Note: Descriptions are shown in the official language in which they were submitted.
1~94044
This invention is concerned with novel chemical pro-
cesses and compositions. In particular, this invention
relates to certain substituted succinic acylating agents;
processes for preparing substituted acylating compositions
and the acylating compositions thus prepared; lubricating
compositions comprising such substituted succinic acylating
agents and such substituted acylating compositions; pro-
cesses for preparing certain carboxylic derivative composi-
tions from such substituted succinic acylating agents and
such substituted acylating compositions; lubricant composi-
tions comprising a major amount of oil of lubricating vis-
cosity and a minor amount of one or more such carboxylic
derivative compositions; processes for preparing post-
treated carboxylic acid derivative compositions and the
post-treated carboxylic acid derivative compositions thus
produced; lubricating compositions comprising a major amount
of oil of lubricating viscosity and a minor amount of at
least one such post-treated carboxylic acid derivative
composition; and concentrates comprising a major amount of a
normally liquid, substantially inert organic solvent/diluent
and from about 10% to about 80% by weight of one or more of
the afore-mentioned substituted succinic acylating agents
and compositions.
From one viewpoint, this invention can be regarded as
an improvement in the known field of lubricant additive
technology whiGh has developed since the l950's around high
molecular weight carboxylic acid acylating agents and various
acylated derivatives thereof. Thus, for example, the patent
literature discloses the preparation of high molecular
weight carboxylic acylating agents by reacting an olefin
- 1 - . ~
1094044
(e.g., a polyalkene such as polybutene) or a derivative
thereof, usually containing at least about 50 aliphatic
carbon atoms, with an unsaturated carboxylic acid or deri-
vative thereof. Typical unsaturated carboxylic acid deri-
vatives include acrylic acid, methylacrylate, maleic acia,
fumaric acid, and maleic anhydxide. Exemplary of the patent
literature are the following United States, British and
Canadian patents: 3,024,237; 3,087,936; 3,172,892; 3,215,707;
3,219,666; 3,231,587; 3,245,910; 3,272,74~^ 3,288,714;
3,312,619; 3,341,542; 3,367,943; 3,381,022; 3,454,607;
3,407,098; 3,630,902; 3,652,616; 3,755,169; 3,868,330;
3,912,764; U.K. 944,136; 1,085,903; 1,162,436; 1,440,219;
and Canadian 956,397. These same patents also establish
that various derivatives of these high molecular weight car-
boxylic acid acylating agents are known to be useful as
additives in fuel and lubricant compositions, especially as
dispersant/detergent additives which function to promote
engine cleanliness, neutralize acidic by-products of com-
bustion, and the like. Some of the compositions disclosed
in the above patents are presently used in substantial
amounts as commercial lubricant additives.
This invention is based on the discovery that a novel
class of high molecular weight carboxylic acid acylating
agents is capable of imparting unique and beneficial pro-
perties to lubricant additives prepared therefrom and lubri-
cating compositions containing such additives while, at the
same time, retaining the desirable properties of similar
lubricant additives and lubricating compositions prepared
from other high molecular weight carboxylic acid acylating
agents of the prior art. In addition, the retained desirable
` 109'~044
properties are themselves not only retained as such but
often enhanced or improved. For example, if the similar
lubricant additives prepared from high molecular weight
carboxylic acylating agents of the prior art are known to
function as ashless dispersants in lubricant compositions,
the corresponding additive prepared from the novel high
molecular weight carboxylic acid compositions often exhibit
improved ashless dispersant properties.
The novel class of high molecular weight carboxylic
acid acylating agents of this invention and derivatives
thereof, especially the latter, impart significant fluidity
modifying properties to lubricant compositions sufficient to
permit elimination of all or a significant amount of vis-
cosity index improver from multigrade lubricant compositions
containing the same; for example, a lOW-30 crankcase engine
oil.
Fluidity modifying lubricant additives, particularly
viscosity index improvers (sometimes referred to hereafter
as "V.I. improver(s)"), which are completely hydrocarbon in
character, such as polybutenes having average molecular
weights of 60,000-80,000 or more and hydrogenated butadiene-
styrene copolymers having average molecular weights of
20,000-200,000, exhibit no dispersant or detergent properties.
That is, they are monofunctional additives imparting to the
lubricant only the desired V.I. improving properties. To
obtain dispersant or detergent properties, such hydrocarbon
viscosity index improvers are used in combination with one
or more dispersant or detergent additives as illustrated by
U.S. Patents 3,554,911 and 3,761,404.
" ~094V44
In general, two approaches have been used to prepare
multifunctional lubricant additives which exhibit both (a)
fluidity modifying properties, especially V.I. improving
properties, and (b) dispersant and/or detergent properties.
One approach involves "suspending" from or "incorporating"
into the hydrocarbon backbone of a high molecular weight
polymer certain polar groups (usually carboxylic acid
derivatives such as amides and esters). The high molecular
weight material thus produced continues to exhibit V.I.
improving properties attributable to its high molecular
Weight hydrocarbon backbone and dispersant or detergent
properties attributable to the polar groups. This approach
is illustrated by U.S. Patents 3,702,300 and 3,933,761. For
- - lack of a better art-recognized descriptive texm, the poly-
mers made pursuant to this approach are sometimes referred
to herein as "dispersant V.I. improver(s)."
The second general approach for preparing multifunctional
lubricant additives involves modifying a dispersant/detergent
additive so as to incorporate into the dispersant/detergent
additive fluidity modifying properties, especially V.I. im-
proving properties. This approach is illustrated by U.S.
Patent 3,219,666. The '666 patent is primarily concerned
with acylated ni~rogen derivatives of high molecular weight
succinic acid acylating agents which derivatives function as
dispersant additives in lubricant compositions. The acylating
agents from which the dispersants are prepared are substi-
tuted succinic acylating agents preferably having a substi-
tuent derived from a polyolefin having a molecular weight of
about 750-5000. However, the patent further teaches that,
if V.I. improving properties are desired in addition to the
1094044
dispersant properties, the substituent should be derived
from higher molecular weight olefin polymers having mole-
cular weights from about 10,000 to about 100,000 or higher.
Again, for lack of a better art-recognized descriptive term,
such multifunctional lubricant additives made pursuant to
this approach (that is, incorporating a very high molecular
weight hydrocarbon substituent into a dispersant) are referred
to herein as "V.I. improving dispersant(s)", "V.I. improving
detergents", and/or "V.I. improving dispersants/detergents".
A third approach for preparing lubricant additives
having both detergency and viscosity index-improving pro-
perties is described in U.S. Patent 3,630,902. This approach
involves reacting a high molecular weight succinimide with a
polymerizable acid to form a polymerizable acyl derivative
of the succinimide. The polymerizable derivative is then
polymerized to produce the desired multifunctional lubricant
additive.
The novel class of carboxylic acid acylating agents of
this invention and the derivatives produced therefrom re-
present a further distinct and hitherto unrecognized approach
for preparing multifunctional lubricating additives.
Accordingly, it is a principal object of this invention
to provide a novel class of substituted succinic acylating
agents.
Another ob~ect is to provide a process for preparing a
novel class of substituted acylating compositions from
polyalkenes, maleic and/or fumaric acid or derivatives
thereof, and ch'orine, as well as to p~^~Tide the novel
substituted acylating compositions thus produced.
`" 1(~94044
A further object is to provide lubricant compositions
and concentrates containing said novel substituted succinic
acylating agents and said novel substituted acylating com-
positions.
A still further object is to provide a process for
preparing carboxylic acid derivatives from said novel sub-
stituted succinic acylating agents and said novel substi-
tuted acylating compositions as well as lubricant compo-
sitions and concentrates containing said carboxylic acid
derivatives.
An additional object is to provide a process for post-
treating said carboxylic acid derivatives and the post-
treated carboxylic acid compositions thus produced as well
as lubricant compositions and concentrates containing such
post-treated carboxylic acid derivatives.
The manner in which these and other objects can be
achieved will be apparent from the following detailed des-
cription of the invention.
In one aspect of this invention, one or more of the
above objectives can be achieved by providing substituted
succinic acylating agents consisting of substituent groups
and succinic groups, wherein the substituent groups are
derived from polyalkene, said polyalkene being characterized
by a Mn value of 1300 to about 5000 and a Mw/Mn value of
about 1.5 to about 4, said acylating agent being charac-
terized by the presence within its structure of an average
of at least 1.3 succinic groups for each equivalent weight
of substituent group.
In another aspect, one or more objects of this invention
can be achieved by providing a process for preparing sub-
l~g4044
stituted acylating compositions comprising heating at a
temperature of at least about 140C.:
(A) Polyalkene characterized by a Mn value of 1300 to
about 5000 and a Mw/Mn value of about 1.5 to about 4,
S (B) One or more acidic reactants of the formula
O O
.~. Il 11
X -- C - -HC = CH - C ---X'
wherein X and X' are each as defined hereinafter with
respect to Formula I,
(C) Chlorine,
wherein the mole ratio of (A):(B) is such that there is at
least 1.3 moles of (B) for each mole of (A) where the number
of moles of (A) is the quotient of the total weight of (A)
divided by the value of Mn, and the amount of chlorine
employed is such as to provide at least about 0.2 mole of
~5 chlorine for each mole of (B) to be reacted with (A), said
substituted acylating compositions being characterized by
the presence within their structure of an average of at
least 1.3 groups derived from (B) for each equivalent weight
of the substituent groups derived from (A); and, in a fur-
~ ther aspect, one or more objects of this invention are
achieved by providing substituted acylating compositions
produced by such a process.
One or more objects of the invention are achieved by
providing a process for preparing carboxylic derivative
compositions comprising reacting one or more substituted
succinic acylating agents or substituted acylating com-
positions, as referred to hereinbefore ~d de.scribed in more
detail hereafter, with a reactant selected from the group
consisting of (a) amine characterized by the presence within
1094044
its structure of at least one H-N\group, (b) alcohol, (c)
reactive metal or reactive metal compound, and (d) a com-
bination of two or more of any of (a) through (c), the
components of (d) being reacted with said acylating agent
simultaneously or sequentially in any order; in addition,
one or more additional objects of the invention are accom-
plished by providing carboxylic acid derivative compositions
produced by such a process.
One or more objects of this invention are achieved by
providing a process for preparing post-treated carboxylic
acid derivative compositions comprising reacting one or more
carboxylic acid derivative compositions as mentioned here-
inabove and described in more detail hereafter, wherein said
reactant is (a) with one or more post-treated reagents
selected from the group consisting of boron oxide, boron
oxide hydrate, boron halides, boron acids, esters of boron
H2S
acids, carbon disulfide,/sulfur, sulfur chloride, alkenyl
cyanides, carboxylic acid acylating agents, aldehydes,
ketones, urea, thiourea, guanidine, dicyanodiamide, hydro-
carbyl phosphates, hydrocarbyl phosphites, hydrocarbyl
thiophosphates, hydrocarbyl thiophosphites, phosphorus
sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl
thiocyanates, hydro_arbyl isocyanates, hydrocarbyl iso-
thiocyanates, epoxides, episulfides, formaldehyde or for-
~5 maldehyde producing compounds plus phenols, and sulfur plus
phenols; further, one or more additional objects of this
invention are accomplished by providing the post-treated
carboxylic acid derivative compositions produced by such a
process.
~094044
One or more additional objects of this invention are
achieved by providing a process for preparing post-treated
carboxylic acid derivative compositions comprising reacting
one or more carboxylic acid derivative compositions mentioned
hereinabove and described in more detail hereinafter wherein
said reactant is (b) with one or more post-treating reagents
selected from the group consisting of boron oxide, boron
oxide hydrates, boron halides, boron acids, esters of boron
acids, sulfur, sulfur chlorides, phosphorus sulfides, phos-
phorus oxides, carboxylic acid acylating agents, epoxides,
and episulfides; in addition one or more further objects can
be achieved by providing the post-treated carboxylic acid
derivative compositions produced by such a process.
One or more additional objects of this invention are
achieved by providing a process for preparing post-treated
carboxylic acid derivative compositions comprising reacting
one or more carboxylic acid derivative compositions as
referred to hereinabove and described in more detail here-
inafter, wherein said reactant is a combination of (a) and
(b), with one or more post-treating reagents selected from
the group consisting of boron oxide, boron oxide hydrate,
boron halides, boron acids, esters of boron acids, carbon
disulfide, sulfur, sulfur chlorides, alkenyl cyanides,
carboxylic acid acylating agents, aldehydes, ketones, urea,
thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates,
hydrocarbyl phosphites, hydrocarbyl thiophosph~tes, hydro-
carbyl thiophosphites, phosphorus sulfides, phosphorus
oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocar-
byl isocyanates, hydrocarbyl isothiocyanates, epoxides,
episulfides, formaldehyde or formaldehyde-producing com-
1094044
pounds plus phenols, and sulfur plus phenols; one or more
additional objects are achieved by providing post-treated
carboxylic acid derivative compositions produced by such a
process.
One or more objects of the invention are also achieved
by providing lubricating compositions comprising a major
amount of lubricating oil of lubricating viscosity and a
minor amount of at least one substituted succinic acylating
agent, substituted acylating composition, carboxylic acid
derivative composition, post-treated carboxylic acid deri-
vative composition, as mentioned above and described in more
detail hereinafter.
One or more additional objects of the invention can be
achieved by providing concentrate compositions comprising
from about 20 to about 90 percent by weight of a normally
liquid, substantially inert, organic solvent~diluent and
from about 10% to about 80~ by weight of at least one
substituted succinic acylating agent, substituted acylating
composition, carboxylic acid derivative composition, post-
treated carboxylic acid derivative composition, as mentioned
hereinabove and described in more detail hereafter.
The Substituted Su~cinic Acylating Agent
The novel class of substituted succinic acylating agent
of this invention are those which can be characterized by
the presence within their structure of two groups or moieties.
The first group or moiety is referred to herein, for con-
venience, as the "substituent group(s)" and is derived from
a polyalkene. ~he polyalkene from wh;-h the substituted
groups are derived is characteri~ed by a Mn (number average
molecular weight) value of from 1300 to a~out 5000 and a
Mw~Mn value of about 1.5 to about 4.
- 10 -
' 1094044
The second group or moiety is referred to herein as the
"succinic group(s)". The succinic groups are those groups
characterized by the structure
O O
Il l l 11
X-C-C-C-C-X' Formula I
wherein X and X' are the same or different provided at least
one of X and X' is such that the substituted succinic acy-
lating agent can function as carboxylic acylating agents.
That is, at least one of X and X' must be such that the
substituted acylating agent can esterify alcohols, form
amides or amine salts with ammonia or amines, form metal
salts with reactive metals or basically reacting metal
compounds, and otherwise function as a conventional car-
boxylic acid acylating agents. Transesterification and
transamidation reactions are considered, for purposes of
this invention, as conventional acylating reactions.
Thus, X and/or X' is usually -OH, -O-hydrocarbyl, -O M+
where M represents one equivalent of a metal, ammonium or
amine cation, -NH2, -Cl, -Br, and together, X and X' can
be -O- so as to form the anhydride. The specific identity
of any X or X' group which is not one of the above is not
critical so long as its presence does not prevent the re-
maining group from entering into acylation reactions.
Preferably, however, X and X' are each such that both car-
O
boxyl functions of t~e succinic group (i.e., both -C-X
and -C-X') can enter into acylation reactions. l l
One of th~ unsatisfied valences in the grouping -C-C-
of Formula I forms a carbon-to-carbon bond with a carbon
1094044
atom in the substituent group. While other such unsatisfied
valence may be satisfied by a similar bond with the same or
different substituent group, all but the said one such
valence is usually satisfied by hydrogen; i.e., -H.
The substituted succinic acylating agents are charac-
terized by the presence within their structure of at least
1.3 succinic groups (that is, groups corresponding to For-
mula I) for each equivalent weight of substituent groups.
For purposes of this invention, the number of equivalent
weights of substituent groups is deemed to be the number
corresponding to the quotient obtained by dividing the Mn
value of the polyalkene from which the substituent is de-
rived into the total weight of the substituent groups pre-
sent in the substituted succinic acylating agents. Thus, if
a substituted succinic acylating agent is characterized by a
total weight of substituent group of 40,000 and the Mn value
for the polyalkene from which the substituent groups are
derived is 2000, then that substituted succinic acylating
agent is characterized by a total of 20 (40,000/2000 = 20)
equivalent weights of substituent groups. Therefore, that
particular succinic acylating agent must also be charac-
terized by the presence within its structure of at least 26
succinic groups to meet one of the requirements of the novel
succinic acylating agents of this invention.
Another requirement for the substituted succinic acy-
lating agents within this invention is that the substituent
groups must have been derived from a polyalkene character-
ized by a Mw/Mn value of about 1.5 to about 4, Mw being the
conventional symbol representing weight average molecular
weight.
l~g4~44
Before proceeding, it should be pointed out that the Mn
and Mw values for polyalkene, for purposes of this invention,
are determined by gel permeation chromatography (GPC). This
separation method involves column chromatography in which
the stationary phase is a heteroporous, solvent-swollen
polymer network of a polystyrene gel varying in permeability
over many orders of magnitude. As the liquid phase (tetra-
hydrofuran) containing the polymer sample passes through the
gel, the polymer molecules diffuse into all parts of the gel
not mechanically barred to them. The smaller molecules
"permeate" more completely and spend more time in the column;
the larger molecules "permeate" less and pass through the
column more rapidly. The Mn and Mw values of the polyalkenes
of this invention can be obtained by one of ordinary skill
in the art by the comparison of the distribution data obtained
to a series of calibration standards of polymers of known
molecular weight distribution. For purposes of this inven-
tion a series of fractionated polymers of isobutene, poly-
isobutene being the preferred embodiment, is used as the
calibration standard.
Polyalkenes having the Mn and Mw values discussed above
are known in the art and can be prepared accordi~g to con-
ventional procedures~ Several such polyalkenes, especially
polybutenes, are commercially available.
Again, turning to the characteristics of the succinic
acylating agents of this invention, the succinic groups will
normally correspond to the formula
~0
CH C R
~ O Formula II
- 13 -
10940~4
wherein R and R' are each independently selected from the
group consisting of -OH, -Cl, -O-lower alkyl, and when taken
together, R and R' are -O-. In the latter case, the suc-
cinic group is a succinic anhydride group. All the succinic
groups in a particular succinic acylating agent need not be
the same, but they can be the same. Preferably, the succinic
groups will correspond to
~0 ~0
CH - C - OH - - CH - C \ Formula III
CH2- C OH , , O
~0 I H2--C/
(A) (B)
and mixtures of III(A) and III(B). Providing substituted
succinic acylating agents wherein the succinic groups are
the same or different is within the ordinary skill of the
art and can be accomplished through conventional procedures
such as treating the substituted succinic acylating agents
themselves (for example, hydrolyzing the anhydride to the
free acid or converting the free acid to an acid chloride
with thionyl chloride) and/or selecting the appropriate
maleic or fumaric reactants.
As previously mentioned, the minimum number of succinic
groups for each equivalent weight of substituent group is
1.3. Preferably, however, the minimum will be 1.4; usually
1.4 to about 3.5 succinic groups for each equivalent weight
of substituent group. An especially preferred minimum is at
least 1.5 succinic groups for each e~ti;valent weight of
substituent group. A preferred range based on this minimum
- 14 -
10!~4044
is at least 1.5 to about 2.5 succinic groups per equivalent
weight of substituent groups.
From the foregoing, it is clear that the substituted
- succinic acylating agents of this invention can be repre-
sented by the symbol --
R~ ( R2)y
where Rl represents one equivalent weight of substituent
group, R2 represents one succinic group corresponding to
Formula I, Formula II, or Formula III, as discussed above,
and y is a number equal to or greater than 1.3; i.e., > 1.3.
The more preferred embodiments of the invention could be
similarly represented by, for example, letting Rl and R2
represent more preferred substituent groups and succinic
groups, respectively, as discussed elsewhere herein and by
letting the value of y vary as discussed above; e.g., Y is
equal to or greater than 1.4 ~y > 1.4); Y is equal to or
greater than 1.5 (y > 1.5); Y equals 1.4 to about 3.5 (y=1.4-
3.5); and Y equals 1.5 to about 3.5 (y=1.5-3.5).
In addition to preferred substituted succinic groups
where the preference depends cn the number and identity of
succinic groups for each equivalent weight of substituent
groups, still further preferences are based on the identity
and characterization of the polyalkenes from which the
substituent groups are derived.
With respect to the value of Mn, for example, a minimum
of about 1500 is preferred with an Mn value in the range of
from about 1500 to about 3200 also being preferred. A more
preferred Mn -.-^'ue is one in the ran~e of from about 1500 to
about 2800. A most preferred range of Mn values is from
- 15 -
~94044
about 1500 to about 2400. With polybutenes, an especially
preferred minimum value for Mn is about 1700 and an espec-
ially preferred range of Mn values is from about 1700 to
about 2400.
As to the values of the ratio Mw/Mn, there are also
several preferred values. A minimum Mw/Mn value of about
1.8 is preferred with a range of values of about 1.8 up to
about 3.6 also being preferred. A still more preferred
minimum value of Mw/Mn i8 about 2.0 with a preferred range
of values of from about 2.0 to about 3.4 also being a pre-
ferred range. An e~pecially preferred minimum value of
Mw/Mn is about 2.5 with a range of values of about 2.5 to
about 3.2 also being especially preferred.
Before proceedin~ to a further discussion of the poly-
alkenes from which the substituent groups are derived, it
should be pointed out that these preferred characteristics
of the succinic acylating agents are, for lack of better
terminology to describe the situation contemplated by this
invention, intended to be understood as being both indepen-
dent and dependent. They are intended to be independent in
the sense that, for example, a preference for a minimum of
1.4 or 1.5 succinic groups per equivalent weight of sub-
stituent groups is not tied to a ~ore preferred value of Mn
or Mw/Mn. They are intended to be dependent in the sense
that, for example, when a preference for a minimum of 1.4 or
1.5 succinic groups is combined with more preferred values
of Mn and~or Mw/Mn, the combination of preferences does in
fact describe still further more preEerred embodiments of
the invention. Thus, the various parameters are intended to
stand alone with respect to the particular parameter being
- 16 -
1094Q44
discussed but can also be combined with other parameters to
identify further preferences. This same concept is intended
to apply throughout the specification with respect to the
description of preferred values, ranges, ratios, reactants,
and the like unless a contrary intent is clearly demonstra-
ted or apparent.
The polyalkenes from whi~h the substituent groups are
derived are homopolymers and interpolymers of polymerizable
olefin monomers of 2 to about 16 carbon atoms; usually 2 to
about 6 carbon atoms. The interpolymers are those in which
two or more olefin monomers are interpolymerized according
to well-known conventional procedures to form polyalkenes
having units within their structure derived from each of
said two or more olefin monomers. Thus, "interpolymer(s)"
as used herein is inclusive of copolymers, terpolymers,
tetrapolymers, and the like. As will be apparent to those
of ordinary skill in the art, the polyalkenes from which the
substituent groups are derived are often conventionally
referred to as "polyolefin(s)".
The olefin monomers from which the polyalkenes are
derived are polymerizable olefin monomers characterized by
the presence of one or more ethylenically unsaturated groups
(i.e.,`C=C'); that is, they are monoolefinic monomers such
as ethylene, propylene, butene-l, isobutene, and octene-l or
polyolefinic monomers ~usually diolefinic monomers) such as
butadiene-1,3 and isoprene.
These olefin monomers are usually polymerizable ter-
minal olefins that is, olefins charac~erized by the pre-
sence in their structure of the group ~C-CH2. However,
~94044
polymerizable internal olefin monomers (sometimes referred
to in the patent literature as medial olefins) characterized
by the presence within their structure of the group~ C-C=C-C~
can also be used to form the polyalkenes. When internal
- 5 olefin monomers are employed, they normally will be employed
with terminal olefins to produce polyalkenes which are
interpolymers. For purposes of this invention, when a
particular polymerized olefin monomer can be classified as
both a terminal olefin and an internal olefin, it will be
deemed to be a terminal olefin. Thus, pentadiene-1,3 (i.e.,
piperylene) is deemed to be a terminal olefin for purposes
of this invention.
While the polyalkenes from which the substituent groups
of the succinic acylating agents are derived generally are
hydrocarbon polyalkenes, they can contain non-hydrocarbon
groups such as lower alkoxy, lower alkyl mercapto, hydroxy,
mercapto, oxo (i.e., ¦¦ as in keto and aldehydo groups; e.g.,
O O
Il 11
- C-C-C - and --C-C-H), nitro, halo, cyano, carboalkoxy (i.e.,
o
-C-O-alkyl where "alkyl" is usually lower alkyl) alkanoyloxy
o
(i.e., alkyl -C-O- where alkyl is usually lower alkyl, and
the like provided the non-hydrocarbon substituents do not
substantially interfere with formation of the substituted
succinic acid acylating agents of this invention. When
present, -uch non-hydrocarbon groups normally will not
contribute more than about 10% by weight of the total weight
of the polyalkenes. Since the polyalkene can contain such
non-hydrocarbon substituent, it is apparent that the olefin
- 18 -
1~4044
monomers from which the polyalkenes are made can also con-
tain such substituents. Normally, however, as a matter of
practicality and expense, the olefin monomers and the poly-
alkenes will be free from non-hydrocarbon groups, except
chloro groups which usually facilitate the formation of the
substituted succinic acylating agents of this invention.
(As used herein, the term "lower" when used with a chemical
group such as in "lower alkyl" or "lower alkoxy" is intended
to describe groups having up to seven carbon atoms.)
Although the polyalkenes may include aromatic groups
(especially phenyl groups and lower alkyl- and/or lower
alkoxy-substituted phenyl groups such as para-(tert-butyl)-
phenyl) and cycloaliphatic groups such as would be obtained
from polymerizable cyclic olefins or cycloaliphatic substi-
tuted-polymerizable acyclic olefins, the polyalkenes usually
will be free from such groups. Nevertheless, polyalkenes
derived from interpolymers of both 1,3-dienes and styrenes
such as butadiene-1,3 and styrene or para-(tert-butyl)-
styrene are exceptions to this generalization. Again,
because aromatic and cycloaliphatic groups can be present,
the olefin monomers from which the polyalkenes are prepared
can contain aromatic and cycloaliphatic groups.
From what has been described hereinabove in regard to
the polyalkene, it is clear that there is a general pre-
ference for aliphatic, hydrocarbon polyal~enes free from
aromatic and cycloaliphatic groups (other than the diene-
styrene interpolymer exception already noted). Within this
general preference, there is a further preference for poly-
alkenes which are derived from the group consisting of
J.09~044
homopolymers and interpolymers of terminal hydrocarbon
olefins of 2 to about 16 carbon atoms. This further pre-
ference is qualified by the proviso that, while interpoly-
mers of terminal olefins are usually preferred, interpoly-
mers optionally containing up to about 40% of polymer units
derived from internal olefins of up to about 16 carbon atoms
are also within a preferred qroup. A more preferred class
of polyalkenes are those selected from the group consisting
of homopolymers and interpolymers of terminal olefins of 2
to about 6 carbon atoms, more preferably 2 to 4 carbon
atoms. However, another preferred class of polyalkenes are
the latter more preferred polyalkenes optionally containing
up to about 25% of polymer units derived from internal
olefins of up to about 6 carbon atoms.
5pecific examples of terminal and internal olefin
monomers which can be used to prepare the polyalkenes accor-
ding to conventional, well-known polymerization techniques
include ethylene; propylene; butene-l; butene-2; isobutene;
pentene-l; hexene-l; heptene-l; octene-l; nonene-l; decene-
1; pentene-2; propylene-tetramer; diisobutylene; isobutylene
trimer; butadiene-1,2; butadiene-1,3; pentadiene-1,2; penta-
diene-1,3; pentadiene-1,4; isoprene; hexadiene-1,5; 2-
chloro-butadiene-1,3; 2-methyl-heptene-1; 3-cyclohexyl-
butene-l; 2-methyl-5-propyl-hexene-1; pentene-3; octene-4;
3,3-dimethyl-pentene-1; styrene; 2,4-dichloro styrene;
divinylbenzene; vinyl acetate; allyl alcohol; l-methyl-vinyl
acetate; acrylonitrile; ethyl acrylate; methyl methacrylate;
ethyl vinyl ether; and methyl vinyl ketone. Of these, the
hydrocarbon polymerizable monomers are preferred and of
these hydrocarbon monomers, the terminal olefin monomers are
. ~
particularly preferred.
- 20 -
1094Q44
Specific examples of polyalkenes include polypropy-
lenes, polybutenes, ethylene-propylene copolymers, styrene-
isobutene copolymers, isobutene-butadiene-1,3 copolymers,
propene-isoprene copolymers, isobutene-chloroprene copoly-
mers, isobutene-(para-methyl)styrene copolymers, copolymers
of hexene-l with hexadiene-1,3, copolymers of octene-l with
hexene-l, copolymers of heptene-l with pentene-l, copolymers
of 3-methyl-butene-1 with octene-l, copolymeræ of 3,3-
dimethyl-pentene-l ~ith hexene-l, and terpolymers of iso-
butene, styrene and piperylene. More specific examples of
such interpolymers include copolymer of 95% (by weight) of
isobutene with 5% (by weight) of styrene; terpolymer of 98%
of isobutene with 1% of piperylene and 1~ of chloroprene:
terpolymer of 95% of isobutene with 2% of butene-l and 3% of
hexene-l; terpolymer of 60% of isobutene with 20% of pentene-
1 and 20% of octene-l; copolymer of 80% of hexene-l and 20
of heptene-l; terpolymer of 90% of isobutene with 2% of
cyclohexene and 8% of propylene; and copolymer of 80% of
ethylene and 20% of propylene. A preferred source of poly-
alkenes are the poly(isobutene)s obtained by polymerization
of C4 refinery stream having a butene content of about 35 to
about 75 percent by weight and an isobutene content of about
30 to about 60 percent by weight in the presence of a Lewis
acid catalyst such as aluminum trichloride or boron tri-
fluoride. These polybutenes contain predominantly (greater
than about 80% of the total repeating units) of isobutene
repeating units of the configuration
CH3
CH2--C--
CH3
- 21 -
1~)94044
Obviously, preparing polyalkenes as described above
which meet the various criteria for Mn and Mw/Mn is within
the skill of the art and does not comprise part of the
present invention. Techniques readily apparent to those in
the art include controlling polymerization temperatures,
regulating the amount and type of polymerization initiator
and/or catalyst, employing chain terminating groups in the
polymerization procedure, and the like. Other conventional
techniques such as stripping (including vacuum stripping) a
very light end and/or oxidatively or mechically degrading
high molecular weight polyalkene to produce lower molecular
weight polyalkenes can also be used.
In preparing the substituted succinic acylating agents
of this invention, one or more of the above-described poly-
alkenes is reacted with one or more acidic reactants selected
from the group consisting of maleic or fumaric reactants of
the general formula
O O
Il li
X-C-CH=CH-C-X' Formula IV
wherein X and X' are as defined hereinbefore. Preferably
the maleic and fumaric reactants will be one or more com-
pounds corresponding to the formula
O O
Il ~i
R-C-CH=CH-C-R' Formula V
wherein R and R' are as previously defined herein. Ordin-
arily the maleic or fumaric reactants will be maleic acid,
fumaric acid, maleic anhydride, or a mixture of two or more
of these. Th~ maleic reactants are s~allY ~referred over
the fumaric reactants because the former are more readily
available and are, in general, more readily reacted with the
polyalkenes (or derivatives thereof) to prepare the sub-
- 22 -
1094044
stituted succcinic acylating agents of the present inven-
tion. The especially preferred reactants are maleic acid,
maleic anhydride, and mixtures of these. Due to availa-
bility and ease of reaction, maleic anhydride will usually
be employed.
The one or more polyalkenes and one or more maleic or
fumaric reactants can be reacted according to any of several
known procedures in order to produce the substituted suc-
cinic acylating agents of the present invention. Basically,
the procedures are analogous to procedures used to prepare
the high molecular weight succinic anhydrides and other
equivalent succinic acylating analogs thereof except that
the polyalkenes (or polyolefins) of the prior art are replaced
with the particular polyalkenes described above and the
amount of maleic or fumaric reactant used must be such that
there is at least 1.3 succinic groups for each equivalent
weight of the substituent group in the final substituted
succinic acylating agent produced.
For convenience and brevity, the term "maleic reactant"
is often used hereafter. When used, it should be understood
that the term is generic to acidic reactants selected from
maleic and fumaric reactants corresponding to Formulas IV
and V above including a mixture of such reactants.
One procedure for preparing the substituted succinic
acylating agents of this invention is illustrated, in part,
in U.S. Patent 3,219,666. This procedure is conveniently
~esignated as the "two-step procedure." It involves first
- 23 -
~094044
chlorinating the polyalkene until there is an average of at
least about one chloro group for each molecular weight of
polyalkene. (For purposes of this invention, the molecular
weight of the polyalkene is the weight corresponding to the
Mn value.) Chlorination involves merely contacting the
polyalkene with chlorine gas until the desired amount of
chlorine is incorporated into the chlorinated polyalkene.
Chlorination is generally carried out at a temperature of
about 75C. to about 125C. If a diluent is used in the
chlorination procedure, it should be one which is not itself
readily subject to further chlorination. Poly- and per-
chlorinated and/or fluorinated alkanes and benzenes are
examples of suitable diluents.
The second step in the two-step chloxination procedure,
for purposes of this invention, is to react the chlorinated
polyalkene with the maleic reactant at a temperature usually
within the range of about 100C. to about 200C. The mole
ratio of chlorinated polyalkene to maleic reactant is usually
about 1:1. (For purposes of this invention, a mole of
chlorinated polyalkene is that weight of chlorinated poly-
alkene corresponding to the Mn value of the unchlorinated
polyalkene.) ~owever, a stoichiometric excess of maleic
reactant can be used, for example, a mole ratio of 1:2. ~f
an average of more than about one chloro group per molecule
of polyal~ene is introduced during the chlorination step,
then more than one mole of maleic reactant can react per
molecule of chlorinated polyalkene. Because of such situ-
ations, it is better to describe the ratio of chlorinated
polyalkene to maleic reactant in terms of equivalents. (An
- 24 -
1094044
equivalent weight of chlorinated polyalkene, for purposes of
this invention, is the weight corresponding to the Mn value
divided by the average number of chloro groups per molecule
of chlorinated polyalkene while the equivalent weight of a
maleic reactant is its molecular weight.) Thus, the ratio
of chlorinated polyalkene to maleic reactant will normally
be such as to provide about one equivalent of maleic reac-
tant for each mole of chlorinated polyalkene up to about one
equivalent of maleic reactant for each equivalent of chlor-
inated polyalkene with the understanding that it is normally
desirable to provide an excess of maleic reactant; for
example, an excess of about 5% to about 25% by weight.
Unreacted excess maleic reactant may be stripped from the
reaction product, usually under vacuum, or reacted during a
further stage of the process as explained below.
The resulting polyalkenyl-substituted succinic acylating
agent is, optionally, again chlorinated if the desired
number of succinic groups are not present in the product.
If there is present, at the time of this subsequent chlorina-
tion, any excess maleic reactant from the second step, the
excess will react as additional chlorine is introduced
during the subsequent chlorination. Otherwise, additional
maleic reactant is introduced during and/or subsequent to
the additional chlorination step. This technique can be
repeated until the total number of succinic groups per
equivalent weight ~f substituent groups reaches the desired
level~
Another procedure for preparinq substituted succinic
acid acylating agents of the invention utilizes a process
described in U.S. Patent 3,912,764 and U.K. Patent 1,440,219
- 2S -
LJ
~0940A4
According to that process, the polyalkene and the maleic
reactant are first reacted by heating them together in a
"direct alkylation" procedure. When the direct alkylation
step is completed, chlorine is introduced into the
reaction mixture to promote reaction of the remaining
unreacted maleic reactants. According to the patents, 0.3
to 2 or more moles of maleic- anhydride are used in the
reaction for each mole of olefin polymer; i.e., polyalkene.
The direct alkylation step is conducted at temperatures
of 180C. to 250C. During the chlorine-introducing
stage, a temperature of 160C. to 225C. is employed. In
utilizing this process to prepare the substituted succinic
acylating agents of this invention, it would be necessary
to use sufficient maleic reactant and chlorine to incorporate
at least 1.3 succinic groups into the final product for each
equivalent weight of polyalkene.
Other processes which can be used to prepare the
substituted succinic acylating agents of this invention are
disclosed in the following commonly assigned copending
Canadian patent application:
Serial No. 279,942 entitled TWO-STEP METHOD FOR
THE PREPARATION OF SUBSTITUTED CARBOXYLIC ACIDS filed June
6, 1976, in the name of Jerome Martin Cohen (assignee
docket number L-1504).
- 26 -
'~`'
~0~4(~44
The process presently deemed to be best for preparing
the substituted succinic acylating agents of this invention
from the standpoint of efficiency, overall economy, and the
performance of the acylating agents thus produced, as well
as the performance of the derivatives thereof, is the so-
called "one-step" process. This process is described in
U.S. Patents 3,215,707 and 3,231,587.
Basically, the one-step process involves preparing a
mixture of the polyalkene and the maleic reactant containing
the necessary amounts of both to provide the desired substi-
tuted succinic acylating agents of this invention. This
means that there must be at least 1.3 moles of maleic
reactant for each mole of polyalkene in order that there can
be at least 1.3 succinic groups for each equi~alent weight
of substituent groups. Chlorine is then lntroduced into the
mixture, usually by passing chlorine gas through the mixture
with agitation, while maintaining a temperature of at least
about 140C.
A variation on this process involves adding additional
maleic reactant during or subsequent to the chlorine intro-
duction but, for reasons explained in 3,215,707 and 3,231,587,
this variation is presently not as preferred as the situation
where all the polyalkene and all the maleic reactant are
~irst mixed before the introduction of chlorine.
Usually, where the polyalkene is sufficiently fluid at
140~C. and above, there is no need to utilize an additional
substantially inert, normally liquid solvent/diluent in the
one-step process. ~owever, as explained hereinhefore, if a
- 27 ~
1094044
solvent/diluent is employed, it is preferably one that
resists chlorination. Again, the poly- and per-chlorinated
and/or -fluorinated alkanes, cycloalkanes, and benzenes can
be used for this purpose.
Chlorine may be introduced continuously or intermittently
during the one-step process. The rate of introduction of
the chlorine is not critical although, for maximum utilization
of the chlorine, the rate should be about the same as the
rate of consumption of chlorine in the course of the reaction.
When the introduction rate of chlorine exceeds the rate of
consumption, chlorine is evolved from the reaction mixture.
It is often advantageous to use a closed system, including
superatmospheric pressure, in order to prevent loss of
chlorine so as to maximi~e chlorine utilization.
The minimum temperature at which the reaction in the
one-step process takes place at a reasonable rate is about
140C. Thus, the minimum temperature at which the process
is normally carried out is in the neighborhood of 140C.
The preferred temperature range is usually between about
160C. and about 220C. Higher temperatures such as 250C.
or even higher may be used but usually with little advantage.
In fact, temperatures in excess of 220C. are often disadvanta-
geous with respect to preparing the particular acylated
succinic compositions o~ this invention because they tend to
"crack" the polyalkenes (that is, reduce their molecular
~eight by thermal degradation) and/or decompose the maleic
reactant. For this reason, maximum temperatures of about
200~ to about 210C. are normally not exceeded. The upper
limit of the useful temperature in the one-step process is
determined primarily by the decomposition point of the
- 2~ -
4044
components in the reaction mixture including the reactants
and the desired products. The decomposition point is that
temperature at which there is sufficient decomposition of
any reactant or product such as to interfere with the produc-
tion of the desired products.
In the one-step process, the molar ratio of maleic
reactant to chlorine is such that there is at least about
one mole of chlorine for each mole of maleic reactant to be
incorporated into the product. Moreover, for practical
reasons, a slight excess, usually in the neighborhood of
about 5% to about 30% by weight of chlorine, is utilized in
order to offset any loss of chlorine from the reaction
mixture. Larger amounts of excess chlorine may be used but
do not appear to produce any beneficial results.
As mentioned previously, the molar ratio of polyalkene
to maleic reactant is such that there is at least about 1.3
moles of maleic reactant for each mole of polyalkene. This
is necessary in order that there can be at least 1.3 succinic
groups per equivalent weight of substituent group in the
product. Preferably, however, an excess of maleic reactant
is used. Thus, ordinarily about a 5% to about 25% excess of
maleic reactant will be used relative to that amount necessary
to provide the desired number of succinic groups in the
product.
A preferred process for preparing the substituted
acylating compositions of this invention comprises heating
and contacting at a temperature of at least about 140C. up
to the decomposition temperature
(A~ Polyalkene characterized by Mn value of about 1300
to about 5000 and a Mw/Mn value of about 1.5 to about
4,
- 29 -
10~044
(B) One or more acidic reactants of the formula
O O
Il ~1
X C CH - CH - C X'
wherein X and X' are as defined hereinbefore, and
(C) Chlorine
wherein the mole ratio of (A):(B) is such that there is at
least about 1.3 moles of (B) for each mole of (A) wherein
the number of moles of (A) is the quotient of the total
weight of (A) divided by the value of Mn and the amount of
chlorine employed is such as to provide at least about 0.2
mole (preferably at least about 0.5 mole) of chlorine for
each mole of (B) to be reacted with (A), said substituted
acylating compositions being characterized by the presence
within their structure of an average of at least 1.3 groups
derived from (B) for each equivalent weight of the substituent
groups derived from (A). The substituted acylated compositions
as produced by such a process are, likewise, part of this
invention.
As will be apparent, it is intended that the immediately
preceding description of a preferred process be generic to
2G both the process involving direct alkylation with subsequent
chlorination as described in U.S. Patent 3,912,764 and U.K.
Patent 1,440,219 and to the completely one-step process
described in U.S. Patents 3,215,707 and 3,231,587. Thus,
said description does not require that the initial mixture
2S of polyal~ene and acidic reactant contain all of the acidic
reactant ultimately to be incorporated into the substituted
acylatin~ composition to be prepared. In other words, all
of the acidic reactant can be present initially or only part
thereof with subsequent addition of acidic r~actant durin~
-- 30 -
044
the course of the reaction. Likewise, a direct alkylation
reaction can precede the introduction of chlorine. Normally,
however, the original reaction mixture will contain the
total amount of polyalkene and acidic reactant to be utilized.
Furthermore, the amount of chlorine used will normally be
such as to provide about one mole of chlorine for each
unreacted mole of (B) present at the time chlorine introduc-
tion is commenced. Thus, if the mole ratio of (A):(B) is
such that there is about 1.5 moles of (B) for each mole of
(A) and if direct alkylation results in half of (B) being
incorporated into the product, then the amount of chlorine
introduced to complete reaction will be based on the unreacted
0.75 mole of (B), that is, at least about ~.75 mole of
chlorine (or an excess as explained above) will then be
introduced.
In a more preferred process for preparing the substituted
acylating compositions of this invention, there is heated at
a temperature of at least about 140C. a mixture comprising:
~A) Polyalkene characterized by a Mn value of about
13Q0 to about 5000 and a Mw/Mn value of about 1.3 to
about 4,
(B) One or more acidic reactants of the formula
O O
Il 11
R - C - HC - CH - C - R'
wherein R and ~' are as defined above, and
(C~ Chlorine,
wherein the mole ratio of (A1:(~) is such that there is at
least about 1.3 moles of (B) for each mole of (A) where the
number of moles of (A3 is a quotient of the total weight of
(~) divided by the value of Mn, and the amount o chlorine
~- 31 -
'lQ~4Q44
employed is such as to provide at least about one mole of
chlorine for each mole of (B) reacted with (A), the substituted
acylating compositions being further characterized by the
presence within their structure of at least 1.3 groups
derived from (B) ror each e~uivalent weight of the substituent
groups derived from (A). This process, as described, includes
only the one-step process; that is, a process where all of
both (A) and (B) are present in the initial reaction mixture.
The substituted acylated composition as produced by such a
process are, likewise, part of this invention.
This is an appropriate point to comment upon the use of
the terminology "substituted succinic acylating agent(s)"
and "substituted acylating composition" as used herein. The
former terminology is used in describing the substituted
succinic acylating agents regardless of the process by which
they are produced. Obviously, as discussed in more detail
hereinbefore, several processes are available for producing
the substituted succinic acylating agents. On the other
hand, the latter terminology; that is, "substituted acylating
composition(s)", is used to describe the reaction mixtures
produced by the specific preferred processes described in
detail herein. Thus, the identity of particular substituted
acylating compositions is dependent upon a particular process
of manufacture. It is believed that the novel acylating
agents of this invention can best be described and claimed
in the alternative manner inherent in the use of this termino-
logy as thus explained. This is particularly ~rue because,
while the pro~ucts of this invention are clearly substituted
succinic acylating agents as defined and discussed above,
their structure cannot be represented by a single specific
- 32 -
~0'~40'~4
chemical formul~. In fact, mixtures of products are inherently
present.
With respect to the preferred processes described
above, preferences indicated hereinbefore with respect to
(a) the substituted succinic acylating agents and (b~ the
values of Mn, the values of the ratio Mw/Mn, the identity
and composition of the polyalkenes, the identity of the
acidic reactant (that is, the maleic and/or fumaric reactants),
the ratios of reactants, and the reaction temperatures also
apply. In like manner, the same preferences apply to the
substituted acylated compositions produced by these preferred
processes.
For example, such processes wherein the reaction tempera-
ture is from about 160C. to about 220C. are preferred.
Likewise, the use of polyalkenes wherein the polyalkene is a
homopolymer or interpolymer of terminal olefins of 2 to
about 16 carbon atoms, with the proviso that said interpolymers
can optionally contain up to about 40% of the polymer units
derived from internal olefins of up to about sixteen carbon
atoms, substituted the preferred aspect of the process and
compositions prepared by the process. In a more preferred
aspect, polyalkenes for use in the process and in preparing
the compositions of the process are the homcpolymers and
interpolymers of 2 to 6 carbon atoms with the proviso that
said interpolymers can optionally contain up to about 25% of
polymer units derived from internal olefins of up to about 6
carbon atoms. Especialiy preferred polyalkenes are polybutenes~
ethylene-propylene copolymers, polypropylenes with the
polybutenes being particularl~ preferred.
~)9404~
In the same manner, the succinic group content of the
substituted acylating compositions thus produced are preferably
the same as that described in regard to the substituted
succinic acylating agents. Thus, the substituted acylating
compositions characterized by the presence within their
structure of an average of at least 1.4 succinic groups
derived from (B) for each equivalent weight of the substituent
groups derived from (A) are preferred with those containing
at least 1.4 up to about 3.5 succinic groups derived from
(B) for each equivalent weight of substituent groups derived
from (A) being still more preferred. In the same way, those
substituted acylating compositions characterized by the
presence within their structure of at least 1.5 succinic
groups are still further preferred, while those containing
at least 1.5 succinic groups derived from (B) for each
equivalent weight of substituent group derived from (A)
being especially preferred.
Finally, as with the description of the substituted
succinic acylating agents, the substituted acylating compo-
sitions produced by the preferred processes wherein the
succinic groups derived from (B) correspond to the formulae
~0 ,0
- CH C OH CH - C
O I \,0
CH - C - OH , CH C ~
and mixtures of these constitute a preferred class.
An especially preferred process for preparing the
substituted acylating compositions comprises heating at a
temperature of about 160C. to about 220C. a mixture com-
prising
- 34 -
1094044
(A) Polybutene characterized by a ~n value of about
1700 to about 2400 and a Mw/Mn value of about 2.5 to about
3.2, in which at least 50% of the total units derived from
butenes is derived from isobutene,
(B) One or more acidic reactants of the formula
O O
Il 11
~--C--~C = CH - C -R'
wherein R and R' are each -OH or when taken together, R and
R' are -O-, and
(C) Chlorine,
lQ wherein the mole ratio of (A):(B) is such that there is at
least 1.5 moles of (B) for each mole of (A) and the number
of moles of (A) is the quotient of the total weight of (A)
divided by the value of Mn, and the amount of chlorine
employed is such as to provide at least about one mole of
chlorine for each mole of (B) to be reacted with (A), said
acylating compositions being characterized by the presence
within their structure of an average of at least 1.5 groups
derived from (B) for each equivalent weight of the substi-
tuent groups derived from (A). In the same manner, substi-
tuted acylating compositions produced by such a process
constitute a preferred class of such compositions.
For purposes of brevity, the terminology "acylating
reagent(s)" is often used hereafter to refer, collectively,
to both the substituted succinic acylating agent of this
invention and to the substituted acylating compositions of
this invention.
The a~ylating reagents of this invention have utility,
in and of themselves, as additives for lubricant and fuel
compositions in the same manner as the known high molecular
1~940~4
weight carboxylic acid acylating agents of the prior art.
For example, the acylating reagents of this invention which
are succinic acids, succinic acid anhydrides, and lower
alkyl esters of succinic acids can be used as fuel additives
to reduce deposit formations for use in concentrations of
about 50 to about lOOOppm in hydrocarbon-based fuels boiling
substantially in the range of 100 to 750F.
U.S. Patent No. 3,346,354 discloses
instructions for using the known high molecular weight car-
boxylic acid acylating agents since those instructions are
applicable to the acylating reagents of this invention.
Similarly~ U.S. Patent 3~288~714 discloses
high molecular weight carboxylic acid acylating agents which
are succinic anhydrides as additives in lubricant composi-
tions where they function as dispersant/detergents since
these teachings are applicable to the acylating reagents of
this invention.
U.S. Patent 3,714,042 discloses how
to use the acylating reagents of this inven-
tion to treat overbased complexes. Thus, the acylating
reagents of this invention containing succinic acid groups,
succinic anhydride groups, and succinic ester groups can be
used to treat basic metal sulfonate complexes, sulfonate-
carboxylate complexes, and carboxylate complexes in the same
manner and a~cording to the same procedure as described in
3,714,042 by replacing the high molecular weight carboxylic
acid acylating agents discussed therein with the acylating
reagents of this invention on an equivalent weight basis.
- 36 -
B
1(~94044
~ecause the acylating reagents of this invention have
utility in and of themselves, beyond that of being inter-
mediates for preparing other novel compositions, lubricant
compositions and concentrates containing the acylating
reagents, as mentioned hereinbefore and described more fully
hereafter constitute a part of this invention.
Nevertheless, the principle use of the acylating re-
agents of this invention is as intermediates in processes
for preparing carboxylic derivative compositions comprising
reacting one or more acylating reagents with a reactant
selected from the group consisting of (a) amine charac-
terized by the presence within its structure of at least one
H-N ~ group, (b) alcohol, (c) reactive metal or reactive
metal compound, and (d) a combination of two or more of (a)
through (c), the components of (d) being reacted with said
acylating reagents simultaneously or sequentially in any
order.
The amine, (that is, (a) above) characterized by the
presence within its structure of at least one H-N ~ group
can be a monoamine or polyamine compound. For purposes of
this invention, hydrazine and substituted hydrazines con-
taining up to three substituents are included as amines
suitable for preparing carboxylic derivative compositions~
Mixtures of two or more amines can be used in the reaction
with one or more acylating reagents of this invention.
Preferably, the amin~ contains at least one primary amino
group (i.e., -NH2) and more preferably the amine is a poly-
- amine, especially a polyamine containing at least two H-N~
groups, either or both of which are primary or secondary
amines. ~he polyamines not only result in carboxylic acid
~ 37 -
'1094044
deri~ative compositions which are usually more effective as
dispersant/ detergent additives, relative to derivative
compositions derived from monoamines, but ~hese preferred
polyamines result in carboxylic derivative compositions
which exhibit more pronounced V.I. improving properties.
Monoamines, and polyamines suitable as (a) are described in
greater detail hereinafter.
Alcohols which can be used as (b) include the mono-
hydric and polyhydric alcohols. Again, the polyhydric
alcohols are pre erred since they usually result in car-
boxylic derivative compositions which are more effective
dispersant/detergents relative to carboxylic derivative
compositions derived from monohydric alcohols. Further, the
carboxylic acid derivative compositions derived from poly-
hydric alcohols exhibit very pronounced V.I. improving
properties and are especially preferred reactants. Alcohols
suitable for use as (b) are described in greater detail
hereinafter.
Reactive metals and reactive metal compounds useful as
(c) are those which are known to form salts and complexes
when reacted with carboxylic acid and carboxylic acid acy-
lating agents. These metals and metal compounds are des-
cribed further hereinafter.
The monoamines and polyamines useful as (a) must be
characterized by the presence within their structure of at
least one H-N ~ group. Therefore, they have at least one
primary (i.e., H2N-~ or secondary amino (i.e., H-N=) group.
The amines can be aliphatic, cycloaliphatic, aromatic, or
heterocyclic, including aliphatic-substituted aromatic,
aliphatic-substituted cycloaliphatic, aliphatic-substituted
3~ -
109 ~04~
aromatic, aliphatic-substituted heterocyclic, cycloali-
phatic-substituted aliphatic, cycloaliphatic-substituted
aromatic, cycloaliphatic-substituted heterocyclic, aromatic-
substituted aliphatic, aromatic-substituted cycloaliphatic,
aromatic-substituted heterocyclic, heterocyclic-substituted
aliphatic, heterocyclic-substituted aliphatic, and hetero-
cyclic-substituted aromatic amines and may be saturated or
unsaturated. If unsaturated, the amine will be free from
acetylenic unsaturation ~i.e., -C-C-). The amines may also
contain non-hydrocarbon substituents or groups as long as
these groups do not significantly interfere with the reac-
tion of the amines with the acylating reagents of this
invention. Such non-hydrocarbon substituents or groups
include lower alkoxy, lower alkyl mercapto, nitro, inter-
rupting groups such as -O- and -S- (e.g., as in such groups
as -CH2CH2-X-CH2CH2- where X i5 -O- or -S-).
With the exception of the branched polyalkylene poly-
amine, the polyoxyalkylene polyamines, and the high mole-
cular weight hydrocarbyl-substitut d amines described more
fully hereafter, the amines used as (a) ordinarily contain
less than about 40 carbon atoms in total and usually not
more than about 20 carbon atoms in total.
Aliphatic monoamines include mono-aliphatic and di-
aliphatic substituted amines wherein the aliphatic ~roups
can be saturated or unsaturated and straight or branched
chain. Thus, they are primary or secondary aliphatic amines.
Such amines include, for example, mono- and di-alkyl-substi-
tuted amines, mono- and di-alkenyl-substituted amines, and
amines having one N-alkenyl substituent and one N-alkyl
substituent and the like. The total number of carbon atoms
- 39 -
1~)9"044
in these aliphatic monoamines will, as mentioned before,
normally not exceed about 40 and usually not exceed about 20
carbon atoms. Speci~ic examples of such monoamines include
ethylamine, diethylamine, n-butylamine, di-n-butylamine,
allylamine, isobutylamine, cocoamine, stearylamine, lauryl-
amine, methyllaurylamine, oleylamine, N-methyl-octylamine,
dodecylamine, octadecylamine, and the like. Examples of
cycloaliphatic-substituted aliphatic amines, aromatic-
substituted aliphatic amines, and heterocyclic-substituted
aliphatic amines, include 2-(cyclohexyl)-ethylamine, benzyl-
amine, phenethylamine, and 3-(furylpropyl)amine.
Cycloaliphatic monoamines are those monoamines wherein
there is one cycloaliphatic substituent attached directly to
the amino nitrogen through a carbon atom in the cyclic ring
structure. ~xamples of cycloaliphatic monoamines include
cyclohexylamines, cyclopentylamines, cyclohexenylamines,
cyclopentenylamines, N-ethyl-cyclohexylamine, dicyclohexyl-
amines, and the like. Examples of aliphatic-substituted,
aromatic-substituted, and heterocyclic-substituted cyclo-
aliphatic monoamines include propyl-substituted cyclohexyl-
amines, phenyl-substituted cyclopentylamines, and pyranyl-
substituted cyclohexylamine.
Aromatic amines suitable as (a) include those mono-
amines wherein a carbon atom of the aromatic ring structure
is attached directly to the amino nitrogen. The aromatic
ring will usually be a mononuclear aromatic ring ~i.e., one
derived from benzene) but can include fused aromatic rings,
especially those deri~ed ~rom naphthylene. Examples of
aromatic monoamines include aniline, di~para-methylphenyl)-
amine, naphthylamine, N-~n-butyl~aniline, and the like.
- 4~ -
1094044
Examples of aliphatic-substituted, cycloaliphatic-substi-
tuted, and heterocyclic-substituted aromatic monoamines are
para-ethoxyaniline, para-dodecylaniline, cyclohexyl-substi-
tuted naphthylamine, and thienyl-substituted aniline.
Polyamines suitable as (a) are aliphatic, cycloali-
phatic and aromatic polyamines analogous to the above-
described monoamines except for the presence within their
structure of another amino nitrogen. The other amino
nitrogen can be a primary, secondary or tertiary amino
nitrogen. Examples of such polyamines include N-amino-
propyl-cyclohexylamines, N-N'-di-n-butyl-para-phenylene
diamine, bis-(para-aminophenyl)methane, 1,4-diaminocyclo-
hexane, and the like.
Heterocyclic mono- and polyamines can also be used as
(a) in making the carboxylic derivative compositions of this
invention. As used herein, the terminology "heterocyclic
mono- and polyamine(s)" is intended to describe those hetero-
cyclic amines containing at least one primary or secondary
amino group and at least one nitrogen as a heteroatom in the
heterocyclic ring. However, as long as there is present in
the heterocyclic mono- and polyamines at least one primary
or secondary amino group, the hetero-N atom in the ring can
be a tertiary amino nitrogen; tha~ is, one that ~oes not
have ~ydrogen attached directly to the ring nitrogen.
Heterocyclic amlnes can be saturated or unsaturated and can
contain various substituents such as nitro, alkoxy, alkyl
merca~to~ alkyl, alkenyl r aryl, alkaryl, or aralkyl substituents.
Generally, the total number o~ carbon atoms in the substituents
will not exceed about 20. Heterocyclic amines can contain
- 41 -
~)940~4
hetero atoms other than nitrogen, especially oxygen and
sulfur. Obviously they can contain more than one nitrogen
hetero atom. The five- and six-membered heterocyclic rings
are preferred.
Among the suitable heterocyclics are aziridines, azeti-
dines, azolidines, tetra- and di-hydro pyridines, pyrroles,
indoles, piperadines, imidazoles, di- and tetra-hydroimidazoles,
piperazines, isoindoles, purines, morpholines, thiomorpho-
lines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,
N-aminoalkylpiperazines, N,N'-di-aminoalkylpiperazines,
azepines, azocines, azonines, azecines and tetra-, di- and
perhydro derivatives of each of the above and mixtures of
two or more of these heterocyclic amines. Preferred hetero-
cyclic amines are the saturated 5- and 6-membered heterocy-
clic amines containing only nitrogen, oxygen and/or sulfur
in the hetero ring, especially the piperidines, piperazines,
thiomorpholines, morpholines, pyrrolidines, and the like.
Piperidine, aminoalkyl-substituted piperidines, piperazine,
aminoal~yl-substituted piperazines, morpholine, aminoalkyl-
substituted morpholines, pyrrolidine, and aminoalkyl-sub-
stituted pyrrolidines, are especially preferred. Usually
the aminoalkyl substituents are substituted on a nitrogen
atom forming part of the hetero ring. Speci~ic examples of
such heterocyclic amines include N-aminopropylmorpholine, N-
aminoethylpiperazine, and N,N'-di-aminoethylpiperazine.
Hydroxyamines both mono- and polyamines, analogous to
those described above are also useful as (a) provided they
contain at least one primary or secondary amino group.
Hydroxy-substitu~ed amines having only tertlary amino nitro-
gen such as in tri-hydroxyethyl amine, are thus excluded as
- 42 -
~09~044
(a) (but can be used as (b) as disclosed hereafter). The
hydroxy-substituted amines contemplated are those having
hydroxy substituents bonded directly to a carbon atom other
than a carbonyl carbon atom; that is, they have hydroxy
groups capable of functioning as alcohols. Examples of such
hydroxy-substituted amines include ethanolamine, di-(3-
hydroxypropyl)-amine, 3-hydroxybutyl-amine, 4-hydroxybutyl-
amine, diethanolamine, di-(2-hydroxypropyl)-amine, N-(hydroxypropyl)-
propylamine, N-(2-hydroxyethyl)-cyclohexylamine, 3-hy-
droxycyclopentylamine, para-hydroxyaniline, N-hydroxyethyl
piperazine, and the like.
Also suitable as amines are the aminosulfonic acids and
derivatives thereof corresponding to the general formula:
o
(RCRbN )x ( Ra ( S-R) Formula VI
_+
wherein R is -OH, -NH2, ONH4, etc., Ra is a polyvalent
organic radical having a valence equal to x + y; Rb and Rc
are each independently hydrogen, hydrocarbyl, and substi-
tuted hydrocarbyl with the proviso that at least one of Rb
or Rc is hydrogen per aminosulfonic acid molecule; x and y
are each integers equal to or great~r than one. From the
formula, it is apparent that each amino sulfonic reactant is
characterized by at least one HN = or H2N- group and at
least one -S-R group. These sulfonic acids can be ali-
I!
phatic, cycloaliphatic, or aromatic aminosulfonic acids and
~5 the corresponding functional derivatives of the sulfo group.
Specifically, the aminosulfonic acids can be aromatic amino-
- 4~ ~
109~044
sulfonic acids, that is, where Ra is a polyvalent aromatic
radical such as phenylene where at least one -S-R group is
o
attached directly to a nuclear carbon atom of the aromatic
radical. The aminosulfonic acid may also be a mono-amino
aliphatic sulfonic acid; that is, an acid where x is one and
Ra is a polyvalent aliphatic radical such as ethylene,
propylene, trimethylene, and 2-methylene propylene. Other
suitable aminosulfonic acids and derivatives thereof
useful as (a) are disclosed in U.S. Patents 3,926,820;
3,029,250; and 3,367,864.
Hydrazine and substituted-hydrazine can also
be used as (a). At least one of the nitrogens in the hydrazine
used as (a) must contain a hydrogen directly bonded thereto.
Preferably there are at least two hydrogens bonded directly to
hydrazine nitrogen and, more preferably, both hydrogens are
on the same nitrogen. The substituents which may be present
on the hydrazine include alkyl, alkenyl, aryl, aralkyl,
alkaryl, and the like. Usually, the substituents are alkyl,
- 44 -
109~044
especially lower alkyl, phenyl, and substituted phenyl such
as lower alkoxy substituted phenyl or lower alkyl substi-
tuted phenyl. Specific examples of substituted hydrazines
are methylhydrazine, N,N-dimethyl-hydrazine, N,N'-dimethyl-
hydrazine, phenylhydrazine, N-phenyl-N'-ethyl-hydrazine, N-
(para-tolyl)-N'-(n-butyl)- hydrazine, N-(para-nitrophenyl)-
hydrazine, N-(para-nitrophenyl)-N-methyl-hydra2ine, N,N'-di-
(para-chlorophenol)-hydrazine, N-phenyl-N'-cyclohexyl-
hydrazine, and the like.
The high molecular weight hydrocarbyl amines, both
mono-amines and polyamines, which can be used as (a) are
generally prepared by reacting a chlorinated polyolefin
having a molecular weight of at least about 400 with ammonia
or amine. Such amines are known in the art and described,
for example, in U.S. Patents 3,275,554 and 3,438,757~
All that is required for use of these amines as (a) is that
they possess at least one primary or secondary amino group.
Another group of amines suitable for use as (a) are
branched polyalkylene polyamines. The branched polyalkylene
polyamines are polyalkylene polyamines wherein the branched
group is a side chain containing on the average at least one
nitrogen-bonded aminoalkylene
H
(i.e., NH2 R- - N- R- x
group per nine amino units present on the main chain, for
examples, 1-4 of such branched chains per nine units on the
main chain, b ~ preferably one side cha~n un ~ per nine main
chain units. Thus, these polyamines contain at least three
primary amino groups and at least one tertiary amino group.
- 45 -
~09404~
These reagents may be expressed by the formula:
H
NH2- (R-N)~RN ¦ RNH2
I rRl I
LNH1 Z
R
NH2 J y
wherein R is an alkylene group such as ethylene, propylene,
butylene and othe_ homologues (both straight chained and
branched), etc., but preferably ethylene; and x, y and z are
integers, x being for example, from 4 to 24 or more but
preferably 6 to 18, y being for example 1 to 6 or more but
preferably 1 to 3, and z being for example 0-6 but pre-
ferably 0-1. The x and y units may be sequential, alter-
native, orderly or randomly distributed.
The preferred class of such polyamines includes those
of the formula
H H
NH 2 - - (R - N ~5 -RN (R--N--t~ n
NH2
wherein n is an integer, for example, 1-20 or more but
preferably 1-3, wherein R is preferably ethylene, but may be
propylene, butylene, etc. (straight chained or branched).
The preferred embodiments are presented by the following
formula:
H H
NH2----~CH2CH21~1) 5--CH2CH2-- I ~CH2CH~N~ 2-----H
CH2
CH2
1H2 n
(n = 1-3).
- 46 -
10~044
The radicals in the brackets may be ~oined in a head-
to-head or a head-to-tail fashion. Compounds described by
this formula wherein n = 1-3 are manufactured and sold as
*
Polyamines N-400, N-800, N-1200 etc. Polyamine N-400 has
the above formula wherein n=l.
U~S. Patents 3,200,106 ~n~ 3,259,578 disclose how
to make such polyamines and processes for reacting them with
carboxylic acid acylating agents since analogous processes
can be used with the acylating reagents of this invention.
Suitable amines also include polyoxyalkylene polyamines,
e.g., polyoxyalkylene diamines and polyoxyalkylene triamines,
having average molecular weights ranging from about 200 to
4000 and preferably from about 400 to 2000. Illustrative
examples of these polyoxyalkylene polyamines may be charac-
terized by the formulae:
Formula VII
NH2-Alkylene ~ O-Alkylene )mNH2
where m has a value of about 3 to 70 and preferably about 10
to 35.
Formula VIII
R-~Alkylene ( O-Alkylene )n NH~] 3-6
where n is such that the total value is from about 1 to 40
with the proviso that the sum of all of the n's is from
about 3 to about 70 and generally from about 6 to aboùt 35
and R is a polyvalent saturated hydrocarbon radical of up t~
ten carbon atoms having a valence of 3 to 6. The alkylene
groups may be straight or branched chains and contain from 1
to 7 carbon atoms, and usually from 1 to 4 carbon atoms.
* trade mark
- 47 -
1~94044
The various alkylene groups present within Formulae VII
and VIII may be the same or different.
More specific examples of these polyamines include:
Formula IX
NH2CHCH2 ( OCH2CH )x NH2
CH3 CH3
wherein x has a value of from about 3 to 70 and preferably
from about 10 to 35 and
Formula X
CH2 (OCH2fH ~x NH2
¦ CH3
CH3-CH2- f -CH2 (OCH2CH )y NH2
I CH3
CH 2 (OCH 2 CH )z NH 2
CH3
wherein x + y + z have a total value ranging from about 3 to
30 and preferably from about 5 to 10.
The preferred polyoxyalkylene polyamines for purposes
of this invention include the polyoxyethylene and polyoxy-
propylene diamines and the polyoxypropylene triamines having
average molecular weights ranging from about 200 to 2000.
The polyoxyalkylene polyamines are commercially available
and may be obtained, for example, from the Jefferson Chemi-
cal Company, Inc. under the trade mark "Jeffamines D-230, D-
400, D-1000, D-2000, T-403, etc.".
U.S. Patents 3 f 804,763 and 3,948,800 disclose
such polyoxyalkylene polyamines and pr~cess for acylating
them with carboxylic acid acylating agents which processes
- 48 -
109'~044
can be applied to their reaction with the acylating reagents
of this invention.
The most preferred amines for use as (a) are the alky-
lene polyamines, including the polyalkylene polyamines, as
described in more detail hereafter. The alkylene polyamines
include those conforming to the formula
H-N--tAlkylene-NR"t-nR" Formula XI
wherein n is from 1 to about 10; each R' is independently a
hydrogen atom, a hydrocarbyl group or a hydroxy-substituted
hydrocarbyl group having up to about 30 atoms, and the
"Alkylene" group has from about 1 to about 10 carbon atoms
but the preferred alkylene is ethylene or propylene. Es-
pecially preferred are the alkylene polyamines where each R"
is hydrogen with the ethylene polyamines and mixtures of
ethylene polyamines being the most preferred. Usually n
will have an average value of from about 2 to about 7. Such
alkylene polyamines include methylene polyamine, ethylene
polyamines, butylene polyamines ! propylene polyamines,
pentylene polyamines, hexylene polyamines, heptylene poly-
amines, etc. The higher homologs of such amines and related
aminoalkyl-substitllted piperazines are also included.
Alkylene polyamines useful in preparing the carboxylic
derivative compositions include ethylene diamine, triethylene
tetramine, propylene diamine, trimethylene diamine, hexa-
methylene diamine, decamethylene diamine, octamethylene
diamine, di(heptamethylene)triamine, tripropylene tetramine,
tetraethylene pentamine, trimethylene diamine, pentaethylene
hexamine, di(trimethylene)triamine, N~ amil.~ .yl~pipera-
zine, 1,4-bis(2-aminoethyl)piperazine, and the like~
_ ~9 _
1094044
Higher homologs as are obtained by condensing two or more of
the above-illustrated alkylene amines are useful as (a) as
are mixtures of two or more of any of the afore-described
polyamines.
Ethylene polyamines, such as those 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 The Encyclopedia of Chemical
Technology, Second Edition, Kirk and Othmer, Volume 7, pages
27-39, Interscience Publishers, Division of John Wiley and
Sons, 1965. Such compounds are
prepared most conveniently by the reaction of an alkylene
ohloride with ammonia or by reaction of an ethylene imine
with a ring-opening reagent such as ammonia, etc. These
reactions result in the production of the somewhat complex
mixtures of alkylene polyamines, including cyclic conden-
sation products such as piperazines. The mixtures are par-
ticularly useful in preparing novel sulfur-containing
compositions of matter of this invention. On the other
hand, quite satisfactory products can also be obtained by
the use of pure alkylene polyamines.
Hydroxyalkyl alkylene polyamines having one or more
hydroxyalkyl substituents on the n~trogen atoms, are also
useful in preparing amide or ester functional derivatives of
the afore-described olefinic carboxylic acids. Preferred
hydroxyalkyl-su~stituted alkylene polyamines are those in
which the hydroxyalkyl group is a lower hydroxyalkyl group,
i.e., having less than eight carbon atoms. Examples of such
hydroxyalkyl-substituted polyamines include N-(2-hydroxy-
- 50 -
~?
j ~...~,
1094044
ethyl)ethylene diamine, N,N-bis(2-hydroxyethyl)ethylene
diamine, l-(2-hydroxyethyl)piperazine, monohydroxypropyl-
substituted diethylene triamine, dihydroxypropyl-substituted
tetraethylene pentamine, N-(3-hydroxybutyl)tetramethylene
diamine, etc. Higher homologs as are obtained by conden-
- sation of the above-illustrated hydroxy alkylene polyamines
through amino radicals or through hydroxy radicals are
likewise useful as (a). Condensation through amino radicals
results in a higher amine accompanied by removal of ammonia
and condensation through the hydroxy radicals results in
products containing ether linkages accompanied by removal of
water.
The carboxylic derivative compositions produced from
the acylating reagents of this invention and the amines
described hereinbefore produce acylated amines which include
amine salts, amides, imides and imidazolines as well as
mixtures thereof. To prepare carboxylic acid derivatives
from the acylating reagents and the amines, one or more
acylating reagents and one or more amines are heated, op-
tionally in the presence of a normally liquid, substantially
inert organic liquid solvent/diluent, at temperatures in the
range of about 80C. up to the decomposition point (where
the decomposition point is as previously defined) but nor- !
mally at temperatures in the range of about 100C. up to
about 300C. provided 300C. does not exceed the decomposi-
tion point. Temperatures of about 125C. to about 250C.
are normally used. The acylating reagent and the amine are
reacted in amounts sufficient to provide from about one-half
equivalent to about 2 moles of amine per equivalent of
acylating reagent. For purposes of this invention an
1~94044
equivalent of amine is that amount of the amine corres-
ponding to the total weight of amine divided by the total
number of nitrogens present. Thus, octylamine has an
equivalent weight equal to its molecular weight; ethylene
diamine has an equivalent weight equal to one-half its
molecular weight; and aminoethylpiperazine has an equivalent
weight equal to one-third its molecular weight.
The numbers of equivalents of acylating reagent depends
O O
il 11
on the number of carboxylic functions (e.g., -C-X, -C-X',
O O
-C-R, and -C-R', wherein X, X', R and R' are as defined
above~ present in the acylating reagent. Thus, the number
of equivalents of acylating reagents will vary with the
number of succinic groups present therein. In determining
the number of equivalents of acylating reagents, those
carboxyl functions which are not capable of reacting as a
carboxylic acid acylating agent are excluded. In general,
however, there are two e~uivalents of acylating reagent for
each succinic group in the acylating reagents or, from
another vie~point, two equivalents for each group in the
acylating reagents derived from (B); i.e., the maleic
reactant from which the acylatng reagent is prepared.
Conventional techniques are readily available for deter-
mining the number of carboxyl functions (e.g., acid number,
saponificatlon number) and, thus, the number of equivalents
of acylating reagent available to react with amine.
Because the acylating reagents of this invention can be
used in the same manner as the high molecular weight acylating
agents of the prior art in preparing acylated amines suitable
- 52 -
1094044
as additives for lubricating oil compositions, U.S. Patents
3,172,892; 3,219,666; and 3,272,746 are relevant
for their disclosure with respect
to the procedures applicable to reacting the acylating
reagents of this invention with the amines as described
above. In applying the disclosures of these patents to the
acylating reagents of this invention, the latter can be
substituted for the high molecular weight carboxylic acid
acylating agents disclosed in these patents on an equivalent
basis. That is, where one equivalent of the high molecular
weight carboxylic acylating agent disclosed in these incor-
porated patents is utilized, one equivalent of the acylating
reagent of this invcntion can be used. These patents are
also relevant for their disclosure of how
to use the acylated amines thus produced as additives in
lubricating oil compositions. Dispersant/detergent pro-
perties can be imparted to lubricating oils by incorporating
the acylated amines produced by reacting the acylating
reagents of this invention with the amines described above
on an equal weight basis with the acylated amines disclosed
in these patents. In fact, equivalent or better dispersant/
detergent results can normally be achieved with lesser
amounts of the product of the acylating reagents of this
invention and-amines.
Alcohols useful as (b) useful in preparing carboxylic
derivative compositions of this invention from the acylating
reagents previously described include those compounds of the
general formula
1~3 (OH)m Formula XII
-- 53 --
L
1094044
Wherein R3 is a monovalent or polyvalent organic radical
joined to the -OH groups through carbon-to-oxygen bonds
(that is, -COH wherein the carbon is not part of a carbonyl
group) and m is an integer of from 1 to about 10, usually 2
to about 6. As with the amine reactant (a~, the alcohols
can be allphatic, cycloaliphatic, aromatic, and hetero-
cyclic, including aliphatic-substituted cycloaliphatic
alcohols, aliphatic-substituted aromatic alcohols, alipha-
tic-substituted heterocyclic alcohols, cycloaliphatic-
substituted aliphatic alcohols, cycloaliphatic-substituted
aromatic alcohols, cycloaliphatic-substituted heterocyclic
alcohols, heterocyclic-substituted aliphatic alcohols,
heterocyclic-substituted cycloaliphatic alcohols, and hetero-
cyclic-substituted aromatic alcohols. Except for the poly-
oxyalkylene alcohols, the mono- and polyhydric alcohols
corresponding to Formula XII will usually contain not more
than about 40 carbon atoms and generally not more than about
20 carbon atoms. The alcohols may contain non-hydrocarbon
substituents of the same type mentioned with respect to the
amines above, that is, non-hydrocarbon substituents which do
not interfere with the reaction of the alcohols with the
acylating reagents of this invention. In general, polyhy-
dric alcohols are preferred. As between amines and alcohols,
the polyhydric alcohols are preferred because the carboxylic
derivative compositions derived therefrom (i.e., esters)
exhibit exceptional V.I. improving qualities as discussed
above. However, combinations of amines and polyhydric
alcohols also result in carboxylic derivative compositions
which have exceptional V.I. improving qualities.
- 54 -
1094044
Among the polyoxyalkylene alcohols suitable as (b) in
the preparation of the carboxylic derivative compositions of
this invention are the polyoxyalkylene alcohol demulsifiers
for aqueous emulsions. The terminology "demulsifier for
aqueous emulsions" as used in the present specification and
claims is intended to describe those polyoxyalkylene alcohols
which are capable of preventing or retarding the formation
of a~ueous emulsions or "breaking" aqueous emulsions. The
terminology "aqueous emulsion~ is generic to oil-in-water
and water-in-oil emulsions.
Many commercially available polyoxyalkylene alcohol
demulsifiers can be used as (b). Useful demulsifiers are
the reaction products of various organic amines, carboxylic
acid amides, and quaternary ammonium salts with ethylene-
oxide. Such polyoxyethylated amines, amides, and quaternary
salts are available from Armour Industrial Chemical Co.
under the names ETHODUOMEEN ~, an ethyleneoxide condensation
product of an N-alkyl alkylenediamine under the name DVOMEEN
* *
T; ETHOMEENS, tertiary amines which are ethyleneoxide conden-
sation products of primary fatty amines; ETHOMIDS, ethyleneox-
ide condensates of fatty acid amides; and ETHOQUAD~, poly-
oxyethylated quaternary ammonium salts such as quaternary
ammonium chlorides.
The preferred demulsifiers are liquid polyoxyalkylene
alcohols and derivatives thereof. The derivatives contem-
plated are the hydrocarbyl ethers and the carboxylic acid
esters obtained by reacting the alcohols with various car-
boxylic acids. Illustrative hydrocarbyl groups are alkyl,
cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc.,
containing up to about forty carbon atoms. Specific hydro-
*~rade marks
1094044
carbyl groups are methyl, butyl, dodecyl, tolyl, phenyl,
naphthyl, dodecylphenyl, p-octylphenyl ethyl, cyclohexyl,
and the like. Carboxylic acids useful in preparing the
ester derivatives are mono- or polycarboxylic acids such as
acetic acid, valeric acid, lauric acid, stearic acid, suc-
cinic acid, and alkyl or alkenyl-substituted succinic acids
wherein the alkyl or alkenyl group contains up to about
twenty carbon atoms. Members of this class of alcohols are
commercially available from various sources; e.g., PLURONIC
polyols from Wyandotte Chemicals Corporation; POLYGLYCOL
112-2, a liquid triol derived from ethyleneoxide and propy-
leneoxide available from Dow Chemical Co.; and TERGITOLS,
dodecylphenyl or nonylphenyl polyethylene glycol ethers, and
UCONS, polyalkylene glycols and various derivatives thereof,
both available from Union Carbide Corporation. However, the
demulsifiers used as (b) must have an average of at least
one free alcoholic hydroxyl group per molecule of polyoxy-
alkylene alcohol. For purposes of describing these polyoxy-
alkylene alcohols which are demulsifiers, an alcoholic
hydroxyl group is one attached to a carbon atom that does
not form part of an aromatic nucleus.
In this class of preferred polyoxyalkylene alcohols arethose polyols prepared as "block" copolymers. Thus, a
hydroxy-substituted compound, R4~(OH)q (where q is 1 to 6,
preferably 2 to 3, and R4 is the residue of a mono- or
polyhydric alcohol or mono- or polyhydroxy phenol, naphthol,
etc.) is reacted with an alkylene oxide, Rs-CH-CH-R6, to
form a hydrophob-~ base, Rs being a lower ~kyl group of up
to four carbon atoms, R6 being H or the same as Rs with the
* trade mark
- 56 -
B
1094044
proviso that the alkylene oxide does not contain in excess
of ten carbon atoms. This base is then reacted with ethyl-
ene oxide to provide a hydrophylic portion resulting in a
molecule having both hydrophobic and hydrophylic portions.
- 5 The relative sizes of these portions can be adjusted by
regulating the ratio of reactants, time of reaction, etc.,
as is obvious to those skilled in the art. It is within the
skill of the art to prepare such polyols whose molecules are
characterized by hydrophobic and hydrophylic moieties pre-
sent in a ratio rendering them suitable as demulsifiers for
aqueous emulsions in various lubricant compositions and thus
suita~le as (b). Thus, if more oil- solubility is needed in
a given lubricant composition, the hydrophobic portion can
be increased and/or hydrophylic portion decreased. If
greater aqueous emulsion breaking capability is required,
the hydrophylic and/or hydrophobic portions can be adjusted
to accomplish this.
Compounds illustrative of R4~tOH)q include aliphatic
polyols such as the alkylene glycols and alkane polyols,
e.g., ethylene glycol, propylene glycol, trimethylene gly-
col, glycerol, pentaerythritol, erythritol, sorbitol, manni-
tol, and the like and aromatic hydroxy compounds such as
alkylated mono- and polyhydric phenols and naphthols e.g.,
cresols, heptylphenols, dodecylphenols, dioctylphenols,
triheptylphenols, resorcinol, pyrogallol, etc.
Polyoxyalkylene polyol demulsifiers which have two or
three hydroxyl groups and molecules consisting essentially
of hydrophobic portions comprising -CHCH20- groups where Rs
Rs
is lower alkyl of up to three carbon atoms and hydrophylic
- 57 -
1094044
portions comprising -CH2CH2O- groups are particularly pre-
ferred as (b). Such polyols can be prepared by first reac-
ting a compound of the formula R4~~OH)q where q is 2-3 with
a terminal alkylene oxide of the formula Rs-CH-CH2 and then
\ /
reacting that product with ethylene oxide. R4~~0H)q can
be, for example, TMP (trimethylolpropane), TME (trimethy-
lolethane), ethylene glycol, trimethylene glycol, tetra-
methylene glycol, tri-(~-hydroxypropyl)amine, 1,4-(2-hydroxy-
ethyl)-cyclohexane, N,N,N',N'-tetrakis(2-hydroxypropyl)-
ethylene diamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylene
diamine, naphthol, alkylated naphthol, resorcinol, or one of
the other illustrative examples mentioned hereinbefore.
The polyoxyalkylene alcohol demulsifiers should have an
average molecular weight of about 1000 to about 10,000, pre-
ferably about 2000 to about 7000. The ethyleneoxy groups
(i.e., -CH2CH20-) normally will comprise from about 5% to
about 40% of the total average molecular weight. Those
polyoxyalkylene polyols where the ethyleneoxy groups com-
prise from about 10% to about 30% of the total average
molecular weight are especially useful as (b). Polyoxy-
alkylene polyols having an average molecular weight of about
2500 to about 6000 where approximately 10%-20% by weight of
the molecule is attributable to ethyleneoxy groups result in
the formation of esters having particularly improved demul-
sifying properties. The ester and ether derivatives of
these polyols are also useful as (b).
Representative of such polyoxyalkylene polyols are the
liquid polyols available from Wyandotte Chemicals Company
under the name PLURONIC Polyols and other similar polyols.
~trade mark
- 58 -
1094044
These PLURONIC Polyols correspond to the formula
HO-(CH2CH20)X(CHcH2o)y(cH2cH2o)z-H Formula XIII
CH3
wherein x, y, and z are integers greater than 1 such that
the -CH2CH20- groups comprise from about 10% to about 15% by
weight of the total molecular weight of the glycol, the
average molecular weight of said polyols being from about
2500 to about 4500. This type of polyol can be prepared by
reacting propylene glycol with propylene oxide and then with
ethylene oxide.
Another group of polyoxyalkylene alcohol demulsifiers
illustrative of the preferred glass discussed above are the
commercially available liquid TETRONIC polyols sold by
Wyandotte Chemicals Corporation. These polyols are repre-
sented by the general formula:
H(c2H4o)b(c3H6o)a\ /(c3H~o)a(c2H4o)bH
NCH2CH2N
H(C2H40)b(C3H60) / (C3H60)a(C2H40)bH
Such polyols are described in U.S. Patent No. 2,979,528.
polyols correspondiny to the above formula having an average
molecular weight of up to about 10,000 wherein the ethylene-
oxy groups contribute to the total molecular weight in the
percentage ranges discussed above are preferred. A specific
example would be such a polyol having an average molecular
~eight of about 8000 wherein the ethyleneoxy groups account
for 7.5~-12~ by weight of the total molecular weight. Such
polyols can be pxepared by reacting an alkylene diamine such
as ethylene diamine, propylene diamine, hexamethylene diamine,
* trade mark
- 59 -
- ' 1094044
etc., with propylene oxide until the desired weight of the
hydrophobic portion is reached. Then the resulting product
is reacted with ethylene oxide to add the desired number of
hydrophylic units to the molecules.
Another commercially available polyoxyalkylene polyol
demulsifier falling within this preferred group is Dow
Polyglycol*112-2, a triol having an average molecular weight
of about 4000-5000 prepared from propylene oxides and
ethylene oxides, the ethyleneoxy groups comprising about 18%
by weight of the triol. Such triols can be prepared by
first reacting glycerol, TME, TMP, etc., with propylene
oxide to form a hydrophobic base and reacting that base with
ethylene oxide to add hydrophylic portions.
Alcohols useful as (b) also include alkylene glycols
and polyoxyalkylene alcohols such as polyoxyethylene alco-
hols, polyoxypropylene alcohols, polyoxybutylene alcohols,
and the like. These polyoxyalkylene alcohols (sometimes
called polyglycols) can contain up to about 150 oxyalkylene
groups in the alkylene radical contains from 2 to about 8
carbon atoms. Such polyoxyalkylene alcohols are generally
dihydric alcohols. That is, each end of the molecule ter-
minates with a -OH group. In order for such polyoxyalkylene
alcohols to he useful as (b), there must be at least one
such -OH group. However, the remaining -OH group can be
esterified with a monobasic, aliphatic or aromatic carboxylic
acid of up to about 20 carbon atoms such as acetic acid,
propionic acid, oleic acid, stearic acid, benzoic acid, and
the like. The monoethers of these alkylene glycols and
polyoxyalkylene glycols are also useful as (b). These
3 include the monoaryl ethers, monoalkyl ethers, and mono-
*trade marX 60
~09~0~4
aralkyl ethers of these alkylene glycols and polyoxyalkylene
glycols. This group of alcohols can be represented by the
general formula
Ho_t_~Ao ~ ~ - ORC Formula XIV
where RC is aryl such as phenyl, lower alkoxy phenyl, or
lower alkyl phenyl; lower alkyl such as ethyl, propyl, tert-
butyl, pentyl, etc.; and aralkyl such as benzyl, phenylethyl,
phenylpropyl, p-ethylphenylethyl, etc.; p is zero to about
150, and RA and ~ are lower alkylene of two up to about
eight, preferably, two to four, carbon atoms. Polyoxyalky-
lene glycols where the alkylene groups are ethylene or
propylene and p is at least two as well as the monoethers
thereof as described above are very useful.
The monohydric and polyhydric alcohols useful as (b)
lS include monohydroxy and polyhydroxy aromatic compounds.
Monohydric and polyhydric phenols and naphthols are pre-
ferred hydroxyaromatic compounds. These hydroxy-substituted
aromatic compounds may contain other substituents in addi-
tion to the hydroxy substituents such as halo, alkyl, alkenyl,
alkoxy, alkylmercapto, nitro and the like. Usually, the
hydroxy aromatic compound will contain 1 to 4 hydroxy
groups. The aromatic hydroxy compounds are illustrated by
the following specific examples: phenol, p-chlorophenol, p-
nitrophenol, beta-naphthol, alpha-naphthol, cresols, resor-
cinol, catechol, carvacrol, thymol, eugenol, p,p'-dihydroxy-
biphenyl, hydroquinone, pyrogallol, phloroglucinol, hexyl-
resorcinol, orcin, guaiacol, 2-chlorophenol, 2,4-dibutyl-
phenol, propenetetramer-substituted phenol, didodecylphenol,
4,4'-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-
- 61 -
10~4044
naphthol, polyisobutenyl-(molecular weight of about 1000)-
substituted phenol, the condensation product of heptylphenol
with 0.5 moles of formaldehyde, the condensation product of
octylphenol with acetone, di(hydroxyphenyl)oxide, di(hydroxy-
phenyl)sulfide, di(hydroxyphenyl)disulfide, and 4-cyclohexyl-
phenol. Phenol itself and aliphatic hydrocarbon-substituted
phenols, e.g., alkylated phenols having up to 3 aliphatic
hydrocarbon substituents are especially preferred. Each of
the aliphatic hydrocarbon substituents may contain 100 or
more carbon atoms but usually will have from 1 to 20 carbon
atoms. Alkyl and alkenyl groups are the preferred aliphatic
hydrocarbon substituents.
Further specific examples of monohydric alcohols which
can be used as (b) include monohydric alcohols such as
methanol, ethanol, isooctanol, dodecanol, cyclohexanol,
cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl
alcohol, isobutyl alcohol, benzyl alcohol, beta-phenethyl
alcohol, 2-methylcyclohexanol, beta-chloroethanol, mono-
methyl ether of ethylene glycol, monobutyl ether of ethylene
glycol, monopropyl ether of diethylene glycol, monododecyl
ether of triethylene glycol, monooleate of ethylene glycol,
monostearate of diethylene glycol, sec-pentyl alcohol, tert-
butyl alcohol, 5-~romo-dodecanol, nitro-octadecanol, and
dioleate of glycerol. Alcohols within (b) may be unsatur-
ated alcohols such as allyl alcohol, cinnamyl alcohol, 1-
cyclohexene-3-ol and oleyl alcohol.
Other specific alcohols useful as (b) are the ether
alcohols and amino alcohols including, for example, the
oxyalkylene, oxy-arylene-, amino-alkylene-, and amino-
3~ arylene-substituted alcohols having one or more oxyalkylene,
- 62 ~
~09 ~044
aminoalkylene or amino-aryleneoxy-arylene radicals. They
are exemplified by Cellosolve, carbitol, phenoxyethanol,
heptylphenyl-(oxypropylene) 6 -OH, octyl-(oxyethylene) 3 o-OH,
phenyl-(oxyoctylene) 2 -OH, mono-(heptylphenyl-oxypropylene)-
substituted glycerol, poly(styreneoxide), aminoethanol, 3-
amino-ethylpentanol, di(hydroxyethyl)amine, p-aminophenol,
tri(hydroxypropyl)amine, N-hydroxyethyl ethylenediamine,
N,N,N',N'-tetrahydroxy-trimethylenediamine, and the like.
The polyhydric alcohols preferably contain from 2 to
about 10 hydroxy radicals. They are illustrated, for exam-
ple, by the alkylene glycols and polyoxyalkylene glycols
mentioned above such as ethylene glycol, diethylene glycol,
triethylene glycol, tet~aethylene glycol, dipropylene
glycol, tripropylene glycol, dibutylene glycol, tributylene
glycol, and other alkylene glycols and polyoxyalkylene
glycols in which the alkylene radicals contains 2 to about 8
carbon atoms.
Other useful polyhydric alcohols include glycerol,
monooleate of glycerol, monostearate of glycerol, monomethyl
ether of glycerol, pentaerythritol, n-butyl ester of 9,10-
dihydroxy stearic acid, methyl ester of 9,10-dihyroxy stearic
acid, 1,2-butanediol, 2,3-hexanediol, 2,4-hexane diol,
pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2-
cyclohexanediol, and xylene glycol. Carbohydrates such as
sugars, starches, celluloses, and so forth likewise can be
used as (b). The carbohydrates may be exemplified by glu-
cose, fructose, sucrose, rhamose, mannose, glyceraldehyde,
and galactose.
Polyhydric alcohols having at least 3 hydroxyl groups,
some, but not all of which have been esterified with an
- 63 -
1094044
aliphatic monocarboxylic acid having from about 8 to about
30 carbon atoms such as octanoic acid, oleic acid, stearic
acid, linoleic acid, dodecanoic acid or tall oil acid are
useful as (b). Further specific examples of such partially
esterified polyhydric alcohols are the monooleate of sorbi-
tol, distearate of sorbitol, monooleate of glycerol, mono-
stearate of glycerol, di-dodecanoate of erythritol, and the
like.
A preferred class of alcohols suitable as (b) are those
polyhydric alcohols containing up to about twelve carbon
atoms, and especially those containing three to ten carbon
atoms. This class of alcohols includes glycerol, erythritol,
pentaerythritol, dipentaerythritol, gluconic acid, glyceral-
dehyde, glucose, arabinose, 1,7-heptanediol, 2,4-heptane-
diol, 1,2,3-hexanetriol, 1,2,4-hexanetrioi, 1,2,5-hexane-
triol, 2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butane-
triol, quinic acid, 2,2,6,6-tetrakis-(hydroxymethyl)cyclo-
hexanol, l,10-decanediol, digitalose, and the like. Ali-
phatic alcohols containing at least three hydroxyl groups
and up to ten carbon atoms are particularly preferred.
An especially preferred class of polyhydric alcohols
for use as (b) are the polyhydric al~anols containing three
to ten carbon atoms and particularly, those containing three
to six carbon atoms and having at least three hydroxyl
groups. Such alcohols are exemplified by glycerol, erythri-
tol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-
methyl-1,3-propanediol(trimethylolethane), 2-hydroxymethyl-
2-ethyl-1,3-propanediol(trimethylopropane), 1,2,4-hexane-
triol, and the liKe.
- 64 -
1094044
From ~hat has been stated above, it is seen that ta)
may contain alcoholic hydroxy substituents and (b) can
contain primary, secondary, or tertiary 2mino substituents.
Thus, amino alcohols can fall into both (a) and (b) provided
S they contain at least one primary or secondary amino group.
If only tertiary amino groups are present, the amino alcohol
belong only in (b).
Amino alcohols contemplated as suitable for use as (a)
and/or (b) have one or more amine groups and one or more
hydroxy groups. Examples of suitable amino alcohols are the
N-(hydroxy-lower alkyl)amines and polyamines such as 2-
hydroxyethylamine, 3-hydroxybutylamine, di-(2-hydroxyethyl)-
amine, tri-(2-hydroxyethyl)amine, di-(2-hydroxypropyl)amine,
N,N,N'-tri-(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetra-
(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)pipera-
zine, N,N'-di-(3-hydroxypropyl~piperazine, N-(2-hydroxy-
ethyl)morpholine, N-(2-hydroxyethyl)-2-morpholinone, N-(2-
hydxoxyethyl)-3-methyl-2-morpholinone, N-(2-hydroxypropyl)-
6-methyl-2-morpholinone, N-(2-hydroxyethyl)-5-carbethoxy-2-
piperidone, N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone,
N-(2-hydroxyethyl)-5-(N-butylcarbamyl)-2-piperidone, N-(2-
hydroxyethyl)piperidine, N-(4-hydroxybutyl)piperidine, N,N-
di-(2-hydroxyethyl)glycine, and ethers thereof with ali-
phatic alcohols, especially lower alkanols, N,N-di(3-hydroxy-
propyl)glycine, and the like. Also contemplated are other
mono- and poly-N-hydroxyalkyl-substituted alkylene poly-
amines wherein the alkylene polyamine are as described
above; especially those that contain two to three carbon
atoms in the alkylene radicals and the alkylene polyamine
contains up to seven amino groups such as the reaction
10~044
product of about two moles of propylene oxide and one mole
of diethylenetriamine.
Further amino alcohols are the hydroxy-substituted
primary amines described in U.S. Patent 3,576,743 by the
general formula
Ra-NH 2
where Ra is a monovalent organic radical containing at least
one alcoholic hydroxyl group, according to this patent, the
total number of carbon atoms in Ra will not exceed about 20.
Hydroxy-substituted aliphatic primary amines containing a
total of up to about 10 carbon atoms are particularly useful.
Especially preferred are the polyhydroxy-substituted alkanol
primary amines wherein there is only one amino group present
(i.e., a primary amino group) having one alkyl substituent
containing up to 10 carbon atoms and up to 6 hydroxyl groups.
These alkynol primary amines correspond to Ra-NH2 where Ra
is a mono- or polyhydroxy-substituted alkyl group. It is
desirable that at least one of the hydroxyl groups be a
primary alcoholic hydroxyl group. Trismethylolaminomethane
is the single most preferred hydroxy-substituted primary
amine. Specific examples of the hydroxy~substituted primary
amines include 2-amino-1-butanol, 2-amino-2-methyl-1-pro-
panol, p-(beta-hydroxyethyl)-analine, 2-amino-1-propanol, 3-
amino-l-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-
2-ethyl-1,3-propanediol, N-~beta-hydroxypropyl)-N'-beta-
aminoethyl)-piperazine, tris(hydroxymethyl)amino methane
(also known as trismethylolamino methane), 2-amino-1-butynol,
ethanolamine, beta-(beta-hydroxy ethoxy)-ethyl amine, glucamine,
glusoamine, 4-amlno-3-hydroxy-3-methyl-1-Duten~ (which can
be prepared according to pr~cedures known in the art by
- 66 -
~o94044
reacting isopreneoxide with ammonia), N-(3-aminopropyl)-4-
(2-hydroxyethyl)-piperadine, 2-amino-6-methyl-6-hepanol, 5-
amino-l-pentanol, N-(beta-hydroxyethyl)-1,3-diamino propane,
1,3-diamino-2-hydroxy-propane, N-(beta-hydroxy ethoxyethyl)-
ethylenediamine, and the like. For further description of
the hydroxy-substituted primary amines contemplated as being
useful as (a), and/or (b), see U.S. Patent 3,576,743.
The carboxylic derivative compositions produced by
reacting the acylating reagents of this invention with
alcohols are esters. Both acidic esters and neutral esters
are contemplated as being within the scope of this inven-
tion. Acidic esters are those in which some of the car-
boxylic acid functions in the acylating reagents are not
esterified but are present as free carboxyl groups. Ob-
viously, acid esters are easily prepared by using an amount
of alcohol insufficient to esterify all of the carboxyl
groups in the acylating reagents of this invention.
The acylating reagents of this invention are reacted
with the alcohols according to conventional esterification
techniques. It is normally involves heating the acylating
reagent of this invention with the alcohol, optionally in
the presence of a normally liquid, substantially inert,
organic liquid solvent/diluent and/or in the presence of
esterification catalyst. Temperatures of at least about
100C. up to the decomposition point are used (the decom-
position point having been defined hereinbefore). This
temperature is usually within the range of ab~u_ 100C. up
to about 300C. with temperatures of about 140C. to 250C.
- 67 -
B
1094044
often being employed. Usually, at least about one-half
equivalent of alcohol is used for each equivalent of acylating
reagent. An equivalent of acylating reagent is the same as
discussed above with respect to reaction with amines. An
e~uivalent of alcohol is its molecular weight divided by the
total number of hydroxyl groups present in the molecule.
Thus, an equivalent weight of ethanol is its molecular
weight while the equivalent weight of ethylene glycol is
one-half its molecular weight.
Many issued patents disclose procedures for reacting
high molecular weight carboxylic acid acylating agents with
alcohols to produce acidic esters and neutral esters. These
same techniques are applicable to preparing esters from the
acylating reagents of this invention and the alcohols described
above. All that is required is that the acylating reagents
of this invention is substituted for the high molecular
weight carboxylic acid acylating agents discussed in these
patents, usually on an equivalent weight basis. The following
U.S. Patents are relevant
for their disclosure of suitable methods for reacting the
acylating reagents of this invention with the alcohols
described above: 3,331,776; 3,381,022; 3,522,179; 3,542,680;
3,697,428; 3,755,169.
Reactive metals or reactive metal compounds useful as
(c) are those which will form carboxylic acid metal salts
with the acylating reagents of this invention and those
~hich will form metal-containing complexes with the car-
boxylic deri~ative compositions produced by reacting the
acylating reagents with amines and/or alcohols as discussed
above. Reactive metal compounds useful as (c~ for the
- 68 -
.
1~4044
formation of complexes with the reaction products of the
acylating reagents of this invention and amines are disclosed
in U.S. Patent 3,306,908. Complex-forming metal reactants
useful as (c) include the nitrates, nitrites, halides,
carboxylates, phosphates, phosphites, sulfates, sulfites,
carbonates, borates, and oxides of cadmium as well as metals
having atomic numbers from 24 to 30 (including chromium,
manganese, iron, cobalt, nickel, copper and zinc). These
metals are the so-called transition or co-ordination metals,
i.e., they are capable of forming complexes by means of
their secondary or co-ordination valence. Specific examples
of the complex-forming metal compounds useful as the reactant
in this invention are cobaltous nitrate, cobaltous oxide,
cobaltic oxide, cobalt nitrite, cobaltic phosphate, cobaltous
chloride, cobaltic chloride, cobaltous carbonate, chromous
acetate, chromic acetate, chromic bromide, chromous chloride,
chromic fluoride, chromous oxide, chromium dioxide, chromic
oxide, chromic sulfite, chromous sulfate heptahydrate,
chromic sulfate, chromic formate, chromic hexanoate, chromium
oxychloride, chromic phosphite, manganous acetate, manganous
benzoate, manganous carbonate, manganese dichloride, manganese
trichloride, manganous citrate, manganous formate, manganous
nitrate, manganous oxalate, manganese monooxide, manganese
dioxide, manganese trioxide, manganese heptoxide, manganic
phosphate, manganous pyrophosphate, manganic metaphosphate,
manganous hypophosphite, manganous valerate, ferrous acetate,
ferric benzoate, ferrous bromide, ferrous carbonate, ferric
formate, ferrous lactate, ferrous nitrate, ferrous oxide,
ferric oxide, ferric hypophosphite, ferric sulfate, ferrous
sul~ite, ferric hydrosulfite, nickel dibromide, nickel
- 69 -
1094044
dichloride, nickel nitrate, nickel dioleate, nickel stearate,
nickel sulfite, cupric propionate, cupric acetate, cupric
metaborate, cupric benzoate, cupric formate, cupric laurate,
cupric nitrite; cupric oxychloride, cupric palmitate, cupric
salicylate, zinc benzoate, zinc borate, zinc bromide, zinc
chromate, zinc dichromate, zinc iodide, zinc lactate, zinc
nitrate, zinc oxide, zinc stearate, zinc sulfite, cadmium
benzoate, cadmium carbonate, cadmium butyrate, cadmium
chloroacetate, cadmium fumerate, cadmium nitrate, cadmium
di-hydrogenphosphate, cadmium sulfite, and cadmium oxide.
Hydrates of the above compounds are especially convenient
for use in the process of this invention.
U.S. Patent 3,30~,908 discloses reactive metal compounds
` 15 suitable for forming such complexes and its disclosure of
processes for preparing the complexes. Basically, those
processes are applicable to the carboxylic derivative-composi-
tions of the acylating reagents of this invention with the
amines as described above by substituting, or on an equiva-
lent basis, the acylating reagents of this invention with
the high molecular weight carboxylic acid acylating agents
disclosed in 3,306,908. The ratio of equivalents of the
acylated amine thus produced and the complex-forming metal
reactant remains the same as disclosed in 3,306,908 patent.
U.S. Reissue Patent 26,443 discloses metals useful in
preparing salts from the carboxylic derivative compositions
of acylating reagents of this invention and amines as described
hereinabove. Metal salts are prepared, according to this
patent, from alkali metals, alkaline earth meta s, zinc,
cadmium, lead, cobalt and nickel. Examples of a reactive
- 70 -
; -
1~940'~4
metal compound suitable for use as (c) are sodium oxide,
sodium hydroxide, sodium carbonate, sodium methylate, sodium
propylate, sodium pentylate, sodium phenoxide, potassium
oxide, potasium hydroxide, potassium carbonate, potassium
methylate, potassium pentylate, potassium phenoxide, lithium
oxide, lithium hydroxide, lithium carbonate, lithium penty-
late, calcium oxide, calcium hydroxide, calcium carbonate,
calcium methylate, calcium ethylate, calcium propylate,
calcium chloride, calcium fluoride, calcium pentylate,
calcium phenoxide, calcium nitrate, barium oxide, barium
hydroxide, barium caronate, barium chloride, barium fluoride,
barium methylate, barium propylate, barium pentylate, barium
nitrate, magnesium oxide, magnesium hydroxide, magnesium
carbonate, magnesium ethylate, magnesium propylate, magnesium
chloride, magnesium bromide, barium, iodide, magnesium
phenoxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc
methylate, zinc propylate, zinc pentylate, zinc chloride,
zinc fluoride, zinc nitrate trihydrate, cadmium oxide,
cadmium hydroxide, cadmium carbonate, cadmium methylate,
cadmium propylate, cadmium chloride, cadmium bromide, cadmium
fluoride, lead oxide, lead hydroxide, lead carbonate, lead
ethylate, lead pentylate, lead chloride, lead fluoride, lead
iodide, lead nitrate, nickel oxide, nickel hydroxide, nickel
carbonate, nickel chloride, nickel bromide, nickel fluoride,
nickel methylate, nickel pentylate, nickel nitrate hexahydrate,
cobalt oxide, cobalt hydroxide, cobaltous bromide, cobaltous
chloride, cobalt butylate, cobaltous nitrate hexahydrate,
etc. The above metal compounds are merely illustrative of
those useful in this invention and the invention is not to
be considered as limited to such.
- 71 -
1094044
U.S. Reissue 26,443 discloses reactiYe metal compounds
useful as (c) and processes for utilizing these compounds in
the formation of salts. A~ain, in applying the teachings of
this patent to the present invention, it is only necessary
to substitute the acylating reagents of this invention on an
equivalent weight basis for the high molecular weight car-
boxylic acylating agents of the reissue patent.
U.S. Patent 3,271,310 discloses the preparation of
metal salt of high molecular weight carboxylic acid acylating
agents, in particular alkenyl succinic acids. The metal
salts disclosed therein are acid salts, neutral salts, and
basic salts. Amon~ the illustrative reactive metal compounds
used to prepare the acidic, neutral and basic salts of the
high molecular weight carboxylic acids disclosed in 3,271,310
are lithium oxide, lithium hydroxide, lithium carbonate,
lithium pentylate, sodium oxide, sodium hydroxide, sodium
carbonate, sodium methylate, sodium propylate, sodium phenoxide,
potassium oxide, potassium hydroxide, potassium carbonate,
potassium methylate, silver oxide, silver carbonate, magnesium
oxide, magnesium hydroxide, magnesium carbonate, magnesium
ethylate, magnesium propylate, magnesium phenoxide, calcium
oxide, calcium hydroxide, calcium carbonate, calcium methylate,
calcium propylate, calcium pentylate, zinc oxide, zinc
hydroxide, zinc carbonate, zinc propylate, strontium oxide,
strontium hydroxide, cadmium oxide, cadmium hydroxide,
cadmium carbonate, cadmium ethylate, barium oxide, barium
hydroxide, barium hydrate, barium carbonate, barium ethylate,
barium pentylate, aluminum oxide, aluminum propylate, lead
oxide, lead hydroxide, lead carbonate, tin oxide, tin butylate,
- 72 -
1094044
cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt
pentylate, nickel oxide, nickel hydroxide, and nickel carbonate.
The present invention is not to be considered as limited to
the use of the above metal compounds; they are presented
merely to illustrate the metal compounds included within the
invention.
U.S. Patent 3,271,310 discloses suitable reactive metal
compounds for forming salts of the acylating reagents of
this invention as well as illustrative processes for preparing
salts of these acylating reagents. As will be apparent, the
processes of 3,271,310 are applicable to the acylating
reagents of this invention merely by substituting on an
equivalent weight basis, the acylating reagents of this
invention for the high molecular weight carboxylic acids of
the patent.
From the foregoing description, it is apparent that the
acylating reagents of this invention can be reacted with any
individual amine, alcohol, reactive metal, reactive metal
compound or any combination of two or more of any of these;
that is, for example, one or more amines, one or more alcohols,
one or more reactive metals or reactive metal compounds, or
a mixture of any of these. The mixture can be a mixture of
two or more amines, a mixture of two or more alcohols, a
mixture of two or more metals or reactive metal compounds,
or a mixture of two or more components selected from amines
and alcohols, from amines and reactive metals or reactive
metal compounds, from alcohols and reactive metals compounds,
or one or more components from each of the amines, alcohols,
and reactive metal or reactive metal compounds. Furthermore,
- 73 -
B
1094044
the acylating reagents of this invention can be reacted with
the amines, alcohols, reactive metals, reactive metal compounds,
or mixtures thereof, as described above, simultaneously
(concurrently) or sequentially in any order of reaction.
Canadian Patent 956,397 discloses procedures for
reacting the acylating reagents of this invention with
amines, alcohols, reactive metal and reactive metal compounds,
or mixtures of these, sequentially and simultaneously. All
that is required to apply the processes of that patent to
this invention is to substitute, on an equivalent weight
basis, the acylating reagents of this invention for the high
molecular weight carboxylic acid acylating agents disclosed
in that Canadian patent. Carboxylic acid derivatives of
this invention prepared utilizing the processes disclosed in
the Canadian patent constitute a preferred class of carboxylic
acids or carboxylic acid derivative compositions. The
following U.S. Patents are counterparts of Canadian patent
956,397: 3,836,469; 3,836,470; 3,836,471; 3,838,050;
3,838,052; 3,879,308; 3,957,854; 3,957,855; 4,031,118. The
Canadian patent and the U.S. patents which are counterparts
thereof as identified above illustrate that the amount of
polyoxyalkylene alcohol demulsifier utilized in preparing
dispersant/detergents from the acylating reagents of this
invention is normally quite small on an e~uivalent basis.
- 74 -
` ` 1094044
It is also pointed out that, among the more preferred
carboxylic derivative compositions of this invention are
those prepared according to the Canadian patent and corres-
ponding U.S. patent and application identified above in
which the polyoxyalkylene alcohol demulsifier has been
omitted. In other words, a preferred class of carboxylic
derivative compositions of this invention are the various
reaction products of the high molecular weight carboxylic
acid acylating agents of the Canadian patent with one or
more amines, alcohols, and reactive metal compounds as
disclosed therein differing only in that the acylating
reagents of this invention are substituted on an equivalent
weight basis and, further, that the polyoxyalkylene alcohol
demulsifier reactant is omitted.
In addition, U.S. Patent 3,8Q6,456 discloses processes
useful in preparing products from the acylated reagents of
this invention and polyoxyalkylene polyamines as described
hereinbefore. Substitution of the acylated reactants of
this invention for the high molecular weight carboxylic acid
acylating agents disclosed in 3,806,456 on an equivalent
weight basis produces compounds of similar utility further
characterized by the desired viscosity index improving
properties discussed hereinbefore.
U.S. Patent 3,576,743 discloses a process for preparing car-
boxylic derivative compositions from both polyhydric alcohols
and amine; in particular, hydroxy-substituted primary amines.
Again, substitution of the acylating reagents of this invention
on an equivalent weight ~asis for the high molecular carboxylic
- 75 -
1094~44
acid acylating agents disclosed in 3,576,743 provides composi-
tions having the desired dispersant/detergent compositions
and the V.I. improving properties alr~ady discussed.
U.S. Patent 3,632,510 discloses processes for preparing
mixed ester-metal salts. Mixed ester-metal salts derived
from acylating reagents of this invention, the alcohols, and
the reactive metal compounds can be prepared by following
the processes disclosed in 3,632,510 but substituting, on an
equivalent weight basis, the acylating reagents of this
invention for the high molecular weight carboxylic acid
acylating agents of the patent. The carboxylic acid deriva-
tive compositions thus produced also represent a preferred
aspect of this invention.
Finally, U.S. Patents 3,755,169; 3,804,763; 3,868,330;
and 3,948,8QQ disclose how to prepare carboxylic acid
derivative compositions. By following the teachings of
these patents and substituting the acylating reagents of
this invention for the high molecular weight carboxylic
acylating agents of the patents, a wide range of carboxylic
derivative compositions within the scope of the present
invention can be prepared.
~eference to so many patents is done for the sake
of brevity and because, it is felt, that the procedures
necessary to prepare the carboxylic derivative compositions
from the acylating reagents and the amines, alcohols, and
reactive metals and reactive metal compounds, as well as
mixtures thereof, is well within the skill of the art, such
that a detailed description herein is not necessary.
- 76 -
P~ .
1094044
Of the carboxylic deriv~tive compositions described
hereinabove, those prepared from novel acylating reagents
and the alkylene polyamines, especially polyethylene poly-
amines, and/or polyhydric alcohols, especially the polyhydric
alkanols, are especially preferred. As previously stated,
mixtures of polyamines and/or polyhydric alcohols are contem-
plated. Normally, all the carboxyl functions on the acylating
reagents of this invention will either be esterified or
involved in formation of an amine salt, amide, imide or
imidazoline in this preferred group of carboxylic derivative
compositions.
~s mentioned previously, in order to achieve the requi-
site degree of viscosity index improving capabilities in the
carboxylic derivative compositions of this invention, it has
been found necessary to react the acylating reagents of this
invention with polyfunctional reactants. For example,
polyamines having two or more primary and/or secondary amino
groups, polyhydric alcohols, amino alcohols in which there
are one or more primary and/or secondary amino groups and
one or more hydroxy groups, and polyvalent metal or polyvalent
metal compounds. It is believed that the polyfunctional
reactants serve to provide "bridges" or cross-linking in the
carboxylic derivative compositions and this, in turn, is
somehow responsible for the viscosity index-improving proper-
ties. However, the mechanism by which viscosity index
improving properties is obtained is not understood and
applicants do not intend to be bound by this theory. Since
the carboxylic derivative compositions derived, in whole or
in part, from polyhydric alcohols appear to be particularly
effective in permitting a reduction of V.I. improver in
1~0~4~4
lubricating compositions, the polyfunctionality of reactants
(a), (b), and (c) may not fully explain the V.I. improving
properties of the carboxylic derivative compositions.
Obviously, however, it is not necessary that all of the
amine, alcohol, reactive metal, or reactive metal compound
reacted with the acylating reagents be polyfunctional.
Thus, combinations of mono- and polyfunctional amines,
alcohols, reactive metals and reactive metal compounds can
be used; for example, monoamine with a polyhydric alcohol, a
monohydric alcohol with polyamine, an amino alcohol with a
reactive metal compound in which the metal is monovalent,
and the like.
While the parameters have not been fully determined as
yet, it is believed that acylating reagents of this invention
should be reacted with amines, alcohols, reactive metals,
reactive metal compounds, or mixtures of these which contain
sufficient polyfunctional reactant, (e.g., polyamine, polyhy-
dric alcohol) so that at least about 25% of the total number
of carboxyl groups (from the succinic groups or from the
groups derived from the maleic reactant) are reacted with a
polyfunctional reactant. Better results, insofar as the
viscosity index-improving facilities of the carboxylic
derivative compositions is concerned, appear to be obtained
when at least 50% of the carboxyl groups are involved in
reaction with such polyfunctional reactants. In most instances,
the best viscosity index improving properties seem to be
achieved when the acylating reagents of this invention are
reacted with a sufficient amount of polyamine and/or polyhydric
alcohol (or amino alcohol) to react with at least about 75%
of the carboxyl ~roup. ~t should be understood that the
- 78 -
1094044
foregoing percentages are "theoretical" in the sense that it
is not required that the stated percentage of carboxyl
functions actually react with polyfunctional reactant.
Rather these percentages are used to characterize the amounts
of polyfunctional re~ctants desirably "available" to react
with the acylating reagents in order to achieve the desired
viscosity index improving properties.
From what has ~een stated, it is apparent that the
carboxylic derivative compositions of this invention can be
considered somewhat analogous to the derivatives prepared
from the high molecular weight carboxylic acid acylating
reagents disclosed in the patents cited.
However, because of their unique multifunctional
properties, the carboxylic derivative compositions of this
invention are uniquely different in important aspects.
Another aspect of this invention involves the post-
treatment of the carboxylic derivative compositions. The
process for post-treating the carboxylic acid derivative
compositions is again analogous to the post-treating processes
used with respect to similar derivatives of the high molecular
weight carboxylic acid acylating agents of the prior art.
Accordingly, the same reaction conditions, ratio of reactants
and the like can be used.
Acylated nitrogen composit~ons prepared by reacting the
acylating reagents of this invention with an amine as described
above are post-treated by contacting the acylated nitrogen
compositions thus formed (e.g., the carboxylic derivative
compositions~ with one or more post-treating reagents selected
from the group consisting of boron oxia~, boro~l oxide hydrate,
boron halides, boron acids, esters of boron acids, carbon
- 79 -
~r~
~ ~_.S
1~94044
disulfide, sulfur, sulfur chlorides, alkenyl cyanides, car-
boxylic acid acylating agents, aldehydes, ketones, urea,
thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates,
hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl
thiophosphites, phosphorus sulfides, phosphorus oxides,
phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl iso-
cyanates, hydrocarbyl isothiocyanates, epoxides, episulfides,
formaldehyde or formaldehyde-producing compounds plus phenols,
and sulfur plus phenols. The same post-treating reagents
are used with carboxylic derivative compositions prepared
from the acylating reagents of this invention and a combina-
tion of amines and alcohols as described above. However,
when the carboxylic derivative compositions of this invention
are derived from alcohols and the acylating reagents, that
is, when they are acidic or neutral esters, the
post-treating reagents are usually selected from the group
consisting of boron oxide, boron oxide hydrate, boron halides,
boron acids, esters of boron acids, sulfur, sulfur chlorides,
phosphorus sulfides, phosphorus oxides, carboxylic acid
acylating agents, epoxides, and episulfides.
Since post-treating processes involving the use of
these post-treating reagents is known insofar as application
to reaction products of high molecular weight carboxylic
acid acylating agents of the prior art and amines and/or
alcohols, detailed descriptions of these processes herein is
unnecessary. In order to apply the prior art processes to
the carboxylic derivative compositions of this invention,
all that is necessary is that reaction conditions, ratio of
reactants, and the like as described ir. the p~_or art, be
applied to the novel carboxylic derivative compositions of
- 80 -
1094044
this invention. The following U.S. patents disclose
post-treating processes and post-treating reagents applicable
to the carboxylic derivative compositions of this invention:
3,087,936; 3,200,107; 3,254,025; 3,256,185; 3,278,550;
3,281,428; 3,282,955; 3,284,410; 3,338,832; 3,344,069;
3,366,569; 3,373,111; 3,367,943; 3,403,102; 3,428,561;
3,502,677; 3,513,093; 3,533,945; 3,541,012(use of acidified
clays in post-treating carboxylic derivative compositions
derived from the acylating reagents of this invention and
amines); 3,639,242; 3,708,522; 3,859,318; 3,865,813; 3,470,098;
3,369,021; 3,184,411; 3,185,645; 3,245,908; 3,245,909;
3,245,910; 3,573,205; 3,269,681; 3,749,695; 3,865,740;
3,954,639; 3,459,530; 3,390,086; 3,367,943; 3,185,704;
3,551,466; 3,415,750; 3,312,619; 3,280,034; 3,718,663;
3,652,616; UK 1,085,903; UK 1,162,436; U.S. 3,558,743. The
processes of these patents, as applied to the
carboxylic derivative compositions of this invention, and
the post-treated carboxylic derivative compositions thus
produced constitute a further aspect of this invention.
As previously indicated, the acylating reagents, the
carboxylic derivative compositions, and the post-treated
carboxylic derivative compositions of this invention are
useful as additives in lubricating oils. From the foregoing
description, it is seen that the acylating reagents, the
carboxylic derivative compositions, and the post-treated
carboxylic derivative compositions, especially the latter
two, function primarily as dispersant/detergents and viscosity
index improvers.
- 81 -
1094044
The lubricant compositions of this invention include
lubricating oils and greases although, for the most part,
they will be lubricating oils. The lubricating oil composi-
tions of this invention are based on natural and synthetic
lubricating oils and mixtures thereof. These lubricants
include crankcase lubricating oils for spark-ignited and
compression-ignited internal combustion engines, such as
automobile and truck engines, marine and railroad diesel
engines, and the like. Automatic transmission fluids,
transaxle lubricants, gear lubricants, metal-working lubri-
cants, hydraulic fluids and other lubricating oil and grease
compositions can also benefit from the incorporation therein
of the acylating reagents and carboxylic derivatiYe composi-
tions of the present invention.
Natural oils include animal oils and vegetable oils
(e.g., castor oil, lard oil) as well as mineral lubricating
oils such as liquid petroleum oils and solvent-treated or
acid-treated mineral lubricating oils of the paraffinic,
naphthenic or 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 halosubstituted hydrocarbon oils such
as polymerized and interpolymerized olefins [e.g., poly-
butylenes, polypropylenes, propylene-isobutylene copolymers,
chlorinated polybutylenes, etc.); poly(l-hexenes), poly(l-
octenes), poly(l-decenes), etc. and mixtures thereof];
alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di(2-ethylhexyl)benzenes, etc.); poly-
phenyls (e.g., biphenyls, terphenyls alkylated polyphenyls,
etc.), alkylated diphenyl ethers and alkylated diphenyl
- 82 -
1094044
sulfides and the derivatives, analogs and homologs thereof
and the like.
Alkylene oxide polymers and interpolymers and
derivatives thereof where the terminal hydroxyl groups have
been modified by esterification, etherification, etc. consti-
tute another class of known synthetic lubricating oils.
These are exemplified by the oils prepared through polymeri-
zation of ethylene oxide or propylene oxide, tne alkyl and
aryl ethers of these polyoxyalkylene polymers (e.g., methyl-
polyisopropylene glycol ether having an average molecular
weight of 1000, diphenyl ether of polyethylene glycol having
a molecular weight of 50~-1000, diethyl ether of polypro-
pylene glycol having a molecular ~eight of 1000-1500, etc.)
or mono- and polycarboxylic esters thereof, for example, the
acetic acîd esters, mixed C3-C9 fatty acid esters, or the
C1 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 alkenyl 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 alcohol, hexyl alcohol,
dodecyl alcohol, 2-ethylhexyl alcohol, ethylene 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 sebacate, the 2-
ethylhexyl diester of linoleic acid dimer, the complex ester
- 83 -
1094(~44
formed by reacting one mole of sebacic acid with two moles
of tetraethylene glycol and two moles of 2-ethylhexanoic
acid, and the like.
Esters useful as synthetic oils also include those made
from Cs to Cl 2 monocarboxylic acids and polyols and polyol
ethers such as neopentyl glycol, trimethylolpropane, penta-
erythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, polyaryl-,
polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils
comprise another useful class of synthetic lubricants (e.g.,
tetraethyl silicate, tetraisopropyl silicate, tetra-(2-
ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate,
tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-
pentoxy)-disiloxane, poly(methyl)siloxanes, poly(methylphenyl)-
siloxanes, etc.). Other synthetic lubricating oils include
liquid esters of phosphorus-containing acids (e.g., tricresyl
phosphate, trioctyl phosphate, diethyl ester of decylphosphonic
acid, etc.), polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils, either natural
or synthetic (as well as mixtures of two or more of any of
these) of the type disclosed hereinabove can be used in the
lubricant compositions of the present 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 directly from distillation or ester
oil obtained directly from an esterification process and
used without further treatment would be an unrefined oil.
Refined oils aL~ similar to the unref ned o ;~ except they
have heen further treated in one or more purification steps
- 84 -
1094044
to improve one or more properties. Many such purification
techniques are known to those of skill in the art such as
solvent extraction, secondary distillation, 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 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.
In general, about 0.05-30, usually about 0.1-15 parts
(by weight) of at least one acylating reagent, carboxylic
derivative composition, or post-treated carboxylic derivative
composition of this invention is dissolved or stably dis-
persed in 100 parts of oil to produce a satisfactory lubricant.
The invention also contemplates the use of other additives
in combination with the compositions of this invention.
Such additives include, for example, fluidity modifiers,
auxiliary detergents and dispersants of the ash-producing or
ashless type, oxidation-inhibiting agents, pour point depres-
sing agents, extreme pressure agents, color stabilizers and
anti-foam agents.
The acylating reagents, carboxylic derivative composi-
tions, and post-treated carboxylic derivative compositions
of this invention can be added directly to a lubricant such
as a lubricating oil to orm the lubricant compositions of
this invention or they can be diluted with at least one sub-
stantially inert, normally liquid organic solvent/diluent
such as low viscosity oil to form concentrates which are
then added to lubricating oils in sufficient amounts to form
- 85 -
1~94Q44
the lubricant compositions of this invention. These concen-
trates normally contain from about 20 to about 90% by weight
of the normally liquid, substantially inert organic solvent/
diluent and from about 10~ to about 80% by weight of the
acylating reagent, carboxylic derivative composition, post-
treated carboxylic derivative composition, or mixtures of
two or more of these. As is conventional in the art, one
or more other additives to be used in the final lubricant
composition can be included in the concentrates of this
invention.
Another advantage of the carboxylic derivative compo-
sitions of this invention, particularly those derived from
the reaction of the acylating reagents of this invention
with polyamines and/or polyhydric alcohols is their effective-
ness as dispersant/detergents in certain "problem" mineral
oils. Many mineral oils contain aromatic hydrocarbon com-
ponents, most of the aromatic hydrocarbon components being
fused ring aromatic hydrocarbons. For reasons not fully
understood, oils containing in excess of about 3~ by weight
of such aromatic hydrocarbons resist improvement with conven-
tional amounts of known dispersant/detergents. The carboxylic
derivative compositions of this invention, especially those
derived from the reaction of the acylating reagents of this
invention with one or more polyethylene polyamines and/or
one or more polyhydric alkanols, have proven unexpectedly
superior to the known dispersant/detergents in treating such
oils.
Various preferred aspects of this invention and the
means for preparing the acylating reagents, carboxylic acid
derivative compositions, and the post-treated carboxylic
- 86 -
109404~
acid derivative compositions are illustrated by the following
examples. These examples illustrate presently preferred
embodiments of this invention. In the following examples,
and elsewhere in the present specification and claims, all
percentages and all parts are intended to express percent by
- 87 -
~094044
Example 1
A mixture of 510 parts (0.28 mole) of polyisobutene (Mn
= 1845; Mw = 5325) and 59 parts (0.59 mole) of maleic anhy-
dride is heated to 110C. This mixture is heated to 190C.
in seven hours during which 43 parts (0.6 mole) of gaseous
chlorine is added beneath the surface. At 190-192C. an
additional 11 parts (0.16 mole) of chlorine is added over
3.5 hours. The reaction mixture is stripped by heating at
190-193C. with nitrogen blowing for 10 hours. The residue
is the desired polyisobutene-substituted succinic acylating
agent having a saponification equivalent number of 87 as
determined by ASTM procedure D-94.
Example 2
A mixture of 1,000 parts (0.495 mole) of polyisobutene
(Mn = 2020; Mw = 6049) and 115 parts (1.17 moles) of maleic
anhydride is heated to 110C. This mixture is heated to
184C. in 6 hours during which 85 parts (1.2 moles) of
gaseous 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
heating at 186-190C. with nitrogen blowing for 2S hours.
The residue is the desired polyisobutene-substituted
succinic acylating agent having a saponification equivalent
number of 87 as determined by ASTM procedure D-94.
Example 3
A mixture of 3,25~ parts of polyisobutene chloride,
prepared by the addition of 251 parts of gaseous chlorine to
3,000 parts of polyisobutene (Mn = 1696; Mw = 6594) at 80C.
in 4.66 hours, an~ 345 parts of maleic anhydride is heated
to 200C. in 0.5 hour. The reaction mixture is held at
-88-
1094044
200-224C. for 6.33 hours, stripped at 210C. under vacuum
and filtered. The filtrate is the desired polyisobutene-
substituted succinic acylating agent having a saponification
equivalent number of 94 as determined by ASTM procedure D-
94.
Example 4
A mixture of 3,000 parts (1.63 moles) of polyisobutene
(Mn = 1845; Mw = 5325) and 344 parts (3.51 moles) of maleic
anhydride is heated to 140C. This mixture is heated to
201C. in 5.~ hours during which 312 parts (4.39 moles) of
gaseous chlorine is added beneath the surface. The reaction
mixture is heated at 201-236C. with nitrogen blowing for 2
hours and stripped under vacuum at 203C. The reaction
mixture is filtered to yield the filtrate as the desired
polyisobutene-substituted succinic acylating agent having a
saponification equivalent number of 92 as determined by ASTM
procedure D-94.
Example 5
A mixture of 3,000 parts (1.49 moles) of polyisobutene
(Mn = 2020; Mw = 6049) and 364 parts (3~71 moles) of maleic
anhydride is heated at 220C. for 8 hours. The reaction
mixture is cooled to 170C. At 170-190C. 105 parts (1.48
moles) of gaseous chlorine is added beneath the surface in 8
hours. The reaction mixture is heated at 190C. with
nitrogen blowing for 2 hours and then stripped under vacuum
at 190C. The reaction mixture is filtered to yield the
filtrate as the desired polyisobutene-substituted succinic
acylating agent.
Example 6
A mixture of 800 parts of a polyisobutene falling
-89-
109~044
within the scope of the claims of the present invention and
having a Mn of about 2000, 646 parts of mineral oil and 87
parts of maleic anhydride is heated to 179C. in 2.3 hours.
At 176-180C. 100 parts of gaseous chlorine is added beneath
the surface over a 19 hour period. The reaction mixture is
stripped by blowing with nitrogen for 0.5 hour at 180C.
The residue is an oil-containing solution of the desired
polyisobutene-substituted succinic acylating agent.
Example 7
The procedure for Example 1 is repeated except the
polyisobutene (Mn = 1845; Mw = 5325) is replaced on an
equimolar basis by polyisobutene (Mn = 1457; Mw = 5808).
Example 8
The procedure for Example 1 is repeated except the
polyisobutene (Mn = 1845; Mw = 5325) is replaced on an
equimolar basis by polyisobutene (Mn = 2510; Mw = 5793).
Example 9
The procedure for Example 1 is repeated except the
polyisobutene (Mn = 1845; Mw = 5325) is replaced on an
equimolar basis by polyisobutene (Mn = 3220; Mw = 5660).
Example 10
A mixture is prepared by the addition of 10.2 parts
(0.25 equivalent) of a commercial mixture of ethylene
polyamines having from about 3 to about 10 nitrogen atoms
per molecule to 113 parts of mineral oil and 161 parts (0.25
equivalent3 of the substituted succinic acylating agent
prepared in ~xample 1 at 138C. The reaction mixture is
heated to 150C. in 2 hours and stripped by blowing with
nitrogen. Th~ reaction mixture is filtered to yield the
filtrate as an oil solution of the desired product.
--90--
1094044
Example 11
A mixture is prepared by the addition of 57 parts (1.38
equivalents) of a commercial mixture of ethylene polyamines
having from about 3 to 10 nitrogen atoms per molecule to
1,067 parts of mineral oil and 893 parts (1.38 equivalents)
of the substituted succinic acylating agent prepared in
Example 2 at 140 to 145C. The reaction mixture is heated
to 155C. in 3 hours and stripped by blowing with nitrogen.
The reaction mixture is filtered to yield the filtrate as an
oil solution of the desired product.
Example 12
A mixture is prepared by the addition of 18.2 parts
(0.433 equivalent) of a commercial mixture of ethylene
polyamines having from about 3 to 10 nitrogen atoms per
molecule to 392 parts of mineral oil and 348 parts (0.52
equivalent) of the substituted succinic acylating agent
prepared in Example 2 at 140C. The reaction mixture is
heated to 150C. in 1.8 hours and stripped by blowing with
nitrogen. The reaction mixture is filtered to yield the
filtrate as an oil solution of the desired product.
Example 13
A mixture of 334 parts (0.52 equivalent) of the poly-
isobutene substituted succinic acylating agent prepared in
Example 2, 548 parts of mineral oil, 30 parts (0.88 equiva-
lent) of pentaerythritol and 8.6 parts (0.0057 equivalent)
of Polyglyco~ 112-2 demulsifier from Dow Chemical Company is
heated at 150C. for 2.5 hours. The reaction mixture is
heated to 210C. in 5 hours and held at 210C. for 3.2
hours. The reaction mixture is cooled to 190C. and 8.5
partC (0.2 equivalent) of a commercial mixture of ethylene
* trade ~ark
,. , --9 1--
.
10940~4
polyamines having an average of about 3 to about 10 nitrogen
atoms per molecule is added. The reaction mixture is
stripped by heating at 205C. with nitrogen blowing for 3
hours, then filtered to yield the filtrate as an oil solu-
tion of the desired product.
Example 14
A mixture is prepared by the addition of 5500 parts of
the oil solution of the substituted succinic acylating agent
prepared in Example 7 to 3000 parts of mineral oil and 236
parts of a commercial mixture of ethylene polyamines having
an average of about 3-10 nitrogen atoms per molecule at
150C. over a one hour period. The reaction mixture is
heated at 155-165C. for two hours, then stripped by blowing
with nitrogen at 165C. for one hour. The reaction mixture
is filtered to yield the filtrate as an oil solution of the
desired nitrogen-containing product.
Examples 15-33 are prepared by following the general
procedure set forth in Example 10.
-92-
109'~l)44
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--9 4--
~09~044
Example 34
A mixture of 2130 parts (1.5 moles) of the polyiso-
butene-substituted succinic acylating agent prepared in
Example 2, 187 parts (1.65 moles) of caprolactam, 575 parts
of mineral oil and 2 parts of sodium hydroxide is heated at
190-193C. for two hours. The reaction mixture is stripped
at 200C. under vacuum and filtered at 150C. to yield an
oil solution of the desired product.
Example 35
A mixture of 3225 parts (5.0 equivalents) of the poly-
isobutene-substituted succinic acylating agent prepared in
Example 2, 2~9 parts (8.5 equivalents) of pentaerythritol
and 5204 parts of mineral oil is heated at 225-235C. for
5.5 hours. The reaction mixture is filtered at 130C. to
yield an oil solution of the desired product.
Example 36
A mixture of 631 parts of the oil solution of the
product prepared in Ex~mple 35 and 50 parts of anthranilic
acid is heated at 195-212C. for four hours. The reaction
mixture is then filtered at 130C. to yield an oil solution
of the desired product.
Example 37
A mixture is prepared by the addition of 14 parts of
aminopropyl diethanolamine to 867 parts of the oil solution
of the product prepared in Example 35 at 190-200C. The
reaction mixture is held at 195C. for 2.25 hours, then
cooled to 120C. and filtered. The filtrate is an oil
solution of the desired product.
-95-
109~044
Example 38
A mixture is prepared by the addition of 7.5 parts of
piperazine to 867 parts of the oil solution of the product
prepared in Example 35 at 190C. The reaction mixture is
heated at 190-205C. for two hours, then cooled to 130C.
and filtered. The filtrate is an oil solution of the
desired product.
Example 39
.
A mixture of 1480 parts of the polyisobutene-substi-
tuted succinic acylating agent prepared in Example 7, 115
parts (0.53 equivalent) of a commercial mixture of C12-18
straight-chain primary alcohols, 87 parts (0.594 equivalent)
of a commercial mixture of C8-10 straight-chain primary
alcohols, 1098 parts of mineral oil a toluene
/
-96-
1094044
is heated to 120C. At 120C., 1.5 parts of sulfuric acid
is added and the reaction mixture is heated to 160C. and
held for three hours. To the reaction mixture is then added
158 parts (2.0 equivalents) of n-butanol and 1.5 parts of
sulfuric acid. The reaction mixture is heated at 160C. for
15 hours, then 12.6 parts (0.088 equivalent) of aminopropyl
morpholine is added. The reaction mixture is held at 160C.
for an additional six hour~, stripped at 150C. under vacuum
and filtered to yield an oil solution of the desired product
Example 40
A mixture of 328 parts (0.5 equivalent) of the polyiso-
butene-substituted succinic acylating agent prepared in
Example 1, 129 parts (1.0 equivalent) of 1-(2-hydroxyethyl3-
2-pyrrolidone and 359 parts of mineral oil is heated at
190C. for 4 hours. During the 4 hours at 190C. water is
removed continuously by blowing with nitrogen. The reaction
mixture is filtered to yield the filtrate as an oil solution
of the desired product.
Exam~le A
A mixture is prepared by the addition of 31 parts of
carbon disulfide over a period of 1.66 hours to 853 parts of
the oil solution of the product prepared in Example 15 at
113-145C. The reaction mixture is held at 145-152C. for
3.5 hours, then filtered to yield an oil solution of the
desired product.
Example B
_
A mixture of 62 parts of boric acid and 2720 parts of
the oil solution of the product prepared in Example 10 is
heated at 15~. under nitrogen for .six h~urs The reaction
mixture is filtered to yield the filtrate as an oil solution
of the desired boron~containing product~
-~7-
1()94044
Example C
An oleyl ester of boric acid is prepared by heating an
equimolar mixture of oleyl alcohol and boric acid in toluene
at the reflux temperature while water is removed azeotropically.
The reaction mixture is then heated to 150C. under vacuum
and the residue is the ester having a boron content of 3.2%
and a saponification number of 62. A mixture of 344 parts
of the ester and 2720 parts of the oil solution of the
product prepared in Example 10 is heated at 150C. for six
hours and then filtered. The filtrate is an oil solution of
the desired boron-containing product.
Example D
Boron trifluoride (34 parts) is bubbled into 2190 parts
of the oil solution of the product prepared in Example 11 at
80C. within a period of three hours. The resulting mixture
is blown with nitrogen at 70-80C. for two hours to yield
the residue as an oil solution of the desired product.
Example E
A mixture of 3420 parts of the oil-containing solution
of the product prepared in Example 12 and 53 parts Gf
acrylonitrile is heated at reflux temperature from 125C. to
145C. for 1.25 hours, at 145C. for three hours and then
stripped at 125C. under vacuum. The residue is an oil
solution of the desired product.
Example F
~ mixture is prepared by the addition of 44 parts of
ethylene oxide over a period of one hour to 1460 parts of
the oil solution of the product prepared in Example 11 at
150C. The rea~tion mixture is held at iJV~C . for one hour,
then filtered to yield the iltrate as an oil solution of
-98-
109~044
the desired product.
Example G
A mixture of 1160 parts of the oil solution of the
product of Example 10 and 73 parts of terephthalic acid is
heated at 150-160C. and filtered. The filtrate is an oil
solution of the desired product.
Example H
A decyl ester of phosphoric acid is prepared by adding
one mole of phosphorus pentaoxide to three moles of decyl
alcohol at a temperature within the range of 32C. to 55C.
and then heating the mixture at 60-63C. until the reaction
is complete. The product is a mixture of the decyl esters
of phosphoric acid having a phosphorus content of 9.9% and
an acid number of 250 (phenolphthalein indicator). A
mixture of 1750 parts of the oil solution of the product
prepared in Example 10 and 112 parts of the above decyl
ester is heated at 145-150C. for one hour. The reaction
mixture is filtered to yield the filtrate as an oil solution
of the desired product.
Example I
A mixture of 2920 parts of the oil solution of the
product prepared in Example 11 and 69 parts of thiourea is
heated to 80C. and held at 80C. for two hours. The
reaction mixture is then heated at 150-155C. for four
hours, the last of which the mixture is blown with nitrogen.
The reaction mixture is filtered to yield the filtrate as an
oil solution of the desired product.
Example J
A mixturc _f 1460 parts of the cil SAlUI __r. of the
product prepared in Example 11 and 81 parts of a 37~ aqueous
~99_
109~0~4
formaldehyde solution is heated at reflux for three hours.
The reaction mixture is stripped under vacuum at 150C. The
residue is an oil solution of the desired product.
Example K
~ mixture of 1160 parts of the oil solution of the
product prepared in Example 10 and 67 parts of sulfur mono-
chloride is heated for one hour at 150C. under nitrogen.
The mixture is filtered to yield an oil solution of the
desired sulfur-containing product.
Example L
A mixture is prepared by the addition of 11.5 parts of
formic acid to 1000 parts of the oil solution of the product
prepared in Example 11 at 60C. The reaction mixture is
heated at 60-100C. for two hours, 92-100C. for 1.75 hours
and then filtered to yield an oil solution of the desired
product.
Example M
A mixture is prepared by the addition of 58 parts of
propylene oxide to 1170 parts of the oil solution of the
product prepared in Example 35 and 10 parts of pyridine at
80-90C. The reaction mixture is then heated at 100-120C.
for 2.5 hours and then stripped to 170C. under vacuum. The
residue is an oil solution of the desired product.
Example N
A mixture of 1170 parts of the oil solution of the
product prepared in Example 35 and 36 parts of maleic
anhydride is heated to 200C. over a 1.5 hour period and
maintained at 200-210C. for 5.5 hours. During the last 1.5
hour period G ~ heating, the reaction ~i~ urc s blown with
3Q nitrogen. The reaction mixture is stripped to 190C. under
--100--
109404~.
vacuum, thell f iltered to yield the f iltrate a- all oil ~olution
of the de~ired product.
-- 101 --
