Note: Descriptions are shown in the official language in which they were submitted.
I
--1--
ADDITIVE COMPOSITIONS CONTAINING AMINO PHENOL
-
COMBINATIONS USEFUL US Lubricant END FUEL ADDITIVES
. , , _ , , .
Field of the Invention
This invention relaxes to nitrogen containing
organic compositions. These compositions are useful as
lubricant and fuel additives. Additionally, this invention
relates to concentrates of these compositions and to Libra-
cant and fuel compositions comprising these compositions.
This invention also relates to a method for operating an
10 internal combustion engine by lubricating said engine during
operation with these lubricating composition.
Summary the Invention
A principal object of the present invention is to
provide novel nitrogen-containing organic compositions.
Another principal object of the present invention
is to provide novel nitrogen-containing organic compositions
which impart to lubricants and fuels one or more of the
hollowing properties: detergent, dispersant, antioxidant,
anticorrosive r antiwar, friction reducing and fluidity
20 modifying properties.
Another object it to provide novel concentrates
comprising these novel nitrogen-containing organic combo-
sessions
Still another object is to provide novel lubricant
25 and fuel compositions containing these novel nitrogen-
containing organic compositions.
.,~ ,~,
I
--2--
An additional object is to provide a method for
lubricating an internal combustion engine which comprises
lubricating said engine during operation with these novel
lubricating compositions.
These and other objects of the invention are
accomplished by providing a nitrogen containing organic
composition comprising a combination of:
(A) at least one amino phenol of the general
formula
(OKAY
c if - -(NH2)b
wherein R is a substantially saturated, hydrocarbon-based
suhstituent of at least aliphatic carbon atoms' a, b and
c are each independently an integer of one up to three times
the number of aromatic nuclei present in An with the proviso
15 that the sum of a, b and c does not exceed the unsatisfied
valences of An; and An is an aromatic moiety having 0-3
optional ubstituen~s selected from the group consisting of
lower alkyd, lower alkoxyl, vitro, halo or combinations of
two or more of said substituentq; and
(B) one or more carboxylic derivative commas-
lions produced by reacting at least one substituted succinic
acylatin~ agent with a reactant selected from the group
consisting ox (a) an amine characterized by the presence
within its structure of at least one H-N = group, (b) an
25 alcohol, (c) a reactive metal or reactive metal compound,
and (d) a combination of two or more of any of (a) through
(c), the components of (do being reacted with said one or
more substituted succinic assaulting agents simultaneously or
sequentially it any order, wherein said substituted succinic
30 assaulting agents consist of substituent groups and succinic
groups wherein the substituent groups are derived from
polyalkene, said polyalkene being characterized by a My
value of 1200 to about 5000 and a Mom value of about 1.5
to about 6, said assaulting agents being characterized by the
I
--3--
presence within their structure of an average of at least
1.3 succinic groups for each equivalent weight ox substitu-
en groups.
One or more object of this invention art Allah
accomplished by providing . nitrogen containing organic
composition comprising a combination of (A) and (9) wherein,
said (B) is a post-treated carboxylic derivative composition
prepared by reacting one or more post-treating reagents with
said one or more carboxylic derivative composition
One or more objects of this invention are also
accomplished by providing compositions wherein the nitrogen-
containing compositions mentionedjhereinabove and described
in detail hereinafter are further combined with (C) at least
one chlorine-con~aining compound selected from the group
15 consisting ox chloroaliphatic hydrocarbon-based compounds,
chloxoalicyclic hydrocarbon-based compounds or mixtures
thereof.
One or more objects of this invention are also
accomplishes by providing a nitrogen-containing organic
20 composition comprising a combination of:
(A) at least one amino phenol of the general
formula
(OWE
(R) - -An - (NH2)b
wherein R is a substantially saturated, hydrocarbon-based
25 substituent of at least 8 aliphatic carbon atoms; a, b and c
are each independently an integer of one up to three times
the number ox aromatic nuclei present in An with the proviso
that the sum of a, b and c does not exceed the unsatisfied
valences of An; and An is an aromatic moiety having 0-3
30 optional substituents selected from the group consisting of
lower alkyd, lower alkoxyl, vitro, halo or combinations of
two or more of said suhstituents; and
(C) at least one chlorine-containing compound
selected from the group consisting of chloroaliphatic
I 3~ii
--4--
hydrocarbon-based compounds, chloroalicyclic hydrocarbon-
based compounds or mixtures thereof.
One or more objects of this invention can be
accomplished by providing compositions wherein the nitrogen
containing composition comprising a combination of (A) and
(C) as mentioned hereinabove and described in detail herein-
after are further combined with at least one sulfurized
olefinically unsaturated compound.
DETAILED DESCRIPTION OF THE INVENTION
(A) The amino Phenol
The Aromatic Moiety An
The amino phenol useful for the purposes of this
invention are of the general formula
(lH)c
c An - (NH2)b
The aromatic moiety, An, can be a single aromatic
nucleus such as a ensign nucleus, a pardon nucleus, a
thiophene nucleus, a 1,2,3,4-tekrahydronaphthalene nucleus,
etc., or a polynuclear aromatic moiety. Such polynuclear
moieties can be ox the fused type; that is, wherein at least
20 one aromatic nucleus is fused at two points to another
nucleus such a found in naphthalene, anthracene, the
azanaphthalenes, etc. Alternatively, such polynuclear
aromatic moieties can be of the linked type wherein a least
two nuclei (either Monroe polynuclear) are linked through
25 bridging linkages to each other. Such bridging linkages can
be chosen prom the group consisting of carbon-to-carkon
single bonds, ether linkages, veto linkages, sulfide link-
ages, polysulfide linkages of 2 to 6 sulfur atoms, sulfinyl
linkages, sulfonyl linkages, Mullen linkages, alkaline
30 linkages, Delaware alkyl)methylene linkages, lower alkaline
ether linkages, alkaline veto linkages, lower alkaline
sulfur linkages, lower alkaline polysulfide linkages of 2 to
6 carbon atoms, amino linkage, palomino linkages and
mixtures ox such diva lent bridging linkages. In certain
35 instances, more than one bridging linkage can be present in
12~Lr ~35
--5--
An between aromatic nuclei. For example, a fluorine nucleus
has two Bunsen nuclei linked by both a ethylene linkage
and a covalent bond. Such a nucleus may be considered to
have 3 nuclei but only two of them are aromatic. Normally,
however, An will contain only carbon atoms in the aromatic
nuclei per so (plus any lower alkyd or alkoxy substituent
present).
he number of aromatic nuclei, fused, linked or
both, in An can play a role in determining the integer
10 values of a, b and c in Formula I. For example, when An
contain a single aromatic nucleus, a, b and c are each
independently 1 Jo JO When An contains two aromatic nuclei,
a, b and c can each be an integer ox 1 to I that is, up to
three times the number of aromatic nuclei present (in
lo naphthalene, 2). With a tri-nuclear An moiety, a, b and c
can each be an integer of 1 to 9. For example, when An is a
biphenyl or a naphthyl moiety, a, b and c can each index
pendently be an integer of 1 to 6. The values of a, b and c
are obviously limited by the fax thaw their sum cannot
20 exceed the total unsatisfied valences of An, that is, the
sum of a, b and c cannot exceed the number of carbon atoms
in the aromatic moiety tar aye would otherwise be bonded
to a hydrogen.
The single ring aromatic nucleus which can be the5 An moiety can be represented by the general formula
arm
wherein en represents a single ring aromatic nucleus ego.,
Bunsen) of 4 to 10 carbons, each Q independently represents
a lower alkyd group, lower alkoxy group, Norway group, or
30 halogen atom, and m is 0 to 3. As used in thus speci~ica
lion and appended claims, "lower" refers to groups having 7
or less carbon atoms such as lower alkyd and lower alkoxyl
groups. Halogen atoms include fluorine chlorine, bromide
and iodine atoms; usually, the halogen atoms are fluorine
35 and chlorine atoms.
583~
Specific examples of single ring An moieties are
the following:
r r To Me
HUH H I H OH
I
= Me Of unit
~12
` " r Ho --I / CH2-CH2
H I\ H 2 N H CH2-CH2
Ho
wherein ye is methyl, Et is ethyl, Pry is n-propyl, and Kit
I vitro.
When An is a polynuclear fused-ring aromatic
10 moiety, it can be represented by the general formula
en en my (Q mm
US
I .
wherein en, Q and m are as defined hereinabove, m' is 1 to 4
and '~~ represents a pair of fusing bonds fusing two rings
so as to make two carbon atoms part of the rings of each of
two adjacent rings Specific examples of fused ring art-
matte moieties An are:
I r
H H H
Me Me Me Nit
AL H H 1
Ho
H H OH
H f H ~l~LH
H Jo H
H H
eta .
I When the axiomatic moiety An is a linked polyp
nuclear aromatic moiety it can be represented by the general
formula
ar-~-Lng-ar my
wherein w it an integer of 1 to about 20, en is as described
15 above with the proviso that there are at least 3 unsatisfied
(i.e., free) valences in the total of en groups, Q and m are
as defined herein before, and each Lung is a bridging linkage
individually chosen from the group consisting of carbonate-
carbon single bonds, ether linkages (e.g. -O ), veto linkages
--8--
(e.g./ -I ), sulfide linkage (e.g., -S-), polysulfide
linkages of 2 to 6 sulfur atoms (e.g., -S2-6), sulfinyl
linkages (e.g., -So-), sullenly linkages (e.g., us 2-) I.
lower alkaline linkages (e.g., -SHEA-, -CH2-CH2-, -SHEA-,
R
etc.), Delaware alkyl)-methylene linkages (e.g., CRY-),
lower alkaline ether linkage (e.g., -SHEA-, -CH20-CH2-,
-CH2-CH20-, -CH2C~20OEIzCH2-, -OEI2CHOCH2~H-, -CH2~HO~HCH2-,
Jo R I R
etc.), lower alkaline sulfide linkages (e.g., wherein one or
more -0-'s in the lower alkaline ether linkages is replaced
10 with an -S- atom), lower alkaline polysulfide linkages
(e.g., wherein one or more -0-'s is replaced with a ~S2-6
group), amino linkages (e.g., -I , -CHIN-, -CH2lCH2-,
-alkali-, where elk is lower alkaline, etc.), palomino
linkages (e.g., -rollick o where the unsatisfied free N
15 valences are taken up with H atoms or R groups), and
mixtures ox such bridging linkages (each R being a lower
alkyd group). It is alto possible that one or more of the
en groups in the above-linked aromatic moiety can be no-
placed by fused nuclei such a art a m'
Specific example of linked moieties are-
or
H H H X
I J
go
Ho
H L H
My 1 0
H Me
ye
H H
J l-lot etc.
Usually all these An moieties are unsub~tituted
except for the R, -OH and -NH2 group (and any bridging
groups).
For such reasons as cost, availability, perform-
ante, etc., the An moiety is normally a Bunsen nucleus,
lower alkaline bridged Bunsen nucleus, or a naphthalene
nucleus. Thus, a a typical An moiety is a Bunsen or
naphthalene nucleus having 3 to 5 unsatisfied valences, so
that one or two of said valences may be satisfied by a
hydroxyl group with the remaining units valences
15 being, insofar as possible, either ortho or pane to a
hydroxyl group. Preferably, An is a Bunsen nucleus having
so
--10--
at least 3 unsatisfied valences so that one can be satisfied
by a hydroxyl group with the remaining 2 or 3 being either
ortho or pane Jo the hydroxyl group
The Substantially Saturated Hydrocarbon-based Group R
The amino phenol of the present invention con-
lain, directly bonded to the aromatic moiety An, a sub-
staunchly saturated monovalent hydrocarbon-based group R of
at least about 8 aliphatic carbon atoms. This R group can
have up to about 750 aliphatic carbon atoms. More than one
10 such group can be present, but usually, no more than 2 ox 3
such grollps are present for each aromatic nucleus in the
aromatic moiety An. The total number of R groups present is
indicated by the value for "a" in generic formula used to
represent the amino phenols useful in the present invention.
15 Usually, the hydrocarbon-based group has at least about 30,
more typically, at least about 50 aliphatic carbon atoms and
up to about 750, more typically, up to about 400 aliphatic
carbon atoms.
Generally, the hydrocarbon-based groups R are made
20 from home- or inter polymers (ego, copolymers, terpolymers)
of Mooney and dolphins having 2 to 10 carbon atoms, such as
ethylene, propylene, buttonhole, isobutene, butadiene, is-
prone, l-hexene, l-octene, etc. Typically, these olefins
are l-monoolefins such a homopolymers of ethylene. The R
25 groups can be derived from the halogenated (e.g., chlorine-
ted or brominated) analogs of such home- or inter polymers.
The R groups can, however, be made from other sources, such
as monomeric high molecular weight alikeness (e.g., l-tetra-
convene) and chlorinated analogs and hydrochlorinated
30 analogs thereof, aliphatic petroleum fractions, particularly
paraffin waxes and cracked and chlorinated analogs and
hydrochlorinated analogs thereof, white oils, synthetic
alikeness such as those produced by the Ziegler-Natta process
(e.g., polyethylene) greases) and other sources known to
35 those skilled in the art. Any unsaturation in the R groups
may be reduced or eliminated by hydrogenation according to
procedures known in the art before the nitration step
described hereafter
~58~
As used herein, the term "hydrocarbon-based"
denotes a group having a carbon atom directly attached to
the remainder of the molecule and having a predominantly
hydrocarbon character within the context of this invention.
Therefore, hydrocarbon-based groups can contain up to one
non-hydrocarbon radical for every ten carbon atoms provided
this non-hydrocarbon radical does not significantly alter
the predominantly hydrocarbon character of the group, Those
skilled in the art will be aware of such radicals, which
10 include, for example, hydroxyl, halo (especially sheller and
Lowry), alkoxyl, alkyd Marquette, alkyd sulfoxy, etc.
Usually, however, the hydrocarbon-based groups R are purely
hydrocarbyl and contain no such non-hydrocarbyl radicals.
The hydrocarbon-ba~ed groups R are substantially
15 saturated. By substantially saturated it is meant that the
group contains no more than one carbon-to-carbon unsaturated
bond for every ten carbon-to-carbon single bonds present.
Usually, they contain no more than one carbon-to-carbon non-
aromatic unsaturated bond for every 50 carbo~-to-carbon
20 bonds present.
The hydrocarbon-baqed groups of the amino phenols
of this invention are also substantially aliphatic in
nature, that is, they contain no more than one non-aliphatic
moiety (cycloalkyl, cycloalkenyl or aromatic) group of six
25 or less carbon atoms fox every ten carbon atoms in the R
group. Usually, however, the R groups contain no more than
one such non-aliphatic group for every fifty carbon atoms,
and in many cases, they contain no such non-aliphatic groups
at all; that is, the typical R groups are purely aliphatic.
30 Typically, these purely aliphatic R group are alkyd or
alkenyl groups.
Specific examples of the substantially saturated
hydrocarbon-based R groups are the following:
a tetra(propylene) group
a tri(i~obutene) group
a tetracontanyl group
a henpentacontanyl group
~23~ 335i
-12-
a mixture of polyethylene propylene groups of
about 35 to about 70 carbon atoms
a mixture of the oxidativeIy or mechanically
degraded polyethylene propylene groups of
about 35 to about 70 carbon atom
a mixture of poly(propylene/l-hexene) groups of
about 80 to about 150 carbon atoms
a mixture ox poly~isobutene) group having between
20 and 32 carbon atoms
a mixture of poly(isobutene) groups having an
average of 50 to 75 carbon atoms
A preferred source of the group R are poly(isobutene)s
obtained by polymerization of a C4 refinery stream having a
butane content of 35 to 75 weight percent and isobutene
15 content of 15 to 60 weight percent in the presence of a
Lewis acid catalyst such a aluminum trichloride or boron
trifluoride. These polybutenes contain predominantly
(greater than 50% of total repeating units) isobutene
repeating units of the configuration
SHEA
- SHEA C -
C~3
The attachment of the hydrocar~on-based group R to
the aromatic moiety An of the amino phenols of this invent
lion can be accomplice by a number of techniques well
known to those skilled in the art. One particularly suite
25 bye technique is the Friedel-Cra~ts reaction, wherein an
olefin (e.g., a polymer containing an ole~inic bond), or
halogenated or hydrohalogenated analog thereof, is reacted
with a phenol. The reaction Occur in the presence of a
Lewis acid catalyst (e.g., boron trifluoride and its come
30 plexus with ethers, phenols, hydrogen fluoride, etc.,aluminum chloride, aluminum bromide, zinc dichlorides etch).
Methods and conditions for carrying out such reactions are
well known to those skilled in the art. See, for example,
isle
-13-
the discussion in the article entitled, "Alkylation of
Phenols" in "Kirk-Othmer Encyclopedia of Chemical Tech-
neology", Second Edition Vol. 1, pages 894-~95l Intrusions
Publishers, a division of John Wiley and Company, NAY.,
1963. Other equally appropriate and convenient techniques
for attaching the hydroearbon-hased group R to the aromatic
moiety An will occur readily to those skilled in the art.
The amino phenols of this invention contain at
least one of each of the following subs~i~uents: a hydroxyl
10 group, an R group as defined above, and a primary amine
group, -NH2. Each of the foregoing groups must be attached
to a carbon atom which is a part of an aromatic nucleus in
the An moiety. They need not, however t each be attached to
the same aromatic ring if more than one aromatic nucleus is
15 present in the An moiety.
In a preferred embodiment, the amino phenols of
this invention contain one each of the foregoing substitu-
ens it a, b and c are each 1) and but a single aromatic
ring, most preferably Bunsen. This preferred class of
20 amino phenols can be represented by the formula
OH
(NH2)1-2
Al l IT (R")z
I/
wherein the R' group it a substantially saturated hydra-
carbon-based group of about 30 to about 400 aliphatic carbon
atoms located ortho or pane to the hydroxyl group, R" is a
25 lower alkyd, lower alkoxyl, nitxo group or halogen atom and
z is 0 or 1. Usually z is 0 and R' is a substantially
saturated, purely hydrocarbyl aliphatic group. Often R' is
an alkyd ox alkenyl group pane to the -OH substituent.
Often there is but one amino group, -NOAH, in these preferred
30 amino phenols but there can be two.
In a still more preferred embodiment of this
invention, the amino phenol is of the formula
I
OH
NH2
wherein R' is derived from homopolymerized or inter polymer-
iced Clue l-olefins and has an average of from about 30 to
about 400 alipha~ic carbon atom and R" and z are as defined
above. Usually R' is derived from ethylene, propylene,
battalion and mixtures thereof. T~plcally, it is derived
from polymerized isobuteneO Often R' has a least about 50
aliphatic carbon atoms and z is 0.
The amino phenol of the present invention can be
10 prepared by a number of ~nythetic routes. These routes can
vary in the type reactions used and the sequence in which
they are employed. For example, an aromatic hydrocarbon,
such as Bunyan, can be alkylated with an alkylating agent
such as a polymeric olefin to form an alkylated aromatic
15 intermediate. This intermediate can then be nitrated, for
example, to form a pollinator intermediate. The pollinator
intermediate can in turn be reduced to a Damon, which can
then be diazotized and reacted with water to convert one of
the amino groups into a hydroxyl group and provide the
20 desired amino phenol. Alternatively, one of the vitro
group in the pollinator intermediate can be converter to a
hydroxyl group through fusion with caustic to provide a
hydroxy-ni~ro alkylated aromatic which can then be reduced
to provide the desired amino phenol.
Another useful route to the amino phenols of this
invention involves the alkylation of a phenol with an
ole~inic alkylating agent to form an alXylated phenol. This
alkylated phenol can then be nerd to form an inter
mediate vitro phenol which can be converted to the desired
30 amino phenols by reducing at least some of the vitro groups
to amino groups.
3 S
~15-
Techniques for alkylating phenols are well known
to those skilled in the art as the above-noted article in
Kirk-Othmer "Encyclopedia of Chemical Technology" demon-
striates. Techniques for nitrating phenols are also known.
See, for example, in Kirk Other "Encyclopedia of Chemical
Technology", Second Edition, Vol. 13, the article entitled
"Nitrophenols", page 888 en seq., as well as thy treatises
"Aromatic Substitution; Nitration and Halogenation" by Pi B.
D. De La Mare and J. H. Rudy N. Y., Academic Press, 1959;
10 "Nitration and Aromatic Reactivity" by J. G. Hogged, London
Cambridge University Press t 1961; and "Thy Chemistry of the
Vitro and Nutrias Group", Henry Fever, Editor, In~erscience
Publishers, NAY., 1969.
Aromatic hydroxy compounds can be nitrated with
15 nitric acid, mixtures of nitric acid with acids such as
sulfuric acid or boron trifluoride, nitrogen tetraoxide,
nitronium tetrafluoroborates and azalea nitrates. generally,
nitric acid ox a concentration of, for example, about 30-90%
is a convenient nitrating reagent. substantially inert
20 liquid delineate and solvents such as acetic or butyric acid
can aid in carrying out the reaction by improving reagent
contact.
Condition and concentrations for nitrating
hydroxy aromatic compounds are also well known in the art
25 For example, the reaction can be carried out at temperatures
ox about -15C. to about 150C. Usually nitration is con-
veniQntly carried out between about 25-75C.
Generally, depending on the particular nitrating
agent about 0.5-4 moles of nitrating agent is used for every
30 mote of aromatic nucleus present in the hydroxy aromatic
intermediate to be nitrated. If more than one aromatic
nucleus is present in the An moiety, the amount of nitrating
agent can be increased proportionately according to the
number of such nuclei pronto. For example, a mole of
35 naphthalene-based aromatic intermediate has, for purposes of
this invention, the equivalent of two "single ring" aromatic
nuclei so that about 1-4 moles of nitrating agent would
~L2~3S
- 16 -
generally be used. When nitric acid is used as a nitrating agent
usually about 1.0 to about 3.0 moles per mole of aromatic nucleus
is used. Up to about a 5-molar excess of nitrating agent (per
"single ring" aromatic nucleus) may be used when it is desired to
drive the reaction forward or carry it out rapidly.
Nitration of a hydroxy aromatic intermediate generally takes
0.25 to 24 hours, though it may be convenient to react the
nitration mixture for longer periods, such as 96 hours.
Reduction of aromatic vitro compounds to the corresponding
amine is also well known. See, for example r the article
entitled lamination by Reduction" in Kirk-Othmer "Encyclopedia
of Chemical Technology", Second Edition Vol. 2, pages 76-99.
Generally, such reductions can be carried out with, for example,
hydrogen, carbon monoxide or hydrazine, (or mixtures of same) in
the presence of metallic catalysts such as palladium, platinum
and its oxides, nickel, copper cremate, etc. Co-catalysts such
as alkali or alkaline earth metal hydroxides or amine (including
amino phenols) can be used in these catalyzed reductions. The
reduction of the amino phenols useful for the purposes of this
invention can be carried out by hydrazine reduction with or
without a catalyst as described in Canadian Pat. No. 1,096,887.
Reduction can also be accomplished through the use of
reducing metals in the presence of acids, such as Hydrochloric
acid. Typical reducing metals are zinc, iron and tin, salts of
these metals can also be used.
Vitro groups can also be reduced in the Xenon reaction,
which is discussed in "Organic Reactions", Vol. 20, John Wiley &
Sons, NAY., 1973, page 455 et seq. Generally, the Xenon
reaction involves reduction of a vitro group with diva lent
negative sulfur compounds, such as alkali metal sulfides,
polysulfides and hydrosulfides.
Lo
~17-
The vitro groups can be reduced by electrolytic
action; see, for example, the lamination by Reduction"
article, referred to above.
Typically the amino phenols of this invention are
obtained by reduction of Nat phenols with hydrazine such
as discussed above. This rewaken it generally carried out
in the absence of a catalyst a temporaries of about 50-
250C., typically, about 100 200C. The reaction time for
reduction usually Aries between about 2-24 hours. Sub-
10 staunchly inert liquid delineates and solvents, such as
ethanol, hexane, cyclohexane~ naphtha, mineral oil, etc.,
can be used to facilitate the reaction. The amino phenol
product is obtained by well-known techniques such as disk
tillation, filtration, extraction, and so forth.
the reduction is carried out until at least about
50~, usually about 80%, ox the vitro groups present in thy
vitro intermediate mixture are converted to amino groups.
The typical route Jo the amino phenols ox this
invention just described can be summarized as
(I) nitrating with at least one nitrating agent
at least one compound of the formula
(OH)
I c
c An
wherein R is a substantially saturated hydrocarbon-based
group of at least 10 aliphatic carbon atoms; a and c are
25 each independently an integer of 1 up to three times the
number ox aromatic nuclei present in An with the proviso
that An contains at least one carbon atom which is part of
the axiomatic nucleus and which is bonded directly to a
hydrogen atom and the sum ox a and c does no exceed the
30 remaining unsatisfied valences of An; and An is an aromatic
moiety having 0 to 3 optional substituents selected from the
group consisting of lower alkyd, lower alkoxyl~ vitro, and
halo, or combinations ox two or more optional sub~tituents,
with the proviso that when An is a Bunsen having only one
- 18 - I
hydroxyl and one R substi~uent, the R substitu~nt is ortho or pane
to said hydroxyl substituent, to form a first reaction mixture
containing a vitro intermediate, and (II) reducing at least about
50% of the vitro groups in said first reaction mixture to amino
groups.
Usually this means reducing at least about 50~ of the vitro
groups to amino groups in a compound or mixture of compounds of
the formula
(Icky
c An (Nub
wherein R is a substantially saturated hydrocarbon-based
substitutent of at least 10 aliphatic carbon atoms; a, b and c
are each independently an integer of 1 up to three times the number
of aromatic nuclei present in An with the proviso that the sum of
a, b and c does not exceed the unsatisfied valences of An; and An
is an aromatic moiety having 0 to 3 optional substituents selected
from the group consisting of lower alkyd, lower alkoxyl, halo, or
combinations of two or more of said optional substituents; with
the proviso that when An is a Bunsen nucleus having only one
hydroxyl and one R substituent, the R substituent is ortho or pane
to said hydroxyl substituent.
The amino phenols useful for the purposes of this invention
and processes for their preparation are described in US. Patent
4,100,082.
I (B) The Carboxylic Derivative Compositions and
Post-Treated Carboxylic Derivative Compositions
The Substituted Succinic Assaulting Agent
The substituted succinic assaulting agent (hereinafter
referred to as the "assaulting agent") useful for making composition
(B) 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 .....
335
--19
referred to herein, for convenience, as the "substituent
groups)" and is derived from a polyalkene. The polyalkene
from which the substituted groups are derived is character-
iced by a My (number average molecular weight) value of from
1200 to about 5000 and a Mom value of about 1.5 to about
I
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
1 0 I c c 1 c x
I J
wherein X and X' are the same or different provided at least
one ox X and X' is such that the assaulting agent can lung-
lion as carboxylic assaulting agents. That is, at feast one
of X and X' must be such that the assaulting agent can
I esterify alcohols, form asides or amine salts with ammonia
or amine, form metal salts with reactive metals ox best-
gaily reacting metal compounds, and otherwise function a a
conventional carboxylic acid assaulting Agents. Transistor-
ligation and tran~amidatisn reactions are considered, for
20 purposes of this invention, as conventional assaulting
reactions.
Thus, X Andre X' is usually OH, -O-hydrocarbyl,
-O My where My represents one equivalent of a metal ammo-
I'm or amine cation, -NOAH -Of, Brie, and together, X and X'
25 be -O- so as to form the android. 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
remaining group prom entering into acylation reactions.
Preferably, however, X and X' are each such that both
I carboxyl functions of the succinic group (i.e., both I
and -C-X') can enter into acylation reactions.
~2~L5~3~
-20~
One ox the unsatisfied valences in the grouping
-C-C- of the succinic group structure hereinabove worms a
carbon-to-carbon bond with a carbon atom in the substituent
group While the other such unsatisfied valence may be
satisfied by a similar bond with the same or aifferen~
substituent group, all but the said one such valence is
usually satisfied by hydrogen; it -H.
The substituted ~uccinic assaulting agents are
characterized by the presence within their structure of at
10 least 1,3 succinic groups or each equivalent weigh of
substituent groups. For purposes of this invention, the
number of equivalent weights of substituent groups it deemed
to be the number corresponding Jo the quotient obtained by
dividing the My value of the polyalkene from which the
15 subsequent it derived into the total weight ox the siesta-
tent groups present in the assaulting agents. Thus, if a
assaulting agent it characterized by a total weight of sub-
stituent group of 40~000 and the My value for the polyalkene
from which the ~ubstituent groups are derived is 2000, then
20 what assaulting agent is characterized by a total of 20
(40,000/2000 = 203 equivalent weights of ~ubstituent groups.
Therefore, that particular assaulting agent must also be
characterized by the presence within its structure of a
least 26 succinic groups to meet one of the requirements of
25 the succinic assaulting agents of this invention.
nether requirement for the assaulting agents
within this invention it that the substituent groups must
have been derived from a polyalkene characterized by a Mom
value of about 1.5 to about 6, My being the conventional
30 symbol representing weight average molecular weight.
Before proceeding, it should be pointed out that
the My and My values for polyalkene, for purposes of this
invention, are determined by gel permeation chromatography
(GPC). This separation method involves column chxomatogra-
35 pry in which the stationary phase is a heteroporous, sol-
vent-swollen polymer network of a polystyrene gel varying in
permeability over many orders of magnitude. As the liquid
33S
-21-
phase (te~rahydrofuran) containing the polymer sample passes
through the gel, the polymer molecule diffuse into all
parts of the gel not mechanically barred Jo them. The
smaller molecules "permeate' more completely and spend more
5 time in the column; the larger molecules "permeate" less and
pass through the column more rapidly. The My and ow 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
10 standards of polymers of known molecular weight disturb-
lion. For purposes of this invention a series of free-
shunted polymers of isobutene, polyisobut~ne being the
preferred embodiment, is used as the calibration standard.
For example, the My values disclosed herein are
15 obtained using a Water Associates model 20Q gel permeation
chromatography equipped with a 2.5 ml siphon, a 2 ml sample
injection loop and four stainless steel columns 7.8 mm in
r diameter by 120 centimeters long a Each column was packed
A with STYROGEL~ a commercially available, rigid, porous gel
20 (in particle form) of cros~linked styrene/divinyl Bunsen
copolymers. These gels are also obtained from Waters
Associates. The first column contains STYROGEL having a
retention volume of AYE. The second and third column
contain 5TYROGEL having a retention size of 500 A. The
25 fourth column contains STYROGEL having a retention volume of
60 A. The first column is connected to the sample loop with
stainless steel tubing, 83.8 cm long. The first column is
connected to the second with a 2.3 cm length of the stain-
less steel tubing. The second and third columns are each
I connected by 10.2 cm lengths of tubing. The fourth column
is connected to the detector by a 25.4 cm length of tubing.
All the connecting tubing is 1.6 cm in diameter.
Calibration standards are prepared by dialyzing a
polyisobutylene sample having a specific gravity at ~0F.
35 (15 5C.) of 0.89 and a viscosity at 210F. t99C.) of 12.50
SUP. A sample of this polymer is fractionated by dialysis
using a rubber membrane and a sixty extraction apparatus
do ok
SUE
-22-
with refluxing petroleum ether as solvents. Eleven free-
lions are taken; one sample each hour for the first seven
hours, then three samples each four hours, and finally ha
residue which did not permeate the membrane over a four-hour
period and the My of each was measured using vapor phase
osmometry and Bunsen solvent
Each calibration sample is then chromatographedO
Approximately 7 my of sample is weighed into a small bottle
which is then filled with 4 ml of reagent grade tetrahydro-
10 Furman. The sealed bottle is stored overnight before an-
aliases. The afore-described liquid phase chroma~ograph is
degassed at 5gC. and a flow rate of 2.0 ml per minute of
tetrahydrofuran maintained. Sample pressure is 180 psi and
the reference pressure 175 psi. The retention time of each
15 sample is measure. The My of each calibration sample is
calculated from the My assuming the relationship 2 My = ow.
The retention times and My for each sample, which are shown
in the following table, are plotted to provide a standard-
ration curve. The My and My for sample polymers is then
20 obtained using this curve and the methods described in
"Topics in Chemical Instrumentation, Volume XXIX, Gel
Permeation Chromatography" by Jack Cages published in The
Journal of Chemical Education, Volume 43, numkaxs 7 and 8,
~1966).
Polyalkenes having the My and My values discussed
above are known in the art and can be prepared according to
conventional procedures. Several such polyalkenes, en-
specially polybutenes, are commercially available.
-23-
aye
Rut* My Rut* My Rut* My
42Z40 40 ~38 50 229
31 26400 41 -539 51 216
32 16~85 42 453 52 202
33 1~780. 43 400 53 18
34 6710 44 361 54 178
4180 45 33~ 55 167
36 2640 I 304. 56 156
37 1756 47 I
38 1200 48 264
39 865 49 2~6
Again, turning to the characteristics of the
succinic assaulting agents of this invention, the succinic
15 groups will normally correspond to the formula
O
- I - C - R
. I .
SHEA - I -R2
I
wherein Al and R2 are each independently Selected from the
group consisting of -OH, -Of, Oilier alkyd, and when taken
together, Al and R2 are O . In the latter case, the
_ _
art - retention time in units of number of times
siphon (2.5ml) empties The siphon empties every 2.5
minutes.
~5~3~i
-24-
succinic group is a succinic android group. ~11 the
succinic groups in a particular assaulting agent need not be
the same, but they can be the: same. Preferably, the sue-
cynic groups will correspond to
- oh_ c ox ; OH - C
C~2 - C OH , ¦ O
O COOK
0
and mixtures thereof. Providing assaulting agents wherein
the sexing groups are the same or different is within the
ordinary skill of the art and canoe accomplished through
conventional procedures such as treating the assaulting
10 agents themselves (for example, hydrolyzing the android to
the free acid or converting the free acid to an acid color-
ire with thinly chloride) and/or selecting the appropriate
malefic or fumaric reactants,
As previously mentioned, the minimum number of
15 succinic groups for each equivalent weight of substituent
group is 1.3. Preferably, however, the minimum will be 1.4;
usually lo to about 3.5 succinic groups for each equivalent
weight of ~ub~tituent group. An especially preferred
minimum is at least 1.5 ~uccinic groups for each equivalent
20 weight of ~ubstituent group. A preferred range based on
this minimum 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 sub-
stituted succinic assaulting agents of this invention can be
25 represented by the symbol
Al ,. (X2 ) y
where Al represents one equivalent weight of substituent
group, X2 represents one succinic group, as discussed above,
and y it a number equal to or greater than 1.3, ivy
30 1.3. The more preferred embodiments of the invention could
be similarly represented by, for example, letting Al and X2
I 33~i
-25-
represent more preferred substituent groups and succinic
groups, respectively, as disc sod 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
(yo-yo); and y equals 1.5 to about 3.5 yo-yo.
In addition to preferred substituted succinic
groups where the preference depends on the number and
identity ox succinic groups for each equivalent weight of
10 substituent group, 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 My, for example, a
minimum of about 1200 is preferred with an My value in the
15 range of from about 1200 to about 3200 also being preferred
A more preferred My value is one in the range of from about
1500 to about 2800. A most preferred range of My values is
from about lS00 to about 2400. With polybutenes, an en-
specially preferred minimum value or My it about 1700 and an
20 especially preferred range of My values is from about 1700
to about 2400.
As to the values of the ratio Mom, there are
also several preferred values. A minimum Mom value of
about I 8 it preferred with a range of values of about 1.8
25 up to about 3.5 also being preferred. A still more pro-
furred monomania value of Mom is about 2.0 with a preferred
range of values of from about 2.0 to about 3.4 also being a
preferred range. An especially preferred minimum value of
Mom is about 2.5 with a range of values of about 2.5 to
30 about 3.2 also being especially preferred.
Before proceeding to a further discussion of the
polyalkenes from which the substituent groups are derived,
it should be pointed out that these preferred characters-
tics of the assaulting agents are, for lack ox better terming
35 olagy to describe the situation contemplated ho this in-
mention, intended to be understood as being both independent
and dependent. They are intended to be independent in the
5~3~
-26-
sense that, for example, a preference for a minimum of I
or 1.5 succinic group per equivalent weight of substituent
groups is no tied to a more preferred value of My or Mom.
They axe 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 My
and/or Mom, the combination of preferences does in fact
describe still further more preferred embodiment of the
invention Thus, the various parameters are intended to
stand alone with respect to the particular parameter bring
discussed but can also ye combined with other parameters to
identify further preference. This some concept is intended
to apply throughout the specification with respect to the
description of preferred values, ranges, ratios, reactants,
15 and the like unless a contrary intent is clearly demonstra-
ted or apparent.
The polyalkene~ from which the substituent groups
in (B) are derived are homopolymers and inter polymers of
polymerizable olefin monomers of 2 to about 16 carbon atoms;
20 usually 2 to about 6 carbon atoms. The inter polymers are
those in which two or more olefin monomers are inter polymer-
iced 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, "inter-
25 polymer' 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 polyp
alikeness from which the ~ubstituent groups are derived are
of tell conventionally referred to as "polyolefin(s)".
The olefin monomers from which the polyalkenes are
derived are polymerizable Olin 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, buttonhole, isobutene, and octene-l or
polyolefinic monomers (usually diolefinic monomers) such as
butadiene-1,3 and isoprene.
~51~35
-27-
They Olin monomers are usually polymerizable
terminal olefins, that is, olefins characterized by the
presence in their structure of the group C=C~2. ivory,
polymerizable internal olefin monomers (sometimes referred
to in the patent literature as medial olefins) characterized
by the presence within their structure of the group
COO C__ can also be use to form the polyalkenes. When
internal olefin monomers are employed, they normally will be
employed with terminal olefins to produce polyalkenes which
10 era inter polymers. For the 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 it
piperylene) is deemed to be a terminal olefin for purpose
15 Of this invention.
White the polyalkenes from which the substituent
groups of the assaulting agents are derived generally are
hydrocarbon polyalkene~, they can contain non-hydrocarbon
group such a lower alkoxy, lower alkyd Marquette, hydroxy,
20 Marquette, ox (i.e., 11 as in veto an alluded groups; e.g.,
O O
~C-~-C=~and ~C-C-H), vitro, halo, cyan, carboalkoxy (i.e.,
-~-O-alkyl where "alkyd" is usually lower alkyd) alkanoyloxy
(i.e., alkyd -C-O- where alkyd is usually lower alkyd) and
the like provided the non-hydrocarbon substituents do not
substantially interfere with formation of the assaulting
agents of this invention. When present, such non-hydro-
carbon 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,
30 it is apparent that the olefin monomers from which the
` polyalkenes are made can also contain such substituents~
Normally, however, as a matter of practicality and expense,
the olefin monomers and the polyalkenes will be free from
non-hydrocarbon groups, except Shari groups which usually
~5~3~;i
I
facilitate the formation of the substituted succinic cay-
feting agents ox this invention. (us used herein, the text
"lower" when used with a chemical group such as in "lower
alkyd" or "lower alkoxy" is intended to describe groups
having up to and including seven carbon atoms)
Although the polyalkenes may include aromatic
groups (especially phenol groups and lower alkyd- and/or
lower alkoxy-substituted phenol groups such as portrait-
butyl)-phenyl~ and cycloaliphatic groups such as would be
obtained from polymerizable cyclic olefins or cycloaliphatic
substituted-polymerizable cyclic olefins t the polyalkenes
usually will ye tree from such groups Nevertheless, polyp
alikeness derived from inter polymers of both Dennis and
styrenes such as butadiene-1,3 and styrenes or portrait-
butyl)-styrene are exceptions to this generalization.
Again, because aromatic an cycl~aliphatic group 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
preference for aliphatic, hydrocarbon polyalkenes free from
aromatic and cycloaliphatic groups (other than the dine-
styrenes inter polymer exception already noted). Within this
general preference, there is a further preference for
polyalkenes which are derived from the group consisting of
homopolymers and inter polymers of terminal hydrocarbon
olefins ox 2 to about 16 carbon atoms. This further prefer-
once is qualified by the proviso that, while inter polymers
of terminal olefins are usually preferred, inter polymers
optionally containing up to about 40% of polymer units
derived prom internal olefins of up to about 16 carbon atoms
are also within a preferred group. A more pre~errPd class
of polyalkenes are those selected from the group consisting
of homopolymers and inter polymers of terminal olefins of 2
to about 6 carbon atoms, more preferably 2 to 4 carbon
atoms. However, another preferred class of polyalkenes are
Sue
-29-
the latter more preferred posy lkenes optionally containing
up to about 25% of polymer unit derived from internal
olefins of up to about 6 carbon atoms.
Specific examples of terminal and internal olefin
monomers which can be used to prepare the polyalkenes
according to conventional, well-known polymerization tech-
piques include ethylene; propylene; buttonhole; button;
isobutene; pentene-l; hexene-l; heptene-l; octene-l; nonene-
l; disannul; pontoon; propylene-tetramer; diisobutylene;
isobutylene triter; butadiene-1,2; butadiene-1,3; pent-
Dunn; pentadiene-1,3; pentadiene-1,4; isoprene; hex-
Dunn; 2-chloro-butadiene-1,3; 2~mekhyl-heptene-1; 3
cyclohexyl-butene-l; 2-methyl-5-propyl-hexenerl; octane;
3,3-dimethyl-pentene~ Turin; 2,4-dichloro styrenes
divinylbenzene; vinyl acetate; ally alcohol; l-methyl-vinyl
acetate; acrylonitrile; ethyl acrylate; methyl methacrylate;
ethyl vinyl ether; and methyl vinyl kitten. I these, the
hydrocarbon polymerizable monomer are preferred and of
these hydrocarbon monomers, the terminal olefin monomers are
particularly preferred.
Specific examples of polyalkenes include polyp
propylene, polybutenes, ethylene-propylene copolymers,
styrene-isobutene copolymers, isobutene-butadiene-1,3
copolymers, propene-isoprene copolymers, isobutene sheller-
prone copolymers, isobutene-(para-methyl)styrene copol~mers,
copol~mers of hexene-l with hexadiene-1,3, copolymers of
oatene-l with hexene-l, copolymers of heptene~l with pen-
tunnel, copolymers of 3-methyl-butene-1 with octene-l,
copolymers ox 3,3-dimethyl pentene-l with hexene-l, and
terpolymers of i30butene, styrenes and pip~rylene. More
specific examples of such inter polymers include copolymer of
95% (by weight) of isobutene with 5% (by weight) of Turin;
terpolymer of 98% of isobuten~ with 1% of piperylene and 1
of chloroprene; terpolymer of 95% of isobutene with 2% of
buttonhole and 3% of hexene~l; terpolymer of 60~ of isobutene
with 20~ of pentene-l and 20% of octene-l; copolymer of 80%
of hexene-l and 20% of heptene-l; terpolymer of 90% of
-30-
isobutene with I ox cyclohexene and I of propylene; and
copolymer of 80% ox ethylene Rand 20~ ox propylene A pro-
furred source of polyalkenes are the polytisobutene~s
obtained by polymerization of I refinery stream having a
butane content of about 35 Jo about 75 percent by weight and
: an isobutene content of about pa to about 60 percent by
weigh in the presence of a Lewis acid catalyst such as
aluminum trichloride or boron trifluoride. These polyp
butanes contain predominantly greater than at least about
50% of the total repeating units) of isobutene repeating
units of the configuration
IH3
_ SHEA - f
SHEA
Obviously, preparing polyalkenes as described
above which meet the various criteria for My and Mom 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 a stripping (including vacuum stripping) a
very light end Andre oxidatively or mechanically degrading
high molecular weight polyalkene Jo produce lower molecular
weight polyalkenes can also be used
In preparing the assaulting agents of this invent
lion, one or more of the above-described polyalkenes is
reacted with one or more acidic reactants selected from the
group consisting of m~leic or fumaric reactants of the
general formula
O o
If 11
X-C-CH=C~-C-X'
~S~3S
I
wherein X and X' are as defined hereinbeforeO Preferably
the malefic an fumaric reactants will be one or more come
pounds corresponding to the formula
O
I CH=CH ~=R2
wherein Al and R2 are as previously defined herein. Ordain-
aridly the malefic or fumaric reactants will be malefic acid,
fumaxic acid, malefic android, or a mixture of two or more
of these The malefic reactants are usually preferred 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-
stituted succinic assaulting agents of the present invention.
The especially preferred reactants are malefic acid, malefic
android, and mixtures of these. Due to availability and
ease of reaction, malefic android will usually be employed.
The one or more polyalkenes and one or more malefic
or fumaric reactants can be reacted according to any of
several known procedures in order to produce the assaulting
agents useful in the present invention. Basically, the
procedures are analogous to procedures used to prepare the
high molecular weight succinic androids and other equiva-
lent succinic assaulting analog whereof except that the
polyalkenes (or polyolefins) of the prior art are replaced
with the particular polyalkenes described above and the
amount of malefic or fumaric reactant used must be such that
there is at least 1.3 su~cinic groups for each equivalent
weigh ox the substituent group in the final substituted
succinic assaulting agent produced.
The process presently deemed to be best for
preparing the substituted succinic assaulting agents of this
invention from the standpoint of efficie~y, overall economy,
and the performance of the acylatiny agents thus produced,
as well as the performance ox the derivatives whereof, is
the so-called "one-step" process. This process is described
l35
- 32 -
in US. Patents 3t215,707 and 3,231,587.
Basically, the one-step process involves preparing a
mixture of the polyalkene and the malefic reactant it the
malefic and fumaric reactants of the formula
O O O O
X-C-CH=CH-C~X' and Rl-C-CH=CH-C-R2~
wherein X, X', Al and R2 are as previously defined containing
the necessary amounts of both to provide the desired assaulting
agents of this invention. This means that there must be at least
1.3 moles of malefic reactant for each mole of polyalkene in order
that there can be at least 1.3 succinic groups for each
equivalent weight of substituent groups. Chlorine is then
introduced into the mixture, usually by passing chlorine gas
through the mixture with agitation, while maintaining a
temperature of at least about 1~0C.
A variation on this process involves adding additional
malefic reactant during or subsequent to the chlorine introduction
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 malefic reactant are first mixed
before the introduction of chlorine
Usually, where the polyalkene is sufficiently fluid at
1~0C., and above, there is no need to utilize an additional
substantially inert, normally liquid solvent/diluent in the one-
I step process. However, if a solvent/diluent is employed, it ispxeferably one that resists chlorination. Again, the polyp and
per-chlorinated and/or -fluorinated alikeness, 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 .....
AYE,
:~2~S1~3S
I
maximum tltilization of the chlorine, the rate should be
about the same a the rate of consumption of chlorine in -the
course of the reaction. When the introduction rate of
chlorine exceeds the rate ox consumption, chlorine is
evolved from the reaction mixture It is often advantageous
to use a closed system including super atmospheric pressure,
in order to prevent loss of chorine so as to maximize
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 it usually between
about 160C~ and about 2203C. Higher temperatures such as
250C. or even higher may be used but usually with little
advantage In fact, temperature in excess of 220C. are
often disadvantageous with respect to preparing the par-
titular assaulting agents useful for this invention because
they tend to "crack" the polyalkenes (that is, reduce their
molecular weight by thermal degradation) and/or decompose
the malefic reactant. For this reasons, maximum temperatures
of about 200 to about 210C. are normally not exceeded.
The upper limit of the useful temperature in the one-step
process it determined primarily by the decomposition point
of the components in the reaction mixture inducing the
reactants and the desired products. The decomposition point
is that temperature at which there is sufficient decompo-
session of any reactant or product such as to interfere with
the production of the desired products.
In the octopi process, the molar ratio of malefic
reactant to chlorine is such what there is at least about
one mole ox chlorine or each mole of malefic 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 chorine, is utilized in
order to offset any loss of chlorine from the reaction
mixture. Laxer amounts of excess chlorine may be use but
do not appear to produce any beneficial results.
~2~83S
-34-
As mentioned previously, the molar ratio of
polyalkene to malefic reactant it such that therm is at least
about 1.3 moles of malefic reactant for each mole of posy
alkeneY This is necessary in order that there can be at
least 1.3 succinic groups per equivalent weight of sub-
stituent group in the product. Preferably, however, an
excess of malefic reactant is used. Thus, ordinarily about a
5% to about 25% excess of malefic rear ant will be used
relative to that amount necessary to provide the desired
number of succinic groups in the product.
. The carboxylic derivative compositions useful for
the purposes of this invention are prepared by the process
comprising reacting one or more substituted succinic azalea-
tying agents with a reactant selected from the group con-
sitting of (a) an amine characterized by the presence within its structure of at least one H-N group, (b) an alcohol,
(c) a reactive metal or reactive metal compound, and (d) a
combination of two or more of (a) through (c), the coupon-
ens of (d) being reacts with said assaulting reagents
simultaneously or sequentially in any order.
The amine, (a), useful for reacting with the
assaulting agent useful for this invention are toss kirk-
terraced by the presence within their structure of at least
one H-N - _ group can be a monoamine or polyamide compound.
US For purposes of this invention, hydrazine and substituted
hydrazines containing up to three substituents are included
as amine suitable for prepaying carboxylic derivative
compositions. Mixtures of two or more amine can be used in
the reaction with one or more assaulting agents useful for
this invention. Preferably, the amine contains at least one
primary amino group (i.e., -NH2) and more preferably the
amine is a polyamide, especially a polyamide containing at
least two H-N - _ groups, either or both of which are
primary or secondary amine. the polyamides result in
carboxylic derivative compositions which are usually more
effective as dispersant/detergent additives, relative to
5~33~;
-35-
derivative compositions derived from monoamine. Suitable
monoamine and polyamides are described in greater detail
hereinafter.
Alcohol, (b), which can be reacted with the
assaulting agents useful for this invention include the
mandrake and polyhydric alcohols. Again, the polyhydric
alcohols are preferrer since they usually result in car-
boxlike derivative compositions which are more effective
dispersant/detergents relative to caxboxylic derivative
compositions derived from mandrake alcohols, Alcohols
suitable for use in this invention 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 assaulting agents. These metals and metal compounds are
described further hereinafter.
The Amine (a)
The monoamine and polyamides useful in this
invention 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., HEN-) or secondary amino
(i.e., H-N=) group. The amine can be aliphatic, cycle-
aliphatic, aromatic, or heterocyclic, including aliphatic-
substituted aromatic, aliphatic-substituted cycloaliphatic,
aliphatic-substituted aromatic t aliphatic-substituted
heterocyclic, cycloaliphatic-substituted aliphatic, cycle-
aliphatic-substituted aromatic, cycloaliphatic-3ubstituted
heterocyclic, aromatic-substituted aliphatic, aromatic-
substituted cycloaliphatic, aromatic-substituted hotter-
cyclic, heterocyclic-substituted aliphatic~ heterocyclic-
substituted cycloaliphatic, and heterocyclic-substituted
aromatic amine and may be saturated or unsaturated. If
unsaturated, the amine will be free from acetylenic unset
unction (i.e., -C-C-). The amine may also contain non-
hydrocarbon substituents or groups as long a these groups
do not significantly interfere with the reaction of the
~L2~5~335
-36
amine with the assaulting reagents of this invention. Such
non-hydrocarbon substitusnta an groups include lower alkoxy,
lower alkyd Marquette, vitro, interrupting groups such as -O-
and -S- (e . g ., as in such groups as -CH2C~2-X-CH2CH2-
where X is -O- or -S-).
With the exception of the branched polyalkylene
polyamide, the polyoxyalkyl~ne polyamides, and the high
molecular weight hydrocarbyl-substitu~ed amine described
more fully hereafter, the amine used in this invention
ordinarily contain less Han about 40 carbon atoms in total
and usually not more than about 20 carbon atoms in total.
Alipha~ic monoamine include mono-aliphatic and
di-aliphatic substituted amine wherein the aliphatic groups
can be saturated or unsaturate and straight or branched
chain. Thus, they are primary or secondary aliphatic
ammonias Such amine include, for example, moo- and at-
alkyl-substituted amine, moo- and do alkenyl-substituted
amine, and amine having one N alkenyl substituent and one
N-alkyl substituent and the like. The total number of
carbon atoms in these aliphatic monoamine will, as men-
toned before, normally not exceed about 40 and usually not
exceed about 20 carbon atoms. Specific examples of such
monoamine include ethyl amine, diethylamine, n-butylamine,
di-n-butylamine, allylamine, isobutylamine, cocoa mine,
stearylamine, laurylamine, methyllaurylamine, oleylamine, N-
methyl-octylamine, dodecylamine, octadecylamine, and the
like. Examples of cycloaliphatic-substituted aliphatic
amine, aromatic-substituted aliphatic amine, and hotter-
cyclic-substituted aliphatic amine, include 2-(cyclohexyl)-
e~hylamine, benzylamine, phenylethylamine, and furl-
propyl)amine~
Cycloaliphatic monoamine are those monoamine
wherein there is one cycloaliphatic substituent attached
directly to the amino nitrogen through a carbon atom in the
cyclic ring structure. Examples of cycloaliphatic moo-
amine include cyclohexylamines, cyclopentylamines, cycle-
hexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamine,
~2~5~
-37
dicyclohexylamines, and the like Example-s of aliphatic-
substituted, aromatic-substLtuted, and hete~ocyclic-sub-
stituted cycloaliphatic monoamine include propyl~substi-
tuned cyclohexylamine~, phenyl-~ubstituted cyclopentyl-
amine, and pyranyl-substituted cyclohexylamine~
Suitable aromatic amine include those monoamine
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 Bunsen) but can include fused aromatic rings,
especially those derived from naphthylene. Examples of
aromatic monoamine include aniline, di(para-methylphenyl)-
amine, naphthylamine, N-~n-butyl)anilinet and the like.
Examples of aliphatic-~ubstituted, cycloaliphatic-substi~
tuned, and he~erocyclic-subs~ituted aromatic monoamine are
para-ethoxyaniline, para-dodecylaniline/ cyclohexyl-sub-
stituted naphthylamine, and thienyl-substituted aniline.
Suitable polyamides are aliphatic, cycloaliphatic
and aromatic polyamides analogous to the above-described
monoamine 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 polyamides include N-aminopropyl-cyclohaxylamines, N-
N'-di-n-butyl-para-phenylene Damon, bis-(para-aminophenyl)-
methane, 1,4-diaminocyclohexana, and the like.
Heterocyclic moo- and polyamides can also be used
in making the substituted carboxylic acid assaulting agent
derivative compositions ox this invention. As used herein,
the terminology "heterocyclic moo- and polyamide" is
intended to describe those heterocyclic amine containing at
least one primary or secondary amino group and at least one
nitrogen as a heteroatom in the haterocyclic ring. However,
as long as there is present in the heterocyclic moo- and
polyamides at least one primary or secondary amino group,
the hetero-N atom in the ring can be a tertiary amino
nitrogen; that it, one that does not have hydrogen attached
directly to the ring nitrogen. Heterocyclic amine can be
~2~5~35
-38-
saturated or unsaturated and can contain various subset-
tents such as vitro, alkoxy, alkyd Marquette, alkyd, at-
Kenya, aureole, alkaryl, or aralkyl substituents. Generally,
the total number of carbon atoms in the subs~ituents will
5 not exceed about 20. Heterocyclic amine can contain
heteroatoms other than nitrogen, especially oxygen and
sulfur. Obviously whey can contain more than one nitrogen
he~eroatom. The five- and six-membered heterocyclic rings
are preferred.
among the suitable heterocyclics are assurance,
azetidinas, azolidines, twitter- and dodder pardons,
pyrolyze, insoles, piperidines, imidazoles, dip and twitter-
hydroimidazoles, piperazines, isGindoles, urines, morph-
links, thiomorpholine , N-aminoalkylmorpholines, N-amino-
alkylthiomorpholines, N-aminoalkylpiperazine~, N!N'-di-
aminoalkylpiperazines, aspens, assassins, assonance, aye-
cones and twitter-, dip and pPrhydro-derivatives of each of
the above and mixtures of two or more of these heterocyclic
amine. Preferred heterocyclic amine are the saturated 5-
and 6-membered heterocyclic amine containing only nitrogen,
oxygen and/or sulfur in the hotter ring, especially the
piperidines, piperazines, thiomorpholines, morpholines,
pyrrolidines, and the like. Piperidine, aminoalkyl-sub-
s-tituted piperidines, pipexazine, aminoalkyl-substituted
piperazines, morpholine, aminoalkyl-su~stituted morpholines,
pyrrolidine, and aminoalkyl-substituted pyxrolidines, are
especially preferred. Usually the aminoalkyl substituents
are substituted on a nitrogen atom forming part of the
hotter ring. Specific examples of such heterocyclic amine
include N-aminopropylmorpholine, N-aminoethylpiperazine, and
N,N'-di-aminoethylpiperazine.
ydroxyamines both moo- and polyamides, analogous
to those described above are also useful in this invention
provided they contain at least one primary or secondary
amino group Hydroxy-substituted amine having only ton-
tiara amino nitrogen such as in tri-hydroxyethyl amine, are
thus excluded as an amine, but can ye used as an alcohol as
~L5~33~
-39-
disclosed hereafter The hydroxy-substituted amine con-
template 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 amine
include ethanol amine, di-(3-hydroxypropyl)-amine, 3 hydroxy-
butyl-amine, 4-hydroxybutyl-amine, diethanolamine, Dow-
hydroxypropyl)-amine, ~-(hydroxypropyl)propylamine, No
hydroxyethyl)-cyclohexylamine, 3-hydroxycycl~pentylamine,
para-hydroxyaniline, N-hydroxyethyl piperazine, and the
like.
The terms hydroxyamine and amino alcohol describe
the same class or compounds and, therefore, can be used
interchangaab7y. Hereinafter, in the specification and
appended claims, the term hydroxyamine will be understood to
include amino alcohols as well as hydroxyamines.
Also suitable as amine are the aminosulfonic
acids and derivatives thereof corresponding to the general
formula:
arc N 3x ( Ray ) Ire
wherein R3 is -OH, -NH2, ONE, etc., Ray is a polyvalent
organic radical having a valence equal to zoo; Rub and I are
each independently hydrogen, hydrocarbyl, and substituted
hydrocarbyl with the proviso that at least one of Rub or Arc
is hydrogen per aminosulfonic acid molecule; x and y are
each integers equal to or greater than one From the for-
mute, it is apparent that each aminosulfonic reactant is
characterized by at least one HO = or HEN group and a
o
least one -~-R3 group. These sulfonic acids can be elf-
phatic, cycloaliphatic, or aromatic aminosulfonic acids and
the corresponding functional derivatives of the sulfa group.
Specifically, the aminosulfonic acids can be aromatic
aminosulfonic acids, that is, where Ray is a polyvalent
~2~5~35
- 40 -
aromatic radical such as phenylene where at least one -S-R3
o
group is attached directly to a nuclear carbon atom of the aromatic
radical. the aminosulfonic acid may also be a monomania aliphatic
sulfonic acid; that is, an acid where x is one and Ray is a
polyvalent aliphatic radical such as ethylene, propylene,
trim ethylene, and 2-methylene propylene. Other suitable amino-
sulfonic acids and derivatives thereof useful as amine in this
invention are disclosed in US. Patents 3l926,820; 3,029,250; and
3,367,864.
Hydrazine and substituted-hydrazine can also be used as amine
in this invention. At least one of the nitrogens in the hydrazine
must contain a hydrogen directly bonded thereto. Preferably there
are at least two hydrogen bonded directly to hydrazine nitrogen
and, more preferably, both hydrogen are on the same nitrogen.
The substituents which may be present on the hydrazine include
alkyd, alkenyl, aureole, aralkyl, alkaryl, and the like. Usually, the
substituents are alkyd, especially lower alkyd, phenol, and
substituted phenol such as lower alkoxy-substituted phenol or lower
alkyl-substituted phenol. Specific examples of substituted
hydrazines are methylhydrazine, N,N-dimethylhydrazine, NUN'-
dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine,
N-lpara-tolyl)-NI-(n-butyl)-hydrazine, N-(para-nitrophenyl)-
hydrazine, N-(para-nitrophenyl)-N-methylhydrazine, N/N'-di-(para-
chlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine, and the
I like.
The high molecular weight hydrocarbyl amine, both monoamine
and polyamides, which can be used as amine in this invention are
generally prepared by reacting a chlorinated polyolefin having a
molecular weight of at least about 400 with ammonia or amine.
Such amine and their methods of preparation are known in the art
and described, for example, in US. Patent 3,~75,554 and 3,438,757.
PA
S
- 41 -
All that is required for use of these amine is that they possess
at least one primary or secondary amino group.
- Another group of amine suitable for use in this invention
are branched polyalkylene polyamides. The branched polyalkylene
polyamides are polyalkylene polyamides wherein the branched group
is a side chain containing on the average at least one nitrogen-
bonded aminoalkylene
r Hi
tire-/ NN2 t R N R
group per nine amino units present on the main chain, for example,
1-4 of such branched chains per nine units on the main chain, but
preferably one side chain unit per nine main primary amino groups
and at least one tertiary amino group.
These reagents may be expressed by the formula:
H _ _
NH2 -(R Nix -[RN~RHl Z RN~2
NH2
_ _ Y
wherein R is an alkaline group such as ethylene, propylene,
battalion and other homology (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 preferably 0-1. The x and y units
may be sequential, alternative, orderly or randomly distributed.
The preferred class of such polyamides includes those of
the formula:
I
- 42 -
NH2 RUN I RN - (R-N - H
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,
battalion, etc. (straight chained or branched.
The preferred embodiments are presented by the following
formula:
H H
NH2 (CH2CH2 I CH2CH2 1 - (Chic 2 I - H
SHEA
NH2
15 (n = 1-3). _ _ n
The radicals in the brackets may be joined 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 Polyamides N-400
N-800, N-1200, etc. Polyamide N-400 has the above formula
wherein nil.
USE patents 3,200,106 and 3,259,578 disclose how to make
such polyamides and processes for reacting them with carboxylic
acid assaulting agents, and analogous processes can be used with
the assaulting reagents of this invention.
Suitable amine also include polyoxyalkylene polyamides,
e.g., polyoxyalkylene dominoes and polyoxyalkylene trimness,
having average molecular weights ranging from about 200 to 4000
and preferably from about 400 to 2000. Illustrative examples of
these polyoxyalkylene polyamides may be characterized by the
formulae:
NH~-Alkylene - O-Alkylene )mNH2
Jo
~5~35
43- .
where m has a value of about 3 to 70 and preferably about 10
to 35;
R alkaline O~Alkylene nun 2]3-6
wherein 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 it from
about 3 to about 70 and generally from about 6 to about 35
and R is a polyvalent saturated hydrocarbyl radical of up to
ten carbon atoms hazing a valence of 3 to 6. The alkaline
groups may be straight or branched chains and contain from 1
to 7 carbon atoms, and usually from 1 to 4 carbon atoms.
The various alkaline groups present within the above for-
mule may be the same or different.
More specific examples of these polyamides in-
elude:
NH2fH-CH2~ OCH2CH I NH2
SHEA SHEA
wherein x has a value of from about 3 to 70 and preferably
from about 10 to 35 and:
CH2-------~0CH~CH OX NH2
¦ SHEA
CH3-CH2--C~-CH2- OCH2CH NH2
I IH3
SHEA- -~OCH2CH - I _NH2
SHEA
wherein x y z have a total value ranging from about 3 to
20 30 and preferably from about 5 to 10.
The preferred polyoxyalkylene polyamides for
purposes of this invention include the polyoxyethylene and
polyoxypropylene dominoes and the polyoxypropylene trimness
having average molecular weights ranging from about 200 to
2000. The polyoxyalk~lene polyamides are commercially
available and may be obtained, for example, from the Jeff
person Chemical Company, Inc. under the trade name "Jeff-
amine D-230, D-400, D-1000, D-20001 T-403, etc.",
335
- I -
US. patents 3,~04,763 and 3,948~800 disclose such
polyoxyalkylene polyamides and processes for assaulting them with
carboxylic acid assaulting agents which processes can be applied
to their reaction with the assaulting reagents of this invention.
The most preferred amine for use in this invention are the
alkaline polyamides, including the polyalkylene polyamides, as
described in more detail hereafter. The alkaline polyamides
include those conforming to the formula:
H-N ~Alkylene-Nt
R" R"
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 "Alkaline"
group has from about 1 to about 10 carbon atoms but the preferred
alkaline is ethylene or propylene. specially preferred are the
alkaline polyamides where each R" is hydrogen with the ethylene
polyamides and mixtures of ethylene polyamides being the most
preferred. Usually n will have an average value of from about 2
to about 7. Such alkaline polyamides include ethylene
polyamides, ethylene polyamides, battalion polyamides, propylene
polyamides, pentylene polyamides, hexylene polyamides,
heptylene polyamides, etc. The higher homology of such amine and
related aminoalkyl-substituted piperazines are also included.
~lkylene polyamides useful in preparing the carboxylic
I derivative compositions include ethylene Damon, triethylene
tetramine, propylene Damon, trim ethylene Damon, hexamethylene
Damon, decamethylene Damon, octamethylene Damon, Dwight-
methylene)triamine, tripropylene tetramine, tetraethylene
pent amine, trim ethylene Damon, pantaethylene examine,
di(trimethylene)triamine, N-(2-aminoethyl)piperazine, Boyce-
aminoethyl)piperazine, and the like. Higher homology as are
obtained by condensing two or more of the above-illustrated
alkaline amine are useful as amine in this invention as are
mixturesQf two or more of any of the afore-described polyamides.
' I
- 45 -
Ethylene polyamides, such as those mentioned above, are
especially useful for reasons of cost and effectiveness Such
polyamides are described in detail under the heading "Dominoes and
Higher Amine" in The Encyclopedia of Chemical Technology, Second
Edition, Kirk and Other, Volume 7, pages 27-39, Intrusions
Publishers, Division of John Wiley and Sons, 1966. Such compounds
are prepared most conveniently by the reaction of an alkaline
chloride with ammonia or by reaction of an ethylene mine with a
ring-opening reagent such as ammonia, etc. These reactions result
in the production of the somewhat complex mixtures of alkaline
polyamides, including cyclic condensation products such as
piperazines.
Hydroxyalkyl alkaline polyamides having one or more
hydroxyalkyl substituents on the nitrogen atoms, are also useful
in preparing compositions of the present invention Preferred
hydroxyalkyl-substituted alkaline polyamides 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 polyamides include N-(2-hydroxyethyl~ethylene Damon,
N,N-bis(2-hydroxyethyl~ethylene Damon, 1 (~-hydroxyethyl)-
piperazine, monohydroxypropyl-substituted diethylene thiamine,
dihydroxypropyl-substituted tetraethylene pent amine, No
hydroxybutyl)tetramethylene Damon, etch Higher homology as are
obtained by condensation of the above-illustrated hydroxy alkaline
I polyamides through amino radicals or through hydroxy radicals are
likewise useful as amine in this invention. 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 substituted carboxylic derivative compositions
produced from the reaction of the assaulting agents and the
amine described herein before yield assaulted amine which
US
-46-
include amine salts, asides, immediacy and imidazolines as well
as mixtures thereof, To prepare carboxylic derivative
composition from the assaulting agents and the amine, one
or more assaulting agents and one or more amine are heated,
optionally in the presence of a normally liquid, suntan
tidally inert organic liquid solven~/diluent, at temperatures
in the range of about 80C. up Jo the decomposition point
(the decomposition point is the temperature at which there
is sufficient decomposition of any reactant or product such
10 as to interfere with the production of the desired product)
but normally at temperature in the range of about 100C. up
to about 300C. provided 300C. does not exceed the decompo-
session point. Temperatures of about 125C. to about 250C.
are normally used. The assaulting agent and the amine are
15 reacted in amounts sufficient to provide from about one-half
equivalent to about 2 mole of amine per equivalent of
assaulting reagent. For purposes of this invention an equip
valet of amine it that amount of the amine corresponding to
the total weight of amine divided by the total number of
20 nitrogens present. Thus, octylamine has an equivalent
weight equal to its molecular weight; ethylene Damon has
an equivalent weigh equal to one half its molecular weight;
and aminoethylpiperazine has an equivalent weight to one-
third its molecular weight. Also, for example, the equip
I valet weight of a commercially available mixture of polyp
alkaline polyamide can be determined by dividing the atomic
weight of nitrogen (14) by the ON contained in the polyp
amine. Therefore, a polyamide mixture having a ON of 34
would have an equivalent weight of 41.2. The number of
30 equivalents of assaulting agent depends on the number of
carboxylic functions (ego carboxylic acid groups or lung-
tonal derivatives thereof) present in the assaulting no-
agent. Thus, the number of equivalents of assaulting agents
will vary with the number of car boxy groups present therein.
35 In determining the number of equivalents of assaulting
agents, those carboxyl functions which are not capable of
reacting as a assaulting agent are excluded In general,
83~
- I -
however, there is one equivalent of assaulting agent or each
car boxy group in the assaulting agents. For example, there would be
two equivalents in the assaulting agents derived prom the reaction
of one mole of olefin polymer and one mole of malefic android.
Conventional techniques are readily available for determining the
number of carboxyl functions (e.g., acid number, saponification
number) and, thus, the number of equivalents of assaulting agent
available to react with amine.
US. Patents 3,172,~92; 3,219,666; and 3,272,746 describe the
preparation of assaulted amine from high molecular assaulting agents
and procedures applicable to reacting the substituted succinic
assaulting agents of this invention with the amine as described
above. In applying the disclosures of these patents to the
substituted assaulting agents of this invention, the latter can be
substituted for the high molecular weight carboxylic acid
assaulting agents disclosed in these patents on an equivalent basis.
That is, where one equivalent of the high molecular weight
carboxylic assaulting agent disclosed in these incorporated patents
is utilized, one equivalent of the assaulting agent of this
invention can be used.
The Alcohols (b)
Alcohols (b) useful in preparing carboxylic derivative
compositions of this invention from the assaulting agents
previously described include those compounds of the general
formula:
3 (Ohm"
wherein R3 is a monovalent or polyvalent organic radical joined to
the -OH groups through carbon-to-oxygen bonds (that is, -COY
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 reactants, the alcohols can be aliphatic, cycloaliphatic,
aromatic, and heterocyclic, including aliphatic-substituted
cycloaliphatic alcohols, us
_ .
~s~35
48-
aliphatic-substituted aromatic alcohols, aliphatic-substi-
tuned heterocyclic alcohols, cycloaliphatic-substituted
aliphatic alcohols cycloaliphatic substituted aromatic
alcohols, cycloaliphatic-substituted heterocyclic alcohols t
heterocyclic-substituted aliphatic alcohols, heterocyclic-
substituted cycloaliphatic alcohols, and heterocyclic-
substituted aromatic alcohols. Except for the polyoxy-
alkaline alcohols, the moo- and polyhydric alcohols cores-
pounding to the formula Rome" will usually contain not
10 more than about 40 carbon atoms and generally not more than
about 20 carbon atoms. The alcohols may contain non hydra-
carbon substituents of the same type mentioned with respect
to the amine above, that is, non-hydrocarbon substituents
which do not interfere with the reaction of the alcohols
15 with the assaulting agents of this invention. In general,
polyhydric alcohols are preferred.
Among the polyoxyalkylene alcohols suitable for
use in the preparation of the carboxylic derivative compost-
lions of this invention are the polyoxyalkylene alcohol
I emulsifiers for aqueous emulsions. The terminology "demur-
sifter for aqueous emulsions" as used in the present specie
ligation and claims it intended to describe those polyp
oxyalkylene alcohols which are capable of preventing or
retarding the formation of aqueous emulsions or "breaking"
25 aqueous emulsions. The terminology "aqueous emulsion" is
generic to oil-in-water and water-in-oil emulsions.
Many commercially available polyoxyalkylene at
cool emulsifiers can be used. Useful emulsifiers are the
reaction products of various organic amine, carboxylic acid
30 asides, and qua ternary ammonium salts with ethylene-oxide.
Such pol~oxyethylated amine, asides, and qua ternary salts
. I era available from Armour Industrial Chemical Co. under the
names E~HODUOMEEN an ethylene oxide condensation product
of an N-alkyl alkylenediamine under the name DAMON I;
35 ETHOMEEN tertiary amine which are ethylene oxide condense-
lion products of primary fatty amine; ETHOMIDS~k ethyl-
eneoxide condensates of fatty acid asides; and ETHOQUAD
to us
i83~i
-49-
polyoxyethylated qua ternary ammonium salts such as qua-
ternary ammonium chloride.
The preferred demu~sifiers are liquid polyoxyalky-
tone alcohols and derivatives thereof. The derivatives
contemplated are the hydrocarbyl ethers and the carboxylic
acid esters obtained by reacting the alcohols with various
carboxylic acids. Illustrative hydrocarbyl groups are
alkyd, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyd,
etch containing up to about forty carbon atom. Specific
10 hydrocarbyl groups are methyl, bottle, dodecyl, toll,
phenol, naphthyl, dodecylphenyl, p-octylphenyl ethyl,
cyclohexyl, and the like. Carboxylic acids useful in
preparing the ester derivatives are moo- or polycarboxylic
acids such as acetic acid, Valerie acid, Laurie acid,
15 Starkey acid, succinic acid, and alkyd or alkenyl-substi-
tuned succinic acids wherein the alkyd or alkenyl group
contains up to about twenty carbon atoms. Members of this
class of alcohols are Marshall available from various
sources; erg, PLURONIC polyols from Wyandotte Chemicals
20 Corporation; POLYGLYCOL 112-2~ a liquid trio derived from
ethylene oxide and ~ropyleneoxide available from Dow Chemical
Co.; and TERGITOL5~ dodecylphenyl or nonylphenyl polyethyl-
one glycol ethers, and ICONS polyalkylene glycols and
various derivatives thereof, both available from Union
25 Carbide Corporation However, the emulsifiers used must
have an average of at least one free alcoholic hydroxyl
group per molecule of polyoxyalkylene alcohol. For purposes
of describing these polyoxyalkylene alcohols which are
demulslfiers, an alcoholic hydroxyl group is one attached to
30 a carbon atom that does not form part of an aromatic nucleus.
In this class of proofer polyoxyalkylene Alcoa
hots are those polyols prepared as "block" copolymers.
Thus, a hydroxy-substituted compound, Wreck (where q is 1
to 6, preferably 2 to 3, and R4 is the residue of a moo- or
35 polyhydric alcohol ox Mooney or polyhydroxy phenol, naphthol,
etc.) it reacted with an alkaline oxide, Rs-CH-/H~R6, to
-Trudy I
I
. -50-
form a hydrophobic base Us being a lower alkyd group of up
to four carbon atom, R6 being H or the same as R5 with the
proviso that the alkaline oxide does not contain in excess
of ten carbon atoms. This base is then reacted with ethyl-
one oxide to provide a hydrophilic portion resulting in molecule having both hydrophobic and hydrophilic portions.
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
10 skill of the art to prepare such polyols whose molecules are
characterized by hydrophobic and hydrophilic moieties pro-
sent in a ratio rendering them suitable as emulsifiers for
aqueous emulsion in various lubricant compositions and thus
suitable as alcohols in this invention. Thus, if more oil-
15 volubility is needed in a given lubricant composition, the
hydrophobic portion can be increased and/or hydrophilic
portion decreased. If greater aqueous emulsion breaking
capability it required, the hydrophilic and/or hydrophobic
portions can be adjusted to accomplish this.
Compound illustrative of Wreck include elf-
phatic polyols such as the alkaline glycols and Al Kane
polyols, e.g., ethylene glycol, propylene glycol, trim ethyl-
one glycol, glycerol, pentaexythritol, erythritol, sorbitol,
minutely, and the like and aromatic hydroxy compounds such
25 as alkylated moo- and polyhydric phenols and naphthols,
e.g., chrysalis, heptylphenols, dodecylphenols, dioctylphenols,
triheptylphenols, resorcinol, pyrogallol, etc.
Polyoxyalkylene polyol emulsifiers which have two
or three hydroxyl groups and molecules consisting Essex-
0 tidally of hydrophobic portions comprising -SHEA group
R5
where R5 is lower alkyd of up Jo three carbon atoms and
hydrophilic portions comprising -CH2CH2O- groups are part-
ocularly preferred. Such polyols can be prepared by first
35 reacting a compound of the formula Wreck where q is 2-3
with a terminal alkaline oxide of the formula Us SHEA
So
-51-
and then reacting that product with ethylene oxide
R4~~0H)q can be, for example, TOP (trimethylolpropane), TOME
ttrimethylolethane), ethylene glycol, trim ethylene glycol,
tetramethylane glycol, trip hydroxypropyl)amine, 1,4-(2-
hydroxyethyl)-cyclohexane, N,N,N',N'-tetrakis(2-hydroxy-
propyl)ethylene Damon, N,N,N',N'-tetraki 5 ( 2-hydroxyethyl)-
ethylene Damon, naphthol, alkylated naphthol, resorcinol,
or one of the other illustrative examples mentioned here-
in before
The polyoxyalkylene alcohol emulsifiers should
have an average molecular weight of 1000 to about 10,000,
preferably 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
15 polyoxyalkylene polyols where the ethyleneoxy groups come
prose from about 10% to about 30% of the total average
molecular weight are especially useful. Polyoxyalkylene
polyols having an average molecular weight of about 2500 to
about 6000 where approximately 10%-20% by weight of the
20 molecule is attributable to ethyleneoxy groups result in the
formation of esters having particularly improved demulsi-
lying properties. The ester and ether derivatives of these
polyols are also useful.
Representative of such polyoxyalkylene polyols are
25 the liquid polyols available from Wyandotte Chemicals Come
puny under the name PLURONIC Polyols and other similar
polyols. These PLURONIC Polyols correspond to the formula
HG-(CH2CH2O)X(lHCH20)y(CH2CH~O)z-H
SHEA
wherein x, y, and z are integers greater than 1 such that
30 the -CH2CH2O- groups comprise prom 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
35 ethylene oxide.
5~3~i
- 52 -
Another group of polyoxyalkylene alcohol emulsifiers
illustrative of the preferred class discussed above are the
commercially available liquid TETRONIC* polyols sold by Wyandotte
Chemicals Corporation. These polyols are represented by the
general formula:
H(C2H4O)b(c3H6o)a \ / (C3H6O~a~c2H4O~b
NCH2CH2N
H(C2~4O)b(c3H6o)a (C3H6O)a(c2H4o~b
Such polyols are described in US. Patent No. 2,979,528. Those
polyols corresponding to the above formula having an average
molecular weight of up to about 10,000 wherein the ethyleneoxy
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 weight of about 8000
wherein the ethyleneoxy groups account for 7.5%-12% by weight of
the total molecular weight. Such polyols can be prepared by
reacting an alkaline Damon such as ethylene Damon, propylene
Damon, hexamethylene Damon etc., with propylene oxide until
the desired weight ox the hydrophobic portion is reached. Then
the resulting product is reacted with ethylene oxide to add the
desired number ox hydrophilic units to the molecules.
Another commercially available polyoxyalkylene polyol
emulsifier falling within this preferred group is Dow Polyglycol
2, a trio having an average molecular weight of about
US 4000-5000 prepared from propylene oxides and ethylene oxides, the
ethyleneoxy groups comprising about 18% by weight of the trio.
Such trios can be prepared by first reacting glycerol, TOME, TOP,
etc., with propylene oxide to form a hydrophobic base and reacting
that base with ethylene oxide to add hydrophilic portions.
Alcohols useful in this invention also include alkaline
glycols and polyoxyalkylene alcohols such as polyoxyethylene
alcohols, polyoxypropylene alcohols, polyoxybutylene alcohols,
and the like. These polyoxyalkylene
* trade mark
~2~33~i
alcohols (sometimes called polyglycol~) can contain up to
about 150 oxyalkylene groups wherein the alkaline radical
contains from 2 to about 8 carbon atoms. Such polyoxy
alkaline alcohols are generally dihydric alcohols. That is,
each end of the molecule terminates with a -OH group. In
order for such polyoxyalkylene alcohols to be useful, there
must be at least one such -OH group However, the remain-
in -OH group can be esterified with a monobasic, aliphatic
or aromatic carboxylic acid of up to about 20 carbon atoms
10 such as acetic acid, prop ionic acid, oleic acid, Starkey
acid, benzoic acid, and the like. The monoethers of these
alkaline ylycols and polyoxyalkyl~ne glycols are also
useful. These include the monorail ether, monoalkyl
ethers, and monoaralkyl ethers of these alkaline glycols and
15 polyoxyalkylene glycols. This group of alcohols can be
represented by the general formula
HO RHO RUB OR
where ARC is aureole such as phenol, lower alkoxy phenol, or
lower alkyd phenol, lower alkyd such a ethyl, propel, left-
20 bottle, pinwheel, etc.; and aralkyl such as bouncily, phenol-
ethyl, phenylpropyl, p-ethylphenylethyl, etc.; p is zero to
about eight, preferably two to four, carbon atoms. Polyp
oxyalkylene glycols where the alkaline groups are ethylene
or propylene and p is at least two as well as the monoethers
I thereof as described above are very useful.
The mandrake and polyhydric alcohols useful in
this invention include monohydroxy and polyhydroxy aromatic
compounds. Mandrake and polyhydric phenols and naphthols
are preferred hydroxyaromatic compounds. These hydroxy-
30 substituted aromatic compounds may contain other subset-
tents in addition to the hydroxy substituents such as halo,
alkyd, alkenyl, alkoxy, alkylmercapto, vitro an the like
Usually, the hydroxy aromatic compound will contain 1 to 4
hydroxy groups. The aromatic hydroxy compounds are thus-
35 treated by the following specific examples: phenol, p-
chlorophenol, p-nitrophenol, beta-naphthol, alpha-naphthol,
33S
-54-
chrysalis, resorcinol, catcall, caxvacrol, thymol, euyenol,
p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol, sheller-
glucinol, hexylresorcinol, orison, gawkily, 2-chlorophenol,
2,4-dibutylphenol, propenetetramer-substituted phenol t
didodecylphenol, 4 t 4'-methylene-bis-me~hylene~bis-phenol,
alpha-decyl-be~a naphthol, polyisobutenyl-(mol~cular weight
(My) of about substituted phenol the condensation
product of heptylphenol with Owe moles of formaldehyde, the
condensation product of octylphenol with acetone, dodder-
10 xyphenyl)oxide, di(hydroxyphenyl)sulfide, di(hydroxyphenyl)-
disulfide, and 4-cyclohexylphenol. Phenol itself and elf-
phatic hydrocarhon-substituted phenols, e.g., alkylated
phenols having up to 3 aliphatic hydrocarbon substituents
are especially preferred. Each of the aliphatic hydrocarbon
lo substituents may contain 100 or more carbon atoms but
usually will have from 1 to 20 carbon atoms. Alkyd and
alkenyl groups are the preferred aliphatic hydrocarbon
substituents.
Further specific examples of mandrake alcohols
20 which can be used include mandrake alcohols such as
methanol, ethanol, i~ooctanol, dodecanol, cyclohexanol,
cyclopentanol, Bunnell alcohol, hexatriacontanol, neopentyl
alcohol, isobutyl alcohol, ensoul alcohol, beta-phenylethyl
alcohol, 2-methyLcyclohexanol, beta-chloroethanol, moo-
25 methyl ether of ethylene glycol, monobutyl ether of ethyleneglycol, monopropyl ether of diethylene glycol, monododecyl
ether of triethylene glycol~ moonlit of ethylene glycol,
menstruate of diethylene glycol, sec-pentyl alcohol,
tertbutyl alcohol, 5-bromo-dodecanol, nitro-octadecanol, and
dwelt of glycerol. Alcohols useful in this invention may
be unsaturated alcohols such as ally alcohol, cinnamyl
alcohol, l-cyclohexene-3-ol and of ye alcohol.
Other specific alcohols useful in this invention
are the ether alcohols and amino alcohols including, for
example, the oxyalkylene, oxy-arylene~, amino-alkylene-, and
amino-arylene-substituted alcohols having one or more ox-
alkaline, aminoalkylene or amino-aryleneoxy~arylene radicals.
-55-
A They are exemplified by CeIlosolve, carbitol, phenoxyethanol,
heptylphenyl-(oxypropylene)6-OH, octyl-(oxyethylene)~o-O~,
phenyl-(oxyoctylene) 2 I mono-(heptylphenyl-oxypropylene)
substituted glycerol, polystyrene oxide amino ethanol, 3-
amino-e~hylpentanol, 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
example, by the alkaline glycols and polyoxyalkylene glycols
mentioned above such as ethylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol, dipropylene guy-
got, tripropylene glycol, dibutylene glycol, tributylene
glycol, and other alkaline glycols and polyoxyalkylene
glycols in which the alkaline radicals contain 2 to about 8
carbon atoms.
Other useful polyhydric alcohols include glycerol,
moonlit of glycerol, menstruate of glycerol, monomethyl
ether of glycerol, pentaerythritol~ n-butyl ester of 9,10-
20 dihydroxy Starkey acid, methyl ester of 9,10-dihydroxy
Starkey acid, l,2-butanediol, 2,3-hexanediol, 2,4-hexane-
Doyle pinnacle, erythritol, arabitol, sorbitol, minutely,
1,2-cyclohexanediol, and zillion glycol. Carbohydrates such
as sugars, starches, cellulose, and so forth likewise can
25 be used. The carbohydrates may be exemplified by glucose,
fructose, sucrose, Remus, muons, ylyceraldehyde, and
galactose~
Polyhydric alcohols having at least 3 hydroxyl
groups, some, but not all of which have been esterified with
30 an aliphatic monocarboxylic acid having from about 8 to
about 30 carbon atoms such as octanoic acid, oleic acid,
Starkey acid, linoleic acid, dodecanoic acid or tall oil
acid are useful. Further specific examples of such par-
tidally esterified polyhydric alcohols are the moonlit of
35 sorbitol, distrait of sorbitol, moonlit of glycerol
menstruate of glycerol, di-dodecanoate of erythritol, and
the like.
I toe we
~Z3~35
-56-
A preferred class of alcohol suitable for use in
this invention are those polyhydric alcohols containing up
to about twelve carbon atoms, and especially those contain-
in three to ten carbon atoms. This class of alcohols
includes glycerol, erythritol, pen~aerythritol, Dupont-
erythritol, gluconic acid, glyceraldehyde, glucose, era-
buoyancy, 1~7-heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol,
1,2,4-hexanetriol, 1,2,5-hexanetriol, 2,3,4-hexanetriol~
1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid, 2,2,6,~
10 tetrakis-(hydroxymethyl)cyclohexanol, 1,10 decanediol,
digitals, and the like. Aliphatic alcohols containing at
least three hydroxyl groups and up to ten carbon atoms are
particularly preferred
An especially preferred class of polyhydric Alcoa
15 hots for use in this invention are the polyhydric alkanolscontaining 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, erythritol, pentaerythritol-, minutely, sorbitol,
20 2hydroxymethyl-2-methyl-1,3-propanediol~trimethylolmethane),
2-hydroxymethyl-2-ethyl-1,3-propanediol(trimethylopropane),
1,2,4-hexanetriol, and the like.
From what has been stated above, it is seen thaw
amine may contain alcoholic hydroxy substituents and Alcoa
25 hots can contain primary, secondary, or tertiary aminosubstituents. Thus, amino alcohols can be catagoriæed as
both amine and alcohol provided they contain a least one
primary our secondary amino group. If only tertiary amino
groups are present, the amino alcohol belongs only in the
30 alcohol category.
Amino alcohols contemplated as suitable for use in
this invention 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 polyamides such as 2-
35 hydroxyethylamine, 3-hydroxybutylamine, di-(2-hydroxyethyl)-
amine, tri-(2~hydroxyethyl~amine, di-(2-hydroxypropyl)amine,
So
I
N,N,N'-tri-(2-hydroxyethyl)ethylenedlamine, N,N,N',N'-tetra-
(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)piper-
amine, N,N'-di-(3-hydroxypropyl)pipexazine, N-(2-hydroxy-
ethyl)morpholine, N-(2~hydroxyethyl)-2-morpholinone, No
S hydroxyethyl~-3-methyl-2-morpholinone, N~(2-hydroxypropyl~-
6-methyl-2-morpholinone, N-(~hydroxyethyl)-5-carbethoxy-2-
piperidone, N-(2-hydroxypropyl)-5-carbethoxy-2-piperiaone,
N-(2-hydroxyethyl)-5~(N-butylcarbamyl)-2-piperidonno, No
hydroxyethyl~piperidinP, N (4-hydroxyhu~yl)piperidine, NUN-
10 di-(2-hydroxyethyl)glycine, and ether thereof with elf-
phatic alcohols, especially lower alkanols, N,N-di(3 ho-
droxypropyl)glycine, and the Mike. Also contemplated are
other moo- and poly-N-hydroxyalkyl-substituted alkaline
polyamides wherein the alkaline polyamides are as described
15 above; especially those that contain two to three carbon
atoms in the alkaline radicals and the alkaline polyamide
contains up to seven amino groups such as the reaction
product of about two moles of propylene oxide and one mole
of diethylenetriamine.
Further amino alcohols are the hydroxy-substituted
primary amine described in US. Patent 3,576,743 by the
general formula
R -NH2
where Ray is a monovalent organic radical containing at least
25 one alcoholic hyrax group, according to this patent, the
total number of carbon atoms in Rod will not exceed about 20.
Hydroxy-substituted aliphatic primary amine containing a
total of up to about 10 carbon atoms are particularly use-
us Especially preferred are the polyhydroxy-substituted
30 alkanol primary amine wherein there is only one amino group
present (i.e., a primary amino group) having one alkyd
substituent containing up to 10 carbon atoms and up to 6
hydroxyl groups. These alkanol primary amine correspond to
Rd-NH2 wherein I is a moo- or polyhydroxy-substituted
35 alkyd group. It is desirable that at least one of the
hydroxyl groups be a primary alcoholic hydroxyl group.
I 33~
- 58 -
Trismethylolaminomethane is the single most preferred hydroxy-
substituted primary amino Specific examples of the hydroxy-
substituted primary amine include 2-amino-1-butanol, 2-amino-
2-methyl-1-propanol, p-(beta-hydroxyethyl)-analine, 2-amino-1-
propanol, 3-amino-1-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-butanol,
ethanol amine, beta-(beta-hydroxy ethoxy)-ethyl amine, glucamine,
glusoamine, 4-amino-3-hydroxy-3-methyl-1-butene (which can be
prepared according to procedures known in the art by reacting
isopreneoxide with ammonia), N-3-(aminopropyl)-4-(2-hydroxy-
ethyl)-piperadine, 2-amino-6-methyl-6-heptanol, 5-amino-1-
pentanol, N-~beta-hydroxyethyl)-1,3-diamino propane, Damon-
2-hydroxy-propane, N-(beta-hydroxy ethoxyethyl)-ethylenediamine,
and the like. For further description of the hydroxy-substituted
primary amine contemplated as being useful as amine and/or
alcohols, see US. Patent 3,576,743.
The carboxylic derivative compositions produced by reacting
the assaulting agents of this invention with alcohols are esters.
Both acidic esters and neutral esters are contemplated as being
within the scope of this invention. Acidic esters are those in
which some of the carboxylic acid functions in the assaulting
reagents are not esterified but are present as free carboxyl
croups. Obviously, acid esters are easily prepared by using an
amount of alcohol insufficient to esterify all of the corbel
groups in the assaulting reagents of this invention.
The assaulting agents are reacted with the alcohols according
to conventional esterification techniques. It normally involves
heating the assaulting agent 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.
5~3~
- 59 -
Temperatures of at least about 100C. up to the decomposition
point are used Tithe decomposition point having been defined
herein before). This temperature is usually within the range of
about 100C. up to about 300C. with temperatures of about 140C.
to 250C. often being employed. Usually, at least about one-half
equivalent of alcohol is used for each equivalent of assaulting
agent. An equivalent of assaulting agent is the same as discussed
above with respect to reaction with amine. An equivalent 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. The
amino-alcohols have equivalent weights equal to the molecular
weight divided by the total number of hydroxy groups and
nitrogen atoms present in each molecule.
Many issued patents disclose procedures for reacting high
molecular weight carboxylic acid assaulting agents with alcohols
to produce acidic esters and neutral esters. These same
techniques are applicable to preparing esters from the assaulting
agents of this invention and the alcohols described above. All
that is required is that the assaulting agents of this invention
are substituted for the high molecular weight carboxylic acid
assaulting reagents discussed in these patents, usually on an
equivalent weight basis. The following US. Patents disclose
suitable methods for reacting the assaulting agents of this
invention with the alcohols described above: 3,331,776; 3,381,022;
3,522,179; 3,542,680; 3,697,428; 3,755,1690
The Reactive Metals or Metal Compounds I
Reactive metals or reactive metal compounds useful as (c) are
those which will form carboxylic acid metal salts with the
assaulting agents of this invention and those which will form
metal-containing complexes with the carboxylic derivative
compositions produced by reacting the assaulting reagents with
amine and/or alcohols as discussed above.
.
60-
Reactive metal compounds useful as (c) for the formation of
complexes with the reaction products of the assaulting
agents and amine are disclosed in US. Patent 3,306,908.
Complex-forming metal reactants useful as (c) include the
nitrates, nitrites, halides, carboxylates, phosphates,
phosphates, sulfates, sulfites, carbonates, borate, and
oxides of cadmium as well as metals having atomic numbers of
24 to 30 (including chromium, manganese, iron, cobalt,
nickel, copper and zinc). These metals are the so-called
10 transition or coordination metals, it whey 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 lo) in this
invention are cobaltous nitrate, cobaltous oxide, cobaltic
15 oxide, cobalt nitrite, cobaltic phosphate, cobaltous color-
ides cobaltic chloride, cobaltous carbonate, crimes
acetate, chronic acetate, chronic bromide, crimes color-
ides chronic fluoride, crimes oxide, chromium dioxide,
chronic oxide, chronic sulfite, crimes sulfate Hyatt-
20 hydrate, chronic sulfate, chronic format, chronic hexano-
ate, chromium oxychloride, chronic phosphate, manganese
acetate, manganese bonniest, manganese carbonate, manganese
dichlorides manganese trichloride, manganese citrate,
muggins format, manganese nitrate, manganese oxalate,
25 manganese monoxide, manganese dioxide, manganese trioxides
manganese heptoxide, manganic phosphate, manganese pyre-
phosphate, manganic metaphosphate, manganese hypophosphite,
manganese vale rate, ferrous acetate, ferris bonniest,
ferrous bromide, ferrous carbonate, ferris ornate ferrous
lactate, ferrous nitrate, ferrous oxide, ferris oxide,
ferris hypophosphite, ferris sulfate, ferrous sulfite,
eureka hydrosulfite, nickel dibromide, nickel dichlorides
nickel nitrate, nickel dwelt, nickel Stewart, nickel
sulfite, cupric preappoint, cupric acetate, cupric mote-
borate, cupric bonniest, cupric format, cupric laurate,cupric nitrite, cupric oxychIoride, cupric palpitate 9 cupric
salicylate, zinc bonniest, zinc borate, zinc bromide, zinc
~2~5i835
- 61 -
chromates zinc dichromate, zinc iodide, zinc lactate, zinc
nitrate, zinc oxide, zinc Stewart, zinc sulfite, cadmium bonniest
cadmium carbonate, cadmium bitterroot, cadmium chloroacetatel
cadmium Enumerate, cadmium nitrate, cadmium dihydrogenphosphate,
cadmium sulfite, and cadmium oxide. hydrates of the above
compounds are especially convenient for use in the process of this
invention.
US. Patent 3,306,908 discloses reactive metal compounds
suitable for forming such complexes and processes for preparing
the complexes. Basically, those processes are applicable to the
carboxylic derivative compositions of the assaulting agents of this
invention with the amine as described above by substituting, or on
an equivalent basis, the assaulting reagents of this invention with
the higher molecular weight earboxylic acid allotting agents
disclosed in US. Patent 3,306,908. The ratio of equivalents of
the assaulted amine thus produced and the complex-forming metal
reactant remains the same as disclosed in 3,306,908 patent.
US. Reissue Patent 26,443 discloses metals useful in
preparing salts from the reaction of allotting agents and amine
as described hereinabove. Metal salts are prepared, according to
this patent, from alkali metals, alkaline earth metals, zinc,
cadmium lead, cobalt and nickel. Examples of a reactive metal
compound suitable for use as (c) are sodium oxide, sodium
hydroxide, sodium carbonate, sodium methyl ate, sodium propylate,
sodium pentylate, sodium phenoxide, potassium oxide, potassium
hydroxide, potassium carbonate potassium methyl ate, potassium
pentylate, potassium phenoxide, lithium oxide, lithium hydroxide,
lithium carbonate, lithium pentylate, calcium oxide, calcium
hydroxide, calcium carbonate, calcium methyl ate, calcium ethyl ate,
calcium replete, calcium chloride, calcium fluoride, calcium
pentylate, calcium phenoxide, calcium nitrate, barium oxide,
barium hydroxide, barium earonbate, barium chloride, barium
fluoride, barium methyl ate, barium propylate, barium pentylate,
barium nitrate, magnesium oxide, magnesium hydroxide, magnesium
I I
62 -
carbonate, magnesium ethyl ate, magnesium propylate, magnesium
chloride, magnesium bromide, barium iodide, magnesium phenoxide,
zinc oxide, zinc hydroxide, zinc carbonate, zinc methyl ate, zinc
propylate, zinc pentylate, zinc chloride, zinc fluoride, zinc
nitrate trihydrate, cadmium oxide, cadmium hydroxide, cadmium
carbonate, cadmium methyl ate, cadmium propylate, cadmium chloride,
cadmium bromide, cadmium fluoride, lead oxide, lead hydroxide,
lead carbonate, lead ethyl ate, lead pentylate, lead chloride, lead
fluoride lead iodide, lead nitrate, nickel oxide, nickel
hydroxide, nickel carbonate, nickel chloride, nickel bromide,
nickel fluoride, nickel methyl ate, nickel pentylate, nickel
nitrate hexahydrate, cobalt oxide, cobalt hydroxide, cobaltous
bromide, cobaltous chloride, cobalt butyla-te, 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.
US. Reissue 26,443 discloses reactive metal compounds useful
as (c) and processes for utilizing these compounds in the
formation of salts. Again, in applying the teachings of this
patent to the present invention, it is only necessary to
substitute the assaulting agents of this invention on an equivalent
weight basis for the high molecular weight carboxylic assaulting
agents of the reissue patent.
US. Patent 3,271,310 discloses the preparation of metal
I salt of high molecular weight carboxylic acid assaulting agents,
in particular alkenyl succinic acids The metal salts disclosed
therein are acid salts, neutral salts, and basic salts. Among
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 methyl ate,
sodium propylate, sodium phenoxide, potassium oxide, potassium
hydroxide, potassium carbonate, potassium methyl ate, silver
.
- 63 5~35
oxide, silver carbonate, magnesium oxide, magnesium hydroxide,
magnesium carbonate, magnesium elite, magnesium propyllate,
magnesium phenoxide, calcium oxide, calcium hydroxide, calcium
carbonate, calcium methyl ate, calcium propylate, calcium pentylate,
zinc oxide, zinc hydroxide, zinc carbonate, zinc propylate,
strontium oxide, strontium hydroxide, cadmium oxide, cadmium
hydroxide, cadmium carbonate, cadmium ethyl ate, barium oxide,
barium hydroxide, barium hydrate, barium carbonate, barium
ethyl ate, barium pentylate, aluminum oxide, aluminum propylate,
lead oxide, lead hydroxide, lead carbonate, tin oxide, tin
butylate, 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 with the invention.
US. Patent 3,271,310 discloses suitable reactive metal
compounds for forming salts of the assaulting reagents of this
invention as well as illustrative processes for preparing salts
of these assaulting reagents. As will be apparent, the processes
of 3,271,310 are applicable to the assaulting reagents of this
invention merely by substituting on an equivalent weight basis,
the assaulting reagents of this invention for the high molecular
weight carboxylic acids of the patent.
Ed) The Combination of Two or More of (a), (b) and (c)
-
From the foregoing description, it is apparent that the
assaulting 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 amine, 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 amine, a mixture of two or more alcohols, a mixture of two
- 64 -
or more metals or reactive metal compounds, or a mixture of two
or more components selected from amine and alcohols, from amine
and reactive metals or reactive metal compounds, from alcohols
and reactive metal compounds, or one or more components from each of
the amine, alcohols, and reactive metal or reactive metal compounds.
Furthermore, the assaulting reagents of this invention can be reacted
with the amine, alcohols, reactive metals, reactive metal compounds,
or mixtures thereof, as described above, simultaneously (concur-
gently) or sequentially in any order of reaction.
Canadian Patent 956,397 discloses procedures for reacting the
assaulting reagents of this invention with amine, 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 assaulting agents of this
invention for the high molecular weight carboxylic acid assaulting
agents disclosed in that Canadian patent. Carboxylic derivative
compositions 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 US. Patents are counterparts of the above
Canadian patent: 3,836,469; 3,836,470; 3,836,471; 3,838,050;
3,838,052; 3,879,308; 3,957,85~; 3,957,855; 4,031,118. The
Canadian patent and the US. patents illustrate that the amount
of polyoxyalkylene alcohol emulsifier utilized in preparing
~ispersant/detergents from the assaulting reagents of this
invention is normally quite small on an equivalent basis.
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 corresponding US.
patent identified above in which the polyoxyalkylene alcohol
emulsifier has been omitted. In other words, a preferred class
it
So
65 -
of carboxylic derivative compositions of this invention are the
various reaction products of the high molecular weight carboxylic
acid assaulting agents of the Canadian patent with one or more
amine, alcohols, and reactive metal compounds as disclosed
therein differing only in that the assaulting agents of this
invention are substituted on an equivalent weight basis and,
further, that the polyoxyalkylene alcohol emulsifier reactant is
omitted.
In addition, US. Patent 3,806,456 discloses processes
useful in preparing products from the assaulted reagents of this
invention and polyoxyalkylene polyamides as described
herein before. Substitution of the assaulted reactants of this
invention for the high molecular weight carboxylic acid assaulting
agents disclosed in 3,806,456 on an equivalent weight basis
produces compounds further characterized by the viscosity index
improving properties.
US. Patent 3,576,743 discloses a process for preparing
carboxylic derivative compositions from both polyhydric
alcohols and amine; in particular, hydroxy-substituted primary
amine. Again, substitution of the assaulting reagents of this
invention on an equivalent weight basis for the high molecular
carboxylic acid assaulting agents disclosed in 3,576,743 provides
compositions having the desired dispersant/detergent compositions
and V.I. improving properties.
I US. Patent 3,632,510 discloses processes for preparing
mixed ester-metal salts. Mixed ester-metal salts derived from
assaulting 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 assaulting reagents of this
invention for the high molecular weight carboxylic acid assaulting
do,
58~
- 66 -
agents of the patent The carboxylic acid derivative compositions
thus produced also represent a preferred aspect of this invention.
Processes for preparing polyamide modified ester-carboxylic
derivative compositions useful as (B) in the present invention
generally comprise:
(I) Reacting, to form a polyester intermediate, (A) at
least one polyhydric alcohol with (B) a substituted succinic acid
assaulting agent, the substituent thereon being derived from at
least one alkene polymer having a number average molecular weight
(My) of at least about 1200 and a ratio of weight average to
number average molecular weight (Mom) of about 1.5-6.0, said
assaulting agent having within its molecular structure an average
of at least about 1.3 succinic groups per substitutent group; and
(II) subsequently reacting said polyester intermediate
with (C) at least one acylatable polyamide to form said amine-
modified polyester composition;
the process comprises carrying out said steps I and II
in such a way that:
a first solution of 35% by weight of said amine-
I modified polyester in a first mineral oil having a kinematic
viscosity at 100C. of 3.6-~.3 centistokes has a nitrogen
content of at least 0.0175% by weight and a first kinematic
viscosity at 100C. of at least about 300 centistokes; and
a second solution prepared by dissolving said first
I solution in a second mineral oil having a kinematic viscosity
at 100C. of about 6.1 centistokes~ at a level to provide 7
by weight of said amine-modified polyester in said second
solution, has a second kinematic viscosity of at least about 9
centistokes.
Jo
~2~5~35
- 67 -
Finally, USE Patents 3,755,169; 3,804,763; 3r868,330;
and 3,948,800 disclose how to prepare carboxylic acid derivative
compositions. By following the teachings of these patents and
substituting the assaulting agents of this invention for the high
molecular weight carboxylic assaulting agents of the patents, a
wide range of carboxylic derivative compositions within the
scope of the present invention can be prepared.
Reference to so many patents has been made because, it is
felt, the procedures necessary to prepare the carboxylic
derivative compositions from the assaulting agents and the amine,
alcohols, and reactive metals and reactive metal compounds, as
well as mixtures thereof, are well within the skill of the art,
such that a detailed description herein is not necessary
Of the carboxylic derivative compositions described
hereinabove, those prepared from the assaulting agents and the
allcylene polyamides, especially polyethylene polyamides, and/or
polyhydric alcohols, especially the polyhydric alkanols, are
especially preferred. As previously stated, mixtures of
polyamides and/or polyhydric alcohols are contemplated.
I Normally, all the carboxyl functions on the assaulting reagents
of this invention will either be esterified or involved in
formation of an amine salt, aside, imide or imidazoline in this
preferred group of carboxylic derivative compositions.
In addition to detergent/dispersant properties, the
I carboxylic derivative compositions and post-treatments thereof
discussed herein function as VI improvers and these viscosity index
improving capabilities are enhanced when prepared from the
reaction or the assaulting agents with polyfunctional reactants.
For example, polyamides having two or more primary and/or
secondary amino groups, polyp .....
~2~3~i
-68-
hydric alcohols, amino alcohols in which where are one or
more primary and/or secondary amino groups and one or more
hydroxy groups, and polyvalent metal or polyvalent metal
compounds. It it believed what the polyunctional reactants
serve to provide "bridges" or cross-linking in the car-
boxlike derivative compositions and this, in turn, is
somehow responsible for the viscosity index-improving
properties. However, the mechanism by which viscosity index
improving properties is obtained is not understood and
10 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
lubricating compositions, the polyfunctionallty of reactants
15 (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 assaulting reagents be polyphonic-
20 tonal. Thus, combinations of moo- and polyfunctional
amine, alcohols, reactive metals and reactive metal come
pounds can be used; for example, monoamine with a polyhydric
alcohol, a mandrake alcohol with polyamide, an amino
alcohol with a reactive metal compound in which the metal is
25 monovalent, and the like.
While the parameters have not been fully deter-
mined as yet, it is believed that assaulting reagents of this
invention should be reacted with amine, alcohols, reactive
metals, reactive metal compounds, or mixtures of these which
30 contain sufficient polyfunctional reactant (e.g., polyp
amine, polyhydric 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 malefic reactant) are
reacted with a polyfunctional reactant. Better results
35 insofar as the Viscosity index-improving facilities of the
carboxylic derivative compositions is concerned, appear to
I 35
-69
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 pro-
pexties seem to be achieved when the assaulting reagents of
this invention are reacted with a sufficient amount of
polyamide and/or polyhydric alcohol or amino alcohol to
react with at least about 75% of the carboxyl group. It
should be understood that the foregoing percentages are
"theoretical" in the sense that it is not required that the
10 stated percentage ox car~oxyl functions actually react with
polyfunctional reactant. Rather these percentages are used
to characterize the amounts of polyfunctional reactants
desirably "available" to react with the assaulting reagents
in order to achieve the desired viscosity index improving
15 properties.
Post-t_eated_Carboxylic Derivative Compositions
Another aspect of this invention, (B), may be
post-treated carboxylic derivative compositions prepared by
reacting one or more post-treating reagents with one or more
20 carboxylic derivative compositions Additionally, (B)
includes mixtures of one or more carboxylic derivative
compositions and one or more post-treated carboxylic don-
ivative compositions.
The process for post-treating the carboxylic acid
I derivative compositions is analogous to the post-treating
processes used with respect to similar derivatives of the
high molecular weight carboxylic acid assaulting agents of
the prior art. Accordingly, the same reaction conditions,
ratio of reactants and the like can be used.
Assaulted nitrogen compositions prepared by react-
in the assaulting agents ox this invention with an amine (a
as described above are post-treated by contacting the
assaulted nitrogen compositions thus formed (ago., the
carboxylic derivative compositions) with one or more post-
35 treating reagents selected from the group consisting of
boron oxide, boron oxide hydrate, boron halides, boron
I
-70-
acids, esters ox boron acids, carbon disulfide, hydrogen
sulfide, sulfur, sulfur chlorides, alkenyl cyanides, car-
boxlike acid assaulting agents such as terephthalic acid,
aldehydes, kittens, urea, Thor, guanidine, Dyson-
doomed, hydrocarbyl phosphates, hydrocarbyl phosphates,
hydrocarbyl thiophosphates, hydrocarbyl thiophosphites,
phosphorus sulfides, phosphorus oxides, phosphoric acid,
hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydra-
corbel isothiocyanates, epoxies, 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 azalea-
cling agents of this invention and a combination of amine
(a) and alcohols (b) as described above. However, when the
carboxylic derivative compositions of this invention are
derived from alcohols (b) and the assaulting agents, 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
assaulting agents such as terephthalic acid, epoxies, 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 assaulting agents of the prior art and amine 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 in the prior art, be
applied to the novel carboxylic derivative compositions ox
this invention. The following US. patents disclose
post-treating processes and post-treating reagents apply-
I 5
- 71 -
cable to the carboxylic derivative compositions of this invention:
3,087,936; 3,200,108; 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 assaulting reagents of
this invention and amine); 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
1,0~35,903; UK 1,162,436; US. 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.
Furthermore, the carboxylic derivative compositions, the
post-treated carboxylic derivative compositions, the assaulting'
agents described hereinabove and processes for their preparation
are described in US. Patent 4,234,435
(C) Chlorine-containing Compounds
The chlorine containing compounds useful for the purposes
of this invention are selected from the group consisting of
chloroaliphatic hydrocarbon-based compounds, chloroalicyclic
hydrocarbon-based compounds or mixtures thereof.
The chloroaliphatic hydrocarbon-based compounds
useful for the purposes of this invention are compounds
which comprise chlorine atoms and aliphatic hydrocarbon-based
radicals. As used herein, the term "aliphatic hydrocarbon-
based radical" denotes a radical having an aliphatic carbon atom directly attached to the chlorine atom ....
I
.. i
~2~35i
-72-
and having predominantly aliphatic hydrocarbon character
within the context of this invention. Such radicals include
the following:
(1) Aliphatic hydrocarbon radicals: e.g., alkyd,
alkenyl, and aromatic- and alicyclic-substituted alkyd and
alkenyl radicals, and the like. Such radicals are known to
those skilled in the art; examples include ethyl, propel,
bottle, ponytail, octal, decal, stroll, dodecenyl and oilily
(all isomers being included).
(2) Substituted aliphatic hydrocarbon radicals;
that is, radicals containing non-hydrocarbon substituents
which, in the context of this invention, do not alter the
predominantly aliphatic hydrocarbon character of the radix
eel. Those skilled in the art will be aware of suitable
15 substituents (erg., alkoxy, hydroxy, alkylthio, carbalkoxy,
vitro).
(3) Heteroaliphatic hydrocarbon radicals; that
is, radicals which, while predominantly allphatic hydra-
carbon in character within the context of this invention,
20 contain atoms other than carton present in a chain or ring
otherwise composed of carbon atoms. Suitable heteroatoms
will be apparent to those skilled in the art and include,
for example, oxygen and nitrogen.
In general, no more than about three substituents
25 or heteroatoms, and preferably no more than one, will be
present fox each 10 carbon atoms in the aliphatic hydra-
carbon-based radical.
Preferably, the aliphatic hydrocarbon-based
radical present in the chlorine compounds of this invention
30 is free from acetylenic and usually also from ethylenic
unsaturation and contains at least five carbon atoms. Most
often it is an alkyl-based radical, usually an alkyd radix
eel.
The term "alkyl-based radical", as used herein,
35 denotes an alkyd radical within the description of the term
"aliphatic hydrocarbon-based radical" and includes alkyd
3 2~L5~3S
-73-
radicals analogous to the "aliphatic hydrocarbon-based
radicals" described hereinabove and such radicals are alkyd-
hydrocarbon radicals, substituted alkyd hydrocarbon radicals
and hetero-alkyl hydrocarbon radicals.
the chloroalicyclic hydrocarbon-based compounds
useful for the purposes of this invention are compounds
comprising chlorine atoms and alicyclic hydrocarbGn-based
radicals. As used herein, the term "alicyclic hydrocarbon-
based radical" denotes a radical having an alicyclic carbon
10 atom directly attached to the chlorine atom and having
predominantly alicyclic hydrocarbon character within the
context of this invention. Such radicals include the
following:
I Alicyclic hydrocarbon radicals; e.g., cry;
15 cloalkyl or cycloalkenyl, and aromatic- and aliphatic-
substituted alicyclic radicals, and the like. Such radicals
are known to those skilled in the art examples include
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycle-
hotly, cyclooctyl, methylcyclohexyl, cyclopentenyl, cycle-
20 pentadienyl and cyclohexenyl.
2) Substituted alicyclic hydrocarbon radicals that is, radicals containing non-hydrocarbon substituents
which, in the context of this invention, do not alter the
predominantly alicyclic hydrocarbon character of the radix
25 eel. Those skilled in the art will be aware of suitablesubstituents ego., alkoxy, hydroxy, alkylthio, carbalkoxy,
Norway).
3) Heteroalicyclic hydrocarbon radicals; that
is, radicals which, while predominantly alicyclic hydra-
30 carbon in character within the context of this inven~ion,contain atoms other than carbon present in a chain or ring
otherwise composed of carbon atoms. Suitable heteroatoms
will be apparent to those skilled in the art and include,
for example, oxygen and nitrogen.
I
-74-
In general, no more than three substituents or
heteroatoms, and preferably no more than one, will be
present for each Zen carbon atoms in the alicyclic hydra-
carbon-based radical.
Preferably, the alicyclic hydrocarbon based
radical present in the chlorine-containing compounds of this
invention is free from acetylenic and usually also free from
ethylenic unsatura~ion and contains at least five carbon
atoms.
As previously stated, the chlorine-containing
compounds may also be mixtures of one or more of the sheller-
aliphatic hydrocarbon-based compounds and/or the sheller
alicyclic hydrocarbon-based compounds. Furthermore, the
chlorine-containing compounds usually contain approximately
lo from about 30 to about 70 percent by weight chlorine The
preparation of the chlorine-containing compounds (c3 is well
known to those of ordinary skill in the art and a detailed
description of the process is unnecessary. Briefly, such
compounds are prepared by reacting chlorine gas with the
20 appropriate hydrocarbon-based compound until the desired
weight gain of chlorine is obtained.
The preferred chlor~ne-containing compounds are
the chlorinated paraffin wax compositions. The molecular
weight of these chlorinated paraffin wax compositions
25 usually range from about 300 up to about 1100, preferably
from about 350 to about 700 and, preferably, contains from
about 35 up to about 50% by weight of chlorine. These
preferred chlorine-containing compounds are commercially
available from Diamond Chemical under the trademark Sheller-
30 wax,
The compositions of this invention may be further combined with at least one sulfurized olefinically unset-
unrated compound.
The olefinically unsaturated compounds which are
sulfurized to provide the sulfurized olefinically unset-
-75-
unrated compounds useful for the purposes of this invention
are diverse in nature. They contain at least one olefinic
double bond, which it defined as a non-aromatic double bond;
that is, one connecting two aliphatic carbon atoms. In its
broadest sense, the olefin may be defined by the formula
R7R8C=CRgRlo, wherein each of R7, Ray Rug and Rio is hydrogen
or an organic radical. In general, the R groups in the
above formula which are not hydrogen may be satisfied by
such groups as -Creole, Conrail, Conrail, -COO,
Al 1
10 -ON, -1, Roll, -X, -Yell or An, wherein:
Each Roll is independently hydrogen, alkyd, at-
Kenya, aureole, substituted alkyd, substituted alkenyl or
substituted aureole, with the proviso that any two Roll groups
can be alkaline or substituted alkaline whereby a ring of up
15 to about 12 carbon atoms is formed;
M is one equivalent of a metal cation (preferably
Group I or II, e.g., sodium, potassium, barium, calcium);
X is halogen (e.g., sheller, broom, or idea);
Y is oxygen or diva lent sulfur;
An is an aureole or substituted aureole radical of up to
about 12 carbon atoms in the substituent.
Any two of R7, R8, R9 and Rl may also together
Norm an alkaline or substituted alkaline group, i.e., the
olefinic compound may be alicyclic.
The nature of the substituents in the substituted
moieties described above are no normally a critical aspect
of the invention and any such substituent is useful Jo long
as it it or can be made compatible with lubricating environ-
mints and does not interfere under the contemplated reaction
30 conditions. Thus, substituted compounds which are so us-
stable as to deleteriously decompose under the reaction con-
dictions employed are not contemplated. However, certain
substituents such as veto or alluded can desirably undergo
sulfurization. the selection of suitable substituents is
35 within the skill of the art or may be established through
1;2 ~L5~35;
Jo
routine testing. Typical of such substituents include any
of the above-listed moieties as well as hydroxy, amidine,
amino, sulfonyl, sulfinyl, sulfonate, vitro, phosphate,
phosphate, alkali metal Marquette and the like.
The olefinically unsaturated compound is usually
one in which each R group which is not hydrogen is indepen-
deftly alkyd, alkenyl or aureole, or (less often) a coxes-
pounding substituted radical. Monoolefinic and diolefinic
compounds, particularly the former, are preferred, and espy-
10 Shelley terminal moncolefinic (Alphonse) hydrocarbons; that
is, those compounds in which R7 and R8 are hydrogen and
R9 and Rl are alkyd or aureole, especially alkyd that is, the
olefin it aliphatic). Olefinic compounds having from about
8 up to about 36 and especially from about 8 up to about 20
15 carbon atoms are particularly desirable.
The C8-36 aliphatic ~-olefin it terminal
Olin is usually one which is unbranched on the ole~inic
carbon atoms; that it which contains the moiety CH2=CH-.
It also usually contains substantially no branching on the
20 allylic carbon atoms; that is, it preferably contains the
moiety CH2=CHCH2-~ The preferred oleflns are those in the
Kiwi range. Mixtures of these olefins are commercially
available and such mixtures are suitable for use in this
invention.
Also, fatty acid esters derived from one or more
unsaturated carboxylic acids are particularly useful as the
oLeinically unsaturated compounds.
The term "fatty azalea" as used herein refers to
acids which may be obtained by hydrolysis of a naturally
30 occurring vegetable or animal fat or oil. These are usually
in the Of 6-2 o range and include oleic acid linoleic acid
and the like.
Fatty acid esters which are useful are primarily
esters of aliphatic alcohols, including mandrake alcohols
I
- 77 -
such as methanol, ethanol, n-propanol, isopropanol, the buttonless,
etc., and polyhydric alcohols including ethylene glycol,
propylene glycol, trim ethylene luckily, neopentyl glycol,
glycerol and the like. Particularly preferred are fatty oils
derived predominantly from unsaturated acids, that is, naturally
occurring triglycerides of long chain unsaturated carboxylic
acids, especially linoleic and oleic acids. These fatty oils
include such naturally occurring animal and vegetable oils as
lard oil, peanut oil, cotton seed oil, soybean oil, corn oil and
the like.
The composition and nature of fatty oils is well known to
those of ordinary skill in the art and can be found in more
detail in MOP. Doss, Properties of the Principal, FATS, Fatty
Oils, Waxes, Fatty Acids and Their Salts, The Texas Company,
1952, which describes the fatty oils and unsaturated carboxylic
acids useful for this invention.
The sulfurization of olefinically unsaturated compounds can
be prepared by reacting, for example, elemental sulfur with one
or more of the olefinically unsaturated compounds described
above at a temperature of from about 100C. up to about 250C.,
preferably, from about 125C. up to about 200C. The amounts of
sulfur per mole of olefinically unsaturated compound are usually
from about 0.3 to about 2.0 gram-atoms, preferably from about
0.5 to about 1.5 gram-atoms.
The following US. patents are illustrative of the
sulfurized olefinically unsaturated compounds useful for this
invention and the processes for their preparation 3,796,661;
3,919,187; 3,850,825; 3,986,966; 4,053,427; 4,119,550.
I 5
-78-
The following specific illustrative examples
describe how to make the amino phenols (A) and the car-
boxlike derivative and post-treated carboxylic derivative
compositions (By which comprise the combination compositions
of this inven~ionA
In these examples, as well as in this specific
cation and the appended claims, all percentages, parts and
ratios are by weight, unless otherwise expressly stated to
the contrary. Temperatures are in degrees centigrade (C.)
10 unless expressly stated to the contrary.
EXAMPLE lo
A mixture of 4578 pats of a polyisobutene~sub-
~tituted phenol prepared by boron trifluoride-phenol
catalyzed alkylation of phenol with a polyisobutene having a
15 number average molecular weight of approximately Lowe (vapor
phase osmometry), 3052 parts of delineate mineral oil and 725
parts of textile spirits is heated to 60 to achieve home-
join. After cooling Jo 30, 319.5 parts of 16 molar
nitric acid in 600 parts of water is added to the mixture.
20 Cooling is necessary to keep the mixture's temperature below
40. After the reaction mixture is stirred for an add-
tonal two hours, an Alcott of 3710 parts is transferred to
a second reaction vessel. This second portion is treated
with an additional 127.8 parts of 16 molar nitric acid in
25 130 parts of water at 25-30. the reaction mixture is
stirred for 1.5 hours and when stripped o 220~30 ion.
Filtration provides an oil solution of the desired inter-
mediate tip).
ExamF~e lo
A mixture of 810 parts of the oil solution of the
(IA) intermediate described in Example lay 405 parts of
isopropyl alcohol and 405 parts of Tulane is charged to an
appropriate sized autoclave. Platinum oxide catalyst (0.81
part) is added and the autoclave is evacuated and purged
35 with nitrogen four times to remove any residual air. Hydra-
gun is fed to the autoclave at a pressure of 29-55 prig
isle
-79-
while the content is stirred and heated to 27-92 or a
total of thirteen hours. Residual excess hydrogen is
removed from the reaction mixture by evacuation and purging
with nitrogen four time. The reaction mixture is then
filtered through diatomaceous earth and the filtrate stripped
to provide an oil solution of the desired amino phenol
This solution contains 0,578% nitrogen.
EXAMPLE 2
An alkylated phenol it prepared by reacting phenol
10 with polybutene having a number average molecular weight of
about 1000 (vapor phase osmometry) in the presence of a
boron trifluoride/phenol catalyst. The catalyst is neutral-
iced and removed by filtration. Stripping of the product
filtrate first to 230~/760 ion (vapor temperature), then to
15 205/50 ion (vapor temperature), provides purified alkylated
phenol as a residue.
To a mixture of 265 parts of purified alkyd
phenol, 176 parts blend mineral oil and 42 parts of pew
trillium naphtha having a boiling point of approximately 20
20 is slowly added a mixture of 18.4 parts concentrated nitric
acid (69-70~) and 35 parts water. The reaction mixture is
stirred for 3 hours at about 30-45, stripped to 120~/20 ion
vapor temperature) and filtered to provide an oil solution
of the desired vitro phenol intermediate.
25 EXAMPLE 3
A mineral oil solution ~1900 parts of an alkyd-
axed, nitrated phenol as described in Example 2 containing
43% mineral oil is heated under a nitrogen atmosphere to
145. Then 70 parts of hydrazine hydrate is slowly added to
30 the mixture over 5 hours while its temperature is held at
about 145. The mixture is then heated to 160 for one hour
while 56 parts of aqueous distillate is collected. An
additional 7 parts of hydrazine hydrate is added and the
mixture is held at 140 for an additional hour. Filtration
35 at 130 provides an oil solution of the desired amino phenol
product containing 0.5~ nitrogen.
~583S
-80-
EXAMPLE 4
_ _ _
To a mixture of 800 parts of polybutene-substi
tuned phenol prepared essentially as described in Example 2
and 944 parts of delineate mineral oil at 59 is added 72
5 parts of concentrated nitric acid. The reaction is con-
trolled so as to keep the reaction temperature between 59
and 68. The reaction mixture is stirred for two hours at
69-73 and then heated to 140 while nitrogen is slowly
passed through it and water is removed by distillation.
10 ~ydrazine hydrate (90 parts) is then slowly added to the
mixture at 130 to 137 over 3 hours. The mixture is
stirred for 0.5 hour at this temperature and then heated to
160 while nitrogen is slowly passed through the mixture and
provision is made for collecting the aqueous distillate.
15 The residue is an oil solution of the desired amino phenol
product.
EXAMPLE 5
. . .
A mixture of 609 parts of polybutene-substituted
phenol prepared essentially as described in Example 2 and
20 454 parts of mineral delineate oil is blended at 57. To this
mixture is added, over 8 hours, 46.5 parts of concentrated
nitric acid (66.3% nitric acid). The mixture is stirred for
1.5 hours at 58~63 and then heated to 142 for 1.7 hours
while nitrogen is slowly passed through the mixture. The
I mixture is held a 143-145 for 0.5 hour and then cooled to
114. During the reaction, 23 parts of distillate is
collected. Filtration of the mixture at 113-126 provides
an oil solution of the desired vitro intermediate having a
nitrogen content of 0.64~.
30 EXAMPLE 6
_. .
To 320 parts of the oil solution of the polyp
butene-substituted nitrated phenol described in Example 5 is
added 12 parts of aqueous hydrazine t64% hydrazlne) over
6.25 hours at a temperature of aye. Filtration provides an
35 oil solution of the desired amino phenol product having a
nitrogen content of 0.59%.
~æ~ss3~
81-
EXAMPLE 7
To a mixture of 3000 parts of an alkylated phenol
made essentially as described in example 2 having a polyp
butane substation of about 70 carbon atoms and 3000 parts
of glacial acetic acid at 51 is added 540 parts of con-
cent rated nitric acid over three hours. During the add-
lion, the mixture is held at 51-63. The mixture is stored
at room temperature for 18 hours and when heated to 120 for
5 hours while nitrogen is slowly passed through the mixture
10 Provision is made for collecting the aqueous distillate.
The reaction it then stripped to 140~28 tot vapor temper
azure) and the residue filtered at 120~ to provide the
desired final product having a nitrogen content of 2.55%.
On this basis, it is calculated that the product contains an
15 average of two vitro groups per alkylated phenol.
EXAMPLE 8
To a mixture of 545 parts of the alkylated donator
phenol described in Example 7 and 340 parts ox delineate
mineral oil at 125 is added 100 parts of hydrazine hydrate.
20 This addition is carried out under a nitrogen atmosphere for
a 2.5 hour period while the temperature is held a 122-125.
The reaction mixture is when reflexed at 123 for 2.5 hours
and heated for an additional 2 hours to 155 while provision
is made for collecting aqueous distillate. A slow stream of
25 nitrogen is passed through the reaction mixture at 150-155
or an additional 2 hours and the residue is filtered to
provide an oil solution of the desired amino phenol product
having a nitrogen content of 1.16%.
EXAMPLE 9
Jo a mixture of 361 parts of tetrapropenyl-sub-
stituted phenol and 271 parts of glacial acetic acid at 7-
17 is added a mixture of 90 parts concentrated nitric acid
~70% HNO3) and 90 parts of glacial acetic acid. The add-
lion is carried out over 1.5 hours while the reaction mix-
35 lure is cooled externally to 7-17. The cooling bath is
removed and the reaction stirred or 2 hours at room temper-
. . .
~2~35
-82-
azure. Stripping to 134/ 35 ion vapor temperature) and
filtration provides as a residue the desired nitrated
intermediate having a nitrogen content of 4.65%.
EXAMPLE 10
To 303 parts of the nitrated intermediate desk
cried in Example 9 at 125 under a nitrogen atmosphere is
added 100 parts of hydrazine hydrate over a 2.4 hour period,
The mixture is reflexed for 2.5 hours and then distilled to
a vapor temperature of 155. A slow stream of nitrogen is
10 passed through the reaction mixture while it is kept at a
temperature of 155 to 190. Filtration of the residue
provides the desired amino phenol product which has a
nitrogen content of 4.89%.
EXAMPLE 11
A mixture of 510 pyres (0.28 mole) of pulse-
butane (My = 1845; My = 5325) and 59 parts (0.59 mole) of
malefic android is heated to 110~. This mixture is heated
to 190. in seven hours during which 43 part (0.6 mole) of
gaseous chlorine it added beneath the surface. At 190-
20 192. an additional 11 parts (OWE mole) of chlorine is
added over 3.5 hours. The reaction mixture is stripped by
heating at 190-193 with nitrogen blowing for 10 hours.
The residue is the desired polyisobutene-substituted sue-
Seneca assaulting agent having a saponification equivalent
25 number of 87 as determined by ASTM procedure D-94.
EXAMPLE 12
A mixer of Lowe parts (0~495 mole of pulse-
button (My = 2020; My = 6049) and 115 parts (1017 moles of
malefic android is heated to 110. This mixture is heated
30 to 184 in 6 hours during which 85 parts ~1.2 moles) of
gaseous chlorine is added beneath the surface. At 184-189
an additional 59 parts (0.83 mole) of chlorine is added over
4 hours. The reaction mixture it stripped by heating at
186-190 with nitrogen blowing for 26 hours. The residue
35 is the desired polyisobutene-substituted succinic assaulting
agent having a saponficiation equivalent number of 87 as
determined by ASSET procedure D-94.
~5~335
-83-
EXAMPLE 13
A mixture of 3251 parts of polyisobutene chloride,
prepared by the addition of 251 parts of gaseous chlorine to
3000 pats of polyi~obutene (My = 1696; My = 6S94) at 80 in
4.66 hours, and 345 par s of malefic android is heated to
200 in 0.5 hour the reaction mixture it held at 200-224
for 6.33 hours, stripped at 210 under vacuum and filtered.
The filtrate is the desired polyisobutene-substituted
succinic assaulting agent having a saponification equivalent
10 number of 94 as determined by ASSET procedure D-94.
EXAMPLE 14
A mixture is prepared by the addition of 10.2
parts (0.25 equivalent of a commercial mixture of ethylene
polyamides having from about 3 to about 10 nitrogen atoms
15 per molecule Jo 113 parts of mineral oil and 161 parts (0.25
equivalent) of the substituted succinic assaulting agent
prepared in Example 11 at 138. The reaction mixture is
heated to 150 in 2 hours and stripped by blowing with
nitrogen, the reaction mixture is filtered to yield the
20 filtrate a an oil solution of the desired product.
EXAMPLE 15
_
A mixture is prepared by the addition of 57 parts
(1.38 equivalents) of a commercial mixture of ethylene polyp
amine having from about 3 to 10 nitrogen atoms per molecule
I to 1067 parts of mineral oil and 893 parts (1.38 equiva-
lunate) of the substituted succinic assaulting agent prepared
in Example 12 at 140 to 145. The reaction mixture is
heated to 155 in 3 hours and stripped by blowing with
nitrogen. The reaction mixture is filtered to yield the
rate as an oil solution of the desired product.
EXAMPLE it
A mixture is prepared by the addition of 18.2
parts (0.433 equivalent) of a commercial mixture of ethylene
polyamides having from about 3 to 10 nitrogen atoms per
35 molecule to 392 parts of mineral oil and 348 parts (0~52
equivalent) of the substituted succinic assaulting agent
I
prepared in Example 12 at 140. The reaction mixture is
heated Jo 150 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 17
A mixture of 334 parts (0.52 equivalent) of the
polyisobutene-substituted succinic assaulting agent prepared
in Example 11, 548 part of mineral oil, 30 parts (0.88
equivalent) of pentaerythritol and 8.6 parts (0.0057 equiva~
10 lent) of Polyglycol 112 2 demulslfier from Dow Chemical
Company is heated at 150 for 2.5 hours. The reaction
mixture is heated to 210 in 5 hours and held at 210 for
3.2 hours. The reaction mixture is cooled Jo 190 and US
parts (0.2 equivalent) of a commercial mixture of ethylene
15 polyamides having an average of about 3 to about 10 nitrogen
atoms per molecule is added The reaction mixture it
stripped by heating at 205 with nitrogen blowing for 3
hours, then filtered to yield the filtrate as an oil soul-
lion of the desired product.
20 EXAMPLE 18
.
A mixture of 3225 parts (5.0 equivalents) of the
polyisobutene-substituted succinic assaulting agent prepared
in Example 12, 289 parts (8.5 equivalents) of punter-
throttle and 5204 parts of mineral oil is heated at 225-235
25 for So hours. The reaction mixture is filtered at 130 to
yield an oil solution of the desired product
EN _ LYE 19
A mixture of 631 parts of the oil solution of the
product prepared in Example 18 and 50 part ox anthranilic
30 acid is heated at 195-212 for four hours. The reaction
mixture is then filtered at 130 to yield an oil solution of
the desired product.
Example` 20
.
A mixture is prepared by the addition of 14 parts
35 of aminopropyl diethanolamine to 867 parts of the oil soul-
lion of the product prepared in Example 18 at 190 200. The
~2~3~i
-85-
reaction mixture is held at 195 for 2.25 hours, then cooled
to 120 and filtered. the filtrate is an oil solution of
the desired product.
EXAMPLE 21
A mixture of 62 parts of boric acid and 2720 parts
of top oil solution of the product prepared in Example 14 is
heated at 150 under nitrogen for six hours. The reaction
mixture is filtered to yield the filtrate as an oil solution
of the desired boron-containing product.
10 EXAMPLE 22
__
n oilily ester of boric acid is prepared by
heating an equimolar mixture of oilily alcohol and boric acid
in Tulane at the reflex temperature while water is removed
azeotropicallyO The reaction mixture is then heated to 150
15 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 14 is heated at
15~ for six hours and then filtered. The filtrate is an
20 oil solution of the desired boron-containing product.
EXAMPLE 23
Boron trifluoride (34 parts) is bubbled into 2190
parts of the oil solution of the product prepared in example
15 at 80 within a period of three hours. The resulting
25 mixture is blown with nitrogen at 70-80 D for two hours to
yield the residue as an oil solution of the desired product.
EXl~PLE 24
A mixture of 3420 parts of the oil-containing
solution of the product prepared in Example 16 and 53 parts
30 of acylonitrile is heated at reflex temperature from 1~5 to
145 for 1.25 hours, at 145 for three hours and then
stripped at 125 under vacuum. The residue is an oil
solution of the desired product.
Example 25
,
A mixture is prepared by the addition of 44 parts
of ethylene oxide over a period of one hour to 1460 parts of
I ii83~i
-86
the oil solution of the product prepared in Example 15 at
150. The ration mixture is held at 150 for one hour,
then filtered to yield the flltxate as an oil solution of
the desired product.
EXAMPLE 26
-
A mixture of 3880 parts of the oil solution of the
product of Example 14 and 120 parts of terephthalic acid is
heated at 150-160 and filtered. The filtrate is an oil
solution of the desired product.
10 EXAMPLE 27
A decal ester of phosphoric acid i prepared by
adding one mole of phosphorus pentaoxide to three moles of
decal alcohol at a temperature within the range of 3~ to
55 and then heating the mixture at 60-~3 until the react
15 lion is complete. The product is a mixture of the decylesters of phosphoric acid having a phosphorus content of
9.9% and an acid number of 250 ~phenolphthaleln indicator.
A mixture of 1750 parts of the oil solution of the product
prepared in Example 14 and 112 parts of the above decal
20 ester is heated at 145-150 for one hour. The reaction
mixture is filtered to yield the filtrate as an oil solution
of the desired product.
EXAMPLE
A mixture of 2920 parts of the oil solution of the
25 product prepared in Example 15 and 69 parts of Thor us
heated to 80 and held at 80 for two hours. The reaction
mixture is then heated at 150-155 for four hours, the last
ox which the mixture is blown with nitrogen. The reaction
mixture is filtered to yield the filtrate as an oil solution
30 of the desired product.
EXILE 29
A mixture of 1460 parts of the oil solution ox the
product prepared in Example 15 and 81 parts of a 37% aqueous
formaldehyde solution is heated at reflex for three hours.
35 The reaction mixture is stripped under vacuum at 150. The
residue is an oil solution of the desired product.
~5~35
-87-
EXAMPLE 30
_ __
A mixture of 1160 parts of the oil solution of the
product prepared in Employ 14 and 67 parts of sulfur moo-
chloride is heated for one hour at 150 under nitrogen. The
S mixture is filtered to yield an oil solution of the desired
sulfur-containing product.
EXAMPLE 31
___
A mixture is prepared by the addition of 11~5
parts of foxmlc acid to 1000 parts of the oil solution of
10 the product prepared in Example 15 at 60. The reaction
mixture is heated at 60-100 for two hours, g2-lOG~ for 1.75
hours and then filtered to yield an oil solution of the
desired product.
EMPLOY 32
.
A mixture is prepared by the addition of 58 parts
of propylene oxide to 1170 parts ox the oil solution of the
product prepared in Example 18 and 10 parts of pardon at
80-90. The reaction mixture is then heated at 100-120 for
2.5 hours and then stripped to 170 under vacuum. The
20 residue is an oil solution of the desired product.
EXAMPLE 33
-
A mixture of 1170 parts of the oil solution of the
product prepared in Example 18 and 36 parts of malefic ashy-
drive is heated to 200 over a 1.5 hour period and main-
25 twined at 200-210 for 5.5 hours. During the last 1.5 hour
period of heating, the reaction mixture is blown with
nitrogen. The reaction mixture is stripped to 190~ under
vacuum, then filtered to yield the filtrate as an oil
solution of the desired product.
As previously indicated, the nitrogen-containing
organic compositions of this invention comprise the come
bination of PA) and (B) or (C). Also, a combination of (A),
(C) and at least one sulfurized olefinically unsaturated
compound is a preferred embodiment of this invention. The
35 nitrogen containing organic compositions comprising a
combination of (A), (B) and (C) is another preferred em-
335
bodimen of this invention. An additional preferred em-
bodiment of the present invention are the nitrogen-con-
twining organic composition comprising a combination of
(A), (B), (C) and at least one sulfurized olefinically
unsaturated compound.
Accordingly, the above compositions may be come
brined simultaneously or sequentially in any order.
The nitrogen-containing organic compositions are
preferably prepared by combining the above-described come
10 potent compositions through the use of conventional blending techniques which include, for example, mixing the component
compositions at a temperature sufficient to insure home-
generous blending and/or the US of a solvent/diluent such as
mineral oil, xylenel naphtha or a normally liquid fuel to
facilitate handling and to insure a homogeneous mixture of
the component compositions. Such techniques are well known
to those of ordinary skill in the art and, therefore,
further discussion is unnecessary. Generally, the weight
ratio of the component composi~lons tub), I and the sulk
foreside olefinically unsaturated compound to the aminoph~nol compounds PA) is about 0.1 to about 10.0 parts to one
part amino phenol.
Toe examples in the following table illustrate the
nitrogen-containing compositions of the present invention.
table
En. Sulfurized**
Nooks. Rex. 14 En. 26 Sheller* I 5-18 ~-Olefin
I 16~5 --- 70 10 3.5
~I16.5 70 --- 10 3.5
III US -I 35 ---
30 IV 20 --- 80
V 20 80
commercially available chlorinated paraffin wax from Diamond
Chemicals containing about 40~ by weight chlorine.
**Prepared by reacting 1 mole ox elemental sulfur with 1 mole
35 of Claus 18 ~-olefin at 170~C. for 9 hours under a blanket of
nitrogen gas.
I 35
-89-
As previously indicated, the compositions of this
invention are also useful as additives for lubricants, in
which they function as an~ioxidants, anticorrosives, deter
gents, dispersants, fluidity modifiers and, in particular,
impart one or more of the following properties to Libra-
cants- anticorrosive, antiwar and friction reducing
properties. These particular properties are unexpected and
are especially effective in protecting silver, copper and
lead parts in diesel engines. whey can be employed in a
10 variety of lubricants based on diverse oils of lubricating
viscosity, including natural and synthetic lubricating oils
and mixtures thereon. these lubricants include crankcase
lubricating oils for spark-ignited and compression ignited
internal combustion engines, including automobile and truck
15 engines, two-cycle engines, aviation piston engines, marine
and railroad diesel engines, and the like. They can also be
used in gas engines, stationary power engines and turbines
and the like. Automatic transmission fluids, transsexual
lubricants, gear lubricants, metal-working lubricants,
20 hydraulic fluids and other lubricating oil and grease combo-
sessions can also benefit from the incorporation therein of
the compositions of the present invention.
Natural oils include animal oils and vegetable
oils (e.g., castor oil, lard oil) as well as liquid pew
US trillium oils and solvent-treated or acid-treated mineral
lubricating oils of the paranoiac, naphthenic and mixed
para~inic-n~phthenic types. Oils ox lubricating viscosity
derived from coal or shale are also useful base oils.
Synthetic lubricating oils include hydrocarbon oils and
30 halo-substituted hydrocarbon oils such as polymerized and
interpolyrnerized olefins rug., polybutylenesl pulpier-
pylons, propylene-isobutylene copolymers, chlorinated
polybutylenes, poly(l-hexenes~, polyp octanes), polyp
doziness), etc. and mixtures thereof; alkylbenzenes ego.,
35 dodecylbenzenes, tetradecylbenzenesO dinonylbenzenes, Dow-
ethylhexyl)benzenes, etc.]; polyphenyls (e.g., biphenyls,
~5~33S
-so
terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl
ethers and alkaloid diphenyl sulfides and the derivatives,
analogs and homology thereof and the like.
Alkaline oxide polymers and inter polymers and
derivatives thereof where the terminal hydroxyl groups have
bee modified by es~erification, etherification, etc. con-
statute another class of known synthetic lubricating oils.
These are exemplified by the oils prepared through polyp
merization of ethylene oxide or propylene oxide, the alkyd
10 and aureole 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 500-1000, deathly ether
of polypropylene glycol having a molecular weight of 1000-
15 1500, etc.) or moo- and polycarboxylic esters thereof, for
example, the acetic acid esters, mixed Coca fatty acid
esters, or the Of 3 Ox acid divester of tetraethylena glycol.
Another suitable class ox synthetic lubricating
oils comprises the esters of dicarboxylic acids ego.,
20 phthalic acid, succinic acid, alkyd succinic acids and
alkenyl succinic acids, malefic acid, azelaic acid, sub Eric
acid, sebacic acid, fumaric acid adipic acid, linoleic acid
dimmer Masonic acid, alkyd Masonic acids, alkenyl Masonic
acids, etc.) with a variety of alcohols ego, bottle Alcoa
25 hot, Huxley 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) subacute, di-n-hexyl
umarate, ductile subacute, disquietly assault, deciduously
30 assault, ductile phthalate, didecyl phthalate, dieicosyl
subacute, the ~-ethylhexyl divester of llnoleic acid diver,
the complex ester formed by reacting one mole of sebacic
acid with two moles of tetraethylene glycol and two mole of
2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those
made from Us to Of 2 monocarboxylic acids and polyols and
I 33~
--91--
polyol ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol, dipentaerythrltol, tripentaPrythritol, etc.
Silicon-based oils such as the polyalkyl-, polyp
aureole-, polyalkoxy-, or polyaryloxy~siloxane oils and sift-
gate oils comprise another useful class of synthetic Libra-
cants [ego, tetraethyl silicate, tetraisopropyl silicate,
twitter (2-ethylhexyl) silicate, tetra-t4-methyl-2-ethylhexyl)
silicate, tetra-(p~tert-bu~ylphenyl) silicate, hooks-
methyl-~-pentoxy)-disiloxane, poly~methyl)-5iloxanes~ polyp
10 ~methylphenyl)siloxanes, etc.]. Other synthetic lubricating oils include liquid esters ox phosphorus-containing acids
ego., tricresyl phosphate, trioctyl phosphate, deathly
ester of decylphosphonic acid, etch polymeric tetrahydro-
furriness and the like.
Unrefined, refined and redefined oils (and mix-
lures of each with each other) of the type disclosed here-
in above 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
20 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 are
25 similar to the unrefined oils except they have been further
treated in one or more purification steps to improve one or
more properties. Many such purification techniques are
known to those of skill in the art such as solvent extract
ton, acid or base extraction, filtration, percolation, etc.
30 Redefined 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 redefined oils are
also known as reclaimed or reprocessed oils and often are
additionally processed by techniques directed to removal of
35 spent additives and oil breakdown products.
33~i
- -92-
Generally, the lubricants of the present invention
contain an amount of the nitrogan-containing organic coy
positrons of this invention sufficient to provide it with
antioxidant, antiwar anticorrosive, detergent, dispersant,
friction reducing or fluidity modifying properties. Norm-
ally this amount will be about 0.05% to about 20~, pro-
fireball about 0.1% to about 10% of the total weight of the
lubricant. In lubricating oil operated under extremely
adverse conditions, such as lubricating oils for marine
10 diesel engines, the compositions of this invention may be
present in amounts of up to about 30% by weight.
The term "minor amount" as used in the specie
ligation and appended claims is intended to mean that when a
composition contains a "minor amount" of a specific material
15 that amount is less than 50% by weight of the composition.
The term 'major amount" as used in the specific
cation and appended claims is intended to mean that when a
composition contains a "major amount" of a specific material
that amount is more than 50% by weight of the composition.
The invention also contemplates the use of other
additives in combination with the compositions of this
invention. Such additives include, for example auxiliary
detergents and dispersants of the ash-producing or cashless
type, auxiliary corrosion- and oxidation-inhibiting agents,
pyre point depressing agents, extreme pressure agents,
copper deactivators, color stabilizers and anti foam agents.
The ash-producing detergents are exemplified by
oil-soluble neutral and basic salts of alkali or alkaline
earth metals with sulfonic acids, carboxylic acids, phenols
o'er organic phosphorus acids characterized by at least one
direct coronet phosphorus linkage such as those prepared
by the treatment of an olefin polymer (e.g., polyisobutene
having a molecular weight of Lowe) with a phosphorizing
agent such as phosphorus trichloride, phosphorus Hyatt-
35 sulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphor-
33S
- 93 -
thwack chloride. The most commonly used salts of such acids are
those of sodium, potassium lithium, calcium, magnesium,
strontium and barium.
The term "basic salt" is used to designate metal salts
wherein the metal is present in stoichiometrically larger amounts
than the organic acid radical. The commonly employed educe for
preparing the basic salts involve heating a mineral oil solution
of an acid with a stoichiometric excess of a metal neutralizing
agent such as the metal oxide, hydroxide, carbonate, bicarbonate,
or sulfide at a temperature above 50C. and filtering the
resulting mass. The use of a "promoter" in the neutralization
step to aid the incorporation of a large excess of metal likewise
is known. Examples of compounds useful as the promoter include
finlike substances such as phenol, naphthol, alkylphenol,
tiophenol, sulfurized alkylphenol, and condensation products of
formaldehyde with a finlike substance; alcohols such as
methanol, 2-propanol, octal alcohol, cello solve, carbitol,
ethylene glycol, stroll alcohol, and cyclohexyl alcohol and
amine such as aniline, phenylenediamine, phenothiazine, phenol-
~-naphthylamine, and dodecylamine. A particularly effective
method for preparing the basic salts comprises mixing an acid
with an excess of a basic alkaline earth metal neutralizing agent
and at least one alcohol promoter, and carbonating the mixture
at an elevated temperature such as 60-200C. The basic alkali
and/or alkaline earth metal carbonate sulfonate and/or fount
useful in combination with the nitrogen-containing organic
compositions ox this invention, are well known to those of
ordinary skill in the art and are described in detail in US.
Patent 3,779~920, as well as processes for their preparation.
auxiliary cashless detergents and dispersants are so called
despite the fact that, depending on its constitution, the
dispersant may upon combustion yield a non-volatile ....
Sue
-94-
material such as boric oxide or phosphorus pent oxide;
however, it does not ordinarily contain metal and therefore
does not yield a metal-containing ash on combustion. Many
types are known in the art, and any of them are suitable for
use in the lubricants of this invention. The following are
illustrative:
(1) Reaction products of carboxylic acids (or
derivatives thereof) containing at least about 34 and
preferably at least about 54 carbon atoms with nitrogen-
10 containing compounds such as amine, organic hydroxy come
pounds such as phenols and alcohols, and/or basic inorganic
materials. Examples of these "carboxylic dispersants" are
described in British Patent 1,306,5~9 and in many USE
patents including the following:
3,1~3,603 3,351,552 3,541,012
3,184,474 3,381,022 3,542,678
3,215,707 3,39~,141 3,542,~8~
3,219,~66 3,~15,750 3,567,637
3,271,310 3,433,744 3,574,101
3,272,746 3,44~,170 3,576,743
3,281,357 3,44~,048 3,630,904
3,306,90~ 3,448,049 3,632,510
3,311,558 3,451,933 3,632,511
3,316,177 3,454,607 3,697,428
3,340,281 3,4~7,668 3,725,441
3,341,542 3,501,405 Rye 26,433
3,346,~93 3,52~,179
2) Reaction products of relatively high mole-
ular weight aliphatic or alicyclic halides with amine,
30 preferably polyalkylene polyamides. These may be kirk-
terraced as "amine dispersants" and examples thereof are
described for example in the following USE patents:
3,275,554 3,45~,555
3,438,757 3,565,804
(3) Reaction products of alkyd phenols in which
the alkyd group contains at least about 30 carbon atoms with
Swahili
95-
aldehydes (especially formaldehyde) and amine especially
polyalkylene polyamides), which may be characterized as
"Mannish dispersants". The materials described in the
following US. patents are illustrative:
2,459,112 3,4~2,~08 3,591,598
2,962,442 3,~48,047 3,~00,372
2,984,550 3,454,497 3,634,515
3,036 t 003 3,459,661 3,64g,229
3,166,516 3,461,172 3,697,574
3,236,770 3,493,5~0 3,725~277
3~355,270 3,~39,633 3,725,~80
3,368,972 3,558,743 3,726,~82
3,413,347 3,586,629 3,980,569
(4) Products obtained by post-treating the car-
15 boxlike, amine or Mannish dispersants with such reagents as
urea, Thor, carbon disulfide, aldehydes, kittens, car-
boxlike acids, hydrocarbon-subskituted succinic androids,
nitrites, epoxies, boron compounds phosphorus compounds or
the like. Exemplary materials of this kind are described in
20 the following US. patents:
3,036,003 3,282,955 3,493,520 3,639,~42
3,~87,936 3,312,619 3,502,677 3,649,2~9
3,~00,10~ 3,36~,569 3,513,093 3,649,659
3,216,93~ 3,367,9~3 3,533,945 3,658,836
25 3,254,025 3,373,111 3,539,633 3,697,574
3,256,185 3,403,102 3,573,010 3,702,757
3,278,550 3,~42,808 Sue 3,703,536
3,280,~34 3,455,~31 3,591,598 3,704,308
3,281,428 3,455,832 3,600,372 3,708,522
(5) Inter polymers ox oil-solubilizing monomers
such as decal methacrylate, vinyl decal ether and high
molecular weight olefins with monomers containing polar
substituents, e.g., aminoalkyl acrylates or acrylamides and
poly-(oxyethylene)-substituted acrylates~ These may be
35 characterized as "polymeric dispersals and examples
thereof are disclosed in the following US. patents:
Sue
96 -
3,32g,658 3,666,730
3,449,250 3,687,849
3,519,565 3,702,300
Extreme pressure agents and auxiliary corrosion- and
oxidation-inhibiting agents are exemplified by sulfurized alkyd-
phenol, phosphosulfurized hydrocarbons such as the reaction
product of a phosphorus sulfide with turpentine or methyl owlet;
phosphorus esters including principally dihydrocarbon and
trihydrocarbon phosphates such as dibutyl phosphate, doughtily
phosphate, dicyclohexyl phosphate, pentylphenyl phosphate,
dipentylphenyl phosphate, tridecyl phosphate, distearyl
phosphate, dim ethyl naphthyl phosphate, oilily 4-pentylphenyl
phosphate, polypropylene (molecular weight substituted
phenol phosphate, diisobutyl-substituted phenol phosphate;
metal thiocarbamates, such as zinc dioctyldithiocarbamate, and
barium heptylphenyl dithiocarbamate; Group II metal
phosphorodithioates such as zinc dicyclohexylphosphorodithioate,
zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphoro
dithioate, cadmium dinonylphosphorodithioate, and the zinc salt
of a phosphorodithioic acid produced by the reaction of
phosphorus pentasulfide with an equimolar mixture of isopropyl
alcohol and n-hexyl alcohol.
Still another additive which may be combined with the
nitrogen-containing compositions of the invention are the 2,5-
bis-C5-C20 alkyldithio thiodiazoles, such as 2,5-bis(octyl~
dithio)thiadiazole, which functions as antioxidant, sulfur
deactivators and antiwar agents. The dithiothiadiazoles are
advantageously employed in an amount of between 0.01 and 1 wt.%,
and preferably between 0.02 and 0.1 wt.% of the finished oil
composition.
The compositions of this invention can be added
directly to the lubricant. Preferably, however, they are
I.
335
-97-
diluted with a substantially inert normally liquid organic
delineate such as mineral oil, naphtha, Bunsen, Tulane or
zillion, to form an additive concentrate. These concentrates
usually contain about guy% by weight of the composition of
5 this invention and may contain/ in addition, one or more
other additives known in the art or described hereinabove.
The fuel compositions of the present invention
contain a major proportion of a normally liquid fuel,
usually a hydrocarbonaceous petroleum distillate fuel such
10 as motor gasoline as defined by ASTM Specification D-439-73
and diesel fuel or fuel oil as defined by ASTM Specification
D-3960 Normally liquid fuel compositions comprising non-
hydrocarbonaceous materials such a alcohols, ethers
organo-nitro compounds and the like (e.g., methanol, ethanol,
15 deathly ether, methyl ethyl ether, nitromethane) are also
within the scope of this invention as are liquid fuels
derived from vegetable or mineral sources such as corn,
alfalfa, shale and coal. Normally liquid fuels which are
mixtures of one or more hydrocarbonaceous fuels and one or
20 more nonhydrocarbonaceous materials era also contemplated.
Examples of such mixtures are combinations of gasoline and
ethanol, and diesel fuel and ether. Particularly preferred
is gasoline, that is, a mixture of hydrocarbons having an
ASTM boiling point of about 60C. at the 10% distillation
punt to about 205C. at the 90% distillation point.
Generally, these fuel compositions contain an
amount of the nitrogen-containing organic composition of
this invention sufficient to impart antioxidant, antiwar,
anticorrosive, friction reducing, detergent or dispersant
proprieties to the fuel; usually this amount is about 0.001
to about I (based on the weight of the final composition),
preferably 0.001% to I
The fuel compositions of this invention can
contain, in addition to the compositions of this invention,
other additives which are well known to those of skill in
the art. These can include antiknock agents such as twitter-
~Z~S~33~
- 98 -
alkyd lead compounds, lead scavengers such as haloalkanes (e.g.,
ethylene dichlorides and ethylene dibromide~, deposit preventers
or modifiers such as triaryl phosphates, dyes, octane improvers,
auxiliary antioxidant such as 2,6-ditertiary-butyl-4-methyl-
phenol, rust inhibitors such as alkylating succinic acids andanhydrides, bacteriostatic agents, gum inhibitors, metal
deactivators/ emulsifiers, upper cylinder lubricants, anti icing
agents and the like.
In certain preferred fuel compositions of the present
invention, the afore-described compositions are combined with an
cashless dispersant in gasoline. such cashless dispersants are
preferably esters of a moo- or polyol and a high molecular weight
moo- or polycarboxylic acid assaulting agent containing at least
30 carbon atoms in the azalea moiety. Such esters and methods for
their preparation are well known to those of skill in the art.
See, for example, French patent 1,396,645, British patents
981,850 and 1,055,337 and US. patents 3,255,10B; 3,311,558;
3,331,776; 3,346,354; 3,522,179; 3,579,450, 3,542,680; 3,381,022;
3,639,242, 3,697,428; 3,708,522; and British Patent
Specification 1,306,529. Generally the weight ratio of the
compositions of this invention to the aforesaid cashless
dispersants is about 0.1 to about 10.0l preferably about 1 to
about 10 parts of composition to 1 part cashless dispersant. In
still another embodiment of this invention, the inventive
I additives are combined with Mannish condensation products formed
from substituted phenols, aldehydes, polyamides, and substituted
prudence. Such condensation products are described in US.
patents 3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,725,277.
The compositions of this invention can be added
directly to the fuel to form the fuel compositions of this
invention or they can be diluted with a substantially inert,
normally liquid organic solvent/diluent such as mineral oil,
I.
33~ii
99-
zillion, or a normally liquid fuel as described above, to
form an additive concentrate which is then added to the fuel
in sufficient amounts to form the inventive fuel composition
described herein. These concentrates generally contain
about 20 to 90 percent of the compositions of this invention
and can contain in addition any of the above-described con-
ventional additives, particularly the afore-described
cashless dispersants in the aforesaid proportions. The
remainder of the concentrate is the solvent/dlluent.
the lubricant, fuel and additive concentrate
compositions of this invention are exemplified by the
following:
Example A
A gasoline having a Reid vapor pressure of 8.4 psi
15 and containing 24 parts per million parts of gasoline of the
nitrogen-containing product described in Example V.
Example B
A diesel fuel oil containing 40 parts per million
parts of fuel of the nitrogen-containing product described
20 in example IV.
A ~ol~ent-refined, neutral SUE 10 mineral oil
containing 7% of the nitrogen-containing product described
in Example II.
25 Example D
A soLvent-refined, SUE 40 mineral oil containing
6% of the nitrogen containing composition described in
Example I.
Example E
A synthetic lubricant comprised predominantly of
C5-Cg normal alcohol esters of a 50/50 molar mixture of
adipic and glutaric acids containing I of the nitrogen-
containing product described in Example II.
Example F
A concentrate comprising 50% of the mineral oil
and 50% of the product described in Example I.
~2~5~335
--10~--
The lubricant and fuel compositions of this invent
lion and the nitrogen containing organic compositions of
this invention and the processes for preparing these pro-
ducts have been specifically exemplified above to aid those
skilled in the art in understanding and practicing the
invention. Many obvious variations and departures from the
specific disclosure will be apparent to those of skill in
the art based on principles and teachings herein and in the
prior art. Such variations and departures are contemplated
10 as being within the scope of the present invention unless
clearly excluded by the appended claims
