Note: Descriptions are shown in the official language in which they were submitted.
~l63~sa
BENZOTRIAZOLE COMPOSITIONS DISPERSIBLE
IN CO~IPOUNDED LUB~ICANTS
This invention relates to new compositions of
matter, methods for their preparation, and lubricants
S containing them. More particularly, it relates to composi-
tions of matter dispersible in compounded lubricants, said
compositions being prepared by reacting at least one sub-
stantially wa~er-insoluble aliphatic amine with at least one
benzotriazole.
It is known that improved oxidation and corrosion
resistance and decreased copper activity can be imparted to
lubricants by the incorporation therein of minor amounts of
benzotriazoles. The preparation of lubricants containing
benzotriazoles is difficult, however, because many benzo-
15 triazoles are solid and most are substantially insoluble
in lubricating oils. It is of interest, therefore, to
develop methods for increasing the compatibility of benzo-
triazole-containing compositions with formulated lubricants.
A principal object of the present invention,
20 therefore, is to provide novel benzotriazole compositions
and a method for their preparation.
A further object is to provide benzotriazole
compositions which may be stably incorporated in lubrica-
ting oils, especially gear lubricants.
A further object i5 to produce lubricants, es-
pecially gear lubricants, which are highly rssistant to
.
.,''' ~
~ 163g9~
--2--
corrosion and oxidation and which are low in copper ac-
tivity.
Other objects will in part be ob~ious and will in
part appear hereinafter.
The benzotriazole used in the method of this
invention may be substituted or unsubstituted. Examples of
suitable compounds are benzotriazole and the tolyltriazoles,
ethylbenzotriazoles, hexylbenzot:riazoles, octylbenzotria~
zoles, phenylbenzotriazoles, chlorobenzotriazoles and
10 nitrobenzotriazoles. Preferred are benzotriazole and the
alkylbenzotriazoles in which the alkyl group contains about
1-8 carbon atoms, especially benzotriazole and tolyltria-
zole.
The amine may be any substantially water-insoluble
15 aliphatic monoamine or polyamine, with monoamines being pre-
ferred. It may be primary, secondary or tertiary, with
amines containing at least one primary amino group being
preferred. For the most part, the water-insoluble aliphatic
amines contain at least one alkyl group having at least
20 about 10 carbon atoms. Suitable ones include the decyl-
amines, didecylamines, tridecylamines, dodecylamines,
tetradecylamines and octadecylamines, with all isomers being
suitable. Mixtures of these amines are also useful for the
purposes of this invention. A preferred class of amines,
25 especially for the preparation of compositions for use in
gear lubricants, comprises the primary amines in which the
alkyl group contains about 10-30 carbon atoms, particularly
those in which the alkyl group is a tertiary group. Illus-
trative amine mixtures of this type (a~ailable from Rohm &
30 ~aas Co.) are "Primene 81R" which is a mixture of Cl 2-1~
tertiary alkyl primary amines, and "Primene JM-T" which is
a similar mixture of C 18-2 2 amines.
A second preferred class of amines, especially for
preparing compositions for use in internal combustion
engine lubricants, comprises the oil-soluble basic nitrogen-
containing dispersants, preferably those containing no more
than 100 and usually no more than about 25 aliphatic carbon
atoms per basic amino group. Dispersants of this type are
.
~ 1~399~
-- 3 --
known in the art and include such subclasses as the "carboxylic
dispersants", "amine dispersants" and "Mannich dispersants".
The carboxylic dispersants are :reaction products of
carboxylic acids (or derivatives the:reof) containing at least
about 44 and preferably at least about 54 aliphatic carbon atoms
with polyamines and optionally also with organic hydroxy compounds
such as phenols and alcohols and/or basic inorganic materials.
Examples of these products are described in many U.S. patents, of
which 3,272,746 is one example.
The amine dispersants are reaction products of aliphatic or
alicyclic halides containing at least about 40 carbon atoms with
polyamines, preferably polyalkylene polyamines. Examples thereof
are described, for example, in the following U.S. patents:
3,275,554 3,454,555
3,438,757 3,565,804
The Mannich dispersants are reaction products of alkyl phenols
in which the alkyl group contains at least about 40 carbon atoms
with aliphatic aldehydes containing at most about 7 carbon atoms
(especially formaldehyde) and polyamines (especially alkylene
polyamines). The materials described in the :Eollowing U.S. patents
are illustrative:
2,459,112 3,442,808 3,591,598
2,962,442 3,448,047 3,600,372
2,984,550 3,454,497 3,634,515
3,036,003 3,459,661 3,649,229
3,166,516 3,461,172 3,697,574
3,236,770 3,493,520 3,725,277
3,355,270 3,539,633 3,725,480
3,368,972 3,558,743 3,726,882
3,413,347 3,586,629 3,980,569
The carboxylic dispersants may be most conveniently and
accurately described in terms of radicals 1 and 2 present therein.
Radical 1 is usually an acyl, acyloxy or acylimidoyl radical
~l containing at least about 34 carbon ............................
;i, .
~ 1~3~9~
atoms. The structures of these radicals, as defined by the
International Union of Pure and Applied Chemistry, are as
follows (each R' individually repreSeTIting a hydrocarbon
or similar grouP):
1
Acyl: R'-C-
o
Acyloxy: R'-C-O-
NR'
~cylimidoyl: R'-C-
Radical 2 is preferably at least one radical in
which a nitrogen or oxygen atom is attached directly to said
10 acyl, acyloxy or acylimidoyl radical, said nitrogen or oxygen
atom also being attached to a hydrocarbon-based radical
containing at least one basic amino group.
The preferred carboxylic dispersants are those
disclosed (for example) in the above-mentioned U.S. Patents
15 3,219,666 and 3,272,746 which also describe a large number
of methods for their preparation. Radical 2 therein is
derived from compounds characterized by a radical of the
structure ~ N~ wherein the two remaining valences of nitro-
gen are satisfied at least in part by organic radicals
20 bonded to said nitrogen atom through direct carbon-to-
nitrogen linkages, said organic radicals containing at least
one basic nitrogen atom. These compounds include aliphatic,
heterocyclic and carbocyclic amines.
Hydroxy amines are included in the class o~
25 useful amines. Such compounds are the hydroxyhydrocarbyl-
substituted compounds such as those having the formulas
HNRIR2, wherein Rl is an alkyl or hydroxy-substituted alkyl
radical of up to lO carbon atoms and R2 is hydrogen or a
radical similar to Rl, at least one of R1 and R2 being
30 hydroxy-substituted. Suitable hydroxy-substituted mono-
amines include ethanolamine, di-3-propanolamine, 4-hydroxy-
butylamine, diethanolamine, N-methyl-2-propylamine, N-
hydroxyethylethylene diamine, N,~-di(hydroxypropyl)propylene
diaminP and tris(hydroxymethyl)methylamine. While in
~ ~63~
--5--
general, hydroxy amines containing only one hydroxy group
will be employed as reactants, those containing more can
also be used.
Heterocyclic polyamines are also useful in making
5 the carboxylic dispersant, prov:Lded they contain at least
two amino groups of which at least one is primary or secon-
dary. The heterocyclic ring can also incorporate unsatu-
ration and can be substituted with hydrocarbon radicals such
as alkyl, alkenyl, aryl, alkaryl or aralkyl. In addition,
10 the ring can also contain other hetero atoms such as oxygen,
sulfur, or other nitrogen atoms including those not having
hydrogen atoms bonded to them. Generally, these rings have
3-10, preferably 5 or 6, ring members. Among such hetero~
cycles are aziridines, azetidines, azolidines, pyridines,
15 pyrroles, piperidines, imidazoles, indoles, piperazines,
isoindoles, purines, morpholines, thiamorpholines, azepines,
azocines, azonines, azecines and tetrahydro-, dihydro- and
perhydro-derivatives of each of the above. Preferred
heterocyclic amines are the saturated ones with 5- and 6-
20 membered rings, especially the piperidines, piperazines andmorpholines described above.
Aliphatic polyamines are preferred for preparing
the carboxylic dispersant. Among the polyamines are
alkylene polyamines (and mixtures thereof) including those
25 having the formula
A-N-~R3-N~-nH
A A
wherein n is an integer between about 1 and 10, preferably
between 2 and 8; each A is independently hydrogen or a
hydrocarbon or hydroxy-substituted hydrocarbon radical
30 having up to about 30 atoms; and R3 is a divalent hydro-
carbon radical having from about 1 to about 18 carbons.
Preferably A is an aliphatic radical of up to about 10 car-
bon atoms which may be substituted with one or two hydroxy
groups, and R3 is a lower alkylene radical having 1-10,
35 preferably 2-6, carbon atoms. Especially preferred are
the alkylene polyamines wherein each A is hydrogen. Such
1 l63s~a
--6--
alkylene polyamines include methylene polyamines, ethylene
polyamines, butylene polyamines, propylene polyamines,
pentylene polyamines, hexylene polyamines and heptylene
polyamines. The higher homologs of such amines and related
5 aminoalkyl-substituted piperazines are also included.
Specific examples of such polyamines include ethylene
diamine, triethylene tetramine, tris(2-aminoethyl)amine,
propylene diamine, trimethylene diamine, hexamethylene
diamine, decamethylene diamine, octamethylene diamine,
10 di(heptamethylene) triamine, tripropylene tetramine, tetra-
ethylene pentamine, trimethylene diamine, pentaethylene
hexamine, di(trimethylene) triamine, 2-heptyl-3-(2-amino-
propyl)imidazoline, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-
aminopropyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and
15 2-methyl-1-(2-aminobutyl)piperazine. Higher homologs,
obtained by condensing two or more of the above-illustrated
alkylene amines, are also useful, as are the polyoxy-
alkylene polyamines (e.g., "Jeffamines").
The ethylene polyamines, examples of which are
20 mentioned above, are especially useful for reasons of cost
and effectiveness. Such polyamines are described in detail
under the heading "Diamines and Higher Amines" in Kirk-
Othmer, Encyclopedia of Chemical Technolo~y, Second
Edition, Vol. 7, pp. 22-39. They are prepared most con-
25 veniently by the reaction of an alkylene chloride withammonia or by reaction of an ethylene imine with a ring-
opening reagent such as ammonia. These reactions result
in the production of the somewhat complex mixtures of
alkylene polyamines, including cyclic condensation products
30 such as piperazines. Because of their availability, these
mixtures are particularly useful in preparing the composi-
tions of this invention. Satisfactory products can also be
obtained by the use of pure alkylene polyamines.
Hydroxy polyamines, e.g., alkylene polyamines
35 having one or more hydroxyalkyl substituents on the nitrogen
atoms, are also useful in preparing the carboxylic dispersant.
Preferred hydroxyalkyl-substituted alkylene polyamines are
1 16~9g8
--7--
those in which the hydroxyalkyl group has less than about 10
carbon atoms. Examples of such hydroxyalkyl-substituted
polyamines include N-(2-hydroxyethyl)ethylene diamine, N,N'-
bis(2-hydroxyethyl)ethylene diamine, l-(2-hydroxyethyl)-
5 piperazine, monohydroxypropyl~substituted diethylene tri-
amine, dihydroxypropyltetraethylene pentamine and N-(3-
hydroxybutyl)tetramethylene dialmine. Higher homologs
obtained by condensation of the above-illustrated hydroxy-
alkyl-substituted alkylene amines through amino radicals or
lO through hydroxy radicals are likewise useful.
The source of radical l in the carboxylic dis-
persant is an acylating agent comprising at least one
carboxylic acid-producing compound containing a hydrocarbon
or substituted hydrocarbon substituent which has at least
15 about 30 and preferably at least about 50 aliphatic carbon
atoms. By "carboxylic acid-producing compound1' is meant an
acid, anhydride, acid halide, ester, amide, imide, amidine
or the like; the acids and anhydrides are preferred.
The carboxylic acid-producing compound is usually
20 prepared by the reaction (more fully described hereinafter)
of a relatively low molecular weight carboxylic acid or
derivative thereof with a hydrocarbon source containing at
least about 30 and preferably at least about 50 carbon
atoms. The hydrocarbon source is usually aliphatic and
25 should be substantially saturated, i.P. ~ at least about 95%
of the total number of carbon-to-carbon covalent linkages
should be saturated. It should also be substantially fxee
from pendant groups containing more than about six aliphatic
carbon atoms. It may be a substituted hydrocarbon source.
30 By "substituted" is meant sources containing substituents
which do not alter significantly their character or reac-
tivity; examples are halide, hydroxy, ether, keto, carboxy,
ester (especially lower carbalkoxy), amide, nitro, cyano,
sulfoxy and sulfone radicals. The substituents, if present,
35 generally comprise no more than about 10% by weight of the
hydrocarbon source.
~ ~ ~i 3 ~9~ a
The preferred hydrocarbon sources are those de~
rived from substantially saturated petroleum fractions and
olefin polymers, particularly polymers of monoolefins
having from 2 to about 30 carbon atoms. Thus, the hydro-
5 carbon source may be derived from a polymer of ethylene,propene, l-butene, isobutene, l-octene, 3-cyclohexyl~l-
butene, 2-butene, 3-pentene or the like. Also useful are
interpolymers of olefins such as those illustrated above
with other polymerizable olefinic substances such as
10 styrene, chloroprene, isoprene, p-methylstyrene, piperylene
and the like. In general, these interpolymers should con-
tain at least about 80~, preferably at least about 95~, on
a weight basis of uni~s derived from the aliphatic mono-
olefins.
Another suitable hydrocarbon source comprises
saturated aliphatic hydrocarbons such as highly refined
high molecular weight white oils or synthetic alkanes.
In many instances, the hydrocarbon source should
contain an activating polar radical to facilitate its
20 reaction with the low molecular weight acid-producing com-
pound. The preferred activating radicals are halogen atoms,
especially chlorine, but other suitable radicals include
sulfide, disulfide, nitro, mercaptan, ketone and aldehyde
groups.
As already pointed out, the hydrocarbon sources
generally contain at least about 40 and preferably at least
about 50 carbon atoms. Among the olefin polymers those
having a number average molecular weight between about 600
and about 5000 (as determined by gel permeation chromato-
30 graphy) are preferred, although higher polymers having
molecular weights from about 10,000 to about 100,000 or
higher may sometimes be used. Especially suitable as hydro-
carbon sources are isobutene polymers wi~hin the prescribed
molecular weight range, and chlorinated derivatives thereof.
Any one of a number of known reactions may be em-
ployed for the preparation of the carboxylic acid-producing
1 ~6399~
_9_
compound. Thus, an alcohol of the desired molecular weight
may be oxidized with potassium permanganate, nitric acid or
a similar oxidizing agent; a halogenated olefin polymer may
be reacted with a ketene; an ester of an active hydrogen-
5 containing acid, such as acetoacetic acid, may be convertedto its sodium derivative and the sodium derivative
reacted with a halogenated high molecular weight hydrocarbon
such as brominated wax or brominated polyisobutene; a high
molecular weight olefin may be ozonized; a methyl ketone of
10 the desired molecular weight may be oxidized by means of the
haloform reaction; an organometallic derivative of a halo-
genated hydrocarbon may be reacted with carbon dioxide; a
halogenated hydrocarbon or olefin polymex may be converted
to a nitrile, which is subsequently hydrolyzed; or an olefin
15 polymer or its halogenated derivative may undergo a reaction
with an unsaturated carboxylic acid or derivative thereof
such as acrylic acidl methacrylic acid, maleic acid, maleic
anhydride, fumaric acid, itaconic acid, itaconic anhydride,
citraconic acid, citraconic anhydride, mesaconic acid,
20 glutaconic acid, chloromaleic acid, aconitic acid, crotonic
acid, methylcrotonic acid, sorbic acid, 3-hexenoic acid,
10-decenoic acid, 2-pentene-1,3,5-tricarboxylic acid, and
the like, or with a halogen-substituted carboxylic acid or
derivative thereof. This latter reaction is preferred, es-
25 pecially when the acid-producing compound is unsaturated and
preferably when it is maleic acid or anhydride. The result-
ing product is then a hydrocarbon-substituted succinic acid
or derivative thereof. The reaction leading to its forma-
tion involves merely heating the two reactants at a temper-
30 ature from about 100 to about 200C. The substitutedsuccinic acid or anhydride thus obtained, may, if desired,
be converted to the corresponding acid halide by reaction
with known ha].ogenating agents such as phosphorus tri-
chloride, phosphorus pentachloride or thionyl chloride.
For the formation of the carboxylic dispersant,
the hydrocarbon-substituted succinic anhydride or acid, or
3s~a
--10--
other carboxylic acid-producing compound, and the alkylene
polyamine or other nitrogen-containing reagent are heated to
a temperature above about 80C., preferably from about 100
to about 250C. The product thus obtained has predominantly
5 amide, imide and/or amidine linkages (containing acyl or
acylimidoyl groups), or, if a hydroxy amine is used, may
contain ester linkages. The process may in some instances
be carried out at a temperature below 80C. to produce a
product having predominantly amine salt linkages (containing
10 acyloxy groups). The use of a diluent such as mineral oil,
benzene, toluene, naphtha or the like is often desirable to
facilitate control of the reaction temperature.
The relative proportions of the carboxylic acid-
producing compound and the alkylene polyamine or the like
15 are such that at least about one-half the stoichiometrically
equivalent amount of polyamine is used for each equivalent
of carboxylic acid-producing compound. In this regard it
will be noted that the equivalent weight of the alkylene
polyamine is based upon the number of amine radicals therein,
20 and the equivalent weight of the carboxylic acid-producing
compound is based on the number of acidic or potentially
acidic radicals. (Thus, the equivalent weight of a hydro-
carbon-substituted succinic acid or anhydride is one-half
its molecular weight.) Although a minimum of one-half
25 equivalent of polyamine per equivalent of acylating agent
should be used, there does not appear to be an upper limit
for the amount of polyamine. If an excess is usecl, it
merely remains in the product unreacted without any apparent
adverse effects. Ordinarily, about 1-2 equivalents of
30 polyamine are used per equivalent of acylating agent.
In an alternative method for producing the car
boxylic dispersant, the alkylene polyamine is first reacted
with a low molecular weight, unsaturated or halogen-
substituted carboxylic acid or derivative thereof (such as
35 maleic anhydride or one of the others previously mentioned)
and the resulting intermediate is subsequently reacted with
the hydrocarbon source as previousl~ described.
1 ~639~8
--11--
It is also possible to prepare carboxylic dis-
persants by reacting the acylating agent simultaneously or,
preferably, sequentially with at least one of the above-
described nitrogen-containing reagents and with at least one
5 hydroxy compound. The hydroxy compounds are usually alco-
hols containing up to about 40 aliphatic carbon atoms.
These may be monohydric alcohols such as methanol, ethanol,
isooctanol, dodecanol, cyclohexanol, neopentyl alcohol,
monomethyl ether of ethylene glycol and the like, or poly-
10 hydric alcohols including ethylene glycol, diethyleneglycol, dipropylene glycol, tetramethylene glycol, penta-
erythritol, glycerol and the like. Carbohydrates (e.g.,
sugars, starches, cellulose) are also suitable as are par-
tially esterified derivatives of polyhydric alcohols having
15 at least three hydroxy radicals. Aliphatic polyols contain-
ing up to 10 carbon atoms and at least 3 hydroxy groups,
especially those with up to 6 carbon atoms and 3-6 hydroxy
groups, are preferred.
The reaction with the hydroxy compound is usually
20 effected at a temperature above about 100C. and typically
from about 150 to about 300C. The relative amounts of the
nitrogen-containing and hydroxy reagents may be between
about 10:1 and 1:10, on an equivalent weight basis.
Typical carboxylic dispersants suitable for use
25 according to this invention are listed in Table I. "Reagent
1" and "Reagent 2" aré, respectively, ~he sources of radi-
cals 1 and 2 as previously defined.
g ~ 8
--12 ~
r~ ~ r~
r~ r~ rl r~ rl r~
1~ O O O O O O O
r~ ~ r-l r~ a) r-l
~1 ~ a) h ~::
r~
.r~ r~ r~rt O
O ~ o Ln Ll~
rl ~) c~ Ln r-
o o o or--l r--
u ~ ~ Ln Ln Ln Ln Ln
o ~I r-l r-l r--
P~ E3 co ~ o
tn
L~
O
C) co r--l r~
O r~
r~
r-l O O r--l r--l~I r-l O
1~ r I
tr
a) a
.r~ .r~
~ r ~ X ~ r--l r~
r~ r
,5~ r~ r--l.C r
~ ~- S: r h E~ ~ $ ~
H ~: r~ 4 ~ al .r l L~ 5-1
a) O ~ a~ a) a) .r-~O X ~ h ~ o-- u~
1~1 tJ ~ O h ~I r-l (I) ~ h O O .
~ ~ U 1`
tq (I) ~ rd ~ rc~
lC p; ~ O ~) ~) ~I r~ h 0 -1 a) r-l
E~ a1 h ut ~ -r~ ~ ~ al 3 ~ r-l 0
r~ r--l ~1 ~i I al a~ O
.5 X O O s ~ I r~ r-l r~l 11~ ~
-1 R h ~) ~ rl ~rl h I ~1 a) O O X til
æ ~ ~:
. ~, ~ o
r~ Ln
3 0 O a~ s o
r~ r~
r--I r~ h r~ ~ Q
Q u ~ ~ ~rl O ~D ~D O ~ a) O
r-l~; u ~ ~ r~ r-l ~) R ~Ir-l r-l r-
-- ~ r~ r~
h ~ h ~ R Cl r4 ~ E3
O::>1~ h ~ r-l X ~r-l rl ~~ rl X X X X
r~ 3 0 .~; O 1~ W
rc~ r-l u ~¦
a~ ~ cn~l S ~1 u~ X ~ X ~ tQU~
r~ \ 3 1~1 ~ 3 fd
U ~ ~ o a) ~ a)a~ a) (D
.r~ r~ ) r-l Ln ~ u ~ ~ k E~ ~i
O Q ~ h ~ h S:: ~ r~ X O O ~rl X O
r-l
X
39~8
--13--
.,~ .~ .,1
O O O
a) ~ ~1 ~1
~ 0
_l S~
.~ a~a) a~ ~ I a
.,1 .,~ .,1 ~,
~ ~ ~ ~ X X
a~
~ S~
O ~ o o
,1 ~ ~1 ~
. o o ~ o ~ o
o ~ O ~ 0 ~1
P; ~ U~ ~
U~
q~
O ~
a) ,~ ~r
O ~I N ~ O el' O O
-
O ~ O ~ ~1 0
a
O--
~1
`~ O '-
~ ~ 'I O
H ~ ~ ~ O ~
~ d ~ ~ a) G) ~1
p:~~ ~n ~ h
E~ ~ O
a)a~ ~ k
o o x ~ ~s~
I o ~ .
. ~ o ~ 3
~ ~ ~ ~O o ~1 o ~
X Q S~0 ~I t) O ~ X
~1~1 a~ ~ o
~ ~ R 3 ~ ~ C)
Q. ~a) ~ h ,1 o ~:1 0
E~ ~a) ~ ~ a) o o Ln a~ ~ ~ o o
~:: ~ u ~ ~ 3a) ~ o~o ~ ,~
X ~~R Q ~ ~ u~~ o r~
~1 ~ X O ~ q~ U 3 0 :~ v~ a) O ~ O
~; ~1 ~ 0~ ~ ~o
1 0 o Z
~ Q) ~ V rl ~ ~ U ~ o
u~I V 3 ~ ; S:~ R ~:: Q 3 ~:; ~ U
a)
~ ~ c~
X
-
~ 1639~8
--14--
~ l l
~ l
,~
~ 5
o ~
,1 ~ o o
. o
o s~ U
~o
o o
~; ~ oo CO
_
..
U~
o
a~
O ~I N CO CO
-
~ ~1 O O
P; ~
.~
X
a~
S
~1
~1 ~ ,, x
~ ~ s ~q
E~
U~
~a I
~ ~rl O
0 3 ss ~ i
c~o o
U~
3 o
o
a~ ~ aJ ~
~ ~ ~ ~D ~ O ~ S
a~ o
rJ ,~ ~ 3 r~
O O ~1'` ~ E3 S O
~ o ,~
a~ o o G)
C~
L~
~1
X
B
--15--
In the preparation of carboxylic dispersants such
as those described in Examples 1-16, reagent 1 is normally
prepared by reacting appro~imately equimolar amounts of the
hydrocarbon source and the low molecular weight carboxylic
5 acid or derivative thereof. It is also within the scope of
the invention, however, to use a carboxylic dispersant pre-
pared by initially reacting substantially more than one mole
of acid or acid derivative with one mole of hydrocarbon
source. In the preferred dispersants of this type, as in
10 those previously described herein, the hydrocarbon source is
an olefin polymer such as polybutene and the carboxylic acid
derivative is maleic anhydride. Dispersants of this type
usually contain up to about 3.5 and most often from about
1.3 to about 3.5 succinic groups for each group derived from
15 the hydrocarbon source.
The method of preparation of dispersants o~ this
type is basically the same as for the carboxylic dispersants
already described. Reagent 1, in particular, may be pre-
pared by a one-step procedure in which the hydrocarbon
20 source is reacted with maleic anhydride; by a two-step
procedure in which the hydrocarbon source is chlorinated and
the chlorinated intermedia~e is reacted with maleic anhy-
dride; or by various combinations of the two procedures.
The following examples illustrate typical methods
25 for the preparation of suitable dispersants of this type.
Example 17
A mixture of lO00 parts (0.~95 mole) of a poly-
butene comprising principally isobutene units and having a
number average molecular weight of 2020 and a weight average
30 molecular weight of 6049 and 115 parts (1.17 moles) of
maleic anhydride is heated to 184C. over 6 hours as 85
parts (1.2 moles) of chlorine is added beneath the surface.
At 184-189C. an additional 59 parts (0.83 mole) of chlorine
is added over 4 hours. The reaction mixture is stripped by
35 blowing with ~itrogen at 186-190C. fox 26 hours to yield a
polybutene-substituted succinic anhydride having a saponifi-
cation number of 87 as determined by ASTM Procedure D94.
~ lfi39~8
- 16 -
To 893 parts (1.38 equivalents) of this substituted succinic
anhydride is added 1067 parts of mineral oil and 57 parts (1.38
equivalents) of a commercial ethylene polyamine mixture
containing from about 3 to about 10 nitrogen atoms per molecule.
The mixture is heated to 140-155C. for 3 hours and is then
stripped by blowing with nitrogen. The stripped liquid is
filtered and the filtrate is the desired dispersant (approximately
50% solution in oil).
Example 18
A mixture of 334 parts (0.52 equivalent) of the polybutenyl
succinic anhydride of Example 17, 548 parts of mineral oil, 30
parts (0.88 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of Polyglycol 112-2 demulsifier from Dow Chemical
Company is heated at 150-210C. for about 11 hours. The mixture is
cooled to 190C. and 8.5 parts (0.2 equivalent) of the ethylene
polyamine mixture of Example 1 is added. The mixture is stripped
by blowing with nitrogen for 3 hours at 205C. and is filtered to
yield the desired dispersant as an approximately 40% solution in
oil.
Also suitable as an alternative to the carboxylic dispersants
hereinabove described, are the Mannich dispersants. These are,
as previously noted, reaction products of certain alkyl phenols
with aldehydes (usually lower aliphatic aldehydes and especially
formaldehyde) and polyamino compounds. The structure of the alkyl
substituent on the phenol is subject to the same preferences as to
source, structure, molecular weight and the like expressed herein-
above with respect to the carboxylic dispersant. The polyamino
compounds are the same as those described with reference to
carboxylic dispersants and are subject to the same preferences.
Suitable Mannich dispersants are illustrated in the working
examples of the aforementioned U.S. Patent 3,980,569. The
following examples are also illustrative.
1~3gn~d
-17-
Example 19
A mixture of 3740 parts (2 equivalents) of a poly-
butenyl phenol in which the polybutene substituent comprises
principally isobutene units and has a molecular weight of
about 1600, 1250 parts of textile spirits and 2000 parts of
isopropyl alcohol is stirred as 352 parts (2.2 equivalents)
of 50% aqueous sodium hydroxide is added, followed by ~80
parts (6 equivalents~ of 38~ aqueous formaldehyde solution.
The mixture is stirred for 2 hours, allowed to stand for 2
days and then stirred again for 17 hours. Acetic acid, 150
parts (2.5 equivalents), is added and the mixture is
stripped of volatile materials under vacuum. The remaining
water is removed by adding benzene and distilling azeo-
tropically; during the distillation, 1000 parts of mineral
15 oil is added in two portions. The distillation residue is
filtered.
To 430 parts (0.115 equivalent) of the filtrate is
added with stirring, at 90C., 14.1 parts (0.345 equivalent)
of the polyethylene amine mixture of Example 1. ~he mixture
20 is heated at 90-120C. for 2 hours and then at 150-160C.
for 4 hours, with nitrogen blowing to remove volatiles. The
resulting solution is filtered to yield the desired Mannich
dispersant (52~ solution in mineral oil) which contains
1.03% nitrogen.
25 Example 20
A mixture of 564 parts (0.25 equivalent) of poly-
butenyl phenol in which the polybutene substituent comprises
principally isobutene units and has a molecular weight of
about 2020, 400 parts of mineral oil and 16.5 parts of iso-
30 butyl alcohol is heated to 65C., with stirring, and 2.15parts (0.025 equivalent) of 50~ aqueous sodium hydroxide
solution is added, followed by 16.5 parts (0.5 equivalent)
of paraformaldehyde. The mixture is stirred at 80-88C. for
6 hours and then 5 parts (0.025 equivalent) of 18.5~ aqueous
35 hydrochloric acid is added slowly, with continued stirring,
followed by 36 parts (0.875 equivalent) of the polyethylene
amine of Example 1, at 88C. ~ixing is continued at
~t~3~
-18-
88-91C. for 30 minutes. The mixture is then heated to
about 15~C. with nitrogen blowing to remove volatiles.
Sulfur, 16 parts (0.5 mole), and 25 parts of a
filter aid material are added slowly at 150C., with
5 stirring, after which the mixture is blown with nitrogen at
150-155C. for 3 hours. The mixture is then cooled to
132C. and filtered to yield the desired sulfurized Mannich
product as a 60% solution in mineral oil; it contains about
0.63~ sulfur.
10 Example 21
A mixture is prepared by the addition of 18.2 parts
(0.433 equivalent) of the ethylene polyamine mixture of
Example 1 to 392 parts of mineral oil and 348 parts (0.52
equivalent) of the substituted succinic anhydride of E~ample
17. The mixture is heated to 150C. over 1.8 hours,
stripped by blowing with nitrogen, and iltered to yield an
oil solution of the desired dispersant.
The compositions of this invention may be prepared
by merely blending the benzotriazole with the amine and
20 allowing the reaction between the two to proceed. If blend-
ing takes place in a substantially inert, normally liquid
organic ailuent such as mineral oil, benzene, toluene,
xylene, petroleum naphtha, an aliphatic ether or the li~e,
the reaction may take place at a temperature as low as about
15C. Ordinarily, it is preferred to carry out the reaction
at a temperature of at least about 50C., especially when no
diluent is used. Temperatures of about 70-200C. are pre-
ferred.
The proportions of the benzotriazola and amine may
vary widely. In general, it is intended to incorporate as
much of the benzotriazole as possible in an oil-dispersible
medium and this is best done by using about 1 equivalent of
amine per equivalent of benzotriazole. (The equivalent
weight of the amine is its molecular weight divided by the
number of basic nitrogen atoms therein, and that of the
benzotriazole is its molecular weight divided by the number
of triazole rings therein.) In some instances, however, it
~ ~ ~3g~3
--19--
may be desirable to use more or less than 1 equivalent of
amine per equivalent of benzotriazole. For example, an
effective amount of benzotriazole for use in an internal
combustion engine lubricant may be less than the equivalent
5 amount based on the dispersant present in the lubricant,
in which case it may be desirable to incorporate a rela-
tively minor amount of benzotriazole in the dispersant for
incorporation in the lubricant.
The precise molecular structuras of the composi-
10 tions of this invention are not known with certainty and arenot critical. It is known, however, that the benzotriazoles
are more acidic than the amines and it is believed that the
compositions may be amine salts of the benzotriazoles.
The preparation of the compositions of this inven-
15 tion is illustrated by the following examples. All partsand percentages are by weight.
Example 2_
Benæotriazole, 464 parts, is added in 20-30 part
increments, with stirring, to 696 parts of "Primene 81R" at
20 61-68C. Stirring is continued as the reaction mixture is
heated for 2-1/2 hours at 75-80C. The mixture is filtered
through a filter aid material to yield the desired product
which has a base number of 172 to bromphenol blue and an
acid number of 187 to phenolphthalein.
25 Example 23
Benzotriazole, 1210 parts, is added over 20
minutes, with stirring, to 1820 parts of "Primene 81R"
maintained at 60C. The mixture is stirred at 80C. for 45
minutes and 303 parts of an aromatic solvent with a dis-
30 tillation range of about 311-344C. is added. The mixture
is stirred at 80C. for an additional 15 minutes and
filtered to yield the desired product having a base number
of 157 to bromphenol blue and acid number of 135 to phenol-
phthalein.
~ 1~3~
-20-
Example 24
Benzotriazole, 20 parts, is added over 10 minutes,
with stirring, to 30 parts of "Primene JM-T" maintained at
60-80C. Xylene, 5 parts, is added and the mixture is
5 filtered to yield the desired product.
Example 25
A mixture of 500 parts of tolyltriazole and 718
parts of "Primene 81R" is heated for 8 hours under nitrogen
at 120-140C., with stirring. Mineral oil, 135 parts, is
added and the solution is filtered to yield the desired
product.
Example 26
Four mixtures of tolyltriazole and the dispersant
of Example 10 are prepared, respectively containing 3, 5, 7
and 9 parts of tolyltriazole and 97, 95, 93 and 91 parts of
the dispersant. Each mixture is heated to 140C. for 1
hour, cooled to 120 and filtered through a filter aid
material to yield a mineral oil solution of the desired
product.
20 Example 27
Following the procedure of Example 26, products are
made from tolyltriazole (3, 5 and 7 parts, respectively) and
the dispersant of Example 17 (97, 95 and 93 parts, respec-
tively).
25 Example 28
Tolyltriazole, 15 parts, is added with stirring at
90C. to 485 parts of the dispersant of Example 21. The
mixture is heated to 140-145C. for 1 hour, cooled to 130C.
and filtered to yield an oil solution o the desired pro-
30 auct.
~ s previously indicated, the compositions of thisinvention are useful as additives for lubricants, in which
~ '3 ~ 5~
-21-
they function primarily as oxidation and corrosion in-
hibitors and inhibitors of copper activity. They can be
employed in a variety of lubricants based on diverse oils
of lubricating viscosity, including natural and synthetic
5 lubricating oils and mixtures thereof. These lubricants
include crankcase lubricating oils for spark-ignited and
compress~on-ignited internal combustion engines, including
automobile and truck engines, two-cycle en~ines, aviation
piston engines, marine and rai:lroad diesel engines, and the
10 like. They can also be used in gas engines, stationary
power engines and turbines and the like. Automatic trans-
missiOn fluids, transaxle lubr:icants, gear lubricants (in
which ~heir use is especially beneficial), metal-working
lubricants, hydraulic ~luids and other lubricating oil and
15 grease compositions can also benefit from the incorporation
therein of the compositions of the present invention.
Natural oils include animal oils and vegetable oils
(e.g., castor oil, lard oil) as well as liquid petroleum
oils and solvent-treated or acid-treated mineral lubricating
20 oils of the paraffinic, naphthenic and mixed paraffinic-
naphthenic types. Oils of lubricating viscosity derived
from coal or shale are also useful base oils. Synthetic
lubricating oils include hydrocarbon oils and halo-substi-
tuted hydrocarbon oils such as polymerized and interpoly-
25 merized olefins [e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes,
poly(l-hexenes), poly(l-octenes), poly(l-decenes), etc. and
mixtures thereof~; alkylbenzenes [e.g., dodecylbenzenes,
tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)ben-
30 zenes, etc.]; polyphenyls (e.g., biphenyls, terphenyls,alkylated polyphenyls, etc.), alkylated diphenyl ethers and
alkylated diphenyl sulfides and the derivatives, analogs and
homologs thereof and the like.
Alkylene oxide polymers and interpolymers and
35 derivatives thereof where the terminal hydroxyl groups have
been modified by esterification, etherification, etc.
constitute another class of known synthetic lubricating
~ l~3s~a
-22-
oils. These are exemplified by the oils prepared through
polymerization of ethylene oxide or propylene oxide, the
alkyl and aryl ethers of these polyoxyalkylene polymers
(e.g., methyl-polyisopropylene glycol ether having an
5 average molecular weight of 1000, diphenyl ether of poly-
ethylene glycol having a molecular weight of 500-1000,
diethyl ether of polypropylene glycol having a molecular
weight of 1000-1500, etc.) or mono- and polycarboxylic
esters thereof, for example, the acetic acid esters, mixed
10 C3-Ca fatty acid esters, or the Cl 3 OXO acid diester of
tetraethylene glycol.
Another suitable class of synthetic lubricating
oils comprises the esters of dicarboxylic acids (e.g.,
phthalic acid, succinic acid, alkyl succinic acids and
15alkenyl succinic acids, maleic acid, azelaic acid, suberic
acid, sebacic acid, fumaric acid, adipic acid, linoleic acid
dimer, malonic acid, alkyl malonic acids, alkenyl malonic
acids, etc.) with a variety of alcohols (e.g., butyl alco-
hol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol,
20ethylene glycol, diethylene glycol monoether, propylene
glycol, etc.). Specific examples of these esters include
dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl
fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl
azelate, dioctyl phthalate, didecyl phthalate, dieicosyl
25sebacate, the 2-ethylhexyl diester of linoleic acid dimer,
the complex ester formed by reacting one mole of sebacic
acid wi~h two moles of tetraethylene glycol and two moles of
2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those
30 made from Cs to Cl 2 monocarboxylic acids and polyols and
polyol ethers such neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Sil:icon-based oils such as the polyalkyl-, poly-
aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili~
35 cate oils comprise another useful class of synthetic lubri-
cants [e.g., tetraethyl silicate, tetraisopropyl silicate,
tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl)
~ 1639g~
-23-
silicate, tetra-(p-tert~butylphenyl) silicate, hexa-(4-
methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes,
poly(methylphenyl)siloxanes, etc.]. Other synthetic lubri-
cating oils include liquid esters of phosphorus-containing
5 acids (e.g., tricresyl phosphate, trioctyl phosphate,
diethyl ester of decylphosphonic acid, etc.), polymeric
tetrahydrofurans and the like.
Unrefined, refined and rerefined oils (and mix-
tures of each with each other) of the type disclosed here-
10 inabove can be used in the lubricant compositions of thepresent invention. Unrefined oils are those obtained
directly from a natural or synthetic source without further
purification treatment. For example, a shale oil obtained
directly from retorting operations, a petroleum oil obtained
15 directly from distillation or ester oil obtained directly
from an esterification process and used without further
treatment would be an unrefined oil. Refined oils are
similar to the unrefined oils except they have been further
treated in one or more purification steps to improve one or
20 more properties. Many such purification techniques are
known to those of skill in the art such as solvent extrac-
tion, acid or base extraction, filtration, percolation, etc.
Rerefined oils are obtained by processes similar to those
used to obtain refined oils applied to refined oils which
25 have been already used in service. Such rerefined oils are
also known as reclaimed or reprocessed oils and often are
additionally processed by techniques directed to removal
of spent additives and oil breakdown products.
` Generally, the lubricants of the present inven-
30 tion contain an amount of the composition of this invention
sufficient to provide it with oxidation, corrosion or cop-
per activity inhibiting properties. Normally this amount
will be about 0.01-10.0~, preferably about 0.01-5.0~, of
the total we:ight of the lubricant. In lubricants operated
35 under extremely adverse conditions, the reaction products
of this invention may be present in amounts up to about 20%
by weight.
ll63ssa
-2~-
The invention also contemplates the use of other
additives in combination with the compositions of this
invention. Such additives include, for example, detergents
and dispersants of the ash~producing or ashless type,
5 auxiliary corrosion- and oxidation-inhibiting agents, pour
point depressing agents, extreme pressure agents, color
stabilizers and anti~foam agents.
The ash-producing detergents are exemplified by
oil-soluble neutral and basic salts of alkali or alkaline
10 earth metals with sulfonic acids, carboxylic acids, or
organic phosphorus acids characterized by at least one
direct carbon-to-phosphorus linkage such as those prepared
by the treatment of an olefin polymer (e.g., polyisobutene
having a molecular weight of 1000) with a phosphorizing
15 agent such as phosphorus trichloride, phosphorus heptasul-
fide, phosphorus pentasulfide, phosphorus trichloride and
sulfur, white phosphorus and a sulfur halide, or phosphoro-
thioic chloride. The most commonly used salts of such acids
are those of sodium, potassium, lithium, calcium, magnesium,
20 strontium and barium.
The term "basic salt" is used to designate metal
salts wherein the metal is present in stoichiometrically
larger amounts than the organic acid radical. The commonly
employed methods for preparing the basic salts involve heat-
25 ing a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal
oxide, hydroxide, carbonate, bicarbonate, or sulfide at a
temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid
30 the incorporation of a large excess of metal likewise is
known. Examples o compounds useful as the promoter include
phenolic substances such as phenol, naphthol, alkylphenol,
thiophenol, sulfurized alkylphenol, and condensation pro-
ducts of formaldehyde with a phenolic substance; alcohols
35 such as methanol, 2-propanol, octyl alcohol, cellosolve,
carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl
alcohol; and amines such as anilina, phenylenediamine,
phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A
~l~3~a
-25-
particularly effective method for preparing the basic salts
comprises mixing an acid with an excess of a basic alkaline
earth metal neutralizing agent and at least one alcohol
promoter, and carbonating the mixture at an elevated tem-
5 perature such as 60-200C.
Ashless detergents and dispersants are so called
despite the fact that, depending on its constitution, the
dispersant may upon combustion yield a non-volatile material
such as boric oxide or phosphorus pentoxide; however, it
10 does not ordinarily contain metal and therefore does not
yield a metal-containing ash on combustion. Many types are
known in the art, and any of them are suitable for use in
the lubricants of this invention. The following are illus-
trative:
(1) Carboxylic dispersants such as those described
hereinabove, and corresponding ester dispersants. These are
described in British Patent 1,306,529, in the aforementioned
U.S. Patent 3,272,746, and in many other U.S. patents
including the following:
3,163,603 3,351,552 3,522,179
3,184,474 3,381,022 3,541,012
3,215,707 3,399,141 3,542,678
3,219,666 3,415,750 3,542,680
3,271,31~ 3,433,744 3,567,637
3,281,357 3,4~4,170 3,574,101
3,306,908 3,448,04~ 3,576,743
3,311,558 3,448,049 3,630,904
3,316,177 3,451,933 3,632,510
3,340,281 3,454,607 3,632,511
3,341,542 3,467,668 3,697,428
3,346,493 3,501,405 3,725,441
Re 26,433
(2) "Amine dispersants" and "Mannich dispersants"
such as those described hereinabove.
(3) Products obtained by post-treating the car-
boxylic~ amine ox Mannich dispersants with such r~agents as
~ 163g~
- 26 -
urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic
acids, hydrocarbon-substituted succinic anhydrides, nitriles,
epoxides, boron compounds, phosphorus compounds or the like~
Exemplary materials of this kind are described in the following
U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,242
3,087,936 3,312,619 3,502,677 3,649,229
3,200,107 3,366,569 3,513,093 3,649,659
3,216,936 3,367,943 3,533,945 3,658/836
3,254,025 3,373,111 3,539,633 3,697,574
3,256,185 3,403,102 3,573,010 3,702,757
3,278,550 3,442,808 3,579,450 3,703,536
3,280,234 3,455,831 3,591,598 3,704,308
3,281,428 3,455,832 3,600,372 3,708,522
(4) Interpolymers of oil-solubilizing monomers such as
decvl methacrylate, vinyl decyl ether and high molecuIar weight
olefins with monomers containing polar substituents, e.g., amino-
alkyl acrylates or acrylamides and poly-(oxyethylene~-substituted
acrylates. These may be characterized as "polymeric dispersants"0 and examples thereof are disclosed in the following U.S. patents:
3,329,658 3,666,730
3,449,250 3,687,849
3,519,565 3,702,300
Extreme pressure agents and auxiliary corrosion- and oxidation-
inhibiting agents are exemplified by chloroinated aliphatic
hydrocarbons such as chlorinated wax; organic suIfides and poly-
sulfides such as benzyl disulfide, bis(chlorobenzyl~disulfide,
dibutyl tetrasulfide, sulfurized methyl ester of oleic acid,
sulfurized alkylphenol, sulfurized dipentene, and sulfurized
terpene; phosphosulEurized hydrocarbons such as the reaction
product of a phosphorus sulfide with turpentine or methyl oleate;
phosphorus esters including principally dihydrocarbon and tri-
hydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite,
1 1639g8
-27-
dicyclohexyl phosphite, pentylphenyl phosphite, dipentyl-
phenyl phosphite, tridecyl phosphite, distearyl phosphite,
dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite,
polypropylene (molecular weight 500)-substituted phenyl
5 phosphite, diisobutyl-substituted phenyl phosphite; metal
thiocarbamates, such as zinc clioctyldithiocarbamate, and
barium heptylphenyl dithiocarbamate; Group II metal phos-
phorodithioates such as zinc cLicyclohexylphosphorodithioate,
zinc dioctylphosphorodithioate, barium di(heptylphenyl)-
10 phosphorodithioate, cadmium dinonylphosphorodithioate, andthe zinc salt of a phosphorodithioic acid produced by the
reaction of phosphorus pentasulfide with an equimolar
mixture of isopropyl alcohol and n-hexyl alcohol.
The compositions of this invention can be diluted
15 with a substantially inert, normally liquid organic diluent
such as mineral oil, naphtha, benzene, toluene or xylene, to
form an additive concentrate which usually contains about
20-90% by weight of said composition and may contain, in
addition, one or more other additives known in the art or
20 described hereinabove. However, their use is advantageous
largely because, while not always s~luble in oil in
amounts suitable for concentrate formation, they are soluble
or at least stably dispersible in compounded lubricants
~e.g., gear lubricants) containing other additives. ~hus,
25 it is usually convenient to add them in the desired amount
to the otherwise fully compounded lubricant. For example, a
suitable gear lubricant consists of an SAE 90 mineral oil
base in combination with 0.04% (by weight) of the product of
Example 25 and 3.25~ of "Anglamol 99", a commercially
30 available additive package ~or gear lubricants. A suitable
internal combustion engine lubricant may comprise an SAE 10
mineral oil and 1~ of the product of ~xample 23.
