DERIVE CARBOXYLIQUE DE MONOAMINE TERTIAIRE-ALCOOL

CARBOXYLIC ACID DERIVATIVES OF ALKANOL TERTIARY MONOAMINES

Abrégé anglais

ABSTRACT OF THE DISCLOSURE
Nitrogen-containing phosphorus-free carboxylic acid
derivatives made by reaction of an acylating agent with an
alkanol tertiary monoamine are described. Typically the
carboxylic acylating agent is an alkyl or alkenyl succinic
anhydride containing about 20 to about 500 carbon atoms in
the alkyl or alkenyl group. A typical amine is diethyl
ethanol amine. These derivatives are useful in incorpora-
ting oil-soluble, water-insoluble functional additives, such
as metal salts of acid phosphate and thiophosphate hydro-
carbyl esters, into water-based functional fluids such as
water-based hydraulic fluids.

Revendications

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A nitrogen-containing, phosphorus-free carboxylic acid
derivative made by reaction of (A) at least one carboxylic
acid acylating agent with (B) at least one alkanol ter-
tiary monoamine, said acylating agent having at least one
hydrocarbyl-based substituent of about 20 to about 500
carbon atoms and said monoamine (B) having one hydroxyl
group and a total of up to about 40 carbon atoms, the
reaction between components (A) and (B) being conducted at
a temperature in the range of about 30°C to about 150°C,
at least a portion of said derivative being in the form of
a salt, said salt being an internal salt wherein carboxyl
groups of said acylating agent are ionically bonded to
nitrogen atoms within the same molecule and/or an external
salt wherein the ionic salt is formed with nitrogen atoms
which are not part of the same molecule.
2. A derivative as claimed in claim 1 wherein said acy-
lating agent (A) can be represented by the formula
<IMG>
<IMG>
or
wherein hyd is a substantially hydrocarbyl alkyl or alkenyl
group of about 30 to about 500 carbon atoms and said amine
(B) can be represented by the formula
<IMG>
wherein each R is independently a hydrocarbyl group of one
to about 20 carbon atoms and R' is an alkylene group of
two to about eighteen carbon atoms.
3. A derivative as claimed in claim 2 wherein said mono-
amine (B) is diethyl ethanol amine and said derivative
16

(A) is an ester/salt.
4. A derivative as claimed in claim 1 wherein the equiva-
lent ratio of acylating agent (A) to monoamine (B) used in
the reaction is in the range of about 1:0.5 to about
1:3Ø
17

5. A derivative as claimed in claim 3 wherein the
equivalent ratio of acylating agent (A) to monoamine (B)
used in the reaction is in the range of about 1:0.5 to about
1:3Ø
6. A derivative as claimed in claim 2 where hyd is a
poly(isobutene) group of about 50 to about 300 carbon atoms
and (A) is the only acylating agent present in the reaction.
7. A derivative as claimed in claim 5 where hyd is a
poly(isobutene) group of about 50 to about 300 carbon atoms
and (A) is the only acylating agent present in the reaction.
8. A derivative as claimed in claim 1 where said
monoamine (B) is the only amine present in the reaction and
the equivalent ratio of acylating agent (A) to monoamine (B)
in the reaction is in the range of about 1:1 to about 1:2.5.
9, A derivative as claimed in claim 1 wherein there
is also present in the reaction (C) at least one supple-
mental alkanol amine in addition to the alkanol tertiary
monoamine (B).
10. A derivative as claimed in claim 3 wherein there
is also present in the reaction (C) at least one supple-
mental alkanol amine in addition to the alkanol tertiary
monoamine (B).
11. A derivative as claimed in claim 5 wherein there
is also present in the reaction (C) at least one supplemen-
tal alkanol amine in addition to the alkanol tertiary mono-
amine (B).
12. A derivative ac claimed in claim 1 wherein said
alkanol tertiary monoamine (B) is the only amine present in
the reaction.
13. A derivative as claimed in claim 3 wherein said
alkanol tertiary monoamine (B) is the only amine present in
18

the reaction.
14. A derivative as claimed in claim 5 wherein said alkanol
tertiary monoamine (B) is the only amine present in the reaction.
15. A water-dilutable lubricant additive composition comprising
40 to 70% by weight of a derivative as claimed in claim 1, 5 to
20% by weight of a non-ionic hydrophilic surfactant or wetting
agent, and 10 to 40% by weight of a water-insoluble oil-
soluble functional additive.
16. A composition as claimed in claim 15 wherein the water-
insoluble functional additive is selected from phosphorous and/or
sulfur-containing anti-wear, extreme pressure and load-carrying
agents.
17, A water-dilutable hydraulic fluid concentrate comprising 95
parts by weight water and 5 parts by weight of a composition as
claimed in claim 15.
18. A lubricant additive concentrate comprising in admixture a
hydrocarbyl oil and a composition as claimed in claim 15, said
hydrocarbyl oil being present in an amount of up to 15% by
weight based on the total weight of the concentrate.
19. The derivative of claim 1 wherein said acylating agent (A)
is represented by the formula
<IMG> or
<IMG>
wherein hyd is said hydrocarbyl-based substituent.
20. The derivative of claim 1 wherein said monoamine (B) is
represented by the formula
19

<IMG>
wherein each R is independently a hydrocarbyl group of one to
about 20 carbon atoms and R' is an alkylene group of two to
about 18 carbon atoms.
21. The derivative of claim 1 wherein said monoamine (B) is
diethyl ethanol amine.
22. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substitutent is an alkyl or an
alkenyl group.
23. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent has about 20 to
about 300 carbon atoms.
24. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent is a poly(isobutene)
group.
25. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent has about 20 to
about 200 carbon atoms.
26. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent is an alkyl or an
alkenyl group of about 30 to about 500 carbon atoms.
27. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent has about 30 to
about 300 carbon atoms.
28. The derivative of claim 1 or composition of claim 15
wherein said hyarocarbyl-based substituent is a poly(isobutene)
group of about 30 to about 500 carbon atoms.

29. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent has about 30 to
about 200 carbon atoms.
30. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent is an alkyl or an
alkenyl group of about 50 to about 500 carbon atoms.
31. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent has about 50 to
about 300 carbon atoms.
32. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent is a poly(isobutene)
group of about 50 to about 500 carbon atoms.
33. The derivative of claim 1 or composition of claim 15
wherein said hydrocarbyl-based substituent has about 50 to
about 200 carbon atoms.
34. The derivative of claim 1 wherein at least one supplemental
carboxylic acylating agent in addition to the acylating agent
(A) is present in the reaction.
35. The derivative of claim 30 wherein said supplemental
acylating agent is a fatty acid of 10 to 18 carbon atoms.
36. The derivative of claim 30 wherein said supplemental
acylating agent is a low molecular weight alkyl or alkenyl
succinic acid.
37. The derivative of claim 30 wherein said supplemental
acylating agent is tetrapropenyl succinic anhydride.
38. The derivative of claim 9 wherein said supplemental
alkanol amine (C) has up to about 26 carbon atoms.
39. The derivative of claim 9 wherein said supplemental
alkanol amine (C) is a primary, secondary or tertiary alkanol
amine.
40. The derivative of claim 9 wherein said supplemental
21

alkanol amine (C) has the formula
R1R2N - R3- OH
wherein R1 and R2 are each independently selected from the
group consisting of hydrogen, alkyl, alkenyl, hydroxy alkyl and
hydroxy alkenyl and R3 is alkylene.
41. The derivative of claim 9 wherein said supplemental alkanol
amine (C) is ethanolamine.
42. A composition comprising (a) at least one normally water-
insoluble, oil-soluble functional additive and (b) a nitrogen-
containing, phosphorus-free carboxylic acid derivative as
claimed in claim 1.
43. A composition comprising (a) at least one normally water-
insoluble, oil-soluble functional additive selected from the
group consisting of phosphorus and/or sulfur-containing anti-
wear, extreme pressure, or load-carrying agents, and (b) a
nitrogen-containing, phosphorus-free carboxylic acid derivative
as claimed in claim 1.
44. A water-based system comprising about 40 to about 70% of
water, from 0 up to about 15% hydrocarbyl oil and a mixture
comprising (a) from about 10 to about 40% of at least one
normally water-insoluble, oil-soluble functional additive
selected from the group consisting of phosphorus and/or sulfur-
containing anti-wear, extreme pressure, or load-carrying agents,
and (b) from about 40 to about 70% of a nitrogen-containing,
phosphorus-free carboxylic acid derivative as claimed in claim
1.
45. A composition comprising (a) at least one normally water-
insoluble, oil-soluble functional additive, (b) a nitrogen-
containing, phosphorus-free carboxylic acid derivative as
claimed in claim 1, and (c) a surfactant.
46. A composition comprising (a) at least one normally water-
insoluble, oil-soluble functional additive selected from the
group consisting of phosphorus and/or sulfur-containing anti-
22

wear, extreme pressure, or load-carrying agents, (b) a
nitrogen-containing, phosphorus-free carboxylic acid
derivative as claimed in claim 1, and (c) a surfactant.
47. A water-based system comprising about 40 to about 70% of
water, from 0 up to about 15% hydrocarbyl oil and a mixture
comprising (a) from about 10 to about 40% of at least one
normally water-insoluble, oil-soluble functional additive
selected from the group consisting of phosphorus and/or
sulfur-containing anti-wear, extreme pressure, or load-
carrying agents, (b) from about 40 to about 70% of a nitrogen-
containing, phosphorus-free carboxylic acid derivative as
claimed in claim 1, and (c) from about 5 to about 20% of a
surfactant.
23

Description

i7'~
This invention relates to nitrogen-containing, phos-
phorus-free carboxylic acid deri~atives. More particularly,
it relates to derivatives made from acylating agents having
hydrocarbyl substituents of about 20 to about 500 carbon
atoms and certain alkanol tertiary monoamines.
Carboxylic acid derivatives made from high molecular
weight carboxylic acid acylating agents and amino compounds
and their use in oil-based lubricants are well known. See,
for example, U.S. Patents 3,216,936; 3,219,666; 3,502,677;
and 3,708,522.
Certain alkyl succinic acid/alkanol amine condensates
have also been described; see, for example, U.S. Patent
3,269,946. Water-in-oil emulsions containing alkyl and
alkenyl succinic acid derivatives are also known; see, ~or
example, U.S. Patents 3,255,108 and 3,252,908.
Oil-soluble, water-insoluble functional additives are
also well known. See, for example, the treatises by C. B.
Smalheer and R. Xennedy Smith, published by Lezlus-Hiles
Co., Cleveland, Ohio, 1967, and by M. W. ~anney, published
by Noyes Data Corp., Parkridge, New Jersey, 1973 both en-
tltled "Lubricant Additives". In this connection, and
throughout the speciication and the following claims, a
water-insoluble functional aaditive i8 one which is not
soluble in water above a level of about 1 gram per 100
m~lliliters of water at 25C. and i9 soluble in mineral oil
at a level above 1 gram per liter.
'

~ 6 ~7'~Z
The reaction of a carboxylic acid acylating agent,
particularly a polycarboxylic agent such as a succinic acid
acylating agent with a poly-functional compound such as
alkanol tertiary monoamine can produce complex products.
For example, diesters, disalts, and ester/ salts could be
produced. Such products could involve reactions of one or
or more acylating agents and/or one or more alkanol amine
molecules. Furthermore, the polarity of such products and
their interaction with hydrophilic and/or lipophilic systems
such as oil and water systems appears to be complex.
It is an object of this invention to produce nitrogen-
containing, phosphorus-free carboxylic acid derivatives of
certain alkanol tertiary monoamines. Other objects and
advantage~ of the invention will be apparent upon the study
of the following specificat~on and claims.
Th~s invention comprises a nitrogen-containing, phos-
phorus-free carboxylic acid derivative made by reaction of
~A) at least one carboxylic acid acylating agent with ~B) at
least one alkanol tertiary amine, said acylating agent
having at least one hydrocarbyl-based æubstituent of about
20 to about 500 carbon atoms and said alkanol amine ~B)
- having one hydroxyl group and a total of up to about 40
carbon atoms.
~he carboxylic acid acylating agent, (A).
The acylating agents used in making the derivatives of
the present invention are well known to those of skill in
the art and have been found to be useul as additives for

-- 3 --
lubricants and fuels and as intermediates for preparing the
same. See, for example, the following U.S. Patents:
3,219,66~; 3,272,746; 3,381,022; 3,254,025; 3,27~,5~0;
3,288,714; 3,271,310; 3,373,111; 3,346,354; 3,272,743;
3,374,174, 3,307,928; and 3,394,179.
Generally, these carboxylic acid acylating agents are
prepared by reacting an olefin polymer or chlorinated analog
thereof with an unsaturated carboxylic acid or derivative
thereof such as acrylic acid, fumaric acid, maleic anhydride
and the like. Typically, these acylating a~ents are poly-
carboxylic acylating agents such as the succinic acid acyla-
ting agents derived from maleic acid, its isomers, anhydride
and chloro and bromo derivatives.
These acylating agents have at least one hydrocar~yl-
15 based substituent of about 20 to about 500 carbon atoms.
Generally, this substituent has an average of at least about
30, and often at least about 50 carbon atoms. Typica]ly,
this substituent has a maximum average of about 300, and
often about 200 carbon atoms. As used herein, the term
"hydrocarbon-based", "hydrocarbon-based substituent" and the
like denotes the substituent having a carbon atom directly
attached to the remainder of the molecule (i.e., the car-
boxylic acylating portion) and having predominantly hydro-
carbyl character within the context of this invention. Such
substituents include the following:
(1) hydrocarbon substituents, that is, aliphatic
(e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl,
i~
~!

7'~
cycloalkenyl) substituents, aromatic, aliphatic and ali-
cyclic-substituted aromatic nuclei and the like as well as
cyclic substituents wherein the ring is completed through
another portion of the molecule ~that is, for example, any
two indicated substituents may together form an alicyclic
radical);
(2) substituted hydrocarbon substituents, that is,
those substituents containing non-hydrocarbon radicals
which, in the context of this invention, do not alter the
predominantly hydrocarbyl substituent; those skilled in the
art will be aware of such radicals (e.g., halo tespecially
chloro and fluoro), alkoxyl, mercapto, alkylmercapto, nitro,
nitroso, sulfoxy, etc.);
~3) hetero substituents, that is, substituents which
will, while having predominantly hydrocarbyl character
within the context of this invention, contain other than
carbon present in a ring or chain otherwise composed of
carbon atoms. Suitable heteroatoms will be appaxent to
those of skill in the art and include, for example, sulfur,
oxygen, nitrogen and such substituents as e.g., pyridyl,
furanyl, thiophenyl, imidazolyl, etc., are exemplary of
these hetero substituents.
In general, no more than about three radicals or hetero-
atoms and preferably no more than one, will be present for
each ten carbon atoms in the hydrocarbon-based substituents.
Typically, there will be no such radicals or heteroatoms in
the hydrocarbon-based substituent and it will, therefore, be
purely hydrocarbyl.
In general, the hydrocarbon-based substituents of at
least about 20 carbon atoms present in the acylating agents

7~
used in this invention are free from acetylenic unsaturation;
ethylenic unsaturation, when present will generally be such
that there is no more than one ethylenic linkage present for
every ten carbon-to-carbon bonds in the substituent. The
substituents are often completely saturated and therefore
contain no ethylenic unsaturation.
As noted above, the hydrocarbon-based substituents
present in the acylating agents of this invention are
derived from olefin polymers or chlorinated analogs thereof.
The olefin monomers from which the olefin polymers are
derived are polymerizable olefins and monomers characterized
by having one or more ethylenic unsaturated group. They can
be monoolefinic monomers such as ethylen~ propylene, butene-
1, isobutene and octene-l or polyolefinic monomers (usually
di-olefinic monomers such as butadiene-1,3 and isoprene).
Usually these monomers are terminal olefins, that is, ole-
fins characterized by the presence of the group ~ C=CH2.
However, certain internal olefins can also serve as monomers
(these are sometimeg referred to as medial olefins). When
such medial olefin monomers are used, they normally are
employed in combination with terminal olefins to produce
olefin polymer~ which are interpolymers. Although the
hydrocarbyl-based substituents may also include aromatic
groups ~especially phenyl groups and lower alkyl and/or
lower alkoxy-#ubstituted phenyl groups such as para~tertiary
butyl~phenyl groups) and alicyclic groups such as would be
obtained from polymerizable cyclic olefins or allcyclic-
sub~tituted polymerizable cyclic olefins. The olefin poly-
mers are usually free from such groups. Nevertheless,
olefin polymers derived from such interpolymers of both 1,3-

7"~
dienes and styrenes such as ~utadiene-1,3 and styrene or
para(tertiary butyl)styrene are exceptions to this general
rule.
Generally the olefin polymers are homo- or interpoly-
mers of terminal hydrocarbyl olefins of about 2 to about 16
carbon atoms. A more typical class of olefin polymers is
selected from that group consisting of homo- and interpoly-
mers of terminal olefins of two to six carbon atoms, espe-
cially those of two to four carbon atoms.
Specific examples of terminal and medial olefin m~no-
mers which can be used to prepare the olefin polymers from
which the hydrocarbon-based substituents in the acylating
agents used in this invention are ethylene, propylene,
butene-l, butene-2, isobutene, pentene-l, hexene-l, heptene-
1, octene-l, nonene-l, decene-l, pentene-2, propylene tetra-
mer, diisobutylene, isobutylene trimer, butadiene-1,2,
butadiene-1,3, pentadiene-1,2, pentadiene-1,3, isoprene,
hexadiene-1,5, 2-chlorobutadiene-1,3, 2-methylheptene-l, 3-
cyclohexylbutene-l, 3,3-dimethylpentene-l, styrenedivinyl-
benzene, ~inylacetate allyl alcohol, l-methylvinylacetate,
acrylonitrile, ethylacrylate, ethylvinylether and methyl-
vinylketone. Of these, the purely hydrocarbyl monomers are
more typical and the terminal olefin monomers are especially
typical.
Often the olefin polymers are poly(isobutene)s such as
obtained by polymerization of a C 4 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 chloride or boron trifluoride. These poly(iso-
butene)s contain predominantly (that is, greater than 80% of
the total repeat units) isobutene repeat units of the con-
figuration
CX 3
~ CH2--C -- --J
CH3
Typically, the hydrocarbyl-based substltuent in the
carboxylic acid acylating agent as used in the present
invention is a hydrocarbyl, alkyl or alkenyl group of about
30, often about 50, to about 500, sometimes to about 300,
carbon atoms. For convenience herein, such substituents are
represented by the indicia "hyd".
AB noted above, typical acylating agents ~A) used in
making the derivatives of this invention are substituted
~uccinic acids or derivatives thereof. In this case, the
acylating agent ~A) can be represented by the formulae:
hyd-fHCOO~ hyd-C~C ~
CH2COOH or ¦ f
CH2C
~0
Such succinic acid acylating agents can be made by the
reaction of maleic anhydride, maleic acid, or fumaric acid
with the afore-described olefin polymer, as is shown in the
patents referred to above. Generally, the reaction involves
merely heating the two reactants at a temperature of about
150 to about 200. Mixtures of these polymeric olefins, as

~ 7~
well as mixtures of these unsaturated mono- and polycar-
boxylic acids can also be used.
The alkanol tertiary monoamines, (B)~
The amines used in making the derivatives of the pre-
sent invention are tertiary monoamines having one hydroxylgroup per molecule and normally up to about 40 carbon atoms.
These hydroxyl groups are bonded to an alkyl group which in
turn is bonded to the amine portion of the molecule. The
two remaining substituents bonded to the tertiary amine
nitrogen are hydrocarbyl groups each having one to about 20
carbon atoms. Usually they will also be alkyl groups, but
they can be alkenyl groups with one olefinic bond. Typi-
cally they are lower alkyl groups of up to seven carbons,
though they can also be aryl, aralkyl, alkaryl, cycloalkyl,
alkyl cycloalkyl, and cycloalkylalkyl groups. Mixtures of
two or more of the amines ~B) can also be used.
A typical class of useful amines can be represented by
the formula
\
j NR'OH
R
wherein each R is independently a hydrocarbyl group of one
to about eighteen carbon atoms and R' is a straight or
branched chain alkylene group of abcut two to about eighteen
carbon atoms. The N/N-dialkyl-alkanol amines within the
above formula are particularly preferred, especlally those
wherein each R is independently a lower alkyl and R' is
lower alkylene. The two R groups can be joined by a carbon-
to-carbon bond or a heteroatom (e.g., -O- or -S-) to form a
5- or 6-membered heterocyclic ring.
Specific examples of useful alkanol amines (B) include

~ 7 ~
N,N-diethyl ethanol amine, N-methyl, N-phenyl-2-hydroxy
propyl amines, N,N-dimethyl-2-hydroxybutyl amine, N,N-
diethyl-2-hydroxy octadecyl amine, N-(2-hydroxy e~hyl)mor-
pholine, N-methyl(2-hydroxy ethyl)cyclohexylamine.
The reaction of the acylating agent (A)
with the alkanol amine (B) to form the
nitrogen-containing derivative.
The reaction of the acylating agent with the alkanol
amine can be carried out at a temperature ranging from about
30 to the decomposition temperature of one or more of the
reaction components and/or products. Typically, it is
carried out at a temperature in the range of about 50 to
about 150. Often the reaction is carried out under ester-
~orming conditions and the product thus formed is an ester
or an ester/salt. This salt can be an internal salt involv-
ing residues of a molecule of acylating agent and of amine,
wherein one of the carboxyl groups becomes ionically bound
to a nitrogen atom within the same group or it may be an
external salt wherein the ionic salt group is formed with a0 nitrogen atom which is not part of the same molecule.
Mixtures of acylating agents and/or mixtures of alkanol
amines can be used. Generally, the equivalent ratio of
acylating agent to alkanol amine formed is in the range of
about 0.5 to about 3 equivalents of amine per equivalent of
carboxylic acylating agent. An equivalent of carboxylic
acylating agent can be determined by dividing the molecular
weight of the acylating agent by the number of carboxyl
functions. This can usually be determined from the struc-
tural formula of the acylating agent or empirically through
well-known titration procedures. Thus a succinic anhydride
has an equivalent weight of half its molecular weight. An
;
_g_

7'~
equiva~ent of alkanol amine is equal to its molecular weight.
Typically, equivalent ratios o~ acylating agent tA) to amine
(B) is in the range of about 1:1 to about 1:2.5.
Usually the agent (A) and amine (B) are reacted at a
temperature below about 100C., often in the absence of
additional solvent/diluents.
Supplemental reagents.
While the afore-described acylating agent (A) and
amines (B) are the only necessary acylating agent and amines
present in the reaction producing the derivatives of this
invention, it is sometimes the case that supplemental car-
boxylic acylating agents (C) and/or alkanol amines (D) are
present. It is, of course, essential that the (A) agents
and ~B) amines be present in significant amounts; this means
at least 50~mole)% of the total acylating agent ~i.e., (A)
plus ~C)) and at least 50(molej% of the total amine (i.e.,
~B) plus lD)) are the essential acylating agent ~A) and
amine ~B), respectively.
Typical supplemental acylating agents ~C) include ~atty
acids of 10 to 18 carbon atoms such as oleic, stearic,
linoleic acids and the well-known commercial fatty acid
mixtures such as coco acids, tallow acids, tall oil acids,
and the like. Low molecular weight alkyl and alkenyl suc-
cinic acid acylating agents such as tetrapropenyl succinic
anhydride can also be included in the supplemental acylating
agent class.
Typical supplemental alkanol amines (D) can contain up
to about 26 carbon atoms and include primary, secondary and
tertiary alkanol amines (e.g., ethanol amine, di-(2-propanol)
amine, N,N-di(2-hydroxy ethyl)ethyl amine, 2-, 3-, and 4-
--10--

hydroxy butanol amines and their monomethyl homolog, N(2-
hydroxyethyl)aniline and triethanol amine. The supplemental
alkanol amines (D) usually will be one or more amines of the
formula
R~R2N - R3- OH
wherein Rl and R~ are each independently selected from the
group consisting of hydrogen, alkyl, alkenyl, hydroxyl
alkyl, and hydroxylalkenyl and R3 is straight or ~ranched
chain alkylene. Usually Rl and R2 will each independently
be hydrogen or lower alkyl and R3 wil~ be lower alkylene.
Ethanol amine is especially preferred. Of course, when one
or more supplemental alkanol amines (D)are present, they
will be different than the alkanol tertiary monoamines ~A).
In other words, it is a proviso that (D) is exclusive of
(A).
As noted a~ove, the supplemental acylating agents (C)
and/or amines (D) can, respectively, constitute no more than
up to about 50(mole)% of the total acylating agent or amine
present in the reaction mixture. Sometimes they are not
present at all and the acylating agent (A) and alkanol amine
(B) are the only acylating agent and amine present.
The following are specific examples of the preparation
of nitrogen-containing, phosphorus-free carboxylic acid
derivatives of the present invention. In these examples all
parts and percentages are by weight unless expressly stated
to the contrary and all temperatures are in degrees Celsius,
as is the case throughout the specification and appended
claims.
Example 1
To a charge of 2240 parts of a poly(isobutene)-sub-
--11--

~ i7 ~
stituted succinic anhydride Ihaving a molecular weigh~ of
1120) heated in a resin kettle with stirring to about 90 is
slowly added over a two-hour period 468 parts of diethyl
ethanol amine. Heating is continued for an additional hour
at about 90~. The desired reaction product is a viscous,
clear, brown-tinted liquid at room temperature.
Example 2
To a charge of 6720 parts of the succinic anhydride
described in Example 1, heated to 90 with stirring, is
slowly added over 1.5 hours, 702 parts of diethyl ethanol
amine. This intermediate mixture is then heated for an
additional 0.5 hour at 90. Then 366 parts of monoethanol
amine is slowly added. The mixture is then held at 90~ for
a final 0.5 hour and cooled to provide a clear brown, vis-
5 COU5 liquid product.
Use of the carbox lic acid derivatives
Y
The carboxylic acid derivatives of this invention can
be used to solubilize normally water-insoluble, oil-soluble
functional additives in water-based systems, particularly in
systems containing less than 15~ hydrocarbyl oil. When so
used, they are often used in conjunction with a non-ionic
; ~ hydrophilic surfactant or wetting agent such as Triton X-
r~ ~
100, an ethoxylated alkyl-substituted phenol having a
molecular weight of approximately 628 and contai~ing an
average of 9-10 ethylene-oxide derived units. This material
is available commercially from the Rohm ~ Haas Company.
Other simllarly useful surfactants will occur to those o~
~kill in the art.
w~en used in conjunction with such a surfactant, the
car~oxylic acid derivatives of this invention are combined
~ V~ -12-

~ ~ ~571~Z
with the surfactant and an oil-soluble, water-insoluble
functional additive. Typical functional additives include
the well-known phosphorus and/or sulfur-containing anti-
wear, extreme pressure (E.P.) and load-carrying agents used
typically in mineral oil-based lubricant and functional
fluid formulations. Exemplary of such materials are those
found in the two books entitled "Lubricant Additives" re-
ferred to above under "Description of the Prior Art".
Specific examples include the Group II metal salts of acid
phosphate and thio (including dithio), phosphate hydrocarbyl
esters; particularly the zinc esters.
The combination of carboxylic acid derivative, sur-
factant and unctional additive can be done in the absence
of any solvent/diluent. Usually, however, it is preferable
to include a solvent/diluent and an ideal one is water.
Such combinations form aqueous concentrates. Such aqueous
concentrates are u~ed merely for convenience and it is
possible to make effective concentrates without water.
Typical water-free concentrates contain 40-70~ carboxylic
acid derivative, 5-20% surfactant and 10-40% functional
additive. Water, when present in such concentrates con-
~titutes 40-70~ of the concentrate and the proportion of
other materials is reduced proportionately. In other words,
the relative proportions of carboxylic acid derivative,
; 25 surfactant and additive, however, remain within the ranges
given above for the water-free concentrate.
Example A
A mixture is prepared of 40 parts of the carboxylic
acid derivative of Example l, lO parts Triton X-100 and
16.67 parts of a commercial anti-wear, load-carrying addi-
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l.~t>'j`7'~
tive, which is the zinc salt of an acid 0,0'-di(alkyl-sub-
stituted phenyl) dithiophosphate. The mixture is stirred
well to insure thorough mixing and transferred to a closed
container for storage. This system is useful as a water-
dilutable hydraulic fluid concentrate, especially whendiluted in the proportions 95 parts water to 5 parts con-
centrate.
Up to 15% hydrocarbyl oil, such as mineral oil, may
also be used in certain concentrates containing the carboxy-
lic acid derivatives of this invention. Here the oil isused to reduce viscosity and thus facilitate handling,
though it may serve other purposes as well. An example of
such a concentrate i6 the following:
Example B
A mixture is formed of 30 parts naphthenic solvent
neutral oil having a visco~ity of 100 SSU, 40 parts of the
carboxylic acid of Example 1 and 30 parts of Minform 2X, a
commercially available surfactant comprising a modified
linear alcohol ethoxylate available commercially from the
Union Carbide Corporation. This concentrate was mixed with
about 30 parts water and observed visually. The mixture
appeared to be clear and not show any of the opaque charac-
teristics of a typical emulsion.
Ten parts of the concentrate of Example B is combined
with one part of a commercial water-insoluble, oil-soluble,
high molecular weight ester dispersant. The resulting
mixture is then diluted to approximately 30% in water.
Again, visual inspection shows no evidence of gross emulsion
formation, i.e., no opaque appearance, phase separation or
the like. Such systems find utility in hydraulic fluids or
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~S7~2
cutting fluid (i.e., metal-forming) formulations.
Finally, it should be noted that while the carboxylic
acid derivatives (A) of this invention have been described
as useful as solubilizing agents for water-insoluble func-
tional additives, it has also been observed that they canprovide lubricity and anti-friction properties to aqueous
lubricating fluids containing them.
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