thereof.
Application No 193507 also includes processes for
preparing the novel substances of that application. Thus,
~pplicatioll No i9350, inci~d~s a process w~herein at ieast
one alkyl-substituted phenol, in which the alkyl
f~ ' ~
.. . .
,
106Z696
subs~ituent contains at least 8 carbon atoms, is
condensed with at least one halogen suhstituted ali-
phatic carboxylic acid or ester thereof.
It is highly desirable to employ an acid acceptor
to neutralise the hydrogen halide liberated in the
condensation of the alkylphenol with the chloroacetic
acid ester. Such acid acceptors are well known and
any suitable material can be used for this purpose,
e.g. a tertiary base such as a pyridine. However, the
preferred acid acceptsr is a metal base such as an
alcoholic solution of an alkali metal hydroxide, part-
icularly sodium or potassium hydroxide or an alkali
metal or alkaline earth metal alkoxide. The latter can ~ ;
be readily prepared by dissolving the metal in an alcohol,
such as methanol or ethanol, in well known manner. The
acid acceptor is preferably used in the stoichiometric
~ quantity required to neutralise the hydrogen halide.
; All the base required to-neutralise the hydrogen halide
may be added initially or the base may be added in
portions throughout the reaction. The portion-wise
addition of the acid acceptor is the pre~erred technique.
The condensation reaction proceeds very readily
in the presence of the acid acceptor and may be carried
out at ambient temperature. Conversely, comparatively
high reaction temperatures can also be used up to the
decomposition temperature of the reaction mixture.
However, to provide a more easily controllable reaction
.
~- at a rate more rapid than at ambient temperature, a
compromise reaction temperature of from 60C to 150C
is preferable, a temperature of from 70C to 100C being
C ! 3-
~062696
the optinum reaction temperature. Under these
conditions the reaction is usually complete within one
hour, completion being denoted when no further base is ~ ~-
consumed. Dropwise addition of the acid acceptor
facilitates the indication of the completion of the
reaction in this way. Alternatively, a pH indicator
or a pH meter may be used.
If desired, the condensation reaction may be
carried out in an inert solvent reaction medium, such ;
as a hydrocarbon solvent or alkanol solvent. Examples
of such inert solvents are benzene, toluene, xylene, ~;
n-butanol, 2-ethylhexanol and mineral oil, especially
a mineral oil of lubricating viscosity.
After completlon of the reaction the product may,
if desired, be washed with water to remove the halide
,~ :
salt of the acid acceptor formed during the reaction.
~; Alternatively the reaction product may be acidified and
washed with aqueous alcohol e.g. aqueous methanol.
Preferred amines are ethylene polyamines having
~ ~ 20 the general formula:-
; ~ H2 N ~ R NH t s H
wherein Rl2 is an ethylene radical and s is an integer ~,r, "~
from l to 6, more preferably from 3 to 5. Examples of
such amines are ethylene diamine, diethylene triamine,
.
~ triethylene tetramine, tetraethylene pentamine, penta-
:
ethylene hexamine and mixed higher polyethylene polyamines.
Useful higher ethylene polyamines have molecular
weights from 300 to l,000 or 5,000, preferably 400 to 600,
i 4-
106Z696
especially those prepared by polymerising ethylene
imine. The process of polymerising ethylene imine gives
rise to mixtures of polyethylene polyamines having a wide
range of molecular weiyhts. These may be divided into
mixtures havincJ narrow ranges of molecular weights,
those indicated being the most useful in this
invention .
Other polyamines which are useful in this invention.
are commercially available mixtures such as that pre-
dominantly consisting of a mixture of isomeric penta-
ethylene hexamines of formula C10 H28 N6 and related
hexamines containing piperazine rings and 12 C atoms.
The average molecular weight of the mixture is approx-
imately that of pentaethylene hexamine, i.e. 233, and
lS the mixture contains a predominance of amines having
2 - 4 primary amino groups and at least two secondary
amino groups.
Further suitable diamino compounds are bis (N-amino-
ethyl) and N-(~ -amino-ethyl) piperazines of formula:
_,,CH2 - CH
2 2C 2 N \ / (CH2 CH2)aH
CH2 - CH2
wherein a is O or 1.
The amine may be reacted with the intermediate
mixture in approximately equimolar proportions. The
resultiny reaction product will contain one or more
residual primary amino groups. Alternatively, with the
preferred linear alkylene polyamines the amine may be
reacted with up to twice the molar quantity of the
intermediate mixture or even more. It is not necessary
f~ ~ 5.
~06Z696
to use exactly molar quantities of the two reactants.
Useful additives can be obtained by employing, for
example, two moles of the intermediate mixture and 1.5
moles of the alkylene polyamine, giving a mixture of
products.
Alternatively, the starting materials are reacted
in equimolar proportions and one or more residual amino
groups are reacted with a carboxylic acid, to form an
amine salt, amide thereof or imidazoline or condensed
with aldehydes, ketones or mixtures thereof or with
mixtures of aldehydes and phenols to form Mannich bases,
in manner known per se. Alternatively, the amine may
be first reacted with appropriate quantities of the ' ,
carboxylic acids, aldehydes, ketones or mixtures of
aldehydes and phenols to provide an amine having a
residual primary or secondary amino group, and the
resulting amine reacted with the intermediate mixture.
In another embodiment of the present invention the
amine is an ethylene polyamine in which one primary
amino group is reacted, either before or after the amine ' ;
has been reacted in equimolar proportions with the
intermediate mixture, with an alkenyl substituted
succinic acid or anhydride thereof containing from 8
to ~00 carbon atoms in the alkyl substituent. Such
substituents are preferably residues of comparatively
low molecular weight polymers or olefins, such as
isobutylene or propylene, or oligomers of such olefins.
In view of the foregoing it will be understood that the
proportions of the co-reactants may be varied according
to the final product required.
' 6.
~ ~ .
~. .,
.
106Z696
The foregoing process of the present invention may
be readily carried out by heating the co-reactants
together and a preferred reaction temperature is from
50 to 250C, more preferably 130 to 220 C, most pre-
ferabl~ from 180 to 220C. An inert solvent, such as
xylene, toluene or mineral oil may be used.
The reaction may be most conveniently carried out
! in a vessel which is open to the atmosphere. However,
if desired the reaction can be carried out under vacuum
or low pressure conditions or under a nitrogen blanket.
The reaction is usually completed within 1 to 6 hours,
2 to 4 hours being most common.
As hereinbefore indicated the present invention
includes lubricant compositions containing dispersing
amounts of the dispersant of the present invention, which
are preferably used in an amount of from 0.3% to 15% by
: weight, more preferably 1~ to 6% by weight, based on
the total weight of the lubricant com.position.
Particularly preferred additives in accordance with
the present invention are the polybutyl phenoxyacetamides
.
derived from polybutenes of molecular weight 900 - 2800
and polyethylene polyamines having an average of from
4 to 6 amino groups, prepared by reactin~ a polybutyl
~:~ phenoxyacetic with the polyethylene polyamine in a molar ~ .
; 25 ratio of 2 : 1 - 1.5. :
:~ Also included within the scope of the present
invention are additive concentrates comprising a minor
amount of a lubricating oil and a major amount of one or
more additives in accordance.with the present invention, ~:
including additive concentrates comprising a minor amount
1062696
of a lubricating oil and a major amount of a combination
of one or more additives in accordance with the present
invention and at least one other lubricant additive.
The lubricating oil used in the lubricating com-
S positions of the present invention may be any of the
well known synthetic ester oils, such as dioctyl sebacate.
The preferred oils, however, are mineral oils o lubrica-
ting viscosity of well known type.
The present invention will now be illustrated with
reference to the following examples.
Example l
(a) Preparation of n-Butyl polyisobutylnhenoxyacetate
To a solution of PIB phenol (107.0g., O.lm.), pre-
2ared by alkylation of phenol with lOOO molecular weight
polyisobutylene using a BF3/nhenol complex as catalyst,
and n-butyl chloroacetate (2~.6g., O.lSm.) in xylene ~ -
(lOOml.) was slowly added, over about one hour, a solution
of sodium methoxide (8.lg., O.lSm.) in anhydrous methanol
(40ml.). The addition was carried out at 100C. and on
~completion the solution was heated at this temperature
;~ for a further one hour. The solution was washed with
10% hydrochloric acid (50ml.) followed by 3 x 80ml.
portions of a~ueous methanol (1:4). After being dried
over magnesium sulphate the solution was stripPed of
solvent.
Yield = 102g.
A sample of this product was saponi.ied with excess
. ~ .
aqueous potassium hydroxide, acidified with hydrochloric
acid and then washed with portions of aqueous methanol
(l:4) untiI acid free. The acid value of the thus
.
1062696
formed PIB phenoxy acetic acid (36.Smg. KOH/a. ) indica-
ted that a conversion of 73~ had been obtained.
(b) Reaction of n-Butyl PolyisobutylPhenoxvacetate
tetra ethvlene ~entamine to form an amide
A mixture of PIB phenoxy butyl acetate (50g.) and
tetra ethylene nentamine (3g.) was heated at 200C. for
four hours under an atmosphere of nitrogen. After dilu-
tion with mineral oil the mixture was filtered to give
a clear product.
% nitrogen = 1.8 (calc. = 1.8)
acidity = 5mg. KOH/g.
TBN = 37mg. KOH/g.
Exam~les 2 to 13
Prenaration of n-ButYl polyisobutylp-henoxyacetate
lS A solution of sodium methoxide, nre?ared by dissol-
ving sodium (43.0g., 1.87 mole) in dried methanol
(60 c.c.) was added to a stirred solution of nolyisobutyl
phenol (1943g., 1.7 ~ole) (prepared by boron trifluoride
catalysed alkylation of phenol with 1000 M.~. polyiso~
butylene) and n-butyl chloroacetate (2~1.4q., 1.87 mole)
in xylene (850 c.c.) at 100C. The addition took 1~
hours and the solution was then stirred at 69C for 2
hours.
The solution was stirred with hydrochloric acid/
water (1-4) (225 c.c.) and allowed to separate. The
organic layer was then washed with water/methanol (1:4)
(3 x 500 c.c.), petroleum spirit (b.p. 62-68C) being
added to assist seoaration. The solution was dried over
magnesium sulphate, filtered and stripped to 170 C. -~
under vacuum.
9.
'
~1
,: ~- - : . . . . - - . : - ,
~ . . - :: .
~06Z6g6
1734g. (7q~) of the intermediate was thus obtained.
Saponification value:- 40.4mg. KOTI/g.
A number of intermediate esters (~xamples 3 to 17)
~ere ~repared by the same general method, details being
given in Table 1. In certain cases, namely ~xamples 3,
4, 5, 6 and 12 the acid treatment was omitted, and the
number of aqueous methanol washes was reduced to 1 or 2.
In some cases, the reaction solvent was mineral oil, as
shown in Table 1.
Exam*le 14
Pre~aration of Tetraethylene ~entamine amide of
Polyisobutyl~henoxyacetic acid.
The product of Example 2 (1500g., 1.03 moles) was
stirred with tetraethylenepentamine (119g., 0.63 mole)
at 200C., in an atmos~here of nitrogen for 4 hours.
"
Evolved n-butanol was permitted to escape during the
reaction. The product was cooled, diluted with mineral
oil (276g.) and~filtered in petroleum ether solution.
Removal of the solvent gave the amide (1650~., ~1~). ;
20 ~ %~ 2.2; (calc. 2.2.~)
Anhydrous TBN 51.5mg. KOH/g.
;~ Examples 15 to 26
~ : , ,
A number of amides were nrepared by the same general
method as for Example 1~, full details heing aiven in
~; 25 Table 2. Products were prepared as approxi~ately 85~
concentrates in mineral oil, except for Examle No. 23
~h ~ and~also where the intermediates were ~renared in oil,
in which case the final products were approximately 60%
oil concentrates. One product (Example 37) was prepared
wlthout oil addition.
,
10 .
~, ,, , .,, ~ , . . .
~06Z6g6
For some pre~arations, particularl~ whcre volatile
amines were used, it was necessary to modi y the prepara-
tive procedure. Ilith ethylenediamine (Example 28) the
reactants were heated under reflux in toluene solution
for ~ hour, the toluene was distilled out, and heating
was continued at 200C. for 3 hours, without a condenser.
Example 27
A solution of sodium methoxide, ~reParec~ by dissol-
ving sodium (12.7g., 0.55 mole) in dry methanol (150
c.c.) was added slowly to a stirred solution of ?olyiso-
butyl phenol (from 1000 M.'l. PIB) (571.5~., 0.5 mole) and
n-butyl chloroacetate (83g., 0.~55 mole) in minera] oil
(438g.) at 70C. ~eaction was continued for 2 hours and
the mixture was then vacuum-strip?ed at 1~0C. and fil-
tered in the petroleum ether solution. mhe resultant
ester had a saponification value of 21.7mg. KOH/g.
600g. (0.23 mole) of the ester were reacted for 4
hours at 200C. with TEPA (26.9g., 0.14 mole), and the
product was filtered.
Yield:- 550g., 90%
%N:- 1.5 (Calc. 1.55%)
TBN:- 39.mg. KOH/g
Spot test rating:- B
Example 28
A further sample of n-butyl PIB phenoxyacetate was
prepared in oil, as described in ~xample 27, except
that the ester was vacuum-stripped in the Presence of a
filter-aid and was filtered neat.
1976g. (0.74 mole) of this ester were reacted for
4 hours at 200 C. with TEPA (70.0g., 0.37 mole), and
Cl ::.
1~6Z696
the product was filtered.
Yield:- 1920~., 96~ ~-
~N:- 1.2 (calc. 1.2~)
TBN:- 30mg. KO~/g.
Spot testing rating:- B
Examples ~a to 31
Free amino groups in the amide of Example 25 were .. t~
further reacted with an aldehyde to form a Schiff's base,
and aldehyde and a phenol to form a Mannich base and
with a carboxylic acid to form an amide. Details of these
~reparations are given in Table 3.
Example 32
An intermediate ester, similar to that of Example
9 (9OOg., 0.60~m) was reacted with TEPA (7.~0g., 0.3~1m)
at 200C. for 4 hours under nitrogen. Polysiobutyl
succinic anhydride (prepared from 650 M.~. PTB) (163g.,
0.153m) was added and reaction was continued at 200C.
for a further ~ hours. The mixture was cooled, diluent
oil (192g.) was added, and the product was filtered in
petroleum ether solution.
%N: 1.9 (Calc., 1.9%)
;~ TBN:- 30mg. KOH/g.
Panel coker rating:- 69.5
Spot test rating:- A
Suitability of the products of the present invention
; for use as ashless dispersants in lubricants were de-
termined by MS VC and Petter AV-B Engine tests, by
Panel Coker Tests and by Spot Tests.
The VC tests were carried out by the standard
method on two formulations containing test additives.
C i :
1062696
Formulation A was a lOI~/30 blend, formulated to
meet U.S. S~ecification MIL-L-46152, containing commer-
cially available metal sulphonate detergents, viscosity
index improver and antioxidant/antiwear additi~e and in
which the ashless dispersant normally present (4.5~) was
replaced by the test additive, also at 4.5~.or at equiva-
lent active dosage. The blend had a sul.phated ash con-
tent of 1%. Formulation B was similar to formulation
A, but having a sulphated ash content of 0.5% and con-
taining ashless corrosion inhibitors.
After the tests, merit ratings were assigned accor-
ding to the condition of the test engine in the usual.
way and these ratings were as follows:-
FORMl1LATION A
.15 Test Average Sludge Average Varnish Piston
Additive(Max lO) (Max lO) Skirt :,
Varnish
(Max lO)
Product of Example
24 (5.3%) 9.0 8.3 8.5 .
~; Additive X(4.5%) 4.9 7.5 7.2
FORMULATIO'~
Test Average Sludge Average Varnish Piston
Additive(Max lO) (Max lO) . Skirt
Varnish :: ?
(Max lO)
Product of Example
~ 14 (475%) 9.0 8.3 8.5
: l3. .~:
~ .
.. , ... . ................... ... . , . ~ . :
~06Z696
FORMULATIO~ B Cont'd
_
Test Average Sludge Average Varnish Piston
Additive (Max 10) (Max lo) Skirt
_._____ _ .. __................. . !.~
Varnish '
(~lax 10)
Product of Example
22 (6.4~) 9.2 8.2 8.3
Additive X is a commercially available ashless
dispersant consisting of a borated Mannich base of a poly-
isobutyl phenol.
The Petter AV-B tests were also carried out according
to the standard procedure and merit ratings (maximum 10)
assigned in the usual way according to the condition, after
test of various parts of the test engine.
Carbon deposition in the grooves of the test en~ine
were also measured. Groove carhon and the overall merit
rating (maximum 100) derived from the individual ratings
were as follows:-
Test Additive Groove Carbon (~) Overall Rating
1st 2nd 3rd
Product of Example
24 (4.06%) 76.8 1.0 Nil 74.8
Product of Example
23 10 Nil Trace 91.4
Product of repeat
of Example 38 Nil Nil 83.3
~; 25 Product of Example
27 (4.95~) 66 3 Nil 70.3
Product of Example
28 (4.95~) 26.1 Nil Nil 87.0
Additive X 93.0 30.1 0.8 50.7
14.
~`1
.
.. ,, ........ .... . - , -
106;~696
.,~,
The test blend used in the AV-B tests was an S~E
30 blend, formulated to meet the requirements of U, S .
S~ecification MIL-L-2104-C, containing commercially
available sulphonate detergents, corrosion inhibitor
and antioxidant/antiwear additive, ancl in which the
ashless dispersant normally present (3.5%) was replaced
by the test additive, also at 3.5% except where stated.
The Panel Coker tests were carried out usiny the
same test blend as for the AV-B test and were carried
out for 3~ hours in a slightly modified form of the
normal apparatus. Instead of continuous oil splashing,
the oil was splashed against the aluminium panel
maintained at 600F. with a cycling procedure consisting
of a splashing period of 15 seconds and a 45 second
period when the paddle was stationary. The apparatus
was further modified to allow a flow of moist air
through the sump a~ove the oil surface at the rate of
2.3 litres per hour. ?
The area of the sump not normally immersed in oil
Z0 was rated according to the percentage cleanliness in
much the same manner as an engine piston is rated after
a test such as the Caterpillar l-G test, to give a ~
Merit Rating (100 = Perfectly clean). It is believed -
that the above-mentioned test correlates well with the ;
Caterpillar 1-G Engine Test.
In the spot tests the test additives were
dissolved in mineral oil (V21o=3.5cS) at 4~, except
where the additives had been prepared as 60~ concentrates
in oil in which cases 5.8~ additive was used. Carbon
black (Spheron 9- ex Cabot Carbon Coy - average particle
'`.
C ~ 15.
~062696
size = 27m) (1~) was added and the mixtures (lOg) were
agitated for 1 hour, using an Ultrasonic Generator in
5" x 1" test-tubes. The tubes were then stored at
50C. for 16 hours and allowed to cool. Drops of
oil, taken from the top ~", were spotted on to
chromatography paper, using a fine glass rod. The
spots were then allowed to develop for 24 hours, and
rated as follows:-
A = Carbon well dispersed
B = Carbon moderately well dispersed
C = Carbon poorl~r dispersed
D = Carbon not dispersed
The ratings obtained in the Panel Coker and spottests are recorded in the following Tables 2 and 3.
15 The Panel Coker tests were carried out at a test
additive concentration of 3.5% except where the
products had been prepared as 60% concentrates in oil
when 5.1% of the products was used. In the same Panel
Coker test a rating of 61.2 was obtained with additive
X. In the spot test a sample of the mineral oil without
additlve gave a D rating.
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1062696
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