Note: Descriptions are shown in the official language in which they were submitted.
L4~i
L-2238R
Title. DIESEL LUBRICANTS AND METHODS
Backqround o~ the Invention
The present invention relates to diesel
lubricants, and more paxticularly to diesel lubricants
containing additives which are ef~ective to minimize
undesirable viscosity increases of the lubricant when
the lubricant is used in diesel engines. The invention
also relates to methods o~ preparing basic alkali metal
sulfonates, particularly basic potassium sulfonates,
and a method of operating diesel engines which
comprises lukricating said engines during operation
with the diesel lubricants o~ the invention.
It is well known that lubricating oils tand to
deteriorate under conditions of use in present day
internal combustion engines resulting in the formation
of sludge, lacquer, carbonaceous materials and resinous
materials which tend to adhere to the various engine
parts, in particular, the engine rings, grooves and
skirts. Furthermore, diesel angines operated at low-
speed and high-torque such as under prolonged idle and
stop-and-go conditions have experienced extensive and
undesirable thicXening of the lubricant. It has been
suggested in the prior art ~hat t~e undesirable
thickening of the oil is caused by the high levels of
insolubles (soot).
- ~ ',
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-' , ~ ` ' ~ ' ' . . ..
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One class of compounds which has been
suggested ~or use in lubricating oils, particularly
diesel oils, are the normal and overbased sul~urized
calcium alkyl phenolates such as described in U.g.
Patents 3,474,035; 3,528,917; and 3,706,632~ These
materials function as detergents and dispersants, and
also are reported to exhibit antioxidant and anti-
thickening properties. Another multi-purpose additive
for lubricating oils having antioxidant, anti-
thickening, anti-corrosion and detergent proparties is
described in U.S. Patent 3,897,352. The additive
described in this patent comprises a sulfurizPd, Group
II me~al nitrated alkyl phenolate.
As will ba dascribed more fully h~reinafter,
the present invention relates to a diesel lubricant
containing certain speci~ied types of carboxylic
derivative compositions as dispersants and certain
basic alkali metal salts. This combination of specific
dispersant and detergent is effectiv2 to minimize
undesirable viscosity increases of diesel lubricants
when used in diesel engines.
Lubricating oil formulations containing oil-
soluble carboxylic acid derivatives, and in particular,
those ob~ained by the reaction of a carboxylic acid
with an amino compound have been described previously
such as in U.S. Patents 3,018,250; 3,0~4,195;
3,172,892; 3,216,936; 3,219,666; and 3,272,746. Many
of the above-identified patents also describe the use
of such carboxylic acid deriva~ives in lubricating oils
in combinat-on with ash-containing detergents including
basic metal salts o~ acidic organic materials such as
sulfonic acids, carboxylic acids, etc~
,
,
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~ he particular type of carboxylic acid
derivative composition utilized in the diesel lubricant
o~ the present invention are described generally in
U.S. Patent 4,234,435. This patent also descrlbe~
lubricating compositions containing said carboxylic
acid derivative compositions in combination with other
additives such as fluidity modifiers, auxiliary
detergents and dispersants of the ash-producing or
ashless-type, oxidation inhibitors, etc. A lubricating
!~ composition containing the carboxylic acid deri~ative,
a basic calcium sulfonate, and other traditional
additives is described in the '435 patent in Col. 52,
lines 1-8.
The second critical component of the diesel
~l lubricants of the present invention is at least one
basic alkali metal salt of at least one acidic organic
compound having a metal ratio of at least about 2.
Such compositions generally are referred to in the art
as metallic or ash-detergents, and the use of such
-~ detergents in the lubricating oil formulations has been
suggested in many prior art patents. For example,
Canadian Patent 1,055~700 describes the use of basic
alkali sulfonate di~persions in crankcase lubricants
for both spark-ignited and compression-ignited internal
combustion engines. The Canadian patent suggests that
the basic alkali sulfonate disperæions can be used
alone or in combination with other lubricant additives
~nown in the art such as ashless dispe~sants including
esters or amides o~ hydrocarbon-substituted succinic
acids.
Even though detergents and dispersants, both
of the ash and the ashless-type have been utilized
previously in diesel lubricants, many of these
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lubricants have continued to exhibit undesirable
thickening, especially under low-speed, high-torque
operation unles~ relatively large amounts o~ khe
detergents and dispersanks are incorporated in~o khe
diesel lubricants. The use o~ large amounts o~
detergents and dispersants generally is undesirable
because of the added~cost.
In order to constitute an acceptable diesel
lubricani, a lubricant must achieve two performance
levels: Classi~ication CC(Caterpillar l-H) and
Clas~i~ication CD(Caterpillar 1-&), with the l-G level
representing more severe, highly super-charged engine
operation. There continues to be a need in the
industry for compositions which can be added to diesel
lubricants which will minimize, i~ not prevent,
undesirable vi~cosity increase of the lubricant when
used in diesel engines, and when formulated into diesel
lubricants, the lubricants are capa~le of achieving
Caterpillar l-H and Caterpillar l-G level par~ormancs
without signi~icantly adding to the cost of the diesel
lubricant.
Summary of the Invention
A diesel lubricant e~hibiting improved ability
to minimize undesirable viscosity increases when used
1~ in diesel engines is described. ~ore particularly, in
accordance with the present invention, a diesel
lubricant is descri~ed which comprises a major amount
of an oil of lubricating viscosity and a minor amount,
sufficient to minimize undesirable viscosity increases
of the lubricant when used in diesel engines, of a
composition comprising (A) at lPast one carboxylic
derivative composition produced by reacting at least
one substitu~ed succinic acylating agent with at least
. ,
.. .
one amino compound containing at least one -NH- group
wherein said acylating agent consists o~ sub~tituent
groups and succinic groups wherein th~ substituent
groups are derived from polyalkene characterized by an
Mn value of a~ least about 1200 and an Mw/Mn ratio o~
at least about 1.5, and wherein said acylating agents
are characterized by the presence within their
structure o~ an average of at least about 1.3 succinic
groups for each equivalent weight of substituent
groups, and (B) at least one basic alkali metal salt of
at least one acidic organic compound having a metal
ratio of at least about 2. The diesel lubricant also
may contain (C) at least one oil-soluble neutral or
basic alkaline earth metal salt of at least one acidic
compound.
Preferably, the basic alkali metal salt (B)
contained in the diesel lubricants of the invention is
at least one sodium salt and more prefarably, a sodium
salt of a sulfonic acid. The inven~ion also includes
methods for preparing basic metal salts, particularly
potassium salts, and methods for operating diesel
engines which comprise lubricating aid engines during
operation with the die~el lubricants o~ the invention.
Description o~ the Pre~erred Embodiments
The diesel lubricants of the present invention
comprise a ma;or amount of an oil of lubricating
viscosity and a minor amount, su~ficient to minimiza
undesirable viscosity increase~ of the lubricant when
used in diesel engines, of a composition comprising a
combination of (A) at least one carboxylic derivative
composition as defined more ~ully below, and (B) at
least one basic alkali metal salt of at least one
acidic organic compound.
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The oil o~ lubricating viscosity which i5
utilized in the preparation of the diesel lubricants of
the invention may be based on natural oils, synkhetlc
oils, or mixture~ thereof.
Natural oils include animal oils and vegetable
oils (e.g., castor oil, lard oil) as well as mineral
lubricating oils such as liquid petroleum oils and
solventotreated or acid-treated mineral lubricating
oils of the para~finic, naphthenic or mixed paraffinic-
naphthenic types. Oils of lubricating viscosity
derived from coal or shale are also useful. Synthetic
lubricating oils include hydrocarbon oils and
halosubstituted hydrocarbon oils such as polymerized
and interpolymerized olefins (e.g., polybutylenes,
polypropylenes, propylene-isobutylene copolymers,
chlorinated polybutylenes, etc.~; poly(l-hexenes),
poly(l-octenes), poly(l-decenes), e~c. and mixtures
thereof; alkylbenzenes (e.g., dodecylbenzenes, tetra-
decylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-
benzenes, etc.); polyphenyls (e.g., biphenyls,
terphenyls, alkylated polyphenyls, etc.); alkylated
diphenyl ethers and alkylated diphenyl sulfides and the
derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and
derivatives thereof where the terminal hydroxyl groups
have been modified by esterification, etheri~ication,
etc., constitute another class of known synthetic
lubricating oils that can be used. These are
exemplified by the oils prepared through polymerizatlon
of ethylene oxide or propylene oxide, the alkyl and
aryl ethers of these polyoxyalkylene polymers (e.g.,
methylpolyisopropylene glycol ether having an average
molecular weight o~ about 1000, dlphenyl ether of
.
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4~L45
--7--
polyethylene glycol having a molecular weight of about
500-1000, diethyl ether of polypropylene glycol having
a molecular weight of about 1000-1500, etc.) or mono~
and polycarboxylic esters khereof, ~or example, the
acetic acid esters, mixed C3-C8 fatty acid esters,
or the C13Oxo acid diester of tetraethylena glycol.
Another suitable class of synthetic
lubricating oils that can be used comprises the esters
of dicar~oxylic acids (e.g , ph~ha~.ic acid, succinic
acid, alkyl succinic acids, alkenyl succinic acids,
maleic acid, azelaic acid, suberic acid, sebacic acid,
fumaric acid, adipic acid, linoleic acid dimer, malonic
acid, alkyl malonic acids, alkenyl malonic acids, etc.)
with a variety of alcohols (e.g., butyl alcohol, hexyl
alcohol, dodecyl alcohol, 2~ethylhexy1 alcohol,
ethylene glycol, diethylene glycol monoether, propylene
glycol, etcl) Specific examples of these esters
include dibutyl adipate, di(~-ethylhexyl) sebacate,
di-n-hexyl fumarate, dioctyl sebacata, diisooctyl
azelate, diisodecyl azelate, dioctyl phthalate, didecyl
phthalate, dieicosyl sebacate, the 2-ethylhexyl diester
of linoleic acid dimer, the complex ester formed by
reacting one mole of sebacic acid with two moles of
tetraethylene glycol and two moles o~ 2-ethylhexanoic
acid and the l.ike.
Esters useful as synthetic oils also include
those made ~rom C5 to C12 monocarboxylic acids and
polyols and polyol ethers such as neopentyl glycol,
trimethylol propane, pentaerythritol, dipentaery-
thritol, tripentaerythritol, etG.
Silicon-based oils such as the polyalkyl-,
polyaryl-~ polyalkoxy-, or polyaryloxy-siloxane oils
and silicate oils comprise another use~ul class of
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~28~
synthetic lubricant~ (e.g., tetraethyl silicake,
tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate,
tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butyl-
phenyl)silicate, hexyl~(4-methyl-2-pentoxy)dlsiloxane,
poly(methyl) 5il oxanes, poly(mekhylphenyl)siloxanes,
etc.). Other synthetic lubricating oils include liquid
esters o~ phosphorus-containing acids ~e.g., tricresyl
phosphate, trioctyl phosphate~ diethyl ester of decane
phosphonic acid, etc.), polymeric tetrahydrofurans and
the like.
Unrefined, re~ined and rere~ined oils, either
natural or synthetic (as well as mixtures of two or
more of any of these) of the type disclosed herein-
above can be used in the concentrates of the present
invention. Unrefined oils are those obtained dir2ctly
from a natural or synthetic source without further
purification txeatment~ For example, a shale oil
obtained dixectly ~rom retor~ing ~perations, a
petroleum oil obtained directly from primary
distillation or ester oil obtained directly from an
esterification process and used without further
treatment would be an unrefined oil. Refined oils ara
similar to the unrefined oils except they have been
further treated in one or more purification steps to
improve one or more pxoperties. Many such purification
techniques are known to those skilled in the art such
as solvent extraction, secondary distillation, acid or
base extraction, ~iltration, percolation, etc~
Rerefined oils are obtained by processes similar to
those used to obtai~ re~ir.ed oils applied to re~ined
oils which have baen already used in service. Such
rerefined oils are also known as reclaim~d or
reprocessed oils and often are additionally processQd
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by techni~ues direc~ed to removal of spent additives
and oil breakdown products.
Component (A) which is utilized in the diesel
lubricants o~ the present invention is at least one
caxboxylic derivative aomposition produced by reacting
at least one substituted succinic acylating agent with
at least one amino compound containing at least one
-N-H- group wherein said acylating agent con~ists of
substituent groups and succinic groups wherein the
substituent groups are derived from polyalkene
characterized by an Mn value of at least about 1200 and
an Mw/Mn ratio of at l~ast about 1.5, and wherein said
acylating agents are characterized by the presence
within their structure of an average of at least about
1.3 succinic groups for each e~uivalent weight of
substituent group~.
The substituted succinic acylating agent
utilized the preparation of the carboxylic deri~ative
can be characterized by the presence within its
structure of ~wo groups or moieties. The first group
or moiety i~ referred to hereinafter, for conv~nience,
as the "su~stituent group(s) 19 and is derived ~rom a
polyalkene. The polyalkene from which the substituted
groups are derived is characterized by an Mn (number
average molecular weight) value of at least 1200 and
more generally from about 1500 to about 5000, and an
Mw/Mn value of at least about 1.5 and more generally
from about 1.5 to about 6. The abbreviation Mw
represents the weight average molecular weight. The
number average molecular weight and the weight average
molecular weight of the polybutenes can be measured by
well known techniques of vapor phase osmometry (VPO~,
membrane osmometry and gel permeation c~romatography
~2~4~5
--10--
(GPC). These techniques are well known to thoae
skilled in the art and need not be described herein
The second group or moiety is re~e~red ~o
herein as the "succinic group(s)". The succinic groups
are those groups characterized by the structure
O ~ I o
X- - ~ C ~ C C X' (I)
wherein X and X' are the same or different provided at
least one of X and X' is such ~hat the substituted
succinic acylating agent can function as carboxylic
acylating agents. That is, at least one of X and X'
must be such that the substituted acylating agent can
form amides or amine salts with, and otherwise function
as a conventional carboxylic acid acylating agents.
Transesterification ~nd tran~amidation reactions are
considered, for purposes of this invention, as
conventional acylating reactions.
Thus/ X and/or X' is usually -OH,
-O-hydrocarbyl, ~O-~ where M~ represents one
equivalent of a metal, a~monium or amine cation,
-NH2, -Cl, -Br, and together, X and X' can be -O- so
a~ to form the anhydride. The specific idantity 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 from entering into acylation
reactions. Preferably, however, X and X' are each uch
that both rarboxyl functions of the succinic group
(i.e., both -C~Q)X and -C(O~X' can enter in~o acylation
reactions.
One of the unsatisfied valences in the
grouping
rC_~_
- ~, ' . ' ,' ' ; .
'
- - .. ' . :
- ..
' . .
~8~L~L~
of Formula ~ forms a carbon-to-carbon bond with a
carbon atom in the substituent group. While other such
unsatisfie~ valence may be satisfied by a similar bond
with the same or different substituent group, all but
the said one such valence is usually sakis~ied by
hydrogen; i.e., -H.
The substituted succinic acylating agents are
characterized by the presence within their structure o~
1.3 succinic groups ~that is, groups corresponding to
Formula I) for each equivalent weight of substituent
groups. For purposes of this inventlon, the number of
equivalent weight of substituent groups is deemed to be
the number corresponding to the quotient obtained by
dividing the Mn value of the polyalkene from which the
substituent is derived into the total weight of the
substituent groups present in the substituted succinic
acylating agents. Thus, if a substituted succinic
acylating agent is characterized by a total weight of
substituent group of 40,000 and the Mn value for the
polyalkene from which the substituent groups are
derived is 2000, then that substituted succinic
acylating ~gent is characterized by a total of 20
(40,00Q/2000=20) equivalent weights of substituent
groups. Therefore, that particular succinic acylating
agent must also be characterized by the presance within
its structure of at least 26 succinic groups to meet
one of the requirements of the novel succinic acylating
agents of this invention.
Another requirement for the substituted
succinic acylating agents within this inven~ion is that
the substituent groups mus~ have bsen derived rom a
polyalkene characterized by an Mw/Mn value of at least
about 1.5.
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Polyalkenes having the Mn and Mw values
discussed above are known in the art and can be
prepared according to conventional proc~dures~ Sevaral
such polyalkenes, especially polybutenes, are
commercially available.
In one preferred embodiment, the succinic
groups will normally correspond to the formula
CH C(O)R
CH~ -C~O)RI (II)
wherein R and R~ are each independently selected from
the group c3nsisting o~ -OH, -Cl, -O-lower alkyl, and
when taken together, R and Rl are -O-. In the latter
case, the succinic group is a succinic anhydride
group. All the succinic groups in a particular
succinic acylating agent need not be the same, but they
can be the same. Preferably, the succinic groups will
correspond to
Q O
- CH - C ~ OH - CH ~ ~
~H2 C ~ OH I / (III)
C~2--C~
o
(A) (B)
and mixtures of (III(A)) and (IIItB)). Providing
substituted succinic acylating agents w~erein the
succinic group~ are the same or different is within the
ordinary skill of the art and can be accomplished
through conventional procedures such as treating the
substituted succinic acylating agents themselves (for
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~L2i~D¢5;
13-
example, hydrolyzing the anhydride to the free acid or
converting the free acid to an acid chloride with
thionyl chloride) and/or selecting the appropriate
maleic or fumaric reactants.
As previously mentione~, the minimum number o~
succinic groups for each equivalent weight o~
substituent group is 1.3. The maximum number generally
will not exceed 6. Preferably the minimum will be 1.4;
usually 1.4 to about 6 succinic groups for each
eguivalent weight of substituent group. A range based
on this minimum is at least 1.5 to about 3.5, and more
generally about 1.5 to about 2.5 succinic yroups per
equivalent weight of ~ubstituent groups.
From the foregoing, it is clear that the
substituted succinic acylating agents of this invention
can be represented by the symbol Rl(R2)y wherein
Rl represents one equivalent weight of substituent
group, R2 represents one succinic group corresponding
to Formula (I~, Formula (II~, or Formula (III), as
discussed above, and y is a number equal to or greater
than 1,3. The more preferred embodiments of the
invention could be similarly represented by, for
example, letting Rl and R2 represent more preferred
substi~uent groups and succinic groups, respectively,
as discussed elsewhere herein and by letting the value
of y vary as discussed above.
In addition to preferred substituted succinic
groups where the preference depends on the number and
identity of succinic groups for each e~uivalent weight
o~ subs~ituent groups, still ~urther preferences are
based on the identity and characterization of the
polyalkenes ~rom which the subs~ituent groups ara
derived.
..:
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~2~
With respect to the value of Mn for example,
minimum of about 1200 and a maximum of abouk 5000 are
preferred with an Mn value in the range of from about
1300 or 1500 to about 5000 also being preferred.
more preferred Mn value is one in the range ~ from
about 1500 to about 2800. A most preferred range of Mn
values is from about 1500 to about 2400. With
polybutenes, an especially preferred minimum value for
Mn is abou~ 1700 and an especially preferred range of
Mn values is from about 1700 to about 2400.
As to the values of the ratio ~Iw/Mn, there are
also several pre~erred values. A minimum ~w/~n value
of about 1.8 is preferred with a range of values of
about 1.8 up to about 3.6 also being preferred. A
s~ill more preferred minimum value o~ Mw/Mn 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 o~ Mw/Mn is about
2.5 with a range of values of about 2.5 to 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 prefarred
characteristics of the succinic acylating agents are
intended to be understood as being both independent and
dependent. They are intended to be independent in the
sense that, for example, a preference for a minimum of
1.4 or 1.5 succinic groups per equivalent weight of
substituent groups is not tied to a more preferred
value of ~n or Mw/Mn. They are intended to be
dependent in the sense ~hat, for example, when a
preference for a minimum of 1.4 or 1.5 succinic groups
is combined with more preferred values of Mn and/or
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Mw/Mn, the combination of preferences does in fact
describe still ~urther more pre~erred embodiments of
the invention. Thus, the various parameters ax~
intended to stand alone with respeat to the particular
parameter being discussed but can also be co~bined wlth
other parameters to identify further preferences. This
same concept is intended to apply throughout the
specification with respect to the description of
preferred values, rangesl ratios, reactants, and the
like unless a contrary intent is clearly demonstrated
or apparent.
The polyalkenes from which the substikuen~
groups are derived are homopolymers and interpolymers
of polymerizable olefin monomers of 2 to about 16
carbon atoms, usually 2 to about 6 carbon atoms. The
interpolymers ara those in which two or more olefin
monomers are inkerpolymerized according to well-known
conventional procedures to form polyalXenes ha~ing
units within their structure derived from each of said
two or more olefin monomers. Thus, I'intexpolymer(s)
as used herein is inclusive of copolymers, terpolymers,
tetrapolymers, and the like. As will be apparent to
those of ordinary s~ill in the art, the polyalkenes
from which the substituent groups are derived are often
conventionally referred to as "polyolefin(s)!'.
The olefin monomers from which the polyalkenes
are derived are polymerizable olefin monomers
characterized by the presence of one or more
ethylenically unsakurated groups (i.e.l >C=CX2~);
that is, they are monoolefinic monomers such as
ekhylene, propylene, butene-l, isobutene, and octene-l
or polyolefinic monomers (usually diolefinic monomers)
such as butadiene-11,3 and isoprene.
~Z;8~5
These olefin monomers are usually polymeriz~
able terminal olefins; that is, olefins charackerized
by the presence in their structure o~ the group
>C=CH2. However, polymerizable inkernal ole~in
monomers (sometimes referred to in the literature as
medial olefins~ characterized by the presence within
their structure of the group
--C-C=~
can also be used to form the polyalkenesO When
internal olefin monomers are employed, they normally
will be employed with terminal olefins to produce
polyalkenes which are interpolymers. For purposes of
this invention, when a particular polymerized olefin
monomer can be classified as both a terminal olefin and
an internal olefin, it will be deemed to be a terminal
ole~in. Thus, pentadiene-1,3 ~i.e., piperylene) is
deemed to be a te~minal olefin for purposes of this
invention.
While the polyalkenes from which the
substituent groups of the succinic acylating agen~s are
deri~ed generally are hydrocarbon groups such as lower
alXoxy, lower alkyl mercapto, hydroxy, mercapto, oxo,
as keto and aldehydro groups, nitro, halo, cyano,
carboalkoxy, (where alkoxy is usually lower alkoxy),
alkanoyloxy, and khe like provided the non~hydrocarbon
substituents do not substantially interfere with
~ormation of the substituted succinic acid acylating
agents of this invention. When present, such
non-hydrocarbon groups normally will not contribute
more than about 10% by weight of the total weight of
the polyalkenes. Since the polyalkene can contain such
'
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~Z8414S
non-hydrocarbon subs~ituent, it is apparent that the
olefin monomers from which the polyalkenes are made can
also contain such substltuents. Normally, however, as
a matter o~ practicality and expense, ~he ole~in
monomers and the polyalkenes will be free from non-
hydrocarbon groups, except chloro groups which usually
facilitate the formation of the substituted succinic
acylating agents of this invention. (As used herein,
the term "lower" when used with a chemical group such
as in "lower alkyl" or "lower alkoxy" is intended to
describe groups having up to 7 carbon atoms).
Although the polyalkenes may include aromatic
groups ~eæpecially phenyl groups and lower alkyl-
and/or lower alkoxy-substituted phenyl groups such as
para-(tert-butyl)phenyl) and cycloaliphatic groups such
as would be obtained from polymerizable cyclic ole~ins
or cycloaliphatic substituted-polymerizable acyclic
olefins, the polyalkenes usually will be free from such
groups. Nevertheless, polyalkenes derived from
interpolymers of both 1,3-dienes and styrenes such as
butadiene-1,3 and styrene or para-(tert-butyl)styrene
are exceptions to this generalization. Again, because
aromatic and cycloaliphatic groups can be present, the
olefin monomers from which the polyalkenes are prepared
can contain aromatic an~ cycloaliphatic groups.
From what has been described hereinabove in
regard to the polyalkene, it i clear that there is a
general pre~erence for aliphatic, hydrocarbon
polyalkenes free from aromatic and cycloaliphatic
groups (other than the diene-styrene interpolymer
exception already noted). Within this general
preference, there is a further preference for
polyalkenes which are derived from the group consis~ing
.: -
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of homopolymers and interpolymers of terminal
hydrocarbon ole~ins o~ 2 to about 16 carbon atoms.
This further pre~erence is qualified by the proviso
that, while interpolymers o~ terminal olefins are
usually preferred, interpolymors optionally contalning
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 preferred class o~
polyalkenes are those sPlected from the group
consisting of homopolymers and interpolymers of
terminal olefins of 2 to about 6 carbo~ atoms, more
preferably 2 to 4 carbon atoms. However, another
preferred class of polyalkenes are the latter more
preferred polyalkenes optionally containing up to about
25% of polymer units derived from internal olefins of
up to about 6 carbon atoms.
Specific examples o~ terminal and internal
olefin monomers which can be used to prepare the
polyalkenes according to conventional, well-known
polymerization techniques include ethylene; propylene;
butene-l; butene-2; .isobutene; pentene-l; hexene-l;
heptene-l; octene-l; nonene-l; decene-l; pentene-2;
propylene-tetramer; diisobutylene; isobutylene trimer;
butadiene-1,2; butadiene-1,3; pentadiene-1,2; penta-
diene-1,3; pentadiene-1,4; isoprene; hexadiene-1,5;
2-chloro-butadiene-1,3; 2-methyl-heptene-1; 3-cyclo-
hexylbutene-l; 2-methyl-pentene-1; styrene; 2l4-
dichloro styren~; divlnylbenzene; vinyl acetate; allyl
alcohol; l-methyl-vinyl acetate; aarylonitrile; ethyl
acrylate; methyl methacrylate; ethyl vinyl ether; and
methyl vinyl ketone. 0~ these, the hydrocarbon
polymerizable monomers are preferred and of these
hydrocarbon monomers, the terminal olefin monomers are
particularly preferred.
~Z1~4~45
--19--
Specific examples of polyalkenes include
polypropylenes, polybutenes, ethylene-propylene
copolymers, styrene-isobutene copolymers, isobutene-
butadiene-1,3 copolymer~, propana-isoprene copolymers,
isobutene-chloroprene copolymers, isobutene-~para-
methyl)styrene copolymers, copolymers o~ hexene~l with
hexadiene-1,3, copolymers of octene-l with hexene-l,
copolymers of heptene-l with pentene-l, copolymers of
3-methyl butene-l with octene-l, copolymers o~ 3,3-
dimethyl-pentene-l with hexene-l, and terpolymers of
isobutene, styrene and piperylene. More specific
examples of such interpolymers include copolymer of 95%
(by weight) of isobutene with 5~ ~by weight) of
styrene; terpolymer of 98~ of isobutene with 1~ of
piperylene and 1% of chloroprene; terpolymer of 95% of
isobutene with 2% of butene-l and 3% of hexene-l;
terpolymer of 60% of isobutene with 20~ of pentene-l
and 20% of octene-l; copolymer of 80% of hexene-l and
20~ of heptene-l; texpolymer of 90% of isobutene with
2% of cyclohexene and 8% of propylene; and copolymsr of
80% of ethylene and 20~ of propylene. A preferred
source of polyalkenes are the polyti~obutene)s obtained
by polymerization of C4 refinery stream having a
butene content of about 35 to about 75~ by weight and
an isobutene content of about 30 to about 60% by weight
in the presence of a Lewis acid catalyst such as
aluminum trichloride or boron trifluoride. These
polybutenes contain predominantly (greater than about
80% of the total repeating units) of isobutene
repeating units of the con~iguration
~H3
CH2 C
CH3
,. -
:
~28~S
-20-
Obviously, preparing polyalkenes as described
above which meet the various criteria for Mn and Mw/Mn
is within the skill of the art and does not compri~e
part of the present invention. Techniques readily
apparent to those in the art include controlling
polymerization temperatures, regulating the amount and
type of polymerization initiator and/or catalyst,
employing chain terminating groups in the
polymerization procedure~ and the like. Other
conventional techniques such as stripping (including
vacuum stripping) a very li~ht end and/or oxidatively
or mechanically degrading high molecular weight
polyalkene to produce lower molecular weight
polyalkenes can also be used.
In preparing the substituted succinic
acylatin~ agents of this invention, one or more of the
above described polyalkenes is reacted with one or more
acidic reactants selacted from the group consisting of
maleic or fumaric reactants of the general formula
X(O)C-CH=~-C(O)X' (IV)
wherein X and X' are as defined hereinbefore.
Preferably the maleic and fumaric reactants will be one
or more compounds corresponding to the formula
RC(O)-CH=CH-C(O)R' (V)
wherein R and R' are as previously defined herein.
Ordinarily, the maleic or fumaric reactants will be
maleic acid, ~umaric acid, maleic anhy~ride, or a
mixture of two or more of~these. The maleic reactants
are usually preferred over ~he fumaric reac~ants
.
- ` ~
~. :
.
s
-21-
because the former are more readily aYailabl~ and are,
in general, more readily reacted with the polyalkenes
(or derivatives thereof) to prepare the substituked
succinic acylating agents o~ the pre6ent invention,
The especially pre~erred reaatants are maleic acid,
maleic anhydride, and mixtures of these. Due to
availability and ease of reaction, maleic anhydride
will usually bP employed.
The one or more polyalkenes and one or more
maleic or fumaric reac~al~,s can be reacte~ according to
any of saveral known procedules in order to produce the
substituted succinic acyl~ti~g agents o~ the present
invention. Basically, th~a procedures are analogous to
procedures used to prepa~e the high molecular weight
succinic anhydrides and other equi~alent succinic
acylating analogs thereof e~cept that the polyalkenes
(or polyolefins) of the prior art are replaced with the
particular polyalkenes described above and the amount
of maleic or fumaric reactant used must be such that
there is a~ least 1.3 succinic groups for each
equivalent weight of the substituent group in the flnal
substituted succinic acylating agent produced~
For conv~nience and brevlty, the term "maleic
reactant" is often used hereafter. When used, it
should be unders~ood ~hat the tarm is generic to acidic
reactants selected from maleic and fumaric reactan~s
corresponding to Foxmulae (IV) and (V) above including
a mixture of such reactants.
One procedure ~or preparing the substituted
succinic acylating agents of this invention is
illustrated, in part, in U.S. Paten~ 3~219,666.
-22-
en~. This procedure is conveni~ntly designated as
the "two-step procedure". It involves first
chlorinating the polyalkene until khere ig an average
of at least about one chloro group ~or each molecular
weight of polyalkene. (For purposes of this invention,
the molecular weight of the polyalkPne is the weight
corresponding to the Mn ~alue.) Chlorination involves
merely contacting the polyalkene with chlorine gas
until the desired amount of chlorine is incorporated
into the chlorinated polyalkene. Chlorination is
generally carried out at a temperature of about 75C
to about 125C. If a diluent is used in the
chlorination procedure, it should be one which is not
itself readily sub;ect to further chlorination. Poly-
and perchlorinated and/or ~luorinated alkanes and
benzenes are examples of suitable diluents.
The second step in the two-skep chlorination
procedure, or purpos~s of this inventionl is to react
the chlorinated polyalkene with the maleic reactant at
a temparature usually within the range of about 100C
to about ~00C. The mole ratio of chlorinated
polyalkene to malei~ -reactan~ i~; usually about 1:1.
(For pur~oses of this invention, a mole of chlorinated
polyalkene is that weight of chlorinatad polyalkene
correspondin~ to the Mn value of the unchlorinated
polyalkene.) However, a stoichiometric excess of
maleic reactant can be used, ~or example, a mole ratio
of 1:2. If an average of more th~n about one chloro
group per molecule of polyalkene is introduced during
the chlorina~ion step, then more than one mole o~
maleic reactant can react per molecule of chlorinated
polyalkene. Because of such situations, it is bPtter
to describe th~ ratio of chlorinated polyalkene to
:
' .
~2~34~
-23-
maleic reactant in terms of equivalents. (An
equivalent weight of chlorinated polyalkene, for
purposes of this invention, is the weight corresponding
to the Mn value divided by the averags number o~ chloro
groups per molecule of chlorinated polyalkene while the
equivalent weight of a maleic reactant is its molecular
weight.) Thus, the ratio of chlorinated polyalkene to
mal~ic reactant will normally be such as to provide
about one equivalent of maleic reactant for each mole
of chlorinated polyalkene up to about one equivalent of
maleic reactant for each equivalent of chlorinated
polyalkene with the understanding that it is normally
desirable to provide an excess of maleic reactant; for
example, an excess of about 5% to about 25% by weight.
Unreacted excess maleic reactant may be stripped from
the reaction product, usually under vacuum, or reacted
during a further stage o~ the process as explained
below.
The resulting polyalkPnyl-substituted succinic
acylating agent is, optionally, again chlorinated if
the desired number of succinic groups are not present
in ~he product If there is present, a~ the time of
this subsequent chlorination, any excess maleic
reactant from the second step, the exces~ will react as
additional chlorine i5 introduced during the su~sequent
chlorination. Otherwise, additional maleic reactant is
introduced during and/or subsequent to the additional
chlorination step. This technique can be repeated
until the total number of succinic groups per
equivalent weight of substituent groups reaches the
desired level.
Another procedure for preparing substituted
succinic acid acylating agents of the in~ention
- . :
.' . ' , - . .
-24-
utilizes a process described in U.S. Patent 3,912,764 and
U.K. Patent 4,440,21~. According to that process, the
polyalkene and the maleic reactant are first ~eacted by
heating them together in a "direct alkylation" procedure.
When the direct alkylation step is completed, chlorine i5
introduced into the reaction mixture to promote reaction
of the remaining unreacted maleic reactants. According to
the patents, 0.3 to 2 or more moles of maleic anhydride are
used in the reaction for each mole of olefin polymer; i.e.,
polyalkene. The direct alkylation step is conducted at
temperatures of 180C to 250C. During the chlorine-
introducing stage, a temperature of 160C to 225C is
employed. In utilizing this process to prepare the
substituted succinic acylating agents of this invention,
it would be necessary to use sufficient maleic reactant and
chlorine to incorporate at least 1.3 succinic groups into
the final product for each equivalent weight of polyalkene.
The process presently deemed to be best for preparing
the substituted succinic acylating agents utilized in this
invention from the standpoint of efficiency, overall
economy, and the performance of the acylating agents thus
produced, as w211 as the performance of the derivatives
thereof, is the so-called "one-step" process. This process
is described in U.S. Patents 3,215,707 and 3,231,587.
Basically, the one-step process involves preparing a
mixture of the polyalkene and the maleic
.
:.
- . - .: .
~L2~
-25-
reactant containing the necessary amounts of both to
provide the desired substituted succinic acylating
agents of this invention. This means that there must
be at least 1.3 moles of maleic reactant for each mole
o~ polyalkene in order that there can be at lea~t 1.3
succinic groups for each equivalent weight o~
substituent groups. Chlorine is then introduced into
the mixture, usualy by passin~ chlorine gas through the
mixture with agitation, while maintaining a temperature
of at least about 140C.
A variation on thls process in~olv~s adding
additional maleic reac~ant duriny or subsequent to the
chlorine introduction but, ~or reasons explained in
U.S. Patents 3,215,707 and 3,231,587, this variation is
presently not as preferred as the situation where all
the polyalkene and all the maleic reactant are first
mixed before the introduction of chlorine.
Usually, where the polyalkene is sufficiently
fluid at 140C and above, there is no need to utilize
an additional substantially inert, normally liquid
solvent/diluent in the one-step process. How~ver, as
explained hereinbe~ore, if a solvent/diluent is
employed, it is preferably one that resists
chlorination. Again, the poly- and per-chlorinated
and/or -fluorinated alkanes, cycloalkanes, ~nd 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 i~ not critical
although, for maximum utilization of the chlorine, the
rate should he about the same as the rate of
consumption of chlorine in the cour~e of the reaction.
When the introduction rate of chlorine exceeds the rate
., ., " ~ . ~ ' - ' '
~. . - :
8~
-26-
of consumption, chlorine is evolved from the reaction
mixture. It is often advantageous to use a alosed
system, including superatmospheric pressure, in order
to prevent loss o~ chlorine so as to maxlmizs chlorine
utilization.
The minimum temperature at which the reaction
in the one-step process takes place at a reasona~le
rate is about 140C. ~hus, the minimum temp~rature
at which the process is normally carried out is in the
neighborhood of 140C. The pre~erred temperature
range is usually between about 160~C and about
220C. Higher temperatures such as 250C or even
higher may be used but usually with litle ad~antage.
In fact, temperatures in excess of 220C are often
disadvantageous with respect to preparing the
particular acylated succinic compositions o~ this
invention because they tend to l'crack" the polyalkenes
(that is, reduce their molecular weight by thermal
degradation) and/or decompose the maleic reactant. For
this reason, maximum temperatures o~ about 200C to
about 210C are normally not exseeded. The upper
limit of the useful temperature in the one-step process
is determined primarily by the decomposition point o~
the components in the reaction mixture includiny the
reactants and the desired products. The decomposition
point is that temperature at which there is sufficient
decomposition of any reactant or product such as to
interfere with the production of the desired products.
In the one-step process, ~he molar ratio of
male.ic reactant to chlorine is such that there is at
least about one mole of chlorin~ for each mole of
maleic reactant to be incorporated into the product.
Moreover, for practical reasons, a slight excess,
,- . , ' . . '
27-
usually in the neighborhood of about 5% to about 30% by
weight of chlorine, is utilized in order to offset any
loss of chlorine from the reaction mixture. Larger
amounts of excess chlorine may be used but do not
appear to produce any beneficial results.
As mentioned previously, the molar ratio of
polyalkene to maleic reactant is such that there is at
least about 1.3 moles of maleic reactant for each mole
of polyalkene. This is necessary in order that there
can be at least 1.3 succinic groups per equivalent
weight of substituent group in the product.
Preferably, however, an excess of maleic reactant is
used. Thus, ordinarily about a 5% to about 25~ excess
of maleic reactant will be used relative to that amount
necessary to provide the desired number of succinic
groups in the product.
A preferred process for preparing the
substituted acylating compositions of this invention
comprises heating and contacting at a temperature of at
least about 140QC up to the decomposition temperature
(A) Polyalkene characterized by Mn value of
about 1200 to about 5000 and an Mw/Mn value of about
1.5 to about 4,
(B) One or more acidic reactants of the
formula
XC(O)-CH=CH-C(O)X'
wherein X and X' are as defined hereinbefore, and
(C~ Chlorine
wherein the mole ratio of (A):(B) is such that there is
at least about 1.3 moles of (B~ for each mole of (A)
wherein the number of moles of (A) is the quotient of
- . . . . .
.
::; . : . .
. . . - :
- . .
: .' : ', . . . .
~L28~ S
-28-
the total weight of (A) di~ided by the value o~ Mn and
the amount of chlorine employed is such as to provide
at least about 0.2 mole (preferably at least about 0.5
mole) of chlorine for each mole of (B) to be reacted
with (A), said substituted acylating compositions being
characterized by the presence within their structure of
an average o~ at least 1.3 groups derived from (B) for
each equivalent weight of the subst.ituent groups
derived from (A). The substituted acylated
compositions as produced by such a process are,
likewise, part of this invention.
As will be apparent, it is intended that the
immediately preceding description of a preferred
process be generic to both the process involving direct
alkylation with subsequent chlorination as described in
U.~. Pa~ent 3,912,764 and U.K a Patent 1,4~0,29 and to
the comple~ely one-s~ep process described in U~S.
Patents 3,215,707 and 3,231,587. Thus, said
description does not require that the initial mixture
of polyalkene and acidic reactant contain all of the
acidic reactant ultimately ~o be incorporated into the
substituted acyiating composition to be prepared. In
other words, all of the acidic reactant can be present
initially or only part thereof with subsequent addition
of acidic reactant during the course of the reaction.
~ikewise, a direct alkylation reaction can precede the
introduction of chlorine. Normally, however, the
original reaction mixture will contain the to~al amount
of polyalkene and acidic raactant to be utilized.
Furthermore, the amount of chlorine used will normally
be such as to provide about one mole of chlorine for
each unreacted mole of (B) present at the ~ime chlorine
introduction is commenced. Thus, if the mole ratio of
,
' . '. ~ ' ' .~
-29-
(A):(B) is such that there is about 1.5 moles of (B)
for each mole of (A) and if direct al~ylation results
in half of (B) being incorporated into the product,
then the amount of chlorine introduced to complete
reaction will be based on the unreac~ed 0.1~ mole o~
(B); that is, at least about 0.75 mole of chlorine (or
an excess as explained above) will then be introduced.
In a more preferred process for prepariny the
substituted acylating compositions of this invention,
~here is heated at a tempera~ure of a~ least about
140C a mixture comprising:
(A) Polykene characterized by an ~n value of
about 1200 to about 5000 and an Mw/Mn value of about
1.3 to about 4,
(B) One or more acidic reactants of the
formula
RC(O)-CH-CH-C(O)R'
wherein R and R' are as defined above, and
(C) Chlorine
wherein the mole ratio of (A):(B) is such that there is
at least about 1.3 moles of (B) for each mole of (A)
where the nu~ber of moles of (A) is a quotient of the
total weight of (A) divided by the valu~ of Mn, and the
amount of chlorine employed is such as to provide at
least about one mole of chlorine or each mole of (B)
reacted with (A), the substituted acylating
compositions being fur~her charact~rized by the
presence within their structure of at least 1.3 groups
derived from (B) for each equivalent weight of the
subs~ituent groups derived from (A). This process/ as
described, includes only the one-step process; tha~ is,
. ~: . . . : .
' ' :,'':' ~ ' ~
~L2~
-30-
a process where all of both (A) and tB) are present in
the initial reaction mixture The substitut2d acylaked
composition as produced by such a proce5s are,
likewise, part of this invention.
The terminology "substituted succinic
acylating agent(s)" is used in describing the
substituted succinic acylating agents regardless of the
process by which they are produced. Obviously, as
discussed in more detail hereinbefore, several
processes are available for producing the substituted
succinic acylating agents. On the other hand, the
terminology "substituted acylating composition(s)", is
used to describe the reaction mixtures produced by the
specific preferred processas described in detail
herein. Thus, the identity of particular substituted
acylating compositions is dependent upon a particular
process of manufacture. It is believed that the novel
acylating agents used in this invention can best be
described and claimed in the alternative manner
inherent in the use of this ~erminology as thus
explained. This is particularly true because, while
the products o~ this inven~ion are clearly substitutad
succinic asylating agen~s as defined and discussed
above, their structure cannot be represented by a
single specific chemical formula. In fact, mixtures of
products are inherently present.
With respect to the pre~erred processes
described above, preferences indicated hereinbefore
with respect to (a) the substituted succinic acylating
agents and (b) the values of Mn, ths values of the
ratio ~w/Mn, the identity and composition of the
polyalkenes, the identity of the acidic reactant ~that
is, the maleic and/or fumaric reactants~, the ratios of
~Z8~5
-31-
reactants, and the reac~ion temperatures also apply.
In like manner, the same preferences apply to the
substituted acylated compositions produced by these
pre~exred processes.
For example, such processe~ wherein the
reaction temperature is from about 160C to abouk
220C are preferred. Likewise, the use of
polyalkenes wherein the polyalkene is a homopolymer or
interpolymer of terminal olefins of 2 to about 16
carbon atoms, with the proviso that said interpolymers
can optionally contain up to about 40% of the polymer
units derived from internal olefins of up to about 16
carbon atoms, constitutes the preferred aspect of the
process and compositions prepared by the process. In a
more preferred aspect~ polyalkenes for use in the
process and in preparing the compositions of the
process are the homopolymers and interpolymers of
terminal olefins of 2 to 6 carbon atoms with the
proviso that said interpolymers can optionally contain
up to about 25% of polymer units derived from internal
olefins of up to about 6 carbon atoms. Especially
preferred polyalkenes are polybutenes, ethylene-
propylene copolymers, polypropylenes with the
polybutenes being particularly preferred.
In the same manner, the succinic group content
of the substituted acylating compositions thus produced
are preferably the same as that describe~ in regard to
the substituted succinic acylating agents. Thus, the
substituted acylating compositions characterized by the
presence within their structure of an average of a~
least 1~4 succinic groups derived fro~ (~) for each
e~uivalent weight of the substituent groups derived
from (A) are preferred with those containing at least
- ' ' `
~Z~ 5
~32
1.4 up to about 3.5 succinic groups derived from (B)
for each e~uivalent weight of substituent group~
derived from (A) being 9till more pre~erred. In khe
same way, those substituted acylating composikions
characteri~ed by the presence within their structure of
at least 1.5 succinic groups derived from (B) for each
equivalent weight of substituent group derived from (A)
are still fuxther prsferred, while those containing at
least 1.5 succinic groups derived from (B) for each
equivalent weight of substituent ~roup derived from (A)
being especially preferred.
Finally, as with the description of the
substituted succinic acylating agents, the substituted
acylating compositisns produced by the preferred
processes wherein the succinic groups derived from (B)
correspond to the formula
CH - C - OH - CH ~ C
~0 ' l /o
CH2-- C - OE CX2 C
o
and mixtures of these constitute a preferred class.
An especially preferred process for preparing
the substituted acylating compositions comprises
heating at a temperature of about 160C to about
220C a mixture comprising:
~ A) Polybutene characterized by an Mn value
of about 1700 to about 2400 and an Mw/Mn value of about
2.5 to about 3.2, in which at least 50% of the total
units derived from butenes is derived from isobutene,
~2841~5
-33-
(B) One or more acidic reactants of the
~ormula
RC(O)-CH-C~-C(O)R'
wherein R and R' are each -OH or when taken together, R
and R' are -O-, and
(C) Chlorine
wherein the mole ratio of (A)~(B) is such that there is
at least 1.5 moles of (B) ~or each mole of (A) and the
number of moles of (A) is the quotient of the total
weight of (A) divided by the value of Mn, and the
amount of chlorine employed is such as to provide at
least ahout one mole of chlorine for each mole of (B)
to be reacted with (A), said acylating compositions
being chara~terized by the presence within their
structure of an average of at least 1.5 groups derived
~rom (B) ~or each equivalent weight o~ the substituent
groups derived from (A)- In the same manner,
substituted acylating compositions produced by such a
process constitute a preferred ~-lass of such
compositions.
For purposes of brevity, the terminology
"acylating reagent(~)" is often used hereafter ~o
re~er, collectively, to both the substituted succinic
acylating agent and to the substituted acylating
compositions used in this invention.
The acylating reagents of this i~vention are
intermediates in processes for preparing the carboxylic
deri~ati~e compositions (A) comprising reacting one or
more acylating reagents with an amino compound
characterized by the presence with~n its structure of
at least one group.
: -
~: .
:
: . - . , .
.
34~4~
-34-
The amino compound characteri~ed by the
presence within its structure of at least one -NH-
group can be a monoamine or polyamine compound. For
purposes of this invention, hydrazine and substituted
hydrazines containiny up to khree substituents are
included as amino compounds suitable for preparing
carboxylic derivative compositions. Mixtures o~ two or
more amino compounds can be used in the reaction with
one or more acylating reagents of this invention.
Preferably, the amino compound contains at least one
primary amino group (i.e., -NH2) and more preferably
the amine is a polyamine, especially a polyamine
containing at least ~wo -NH- groups, either or both of
which are pximary or secondary amines. The polyamines
not only result in carboxylic acid derivative
compositions deriv~d from monoamines, but these
pre~erred polyamines result in carboxylic derivative
compositions which exhibi~ more pronounced V.I.
improving properties.
The monoamines and polyamines must be
characterized by the presence within their structure of
at least one -NH- group. Therefor~, they have at least
one primary (i.e., H2N-3 or secondary amino (i.e.,
H-N=) group. The amines can ~e aliphatic, cyclo-
aliphatic, aromatic, or heterocyclic, including
aliphatic-substituted cycloaliphatic, aliphatic-
substituted aromatic, aliphatic-substituted hetero-
cyclic, cycloaliphatic-substituted aliphatic, cyclo-
aliphatic-substituted heterocyclic, aromatic-substi-
tuted aliphaticl aromatic-substituted cycloaliphatic,
aromatic-substituted he~erocyclic, heterocyclic-substi-
tuted aliphatic, heterocyclic-substituted alicyclic,
and heterocyclic-substituted aromatic amines and may be
,
,
~2~
-35-
saturated or unsaturated. If unsaturated, the amine
will be free from acetylenic unsaturation. The amines
may also contain non-hydrocarbon substituents or groups
as long as these groups do not signi~icantly inkerfere
with the reaction o~ the amines with thQ acyla~ing
reagents of this invention. Such non-hydrocarbon
substituents or groups include lower alkoxy, lower
alkyl mercapto, nitro, interrupting groups such as -o-
and --S- (e.g., as in such groups as -CH2CH2 X-
C~2CH2- where X is -0- or -S-).
With the exception of the branched
polyalkylene polyamine, the polyoxyalkylene polyamines,
and the high molecular weight hydrocarbyl-substituted
amines described more fully hereafter, the amines
ordinarily contain less than about 40 carbon atoms in
total and usually not more than about 20 carbon atoms
in total.
Aliphatic monoamines include mono-aliphatic
and di-aliphatic substituted amines wherein the
aliphatic groups can be saturated or unsaturated and
straiyht or branched chain. Thus, they are primary or
secondary aliphatic amines. Such amines include, for
example, mono- and di-alkyl-substituted amines, mono-
and di-alkenyl-substituted amines, and amines having
one N-alkenyl substituent and one N-alkyl substituent
and the like. Ths total number of carbon atoms in
these aliphatic monoamines will, as mentioned before,
normally will not exceed about 40 and usually not
exceed abou~ 20 carbon a~oms. Specific examples of
such monoamines include ethylamine, diethylamine,
n-butylamine, di-n-butylammine, allylamine, isobutyl-
amine, G~coamine, stearylamine, laurylamine, methyl-
laurylamine, oleylamine, N-methyl-octylamine, dodecyl-
. .
', . ,. :.
'
'.`, ' ... ' ~: .
~%334~5
-36-
amine, octadecylamine, and the like. Examples o~
cycloaliphatic-substituted aliphatic amines, aromatic
substituted aliphatic amin~s, and heterocyclic-sub ti-
tuted alipha~ic amines, include 2-(cyclohexyl)-ethyl-
amine, benzylamine, phenekhylamine, and 3-(~urylpropyl)
amine~
Cycloaliphatic monoamines are those monoamines
wherein there is one cycloaliphatic substituent
attached directly to the amino nitrogen through a
carbon atom in the cyclic ring structure. Examples o~
cycloaliphatic monoamines include cyclohexylamines,
cyclopentylamines, cyclohexenylamines, cyclopentyl-
amines, N-ethyl-cyclohexylamine, dicyclohexylamines,
and the like. Examples o~ aliphatic-substitut~d,
aromatic-substituted, and heterocyclic- ubstituted
cycloaliphatic monoamines include propyl-substituted
cyclohexylamines, phenyl-substituted cyclopentylamines,
and pyranyl-substituted cyclohexylamine.
Aromatic amines include those monoamines
wherein a carbon atom of the aromatic ring structure is
attached directly to the amino nitrogen. The aromatic
ring will usually be a mononuclear arom~tic ring (i.e.,
one deri~ed from benzene) but can include fused
aromatic rings, especially those deriv~d ~rom
naphthalene. Examples of aromatic monoamines include
aniline, di(para-methylphenyl) amine, naph~hylamine,
N-(n-butyl)aniline, and the like. Examples of
aliphatic-substituted, cycloaliphatic-substituted, and
heterocyclic-substituted aromatic monoamines are
para-etho~yaniline, para-dodecylaniline/ cyclohexyl-
substituted naphthylamine, and thienyl-substituted
aniline.
~Lf~8'9L1~L5
-37-
Polyamines are aliphatic, cycloaliphatic and
aromatic polyamines analogous to the above~described
monoamines except ~or the presence within their
structure o~ another amino nitrogen. The other amino
nitrogen can be a primary, secondary or terkiary amino
nitrogen. Examples o~ such polyamines include N-amino-
propyl-cyclohexylamines, N,N'-di-n-butyl-para-phenylene
diamine, bis-~para-aminophenyl)methane, 1,4-diamino-
cyclohexane, and the like.
Heterocycic mono- and polyamines can also be
used in making the carboxylic derivative compositions
of this invention. As used herein, the terminology
"heterocyclic mono- and polyamine(s)" is intended to
describe those heterocyclic amines containing at least
one primary or secondary amino group and at least one
nitrogen as a heteroatom in ~he heterocyclic ring.
However, as long as there is present in the
heterocyclic mono- and polyamines at least one primary
or secondary ~mino group, the hetero-N atom in the ring
can be a ter~iary amino nitrogen; that is, one that
does not have hydrogen attached directly to the ring
nitrogen. Heterocyclic amines can be saturated or
unsaturated and can contain various substituents such
as nitro, alkoxy, alkyl mercapto, al~yl, alkenyl, aryl,
alkaryl, or aralkyl substituents. Generally, the total
number of carbon atoms in the substituents will not
exceed about 20. Hsterocyclic amines can contain
hetero atoms other than nitrogen, especially oxygen and
sulfur. Obviously they can contain more than one
nitrogen hetero a~om. ~he five- and six-membered
heterocyclic rings are preferred.
Among the suitable heterocyclics are
aziridine~, azetidines, azolidines, tetra- and di-hydro
~;28~4~
-38-
pyridines, pyrroles, in~oles, piperidines, imidazoles,
di- and tetrahydroimidazoles, piperazines, isaindoles,
purines, morpholines, thiomorpholines, N-aminoalk~l-
morpholines, N-aminoalkylthiomorpholines, N-aminoalkyl~
piperazines, N,N'-di-aminoalkylpiperazines, azeplnes,
azocines, azoninec, azecines and tetra-, di- and
perhydro derivatives of each of the above and mixtures
Qf two or more of these heterocyclic amines. Preferred
heterocyclic amines are the saturated 5- and 6~membered
heterocyclic amines containing only nitrogen, oxygen
and/or sulfur in the hetero ring, especially the
piperidines, piperazines, thiomorpholines, morpholines,
pyrrolidines, and the like. Piperidine, aminoalkyl-
substituted piperidines, pipera~ine, aminoalkyl~
substituted morpholines, pyrrolidine, and aminoalkyl-
substituted pyrrolidines, are especially preferred.
Usually the aminoalkyl substltuents are substituted on
a nitrogen atom forming part of the hetero ring.
Specific examples of such heterocyclic amines include
N-aminopropylmorpholine, N-aminoethylpiperazine, and
N,N'-di-aminoethylpipera2ine.
Hydroxyamines both mono- and polyamines,
analogous to those described above arP also useful as
(a) provided they contai~ at leas~ one primary or
secondary amino group. Hydroxy-substituted amines
having only terkiary amino nitro.~en such as in
tri-hydroxyethyl amine, are thus excluded as (a) (but
can be used as (b) as disclosed hereafter). The
hydroxy-substituted amines contamplated are those
having hydroxy substituents bonded directly to a carbon
atom other than a carbonyl carbon atom; that is, th~y
have hydroxy groups capable of functioning as
alcohols. Examples of such hydroxy-suhstituted amines
~2~
-39-
include ethanolamine, di-(3-hydroxypropyl)-amine,
3-hydroxybutyl-amine, 4-hydroxybutyl-amine, diethanol-
amine, di-(2 hydroxypropyl) amine, N-(hydroxypropyl)-
propylamine, N (2-hydroxyethyl)-cyclohexylamine, 3-hy-
droxycyclopentylamine, para-hydroxyaniline, N-hydroxy-
ethyl piperazine, and the like.
Hydrazine and substituted-hydrazine can also
be used. At least one of the nitrogens in the
hydrazine must rontain a hydrogen directly bonded
thereto. Prefera~ly there are at least two hydro~ens
bonded directly to hydrazine nitrogen and, more
preferably, both hydrogens are on the same nitrogen.
The substituents which may be present on the hydrazine
include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the
like. Usually, the substituents are alXyl, especially
lower alkyl, phenyl, and substi~uted phenyl such as
lower alkoxy substituted phenyl or lower alkyl
substituted phenyl. Specific examples of substituted
hydrazines are methylhydrazine, N,N-dimethyl-hydrazine,
N,N'-dimethylhydrazine, phenylhydrazine, N-p~enyl-N'
ethylhydra~ine~ N-(para-tolyl)-N'-(n-b.utyl)-hydrazine,
N-(para-nitrophenyl)-hydrazine, N-(para-nitrophenyl)-
N-methyl-hydrazine, N,N'-di(para--chlorophenol)-hydra-
zine, N~phenyl-N'-cyclohexylhydrazine, and the like.
Th~ high molecular weight hydrocarbyl amine~,
both mono-amines and polyamine~, which can b~ u~ed as
(a) are generally prepared by reacting a chlorinated
polyole~in having a molecular weight o at leask about
400 with ammonia or amine. Such amines are known in
the art and described, ~or example, in U.S. Patents
3,275,554 and 3,438,757,
;' ~ ' ' ''
~28A~LAS
-40-
All that is required for use of these amines is that they
possess at least one primary or secondary amino group.
required for use of these amines 15 ~nat tney possess
at least one primary or secondary amino group.
~ nother group of amines suitable ~or use are
branched polyalkylene polyamines. The branched
polyalkylene polyamines are polyalkylene polyamine~
wherein the branched group iR a side chain containing
on the average at least one nitrogen-bonded
aminoalkylene
rH -i
(i.e., NH2 - R t N - RJ x
group per nine amino units present on the main chain,
for example, 1-4 of such branched chain~ per nine units
on the main chain units. Thus, these polyamines
contain at .l.east three primary amino groups and at
least one tertiary amino group.
Suitable amines also include polyoxyalkylene
polyamines, e.g., polyoxyalkylene diamines and
polyoxyalkylene triamines, having average molecular
weights ranging from about 200 to 4000 and preferably
from about 400 to 2000. Illustrative examples of these
polyoxyalkylene polyamines may be charac~erized ~y the
formulae
N~2-Alkylene ~O-Alkylene t NH2 (~I)
wherein m has a value of about 3 to 70 and preferably
about 10 to 35.
R-~-Alkylene t O-AlkYlen~ ~-nNH2)3-6 (VII)
,`i~,_
.
. : :
~Z~4~L~LS
wherein n is such that the total value i5 ~rom about 1
to 40 wi~h ~he proviso that the sum o~ all o~ the n's
is from about 3 to about 70 and generally from about 6
to about 35 and R is a polyvalent saturated hydroc~rbon
radical o~ up to 10 carbon atoms having a val~nc~ Or 3
to 6. The alkylene groups may ~e straight or branch~d
chains and contain from 1 to 7 carbon atoms and usually
from 1 to 4 carbon atoms. The various alkylene group~
present within Formulae (VI) and (VII) may be th2 sa~e
or differentO
The pxeferr~d polyoxyalkyl~ne polyamines
include the polyoxyethylene and polyoxypropylene
diamines and the polyox~propylene triamines ha~ing
a~erage molecular weights ranging from ahout 200 to
2000. The polyoxyalkylene polyamines are commercially
available and ~ay be ob~ained, for example, from the
Je~ferson C~emical Company, Inc. under the trade nam~
"~effamines D-230, D-400, D-1000, D-2000, T-403, etc~".
U.S. Patents 3,804,763 and 3,948,800 are p~rticularly
relevant for their disclosure of such polyoxyalkylene
polyamines and pxocess for acylating them with carboxylic
acid acylating agents which processes can be applied to
their reaction with the acylating reagents of this
invention.
The most preferred amines are the alkylene polyamines,
including the polyalkylene polyamines, as de~cribed in more
detail hereafter. The alkylene polyamines include those
conforming to the formula
~3 - N- (U-N3n R3 (VIII)
R3 ~3
, ,.~,
~z134~
-42-
wherein n is from 1 to aboui 10; each R3 is
independently a hydrogen atom, a hydrocarbyl group or a
hydroxy-substitute~ hydrocarbyl group having up ~o
about 30 atoms, with ~ha proviqo that at least one R3
group is a hydrogen atom and u is an alkylene group of
about 2 to about 10 carbon atoms. Pre~erably u ls
ethylene or propylene. Especially pre~erred are the
alkylene polyamines where each R3 is hydrogen with
tne ethylene polyamines and mixtures o~ ethylene
polyamines being the most preferred. Usually n will
have an average value of ~rom about 2 to about 7~ Such
alkylene polyamines include methylene polyamine,
ethylene polyamines, butylene polyamines, propylene
polyamines, pentylene polyamines, hexylene polyamines,
heptylene polyamines, etc. The higher homologs of such
amines and related amino alXyl-substituted piperazines
are also included.
Alkylene polyamines useful in preparing the
carboxylic derivative compositions include ethylene
diamine, triethylene tetramine, propylene diamine,
trimethylene diamine, hexamethylene diamine, deca
methylene diamine, hexamethylene diamine, decamethylene
diamine, octamethylene diamine, di~heptamethylene~
triamine, tripropylene tetramine, tetraethylene
pentamine, trimethylene diamine, pentaekhylene
hexamine, di(trimethylene)triamine, N--(2-amino-
ethyl)piperazine, 1,4-bis(2,aminoethyl)pipera7ine, and
the like. Higher homologs as are obtained by
condensing two or more of the above-illustra~ed
alXylene amines are useful as (a) a~ are mixtures of
two or more of any of the afore-described polyamines.
Ethylene polyamines, such as those mentioned
above, are especially use~ul for reasons of cosk and
~LZ~ 5
-43-
effectiveness. Such polyamines are described in detail
under the heading ~'Diamines and Higher Amines" in The
Encyclopedia of Chem~cal Technology, Second Edltion, Kirk
and Othmer, Volume 7, pages 27-39, Interscience Publishers,
Division of John Wiley and Sons, 1965. Such compounds are
prepared most conveniently by the reaction o~' an
alkylene chloride with ammonia or by reaction of an
ethylene imine with a ring-opening reagent such as
ammonia, etc. These reactions result in the production
of the somewhat complsx mixtures of alkylene
polyamines, including cyclic condensation products such
as piperazines. The mixtures are particularly useful
in preparing novel sulfur-containing compositions of
matter of this invention. On the other hand, quite
satisfactory products can also be obtained by the use
of pure alkylene polyamines.
Other useful types of polyamine mixtures are
those resulting from stripping of the ~bove-described
polyamine mixturesO In ~his instance, lower molecular
weight polyamines and volatile contaminan~s are removed
from an alkylene polyamin~ mixture to leave as residue
what is often termed l'polyamine bottoms". ~n general,
alkylene polyamine ~ottoms ~an be characterized as
having less than two, usually lsss than one percent (by
weight) material boiling below about 200C. In the
lnstance of ethylens polyamine bo~toms, which are
readily available and found to be quite u~eful, the
bottoms contain lees than about two percen~ (by weight)
total diethylene triamine (DETA) or triethylene
tetramine (TETA). A typical sample of suGh ethylene
polyamine bottoms obtained from the Dow Chemical
.
. .
;.
-
-
~L2~4~5
-44-
Company o~ Freepor~, Texas designated "E-100" showed a
specific gravity at 15.6C of 1.0168, a pe~cent
nitrogen by weight o~ 33.15 and a viscos~ty at 40C
of 121 centistokes. Gas chromatography analysis of
such a sample showed it to contain about 0.93% "~ight
Ends" (DETA?), 0.72~ TETA, 21.74% tetraethylene
pentamine and 76.61% pentaethylene hexamine and higher
(by weight~. These alkylene polyamine bottoms includa
cyclic condensation products such as piperazine and
higher analogs of diethylene triamine, triethylene
tetramine and the like.
These alkylene polyamine bottoms can be
reacted solely with the acylating agent, in which case
the amino reactant consists essentially of alkylene
polyamine bottoms, or they can be used with other
amines and polyamines, or alcohols or mixtures
thereof. In these latter cases at least one amino
reactant comprises alkylene polyamîne bottoms.
Hydroxylalkyl alkylene polyamines having one
or more hydroxyalkyl substituents on the nitrogen
atoms, are also useful in preparing derivatives of the
afore-described olefinic carboxylic acids. Preferred
hydroxylalkyl-subs~ituted alkylene polyamines are those
in which the hydroxyalkyl group is a lower hydroxyalkyl
group, i.e., having less than eight carbon atoms.
Examples of such hydroxyalkyl-substi~uted polyamines
include N-(2-hydroxyethyl)ethylene diamine,N,N-bis~2-
hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl~
piperazine, monohydroxypropyl-~ubstituted diethylene
triamine, dihydroxypropyl-substituted tetraethylene
pentamine, N-(2-hydroxybutyl)tetramethylene diamine,
etc. Higher homologs as are obtained by condensation
o~ the above-illustrated hydroxy alkylene polyamines
8Al4!~
-45-
through amino radicals or through hydroxy radicals are
likewise useful as (a). Condensation through amino
radicals results in a higher amine accompanied by
removal o~ ammonia and condensation ~hrough the hydroxy
radicals results in products containing ether linkages
accompanied by removal of water.
The carboxylic derivative compositions (A)
produced ~rom the acylating reagents and the amino
compounds described hereinbefore produce acylated
amines which include amine salts, amides, imides and
imidazolines as well as mixtures thereof. To prepare
carboxylic acid derivatives ~rom the acylating reagents
and the amino compounds, one or more acylating reagents
and one or more amino compounds are heated, optionally
in the presence of a normally liquid, substantially
inert organic liquid solvent/diluent, at temperatures
in the range o~ about 80C up to the decomposition
point (where the decomposition point is as previously
defined) but normally at temperatures in the range o~
about 100C up to about 300C provided 300C does
not exceed the decomposition point. ~emperatures of
about 125C to a~out 250C are normally used. The
acylating reagent and the amino compound are reacted in
amounts sufficient to provide from about one-hal~
equivalent to about 2 moles of amino co~pound per
equivalent of acylating reagent. For purposes of this
invention an eguivalent of amino compound is that
amount of the amino compound corresponding to the total
weight of amino compound divided by the total number of
nitrogens present. Thus, oc~ylamine has an equivalent
weight equal to its molecular weight; ethylene diamine
has an equivalent weight equal to one-hal~ its
molecular weight; and aminoethylpiperazine has an
' ' '
`. ., - ` ::
. ., ~ . . ..
;
-46-
equivalent weight equal ko one-third its molecular
weight.
The numbers of equivalents o~ acylati~g
reagent depends on the number o~ carbo~ylic function~
(e.g., -C(o)X, -CtO)X', -C(O)R, and -C(O)R', wherein X,
X', R and Rl are as defined above) present in the
acylating reagent. Thus, the number of e~uiYalents of
acylating reagents will vary with the number o~
succinic groups present therein. In determining the
number of eguivalent~ of acylating reagents, those
carboxyl function which are not capable of reacting as
a carboxylic acid acylating agent are excluded. In
general, however, there are two equivalents o~
acylating reagent for each succinic group in the
acylating reagents or, from ano~her viewpoin~, two
equivalents for each group in the acylating reagents
d~rived from (~); i.e., the maleic reactant from which
the acylating reagent is prepared. conventional
techniques are readily available ~or determining the
number of carboxyl functions (e.g., acid num~er,
saponification number) a~d, thus, the number of
equivalents of acylating reagent available to react
with a~ine.
Because the acylating reagents can be used in
the same manner as the high mol~cular weight acylatt~g
agents o~ the prior art in preparing acylatad amines
suitable for use a3 component (A) in the diesel
lubr~cants o~ this i~ention, U.S. Patents 3,172!892;
3,219,666; 3,272,746; and 4,234,435 are particularly
relevant for their disclosure with respect to the
procedures applicable to reacting the acylating reagents
with the amino compounds as described above. In applying
the disclosures of these
~.~8~5
-47-
patents to the acylating reagents, the latter can be
substituted for the high molecular weight carboxylic
acid acylating a~ents disclosed in these pakents on an
equivalent basis. That is, where ons equivalent o~ khe
high molecular weight carboxylic acylating ayenk
disclosed in these incorporated patents is utilized,
one equivalent of the acylating reagent of this
invention can be used.
In order to produce carboxylic derivative
composition~ exhibiting viscosity index improving
capabilities, it has been found generally necessary to
react the acylating reagents with poly~unctional
reactants. For example, polyamines having two or more
primary and/or secondary amino groups are preferred.
It is believed that the polyfunctional reactants serve
to provide "b~ridges" or cross-linking in the carboxylic
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 there is no intention to be bound by
thls theory.
Obviously, howaver, it is not necessary that
all of the amino compound reacted with the acylating
reagents b~ polyfunctional. Thus, co~bina~ions of
mono- and polyfunctional amino compounds be used.
While the paxameters have not been fully
determined as yet, it is believed that acylating
reagents of this invention should be reacted with amino
compounds- which contain sufficient polyfunctional
reactant, (e.g., polyamine) so that at least about 25%
of the total number of carboxyl groups (from the
succinic groups or from the groups derived from the
~2~34~
-48-
maleic reactant) are reacted with a polyfunctional
reactant. Better results, insofar as the viscosity
index-improving facilities o~ ~he carboxylic derivative
compositions is concerned, appear to be obtained when
at least 50% of the carboxyl groups are involved in
reaction with such polyfunctional reactants. In mos~
instances, the best viscosity index improving
properties seem to be achieved when the acylating
reagents of this invention are reacted with a
sufficient amount of polyamine 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 stated percentage of carboxyl functions actually
react with polyfunctional reactant. Rather these
percentage~ are used to charac~erize the amounts of
polyfunctional reactants desirably "available" to react
with the acylating reagents in oxder to achieve the
desired viscosi~y index improving properties.
Another optional aspect o~ this illvention
involves the post-treatment of the carboxylic
derivative compositions (A). The process for post-
treating thP carboxylic acid deriv~tive compositions is
again analogous to the post treating processes used
with respect to similar derivatives o~ the high
molecular weight carboxyllc acid acylating a~ents of
the prior art. Accordingly, the same reaction
conditions, ratio of reactants and the like can be
used.
Acylated nitrogen compositions prepared by
reacting the acylating reagents with an amino compound
as dascribed above are post-treated by contacting tha
acylated nitrogen compositions thus formed (e.g., the
~Z8~
. -4~
carboxylic deri~ative compositions) with one or more
post-treating reagents selected ~rom th~ group
consisting of boron oxide, bcron oxide hydrate, boron
halides, boron acids, esters o~ boron acid~, carbon
disulfide, sul~ur, sulfur chlarides, alkenyl cyanides,
carboxylic acid acylating agents, ald~hydes, ketone~,
urea, thiourea, guanidine, dicyanodiamide, hydrocar~yl
phosphates, hydrocarbyl phosphites, hydrocarbyl
thiophosphates, hydrocarbyl thiophosphi~es, phosphorus
sulfides, phosphorus oxides, phosphoric acid,
hydrocarbyl thiocyanates, hydrocarbyl isocyanates,
hydrocarbyl lsothiocyanates, epoxides, episulfid~s,
formaldehyde or formaldehyde-~roducing compounds plus
phenols, and sul~ur plus phenols.
Slnc~ post-treating processes involving the
use of these post-treating re~gents are known inso~ar
as application to reaction products of high molec~lar
weight carb~.~lic acid acylating agents o~ the prior
art and amlne~ and/or alcoholq, de~ail~d descrip~ions
o~ these processe~ herein are unn~.cessary. In order to
apply the prior art processes to the carboxylic
derivati~e compositions of this invention, all that is
necessary is that reaction conditions, ratio
reactants/ and the like as da~cribed in the prior art,
be applied to the carboxylic derivativ.e compositions
(A). In particular, U.S. Patent 4,234,435 is particularly
relevant for its disclosure of post-treating procasses and
post-treating reagents applicable to the carboxylic
derivative compositions (A). The following U.S. patents
also describe post-treating processes and post treating
reagents applicable to ~the carboxylic derivative
compositions (A): U. S . Patents 3, 200 ,107; 3, 254, 025:
3,2561185;
,
:; .'. :
.
-
.
~28~4~;
- 50 -
3,282,955; 3,284,410; 3,366,569; 3,403,102; 3,428,561;
3~502,677; 3,639,242; 3,708,522; 3,865,813; 3,865,7~0;
3,954;639.
The preparation of khe acylating agent and
the carboxylic acid derivakive composition~ (A), as
well as the post-treated carboxylic acid derivative
compositions i5 illustra~ed by the following examples.
These examples illustrate presently pre~erred
embodiments. In the ~ollowing examples, and elsewhere
in ths specification and claims, all percentages and
parts are ~y weight unless otherwise clearly indicated,
Example A-l
A mixture of 510 parts (0.28 mole) of
polyisobutene (Mn-1845; Mw=5325) and 5g parts (O.59
mole) of maleic anhydride is heated to 110C. This
mixture is heated to 190C in 7 hours during which 43
parts (0.6 mole) of gaseous chlorine is added beneath
the surface. At 190-192C an additional 11 parts
(0.16 mole) of chlorine is added over 3.5 hours. The
reaction mixture is stripped by heating at 190-193C
with nitrogen blowing for 10 hours. The residue is the
desired polyisobutene-substi~uted succinic acylating
agent having a saponification equiva}ent number o~ 87
as determined by ASTM procedure D-94.
Example A-2
A mixture of lO00 parts (0.495 mole) of
polyisobutene ~Mn-2020; ~w-6049) and 115 parts (1.17
moles) of maleic anhydride is heated to 110C. This
mixture is heated to 184C in 6 hours durin~ which 85
paxts (1.2 moles) of gaseous chlorine is added beneath
the surface. At 184-189C an additional 59 parts
(0.83 mole) of chlorine is added over 4 hours. The
reaction mixture is stripped by heating at 186-190C
,. - . :
,' ,
~ . . , : , .: ~
-
~L2~34~
-51-
with nitrogen blowing for ~6 hours. The residue is the
desired polyisobutene-substituted succinic acylating
agent having a saponification equivalenk number o~ ~7
as determined by ASTM procedure D~94.
Example A-3
A mixture o~ 3251 parts o~ polyisobukene
chloride, prepared by the addition of 251 parts of
gaseous chlorine to 3000 parts of polyisobutene
(Mn=1696; Mw-6594) at 80C in 4.66 hours, and 345
parts of maleic anhydride is heated to 200C in 0.5
hour. The reaction mixture is held at 200-224C for
6.33 hours, stripped at 210C under vacuum and
filtered. The filtrate is the desired
polyisobutene-substituted succinic acylating agent
having a saponification equivalent number of 94 as
determined by ASTM procedure D-94.
Example A-4
A mixture o~ 3000 parts (1.63 moles) of
polyisobutene (Mn=1845: Mw=5325) and 344 parts (3.51
moles) of maleic anhydride is heated to 140C. This
mixturs is hPated to 201C in 5.5 hours during which
312 parts (4.3~ moles) of gaseous chlorine is added
beneath the surface. The reackion mixture ls heated at
201-236C with nitrogen blowing for 2 hours and
stripped under vacuum at 203c. The reaction mixture
is filtered to yield the ~iltrate as the desired
polyisobutene-substituted succinic acylating agent
having a saponi~ication e~uivalent number of 92 as
determined by ASTM procedure D-94.
Example A-5
A mixture of 3000 parts (1.49 moles~ of
polyisobutene (Mn=2020; Mw=6049) and 364 parts ~3.71
moles) of maleic anhydride is heatsd at 220C for 8
.
.
- ~ . .
.
- ; ,, ~
, , ' :
- .. : .
~X84~
-52-
hours. The reaction mixture is cooled to 170C. At
170-190C, 105 parts (1.48 moles) of gaseous chlorine
is added beneath the sur~ace in 8 hours. The reackion
mixture is heated at 190C with nitrogen blowing ~or
Z hours and then stripped under vacuum at 190C. The
reaction mixture is filtered to yield the ~iltrate as
the desired polyisobutene-substi~uted succinic
a?ylating agent.
Example A 6
A mixture of 800 parts of a polyisobutene
falling wi~hin the scope of the claims of the presant
invention and having an Mn of about 2000, 646 parts of
mineral oil and 87 parts of maleic anhydride is heated
to 179~ in 2.3 hours. At 176-180C, 100 parts of
gaseous chlori.ne is added beneath the surface over a
l9-hour period. The reaction mixture is stripped by
blowing with nitrogen for 0.5 hour at 180~. The
residue is an oil-containing solution of the desired
polyisobutene-substituted succinic acylating agent.
Example A-7
The procedure for Example A-l is repeated
except the polyisobutene (Nn-1845; Mw=5325) is replaced
on an equimolar basis by polyisobutene (~n=1457,
Mw=5808).
Example A-8
The procedure for Example A-l is repeated
except the polyisobutene (Mn=1845; Mw=5325) is replaced
on an equimolar ba~is by polyisobutene (Mn=2510;
Mw=5793)-
~xample A-g
The procedure for Example A-l is repeated
except the polyisobutene (Mn-1845; ~w=5325) is replaced
on an equimolar basis by polyisobu~ene (Mn=32~0;
~w=5660).
, ~ . ., '~
' '
~z~
o53
Example A-10
A mixture is prepared by the addition of 10.2
parts (O.25 equivalent) of a commercial mixture of
ethylene polyaminss having from about 3 to about 10
nitrogen atoms per molecule to 113 parts o~ mineral oil
and 161 parts (0.25 equivalent) o~ the subst1tuted
succinic acylating agent prepared in Example A-l at
138C. The reaction mixture is heated to 150C in
2 hours and stripped by blowing with nitrogen. The
reaction mixture is filtered to yield the filtrate as
an oil solution o~ tha desired product.
Example A-ll
A mixture is prepared by the addition o~ 57
partC (1.38 equivalents) of a commercial mixture of
athylene polyamines having from about 3 to 10 nitrogen
atoms per molecule to 1067 parts of mineral oil and 893
parts (1.38 ~equivalents~ of the substituted succinic
acylating agent prepared in Example A-2 at
140-145C. Tha reaction mixture is heated to 155C
in 3 hours and strippQd by blowing with nitrogen. The
reaction mixture is filtered to yield the filtrate as
an oil solution of the desired product.
Example A-12
A mixture is prepared by the addition of 18.2
parts ~0.433 equivalent) of a commercial mixture of
ethylene polyamines having from about 3 to 10 nitrogen
atoms per molecule to 3~2 parts of mineral oil and 34~
parts (O.52 equivalent~ of the substituted succinic
acylating agent prepared in Example A 2 at 1~0C.
The reaction mixture is heated ~o 150C in 1.8 hours
and stripped by blowing wi~h nitrogen. The reaction
mixture is filtered ~o yield the ~iltrate as an oil
solution of the desired product.
-
- : ,
-:
:' ' ' ,. ~
~. . . .
~IL2~
-54-
Example A-13
A mixture is prepared by the addition of 5500
parts of the oil solution of the substituted succinic
acylating agent prepared in Example A-7 to 3000 paxts
of mineral oil and 236 parts o~ a commercial mixture o~
ethylene polyamines having an average of about 3-10
nitrogen atoms per molecule at 150C over a one-hour
period. The reaction mixture is heaked at 155-165C
for two hours, then stripped by blowing wikh nitrogen
at 165C for one hour. The reaction mixture is
filtered to yield the filtrate as an oil solution of
the desired ni~rogen~containing product.
Examples A-14 through A-27 are prepared by
following the general procedure set forth in Example
A-lO.
~ .
.
~z~
-55-
Ratio of Sub-
stituted Suc-
cinic Acylating
Example Agent To Percent
Number Reactant~s) Reactants _ Diluent
A-14 Pentaeth~lene 1:2 equi~alents 40%
hexamine
A-15 Tris(2-aminoethyl) 2:1 moles 50%
amine
A-16 Imino-bis-propyl- 2:1 moles` 40
amine
A-17 Hexamethylene 1:2 moles 40%
diamine
A-18 1-(2-Aminoethyl)- 1:1 equivalents 40%
2-methyl-2-
imidazoline
A-l9 N-aminopropyl- 1:1 moles 40%
pyrrolidone
a A commercill mixture of ethylene polyamines
corresponding in empirical ~ormula to pentaethylene
hexamine.
b A commercial mixture of ethy}ene polyamines
corresponding in empirical formula to diethylene
triamine.
c A commercial mixture of ethylene polyamines
corre~ponding in empirical formula to triethylene
tetramine.
:: .
.
' ,: . :
~.
. ' ~ . ': ~ ,
s
-56-
Ratio of Sub-
stltuted Suc-
cinic Acylatlng
Example Agent To Percent
Number ReactantLsL ~eactants Diluent
A-20 N,N-dimethyl-1,3- l:l equivalents 40%
Propane diamine
A-21 Ethylene diamine 1:4 equivalents 40%
A-22 1,3-Propane l:l moles 40%
diamine
A-23 2~Pyrrolidinone 1:1.1 moles 20%
A-24 Urea 1:0.625 moles 50%
A-25 Dieth~lenetri- 1:1 moless 50
amine
A-26 Triethylene- 1:0.5 moles 50%
amine
~-27 Ethanolamine l:l moles 4g%
a A commercial mixture of ethylene polyamines
corresponding in empirical formula to pentaethylene
hexamine.
b A comm~rcial mixture of ethylene polyamines
corresponding in empirical ~ormula to diethylene
triamine.
c A commercial mixture of ethylene polyamines
corresponding in empirical formula to triethylene
tetramine.
~ - , '', , ,
.. ;- , ,
:. . . .
~8~
-57-
Example A-28
A mixture is prepared by the addi~ion o~ 31
parts of carbon disulfide over a period o~ 1.66 hours
to 853 parts o~ the oil solution of the produck
prepared in Example A-14 at 113-145C. The reackion
mixture is held at 145-152C for 3.5 hours, then
filtered to yield an oil solution o~ the desired
product.
~xample A-29
A mixture of 62 parts of boric acid and 27~0
parts of the oil solution of the product prepared in
Example A-10 is heated at 150C under nitrogen for 6
hours. The re~ction mixture is filtered to yield the
filtrate as an oil solution of the desired boron-
containing product.
Example A-30
An oleyl ester of boric acid is prepared by
heating an equimolar mixture of oleyl alcohol and boric
acid in toluene at the reflux temparature while water
is removed azeotropically. The reaction mixture is
then heated to 150C under vacuum and the residue is
the ester having a boron content of 3.2% and a
saponification number of ~2. A mixture of 344 parts o~
the heater and 2720 parts of the oil solution of the
product prepared in Example A-10 is heated at 150C
~or 6 hours and then filtered. The filtrate is an oil
solution of the desired boron-containing product.
Example A 31
Boron trifuoride (34 parts) is bubbled into
2190 parts of the oil solution o~ the product prepared
in Example A-11 at 80C within a period of 3 hours.
The re~ulting mixture is blown with nitrogen at
70-80C for 2 hours to yield the residue as an oil
solution o~ ~he desired product.
,~ .
-5~-
Example ~-32
A mixture of 3420 parts of the oil-containing
solution of the product prepared in Example A-12 and 53
parts of acrylonitrile is heaked at reflux temperature
from 125-145C for 1.25 hours, at 145C ~or 3 hours
and then stripped at 125C under vacuum. The residue
is an oil solution of the desired productO
Example A-33
A mixture is prepared by the addition of 44
parts of ethylene oxide over a period of one hour to
1460 parts of the oil solution of the product prepared
in Example A-ll at 150C. The reaction mixture is
held at 150C for on2 hour, then filtered to yield
the filtrate as an oil solution of the desired product.
Example A-34
- A mixtur~ Qf 11~0 parts of the oil solution of
the product of ~xample A-10 and 73 pax~s of
terephthalic acid is heated at 150-160C and
filtered. The filtrate is an oil solution of the
desired product.
Example A-35
A decyl ester of phosphoric acid is prepared
by adding one mole of phosphorus pentaoxide to three
moles of decyl alcohol at a temperature within the
range of 32-55C and then heating the mixture at
60-63C until the reaction is ~omplete. The product
is a mixture of the decyl esters of phosphoric acid
having a phosphorus content of 9.9% and an acid number
of 250 (phenolphthalein indicator). A mixture of 1750
parts of the oil solution of the product prepared in
Example A-10 and 112 parts of the above decyl ester is
heated at 145-159C for one hourO The reaction
mixture is filtered to yield the filtrate as an oil
solution o~ the desired product.
:
. : ' .
~L2~ 4S
~59-
Example A-36
A mixture of 2920 parts of the oil solution of
the product prepared in Example A-ll and ~9 parts o~
thiourea is heated to 80C and held at 80C ~or 2
hours. The reaction mixture is then heated at
150-155C for 4 hours, the last o~ which the mixture
is blown with nitrogen. The reaction mixture is
~iltered to yield the filtrate as an oil solution of
the desired product.
Example A~37
A mixture of 1460 parts of the oil solution of
the product prepared in Example A-ll and 81 parts of a
37~ aqueous formaldehyde solution is heated at reflux
~or 3 hours. The reaction mixture is stripped under
vacuum at 150C. The residue is an oil solution of
the desired product.
Example A-38
A mixture o~ 1160 parts of the oil solution of
the product prepared in Example A-10 and 67 parts o~
sul~ur monochloride is heated for one hour at 150C
under nitrogen. The mixture is filtered to yield an
oil solution of ~he desired sulfur-containing product.
Example A-39
A mixtura is prepared by the addition of 11.5
parts of formic acid to 1000 parts o~ the oil solution
of the product prepared in Example A-ll at 60~C. The
reaction mixture is heated at 6Q-100C for 2 hour ,
92-100C for 1 A 75 hours and then filtared to yiald an
oil solution of the desired product.
Example A-40
An appropriate size flask fitted with a
stirrer, nitrogen inlet tube, addition funnel and Dean-
Stark trap/condenser is charged with a mixture of 2483
.
.
. : . ' -: . ":' :
, . : ~ .
~2~34~a~5
-60-
parts acylating agent (4.2 e~uivalents) as described in
Example A-3, and 11~4 parts oil. This mixture is
heated to 210C while nitrogen was 510wly bubbled
through it. Ethylene polyamine bottoms (134 parts,
3.1~ equivalents) is slowly added over about one hour
at this temperature. The temperature i5 maintained at
about 210C for 3 hours and then 3688 parts oll is
added to decrease the temperature to 125Co After
storaye at 138C for 17.5 hours, the mixt~re is
filtered through diatomaceous earth to provide a 65%
oil solution o~ the desired acylated amine bottoms.
Component (B) of the diesel lubricants of this
invention is at least one basic alkali metal salt of at
least one acidic organic compound. Thi~ component is
among those art-recognized metal-containing composi-
tions variously refered to by such names as "ba~ic",
"super~ased" and "overbased" salts or complexes. The
method for their preparation is commonly referred to as
"overbasing". The ~erm "metal ratio" is often used to
define tke quantity of metal in these salts ox
co~plexes relative to the quantity of organic anion,
and is defined as the ratio of the number of
equivalents thereof which would be present in a normal
salt based upon the usual stoichiometry o~ the
compounds involved.
The alkali metals present in the basic alkali
metal salt~ includa principally lithium, sodium and
potassium, with sodium and potassium being prefexred.
The most useful acidic organic compounds are sulfur
acids, carboxylic acids, organic phosphorus acids and
phenols.
-
.
- ,. ,
~Z84~S
-61-
The sulfur acids include sul~onic, sulf~mic
thiosulfonie, sulfinic sulfenic, partial ~ster
sulfuric, sul~urous and ~hlosul~urlc acids. Generally
the sulfur acid is a sul~onic acid.
The sulfonic acids axe preferred as component
(B) in the diesel lubricants of the invention. They
include those represented by the formulae
Rl(S03H)r and (R2)XT(so3H~y~ In these
formulae, Rl is an aliphatic or aliphatic-substituted
cycloaliphatic hydrocarbon or essentially hy~rocarbon
radical free ~rom acetylenic unsaturation and
containing up to about 60 carbon atoms. When Rl is
aliphatic, it usually contains at least about 15 carbon
atoms: when it is an aliphatic-substituted
cycloaliphatic radical, the aliphatic substituents
usually contain a to~al of at least about 12 carbon
atoms. Examples of Rl are alkyl, alkenyl and
alkoxyalkyl radicals, and aliphatic-substituted
cycloaliphatic radicals wherein the aliphatic
substituen~s axe alkyl, alkeny~, alkoxy, alkoxyalkyl,
carboxyalkyl and the like. Generally, the
cycloaliphatic nucleus is derived from a cycloalkane ox
a cycloalkene such as cyclopentane, cyclohexane,
cyclohexene or cyclopentane. Speci~ic examples of
are cetylcyclohexyl, laurylcyclohe~yl, cetylo~yethyl,
octadecenyl, and radicals derived from pet~oleum,
saturated and unsaturated paraffin wax, and olefin
polymers including polymerized monoolefins and
diolefin~ containing about ~-8 car~on a~oms ~per
olefinic monom~r unit. Rl can also con~ain o~her
substituents such as phenyl, cycloalkyl, hydroxy,
mercapto, halo, nitro, amino, nitroso; lower alkoxy,
lower al~ylmercapto, carboxy, carbalkoxy, oxo or thio,
, .. .
.
. ' - , : ~' ' -,
.
.
~ILZ84 11 ~S
-62-
or interrupting groups such as -NH-, -O- or -S-, as
long as the essentially hydrocarbon character thereo~
is not destroyed.
R2 is generally a hydrocarbon or e~sentlally
hydrocarbon radical free ~rom acetylenic un~aturation
and containing from about ~ to about 60 aliphatic
carbon atoms, pre~erably an aliphatic hydrocarbon
-radical such as alkyl or alkenyl. It may also,
however, contain substituents or interrupting groups
such as those enumerated above provided the essentially
hydrocarbon character thereof is retained. In general,
any non-carbon atoms present in Rl or R2 do not
account for more than 10% of the total weight thereof.
~ is a cyclic nucleus which may be derived
from an aromatic hydrocarbon such as benzene,
naphthalene, anthracene or biphenyl, or from a
heterocyrllic compound such as pyridine, indole or
isoindole. Ordinarily, T is an aromatic hydrocarbon
nucleus, Pspecially a benzene or naphthalene nucleus.
The subscript x is at leas~ 1 and is generally
1~3. The subscripts r and y hav~ an average value of
about l-4 per molecule and are generally also 1.
The following are speaific examples of
sulfonic acids useful in preparing the salts (B). It
is to be understood that such examples serve also to
illustrate the salts of such sulfonic acids useful as
component (B). In other words, for every sulfonic acid
enumerating, it is intended that the corresponding
basic alkali metal salts thereo~ are also under tood to
be illustrated. (~he same applies to the lists of
other acid materials listed below, i.e., the carbo~ylic
acids, phosphorus acids and phenols~) Such sulfonic
acids include mahogany sul~onic acids, bright stock
lZ~A~S
-63~
sul~onic acids, pe~rolatum sul~onic acids, mono- and
polywax substituted naphthalene sulfonlc acids, cekyl-
chlorobenzene sulfonia acids, ~etylphenol sulfonic
acids, cetylphenol disulfide sulfonic acids, cetoxy-
capryl benzene sulfonic acids, dicetyl thianthrene
sulfonic acids, dilauryl beta-naphthol sulfonic acids,
dicapryl nitronaphthalene sulfonic acids~ saturated
paraffin wax sulfonic acids, unsaturated paraffin wax
sulfonic acids, hydroxy-sukstituted paraffin wax
sul~onic acids, tetraisobutylene sulfonic acids,
tetra-amylene sul~onic acids, chloro-substituted
paraffin wax sulfonic acids, nitroso-substi~uted
paraffin wax sulfonic acids, petroleum naphthene
sulfonic acids, cetylcyclopentyl sulfonic acids, lauryl
cyclohexyl sulfonic acids, mono- and polywax-substi-
tu~ed cyclohexyl sulfonic acids, postdodecylbenzene
sulfonic acids, "dimer alkylate" sulfonic acids, and
the like.
Alkyl-substituted ~enzene sulfonic acids
wherein the alkyl group contains at least 8 carbon
atoms including dodecyl ben7ene "bottoms" sulfonic
acids are particularly useful The latter are acids
derived from benzene which has been alkylated with
propylene tetramers or isobutene trimers to introduce
1, 2, 3, or more branched-chain C12 substituents on
the benzene ring. Dodecyl benzene bottoms, principally
mixtures of mono- and di dodecyl benzenes, are
available as by-products from the manufacture of
household deterg~nts. Similar products obtained from
alkylation bottoms formed during manufacture of linear
alkyl sulfonates (LAS) are also useful in making the
sul~onates used in this inv~ntion.
~284L~
-64-
The production of sulfonates from detergent
manufacture by-products by reaction with, e.g., SO3,
is well known to those skilled in thQ art. S~e, ~o~
example, the article "Sul~onates" in Kirk-Othm~r
"Encyclopedia of Chemical Technology", Second Edition,
Vol. 19, pp. 291 et seq. published by John Wiley &
Sons, N.Y. (1969).
O~her descriptions of basic sulfonate salts
and techniques ~or making them can be found in the
following U.S. Patents: 2,17~,110; 2,202,781;
2,239,974; 2,319,121; 2,337,552; 3,4~8,284; 3,595,790;
and 3,798,012.
Suitable carboxylic acids include aliphatic,
cycloaliphatic and aromatic mono- and polybasic
car~oxylic acids free from acetylenic unsaturation,
including naph~henic acids, alkyl- or alkenyl
substituted cyclopentanoic acids, alkyl- or alkenyl-
substitutad cyclohexanoic acids, and alkyl- or
alkenyl~ubstituted aromatic carboxylic acids. The
aliphatic acid~ generally contain ~rom abou~ 8 to abou~
50, and preferably from about 12 to about 25 carbon
ato~s. The cycloaliphatic and aliphatic carboxylic
acids are preferred, and they can be sa~ura~ed or
unsaturated. Specific examples include 2-ethylhexanoic
acid, linolenic acid, propylene tetramer~substituted
maleic acid, behenic acid, isostearic aGid, pelargonic
acid, capric acid, palmitoleic acid, linoleic acid,
lauric acid, oleic acid, ricino~eic acid, underyclic
acid, dioctylcyclopentanecarboxylic acid, myristic
ac~d, dilau~yldecahydronaphthalene-carboxylic acid,
stearylocta~ydro$nden~carboxy1ic acid, pal~tic acid,
alkyl- and alkenylsuccinic acids, acids formed ~y
. . .. .
, ' ' , .
~:8~
oxidation o~ petrolatum or of hydrocarbon waxes, and
commercially available mixtures of two or more
carboxylic acids such as tall oil acids, rosin acids~
and the like.
The pentavalenk phosphorus acids use~ul in the
preparation of component (B) may be represenked by the
formula
R (X )a ~ 11 3
R4(X2)b
wherein each f R3 and R4 is hydrogen or a
hydrocarbon or essentially hydrocarbon group preferably
having from about ~ ~o about 25 carbon atoms, at least
one of R3 and R4 being hydrocarbon or essentially
hydrocarbon; each of Xl, X2, X3 and X4 is
oxygen or sulfur; and each of a and b is o or 1. Thus,
it will be appreciated that the phosphorus acid may be
an organophosphoric, phosphonic or phosphinic acid, or
a thio-analog o~ any of thesa.
The phosphorus acids may be those of the
formula
R30 \ 1
/ P-OH
R40
wherein R3 is a phenyl group or (preferably) an alkyl
group having up to 18 carbon atoms, and R4 is
hydrogen or a similar phenyl or alkyl group. Mix~ures
of such phosphorus acids are often pre~erred because of
their ease of preparation.
-66-
Component tB) may also be prepared from
phenols; that is, compounds containing a hydroxy group
bound directly to an aromatic ring. The term 'Iphenol''
as used herein includes compounds having more than one
hydroxy group bound to an aromatic r~ng, such as
catechol, resorcinol and hydroquinone. It also
includes alkylphenols such as the cresols and
ethylphenols, and alkenylphenols. Preferred are
phenols containing at least one alkyl substituent
containing about 3-100 and especially about 5-50 carbon
atoms, such as heptylphenol, octylphenol, dodecyl-
phenol, te~rapropene-alkylated phenol, octadecylphenol
and polybutenylphenols. Phenols containing more than
one a}kyl substituen~ may also be used, but ~he
monoalkylphenols are pre~erred because of their
availability and ease of production.
Also useful are condensation products of the
above-described phenols with at least one lower
aldehyde or ketone, the term "lower" denoting aldehydes
and ketones containing no~ more than 7 carbon atoms.
Suitable aldehydes include for~aldehyde, acetaldehyde,
propionaldehyde, the butyraldehydes, the valexaldehydes
and benzaldehyde. Also suitable are aldehyde-yielding
reagents such as para~ormaldehyde, trioxane, methylol,
Nethyl Formcel and paraldehyde. Formaldehyde and the
formaldehyde-yielding reagents are especially
preferred.
The equivalent weight of the acidic organic
compound is its molecular weight divided by th number
of acidic groups (i.e., sul~onic acid, carboxy or
acidic hydroxy groups) present per molecule.
In one preferred embodiment, the alkali metal
salts (B) are basic alkali me~al salts having metal
- . - :
- .
-~7-
ratios of at least about 2 and more generally rom
about 4 to about ~0, pre~erably from about 6 to about
30 and especially f rom about 8 to about 25.
In another and preferred embodiment, the ba~ic
salts ~B) are oil-soluble dispersions prepared by
contacting for a period of time sufficient to form a
stable dispersion, at a temperature between the
solidif ication temperature of the reaction mixture and
its decomposition temperature:
(B-l) at least one acidic gaseous material
selected from the group consisting of carbon dioxide,
hydrogen sulfide and sulfur dioxide, with
(B-2) a reaction mixture comprising
tB-2-a) at least one oil-soluble
sulfonic acid, or derivative thereof suscep~ible to
overbasing;
(B-2-b) at least one alkali metal or
basic alkali metal compound;
(B-2-c) at least one lower aliphatic
alcohol, alkyl phenol~ or sulfurized alkyl phenol; and
(B-2-d) at least one oil-soluble
carboxylic acid or functional derivative thereof. When
(B-2-c~ is an alkyl phenol or a sulfuri~ed alkyl
phenol, component (B-2-d) is optional. A satisfactory
basic sulfonic acid salt can be prepared with or
without the carboxylic acid in the mixture (B~2)~
Reagent (B-l) is at least one acidic gaseous
material which may be carbon dioxide~ hydrogen sulfide
or sulfur dioxide; mixtures of these gases are also
useful. Carbon dioxide is preferred.
As mentioned above, reagent ~B-2) generally is
a mixture containing at least four components of which
component (B-2-a) is at least one oil-soluble sulfonic
-68~
acid as previously defined, or a derivative knereof
susceptible to overbasing. Mixtures of sulfonic acids
and/or their derivatives may also be used. Sulfonic
acid derivatives susceptible to overbasing include
their metal salts, especially ~he alkaline ear~h, zinc
and lead salts; ammonium salts and amine salts ~e.g.,
the ethylamine, butylamine and ethylene polyamine
salts); and esters such as the ethyl, butyl and
glycerol esters.
Component (~-2 b) is at least one alkali metal
or a basic compound thereof. Illustrative of basic
alkali metal compounds are the hydroxides, alkoxides
~typically those in which the alkoxy group contains up
to 10 and preferably up to 7 carbon atoms~, hydrides
and amides. Thus, useful basic alkali metal compounds
include sodium hydroxide, potassium hydroxide, lithium
hydroxide, sodium propoxide; lithium methoxide~
potassium ethoxide, sodium butoxide, lithium hydride,
sodium hydride, potassium hydride, lithium amide,
sodium amide and potassium amide. Especially preferred
are sodium hydroxide and the sodium lower alkoxides
(i.e., those containing up to 7 carbon atoms). The
equivalent weight of component (B-2-b) for the purpose
of this invention is equal to its molecular weight,
since the alkali metals are monovalent.
Component (R-2-c) may be at least one lower
aliphatic alcohol, preferably a monohydric or dihydric
alcohol. Illustrative alcohols are mekhanol, ethanol,
l-propanol, l-hexanol, i~opropanol, isobu~anol,
2-pentanol, 2,2-dimethyl-1-propanol, ethylene glycol,
1-3-propanediol and 1,5-pentanediol. The alcohol also
may be a glycol ether such as Methyl Cellosolve. Of
these, the preferred alcohols are me~hanol, ethanol and
propanol, with methanol being especially preferred.
.
.
.
,
~;28~4~i
~69-
Component (B-2-c) also may be at least one
alkyl phenol or sulfurized alkyl phenol. The
sulfurized alkyl phenols are preferred, especially when
(B-2-b) is potassium or one of its basic compounds such
as potassium hydroxide. As used herein, the term
"phenol" includes compounds having more than one
hydroxy group bound to an aromatic ring, and the
aromatic ring may be a benzyl or naphthyl ring. The
term "alkyl phenol" includes mono- and di-alkyla~ed
phenols in which each alkyl substituent contains from
abou~ 6 to about 100 carbon atoms, preferably about 6
to about 50 carbon atoms.
Illustrative alkyl phenols include heptyl-
phenols, octylphenols, decylphenols, dodecylphenols,
polypropylene (M.W. of about 150)-substitutèd phenols,
polyisobutene (M.W. of about 1200)-substituted phenol~,
cyclohexyl phenols.
Also useful are condensation products of the
above-described phenols with at least one lower
aldehyde or ketone, the term "lower" denoting aldehydes
and ketones containing not more than 7 carbon atomsO
Suitable aidehydes include formaldehyde, ace~aldehyde~
propionaldehyde~ the butyraldehydes, the valeraldehydes
and benzaldehyde. Also suitable are aldehyde-yielding
reagents such as paraformaldehyde, trioxane, methylol,
Methyl Formcel and paraldehyde. Formaldehyde and the
formaldehyde-yielding reagents are especially
preferred.
The sulfurized alkylphenols include phenol
sulfides, disulfides or polysulfides. The sulfurized
phenols can be derived from any sui~able alkylphenol by
technique known to those skilled in the artf and many
sulfurized phenols are commercially availableO The
8 ~ ~ ~ S
-70-
sulfurized alkylphenols may be prepared by reacting an
alkylphenol with elemental sulfur and/or a sulfur
monohalide (eOg., sulfur monochloride). This reaction
may be conducted in the presence o~ excess ba~e to
result in the salts o the mixture of sulfides,
disulfides or polysulfides that may be produced
depending upon the reaction conditions. It is the
resulting product of this reaction which is used in the
preparation of component (B-2) in the present
invention. U.S. Patents 2,971,9~0 and 4,309,293
disclose various sulfurized phenols which are
illustrative of component (B-2-c).
The following non-limiting examples illustrate
the preparation of alkylphenols and sulfurized
alkylphenols useful as component (B-2-c).
Example 1
While maintaining a temp~rature of 55C, 100
parts phenol and ~8 parts sulfonated polystyrene
catalyst (marketed as Amberlyst-15 by Rohm and Haas
Company) are charged to a reactor equipped with a
stirrer, condenser, thermometer and subsurface gas
inlet tube. The reactor contents are then heated to
120 while nitrogen blowing for 2 hoursO Propylene
tetramer (1232 parts) is charged, and the reaction
mixture is stirred at 120C for 4 hours. Agitation
is stopped, and the batch is allowed to settle for 0.5
hour. The crude supernatant reaction mixture is
filtered and vacuum stripped until a maximum of 0.5%
residual propylene tetramer remains.
Example 2
Benzene (217 parts) is added to phenol (324
parts, 3.45 moles) at 38C and the mixture is heated
to 47C~ Boron trifluoride (8.8 parts, 0.13 mole) is
~ ,
.
. .
-71-
blown into the mixture over a one-half hour period at
38-52C. Polyisobutene (1000 parts, 1.0 mole)
derived from the polymerization of C4 monomers
predominating in isobutylene is added to the mixture at
52-58C over a 3.5 hour period. The mixtu~e i~ held
at 52C for 1 additional hour. A 26% solution o~
aqueous ammonia (15 parts) is added and the mixture is
heated to 70C over a 2-hour period. rhe mixture is
then filtered and the filtrate is the desired crude
polyisobutene-substituted phenol. This intermediate is
stripped by heating 1465 parts to 167C and the
pressure is reduced to 10 mm~ as the material is heated
to 218C in a 6-hour period. A 64% yield of stripped
polyisobutene substituted phenol ~Mn=885) is obtained
as the residue.
- Example 3
A reactor equipped with a stirrer, condenser,
thermometer and subsur~ace addition tube is charged
with 1000 p~rts of the reaction product of Example 1.
The temperature is adjusted to 48-49 and 319 parts
sulfur dichloride is added while the temperature is
kept below 60. The batch is then heated to 88-93
while nitrogen blowing until the acid number ~using
bromphenol blue indicator) is less than 4.0~ 400 par~s
diluent oil is then added, and the mixture is mixed
~horoughly.
Example 4
Following the procedure of Example 3, 1000
parts of ~he reaction product of ~xamplP 1 is reacted
with 175 parts of sulfur dichloride. The reaction
product is diluted with 4~0 parts diluent oil.
Example 5
Following the procedure of ~xample 3, 1000
parts of the reaction product of Example 1 is reacted
'"
.
.
-72-
with 319 parts of sulfur dichloride. Diluent oil (788
parts) is added to the reaction product, and the
materials are mixed thoroughly.
Example 6
Following the procedure of Example 4, 1000
parts of the reaction product of Example 2 are reacted
with 44 parts of sulfur dichloride to produce the
sulfurized phenol.
Example 7
Following the procedure of Example 5, 10~0
parts of the reaction product of Example 2 are reacted
with 80 parts of sulfur dichloride.
The equivalent weight of component (B-2-c) is
its molecular weight divided by the number of hydroxy
groups per molecule.
Component (B-2-d) is at least one oil-soluble
carboxylic acid as previously described, or functional
derivative thereof. Especially suitable carboxylic
acids are those of the formula R5(COOH)~, wherein n
is an integer from 1 to 6 and is preferably 1 or 2 and
R5 is a saturated or substantially satura~ed
aliphatic radical (preferably a hydrocarbon radical)
having at least 8 aliphatic carbon atoms. Depending
upon the value of n, R5 will be a monovalent to
hexavalent radical.
R5 may contain non-hydrocarbon substituents
provided they do not alter substantially its
hydrocarbon character. Such substituents are
preferably present in amounts of not more than about
20% by weight. Exemplary substituents include the non-
hydrocarbon substituents enumerated hereinabove with
reference to component (B-2-a)O R5 may also contain
olefinic unsaturation up to a maximum of about 5% and
'''. ' ''
.
-
~a~
-73-
preferably not more than 2% ole~inic linkages based
upon the total number of carbon-to-carbon covalent
linkages present. The number of carbon atoms in R5
is usually about 8-700 depending upon the source o~
R5. AS discussed below, a preferred series of
carboxylic acids and derivatives is prepared by
reacting an olefin polymer or halogenated ole~in
polymer with an alpha,beta-unsaturated acid or its
anhydride such as acrylicJ methacrylic, maleic or
fumaric acid or maleic anhydride to form the
corresponding substituted acid or derivative thereo.
The R5 groups in these products have a number average
molecular we.ight from about 150 to about 10,000 and
usually rom about 700 to about 5000, as determined,
for example, by gel permeation chromatographyO
The monocarboxylic acids useful as component
(B-2-d) have the formula R5CooH. Examples of such
acids are caprylic, capric, palmitic, stearic,
isostearic, linoleic and behenic acids. A particularly
preferred group of monocarboxylic acids is prepared by
the reaction of a halogenated olefin polymer, such as a
chlorinated polybutene, with acrylic acid or
methacrylic acid.
Suitable dicarboxylic acids include the
substituted succinic acids having the formula
R6CHCOOH
CH2COOH
wherein ~6 is the same as R5 as defined above.
R6 may be an olefin polymer-derived group formed by
polymerization of such monomers as ethylene, propylene,
l-butene, lsobutene, l-pentene, 2-pentene~ 1-he~ene and
~za4L~
-74-
3-hexene. R6 may also be derived from a high
molecular weight substantially saturated petroleum
fraction. The hydrocarbon~substituted succinic acids
and their derivatives constitute the most pref0rred
class of carboxy~ic acids for use as component tB-2-d)-
The above-described classes of carboxylic
acids derived from olefin polymers, and their
deriva~ives, are well known in the art, and me~hods for
their preparation as well as representative exam~les of
the types use~ul in the present inventlon are also well
known.
Functional derivatives of the above-discussed
acids useful as component (B-2-d) include the
anhydrides, esters, amides, imidesf amidines and metal
or ammonium salts. The reaction products of olefin
polymer-substituted succinic acids and mono~ or
polyamines, particularly polyalkylene polyamines,
having up to about 10 amino ni~rogens are especially
suitable. These reaction produc~s generally comprise
mixtures of one or more of amides, imides and
amidines. The reaction products of polyethylene amines
containing up to a~out 10 nitrogen a~oms and
polybutene-substituted succinic anhydride wherein the
polybutene radical comprises principally isobutene
units are particularly useful. Included in this group
of functional derivatives are the compositions prepared
by post-treating the amine-anhydride reaction product
with carbon disulfide, boron compounds, nitriles, urea,
thiourea, guanidine, alkylene oxid~s or the like. The
half-amide, half-metal salt and half-ester, half-metal
salt derivatives of such substituted succinic acids are
al~o useful.
.~ .
,
,~, . . -
--
~2 ~
-75-
Also useful are the esters prepared by the
reaction of the substituted acids or anhydrides with a
mono- or polyhydroxy compound, such as an aliphatic
alcohol or a phenol. Preferred are the esters o
olefin polymer-substituted succinic acids or anhydrides
and polyhydric aliphatic alcohols containing 2-10
hydroxy groups and up to about 40 aliphatic carbon
atoms. This class of alcohols includes ethylene
glycol, glycerol, sorbitol, pentaerythritol, poly
ethylene glycol/ diethanolamine, triethanolamine,
N,N'-di(hydroxyethyl)ethylene diamine and the like~
When the alcohol contains reactive amino groups, the
reaction product may comprise products resulting from
the reaction of the acid group with both the hydroxy
and amino functions. Thus, this reaction mixture can
include half-esters, half-amides, esters, amides, and
imides.
The ratios of equivalents of the constituents
of reagent (E~-2) may vary widely. In general, the
ratio of component (B-2-b) to (B-2~a) is at least about
4:1 and usually not more than about 40:1, preferably
between 6:1 and 30:1 and most preferably between 8:1
and 25~ hile this ratio may sometimes exceed 40:1,
such an excess normally will serve no useful purpose.
The ratio of equivalents of component (B-2-c)
to component (B-2-a) is between about 1:20 and 80:1,
and preferably between about 2:1 and sa: 1 . As
mentioned above, when component (B-2-c) is an alkyl
phenol or sulfurized alkyl phenol, tbe inclusion of the
carboxylic acid (B-2-d) is optional. When present in
the mixture, the ratio of equivalents of component
(B-2-d) to component (B-2-a) g nerally is from about
1:1 to about 1:20 and preferably from about 1:2 to
about l lOo
.
.
~34~
-76-
Reagents (B-l) and (B-2) are generally
contacted until there is no further reaction between
the two or until the reaction substantially ceases.
While it is usually preferred that the reaction be
continued until no urther overbased product is Eormed,
useful dispersions can be prepared when contact between
reagents (B-l) and (B-2) is maintained for a period of
time sufficient for about 70% of reagent (B-l),
relative to the amount required if the reaction were
permitted to proceed to its completion or "end point",
to react.
The point at which the reaction is completed
or substantially ceases may be ascertained by any of a
number of conventional methods. One such method is
measurement of the amount of gas (reagent tB-l))
entering and leaving the mixture the reaction may be
considered substantially complete when the amount
leaving is about 90-100% of the amount entering. These
amounts are readily determined by the use of metered
inlet and outllet valves.
When (B-2-c) is an alcohol, the reaction
temperature is not ~ritical. Generally~ it will be
between the solidification temperature of the reaction
mixture and its decomposition temperature ~i.e., the
lowest decomposition temperature of any component
thereof). Usually, the ~em~erature will be from about
25 to about 200C and preerably from about 50
to about 150C. Reagents (B-l) and (B-2) are
conveniently contacted at the reflux temperature of ~he
mixture. This ~emperature will obviously depend upon
the boiling points of the various components; thus,
when methanol is used as component (B-2-c), the contact
temperature will be ~t or below the reflux temperature
of methanol.
- : .
.
. ' '
4~
-77-
When reagent ~B-2-c) is an alkyl phenol or a
sulfuri~ed alkyl phenol, the temperature of the
reaction must be at or above the water-diluent
azeotrope tempera~ure so that the water ~ormed in the
reaction ca~ be removed. Thus the diluent in such
cases generally will be a volatile organlc liquid such
as aliphatic and aromatic hydrocarbons. E~amples of
such diluents include heptane, decane, toluene, xylene,
etc.
The reaction is ordinarily conducted at
atmospheric pressure, although superatmospheric
pressure often expedites the reaction and promotes
optimum utilization of reagent (B-l). The process can
also be carried out at reduced pressure but, for
obvious practical reasons, this is rarely done.
The reaction is usually conducted in the
presence of a substantially inert, normally liquid
organic diluent, which functions as both the dispersing
and reaction medium. This diluent will comprise at
least about 10% of the total weight of the reaction
mixture. Ordinarily it will not exceed about 80% by
weight, and it is preferably about 30-70~ thereof~
Although a wide variet:y of diluents are
useful, it is preferred to use a diluent which is
soluble in lubricating oil~ The diluen~ usually itself
comprises a low viscosity lubricating oil.
Other organic diluents can be employed ei~her
alone or in combination with lubricating oil
Preferred diluents for this purpose include the
aromatic hydrocarbons such as benzene, toluene and
xylene; halogenated derivatives thereof such as
chlorobenzene; lower boiling petroleum distillates such
as petroleum ether and various naphthas; normally
, ~
-78-
liquid aliphatic and cycloaliphatic hydrocarbons such
as hexane, heptane, hexene, cyclohexene, cyclopentane,
cyclohexane and ethylcyclohexane, and their halogenated
derivatives. Dialkyl ketones such as dipropyl ketone
and ethyl butyl ketone, and the alkyl aryl ketones such
as acetophenone, are likeuise useul, as are ethers
such as n-propyl ether, n-butyl ether, n-butyl methyl
ether and isoamyl ether.
~ hen a combination of oil and other diluent is
used, the weight ratio of oil to the other diluent is
generally from about 1:20 to about 20:1. It is usually
desirable for a mineral lubricating oil to com~rise at
least about 5~% by weight of the diluent, especially if
the product is to be used as a lubricant additive. The
total amount of diluent present is not particularly
critical since it is inactive. However, the diluent
will ordinarily comprise about 10-80% and preferably
about 30-70~ by weight of the reaction mixture.
Upon completion of the reaction, any solids in
the mixture are preferably removed by filtration or
other conventional means. Optionally, readily
removable diluents, the alcoholic promoters, and water
formed during ~he reaction can be removed by
conventional techniques such as distillation~ It is
usually desirable to remove substantially all water
from the reaction mixture since the presence of water
may lead to difficulties in filtration and to the
formation of undesirable emulsions in fuels and
lubrican~s Any such water present is readily removed
by heating at atmospheric or reduced pressure or by
azeotropic distillation. In one preerred embodiment,
when basic potassium sulfonates are desired as
component (B), the potassium salt is prepared using
-79-
carbon dioxide and the sulfurized alkylphenols as
component (B-2-c). The usc of the su}furiæed phenols
results in basic salts of higher metal ratios and the
formation of more uniform and stable salts. Also, the
reaction generally is conducted in an aromatic diluent
such as xylene, and water is removed as a xylene-water
azeotrope during the reaction.
The chemical structure of component ~B) is not
known with certainty. The basic salts or complexes may
be solutions or, more likely, stable dispersisns~
Al ernatively, they may be regarded as "polymeric
salts" formed by the reaction of the acidic material,
the oil-soluble acid being overbased, and the metal
compound. In view of the above, these compositions ar0
most conveniently defined by reference to the method by
which they are formed.
The above-described procedure for preparing
alkali metal salt-~ of sulfonic acids having a m~al
ratio of at least about 2 and preferably a metal ratio
between about 4 to 40 using alcohols as component
(B-2-c) is ~escribed in more detail in Canadian Patent
1,055,700 which corresponds to British Patent
1,481,553. The preparation of oil-soluble dispersions of
alkali metal sulfonates useful as component (B) in the
diesel lubricants of this invention is illustrated in the
following examples.
Example B-l
To a solution of 790 parts (1 equivalen~ of
an alkylated benzenesul~onic acid and 71 parts of
polybutenyl succinic anhydride (equivalent weight about
560) containing predominantly isobutene units in 176
.
-80-
parts of mineral oil is added 320 parts (8 e~uivalents)
of sodium hydroxide and 640 parts ~2Q equivalents) of
methanol. The temperature of the mixture increases to
89C (reflux) over 10 minutes due to exotherming.
During this period, the mixture is blown with carbon
dioxide at 4 cfh. (cubic feet/hr.). Carbonation is
continued for about 30 minutes as the ~emperature
gradually decreases to 74C. The methanol and other
volatile materials are stripped from the carbonated
mixture by blowing nitrogen through it at 2 cfh. while
the temperature is slowly increased to 150C over 90
minutes. After stripping is completed, the remaining
mixture is held at 155-165C for about 30 minutes and
filtered to yield an oil solution of the desired basic
sodium sulfona~e having a metal ratio o about 7.75.
This solution contains 12.5% oil.
Example B-2
Following the procedure of Example B-l, a
solution of 780 parts (1 equivalent) of an alkyla~ed
benzenesulfonic acid and 119 parts of the polybutenyl
succinic anhydride in 442 parts of mineral oil is mixed
with 800 parts (20 equivalents) of sodium hydroxide and
704 parts (22 equivalents) of methanol. The mixture is
blown with carbon dioxide at 7 ch. for 11 minutes as
the temperature slowly increases to 97C. The rate
of carbon dioxide flow is reduced to 6 cfh. and the
temperature decreases slowly to 88C over about 40
mlnutes. The ra~e of carbon dioxide flow is reduced to
cfh. for about 35 minutes and the temperature slowly
decreases to 73C. The volatile materials are
stripped by blowing nitrogen through the carbonated
mixture at 2 cfh. for 105 minutes as the temperature is
slowly increased to 160C~ After stripping i5
.
~L2~ 5
-81-
completed, the mixture is held at 160C for an
additional 45 minutes and then filtered to yield an oil
solution of the desired basic sodium sulonate having a
metal ratio of about 19.75. This solution contains
18.7% oil.
Example B 3
Following the procedure of Example B-l, a
solution of 3120 parts (4 equivalents) of an alkylated
benzenesulfonic acid and 284 parts of the polybutenyl
succinic anhydride in 704 parts of mineral oil is mixed
with 1280 parts (32 equivalents) of sodium hydroxide
and 2560 parts (80 equivalents~ of methanol. The
mixture is blown with carbon dioxide at 10 cfh~ for 65
minutes as the temperature increases to 90C and then
slowly decreases to 70C. The volatile material is
stripped by blowing nitrogen at 2 cfh~ for 2 hours as
the temperature is slowly increased to 160C. After
stripping is completed, the mixture is held a~ 160C
for 0.5 hourl, and then filtered to yield an oil
solution of the desired basic sodium sulfonate having a
metal ratio of about 7.75. This solution contains
12.35% oil content.
Example B-4
Following the procedure of Example B-l, a
solution of 3200 parts (4 equivalents) of an alkylated
benzenesulfonic acid and 284 parts of the polybutenyl
succinic anhydride in 623 parts of mineral oil is mixed
with 1280 parts (32 equivalents) of sodium hydroxide
and 2560 parts (80 equivalents) of methanol~ The
mixture is blown with carbon dioxide at 10 cfh. for
about 77 minutes. During this time the temperature
increases to 9~C and then gradually drops to
73C. The volatile materials are stripped by blowing
~284~
-82-
with nitrogen gas at 2 cfh. for about 2 hours as the
temperature of the reaction mixture is slowly increased
to 160C. The final traces of volatile material are
vacuum stripped and the residue is held at 170C and
then filtered to yield a clear oil solu~ion o~ the
desired sodium salt, having a metal ratio o~ about
7.72. This solution has an oil content of 11%.
Example B-5
- Following the procedure of Example B-l, a
solution of 780 parts (1 equivalent) of an alkylated
benzenesulfonic acid and 8S parts of the polybutenyl
succinic anhydride in 254 parts of mineral oil is mixed
with 480 parts (12 equivalents) of sodium hydroxide and
640 parts (20 equivalents) of methanol. The reaction
mixture is blown with carbon dioxide at 6 cfh. for
about 45 minutes. During this time the temperature
in~reases to 95C and then gradually decreases to
74C. The volatile material is stripped by blowing
with nitrogen gas at 2 cfh. for about one hour as the
temperature is increased to 160C. After stripping
is complete the mixture is held at 160C for 0.5 hour
and then filtered to yield an oil solution of the
desired sodium salt, having a metal ratio of 11.8. The
oil content of this solution is 14.7%.
Example B-6
Following the procedure of Example B-l, a
solution of 3120 parts (4 equivalents) of an alkylated
benzenesulfonic acid and 344 parts of the polybutenyl
succinic anhydride in 1016 parts of mineral oil is
mixed with 1920 parts (48 equivalents) of sodium
hydroxide and 2560 parts (80 equivalents) of methanol~
The mixt~re is blown with carbon dioxide at 10 cfh. for
about 2 hours. During this time t~e temperature
' .
-83-
increases to 96C and then gradually drops to
74C. The volatile materials are stripped by blowing
with nitrogen gas at 2 cfh. for about 2 hours as the
temperature is increased from 74 to 160C by
external heating. The stripped mixture is heated for
an additional hour at 160C and filtered. The
filtrate is vacuum stripped to remove a small amount of
water, and again filtered to give a solution of the
desired sodium salt, having a metal ratio of about
11.8. The oil content of this solution is 14.7%.
Example B-7
Following the procedure of Example B-l, a
solution of 2800 parts ~3.5 equivalents~ of an
alkylated benzenesulfonic acid and 302 parts of the
polybutenyl succinic anhydride in 818 parts of mineral
oil is mixed with 1680 parts (42 equivalents) of sodium
hydroxide and 2240 parts (70 equivalents) of methanol.
The mixture is blown with carbQn dioxide for about 30
minutes at 10 cfh During this period, the temperature
increases to 96C and then slowly drops to 76C.
The volatile materials are stripped by blowing with
nitrogen at 2 cfh. as the temperature is slowly
increased from 76C to 165C by external heating.
Water is removed by vacuum stripping. Upon filtration,
an oil solution of the desired basic sodi~m salt is
obtained. It has a metal ratio of abou~ 10.8 and the
oil content is 13.6~.
Example B-8
Following the procedure of Example B 1~ a
solution of 780 parts ~1 equivalent) of an alkylated
benzenesulfonic acid and 103 parts of the polybutenyl
succinic anhydride in 350 parts of mineral oil is mixed
with 640 parts (16 equivalents) of sodium hydroxide and
.. ,. ~ ~,. -
~z~ s
-84-
640 parts ~20 equivalents) of methanol. This mixture
is blown with carbon dioxide for about one hou,r at 6
cfh. During this period, the temperature increases to
95C and then gradually decreases to 75C. The
volatile material is stripped by blowing with
nitrogen. During stripping, the temperature initially
drops to 70C over 30 minutes and then slowly rises
to 78C over 15 minutes. The mixture is then heated
to 155C over 80 minutes. The stripped mixture is
heated for an additional 30 minutes at 155-160C and
filtered. The filtrate is an oil solution of the
desired basic sodium sulfonate~ having a metal ratio of
about 15.2. It, has an oil content of 17.1%.
Example B-9
Following the procedure of Example B-l, a
solution of 2400 parts (3 equivalents) of an alkylated
benzenesulfonic acid and 308 parts of the polybutenyl
succinic anhydride in 991 parts of mineral oil is mixed
with 1920 parts (48 equivalents) of sodium hydroxide
and 1920 parts (60 equivalents) of methanol. This
mixture is blown with carbon dioxide at lO cfh. for 110
minutes, during which time the temperature rises to
98C and then slowly decreases to 76C over about
minu~es. The methanol and water are stripped by
blowing with nitrogen at 2 ch. as the temperature of
the mixture slowly increases to 165C. The last
traces of volatile material are vacuum stripped and the
residue is filtered to yield an oil solution of the
desired sodium salt having a metal ratio of 15.1. The
solution has an oil content of 16.1~.
Example B-10
Following the procedure of Example B-l, a
solution of 7~0 parts (1 equivalent) of an alkylated
. -
- ;, .
- ~
~28~14~;i
-85-
benzenesulfonic acid and 119 parts of the polybutenyl
succinic anhydride in 442 parts of mineral oil is mixed
well with 800 parts (20 equivalents) of sodium
hydroxide and 640 parts (20 equivalents) o~ methanol,
This mixture is blown with carbon dioxide for about 55
minutes at 8 cfh. During this periodt the temperature
of the mixture increases to 95C and then slowly
decreases to 67C. The methanol and water are
stripped by blowing with nitrogen at 2 cfh. for about
minutes while the temperature is slowly increased to
160C. After stripping, the temperature of the
mixture is maintained at 160-165C for about 30
minutes. The product is then filtered to give a
solution of the corresponding sodium sulfonate having a
metal ratio of about 16.8. This solution contains
18.7% oil.
Example B-ll
Following the procedure of Example B-l, 836
parts (1 equivalent) of a sodium petroleum sulfona~e
(sodium ~Petronaten) in an oil solution containing 48~
oil and 63 parts of the polybutenyl succinic anhydride
is heated to 60C and treated with 280 parts (7
equivalents) of sodium hydroxide and 320 parts (10
e~uivalents) of methanol. The reaction mixture is
blown with carbon dioxide at 4 cfh. for about 45
minutes. During this time, the temperature increases
to 85C and then slowly decreases to 74C. The
volatile material is stripped by blowing with nitrogen
at 2 cfh. while the temperature is gradually increased
to 160C. After stripping is completedr the mi~ture
is heated an additional 30 minutes at 160C and tben
is filtered to yield the sodium salt in solution. The
product has a metal ratio of 8~0 and an oil content of
22.2%.
.
- .. ~ ' ':' '
.
-86-
Example B-12
Following the procedure of Example B-ll, 1256
parts (1.5 equivalents) o~ the sodium petroleum
sulfonate in an oil solution contalning 4~ oil and 95
parts of polybutenyl succinic anhydride is heated to
60C and treated with ~20 parts ~10.5 equivalents) of
ssdium hydroxide and 960 parts (30 equivalents) of
methanol. The mixture is blown with carbon dioxide at
4 cfho for 60 minutes. During this ~ime, the
temperature is increased to 90C and then slowly
decreases to 70C. The volatile materials are
stripped by blowing with nitrogen and slowly increasing
the temperature to 160C. After stripping, the
reaction mixture is allowed to stand at 160C for 30
minutes and then is filtered to yield an oil solution
of sodium sulfonate having a metal ratio of about 8Ø
The oil content of the solution is 22.2%.
Example B-13
A mixture of 584 parts (0.75 mole) of a
commercial dialkyl aromatic sulfonic acid, 144 parts
(0O37 mole) of a sulfurized tetrapropenyl phenol
prepared as in Example 3, 93 parts of a polybutenyl
succinic anhydride as used in Example B~l, 500 parts o
xylene and 549 parts of oil is prepared and heated with
stirring to 70C whereupon 97 parts of potassium
hydroxide are added. The mixture is heated to 145C
while azeotroping water and xylene. Additional
potassium hydroxide (368 parts) is added over 10
minutes and heating is continued at about 145-150C
whereupon the mixture is blown with carbon dioxide at
1.5 cfh. for about 110 minutes. The volatile materials
are stripped by blowing with nitrogen and slowly
increasing the temperature to about 160C. After
- .
~L2~
-87-
stripping, the reaction mixture is filtered to yield an
oil solution of the desired potassium sulfonate having
a metal ratio of about 10. Additional oil is added to
the reaction product to provide an oil content of the
final solution o~ 39%.
Example B-14
A mixture of 705 parts (0.75 mole) of a
commercially available mixture of straight and branched
chain alkyl aromatic sulfonic acid, 98 parts (0.37
mole~ of a tetrapropenyl phenol prepared as in Example
1, 97 parts of a polybutenyl succinic anhydride as used
in Example B-l, 7S0 parts of xylene, and 133 parts of
oil is prepared and heated with stirring to about
50C whereupon 65 parts of sodium hydroxide dissolved
in 100 parts of water are added. The mixture is heated
to about 145C while removing an azeotrope of water
and xylene. After cooling the reaction mixture
overnight, 279 parts of sodium hydroxide are added.
The mixture is heated to 145C and blown with carbon
dioxide at about 2 cfh. for 1.5 hours. An azeotrope of
water and xylene is removed. ~ second increment of 179
parts of sodium hydroxide is added as the mixture is
stirred and hea~ed to 145C whereupon the mixture is
blown with carbon dioxide at a rate of 2 cfh~ for about
2 hours. Additional oil (133 parts) is added to the
mixture after 20 minutes. A xylene:wa~er azeotrope is
removed and the residue is stripped to 170C at 50
mm. Hg. The reaction mixture is filtered through a
filter aid and the filtrate is the desired product
containing 17.01% sodium and 1.27~ sulfur.
Example B-15
A mixture of 386 parts (0~75 mole~ of a
commercially available primary branched chain monoalkyl
.
.. .. ~ . ~ . -
-88-
aromatic sulfonic acid, 58 parts (0.15 mole) of a
sulurized tetrapropenyl phenol prepared as in Example
3, 926 grams of oil and 700 grams of xylene is
prepared, heated to a temperature o 70~ whereupon
97 parts of potassium hydroxide are added over a period
of 15 minutes. The mixture is heated to 145C while
removing water. An additional 368 parts of potassium
hydroxide are added over 10 minutes, and the stirred
mixture is heated to 145C whereupon the mixture is
blown with carbon dioxide at 1.5 cfh. for about 2
hours. The mixture is stripped to 150C and finally
at 150C at 50 mm. Hg. The residue is filtered, and
the fil~rate is the desired product.
The diesel lubricants of the present invention
containing components (A) and (B) as described above
may be further characterized as containing at least
about 0.8 sulfate ash and more generally at least about
1% sulfate ash. The amounts of components tA) and tB)
included in the diesel lubricants o~ the present
invention may vary over a wide range as can be
determined by one skilled in the art. Generally,
however, the diesel lubricants of the present invention
will contain from about 1.0 to about 10% by weight of
component tA) and from about 0.05 to about 5% and more
generally up to about 1% by weight of component tB).
In another preferred embodiment, the diesel
lubricants o~ the present invention also contain tC) at
least one oil-soluble neutral or basic alkaline earth
metal salt of at least one acidic organic compound.
Such salt compounds genera1ly are referred to as ash-
containing detergents. The acidic organic compound may
be at least one sulfur acid, carboxylic acid,
phosphorus acid, or phenol, or mixtures thereof.
-,
- . :
~ .; ... . .
.. ~ -.... .. -
' . . ~: .
,
2 ~
-89-
Calcium, magnesium and barium are the
preferred alkaline earth metals. Salts containing a
mixture of ions of two or more of these alkaline earth
metals can be used.
The salts which are useful as component (C)
can be neutral or basic. The neutral salts contain an
amount of alkaline earth metal which is just sufficient
to neutralize the acidic groups present in the salt
anion, and the basic salts contain an excess of the
alkaline earth metal cation.
The commonly employed methods for preparing
the basic salts comprises heating a mineral oil
solution of ~he acid with a stoichiometric excess of a
metal neutralizing agent, e~g., a metal oxide,
hydroxide, carbona~e, bicarbonate, sulfide, etc., at
temperatures above about 50C. In addition, various
promo~ers may be used in the neutralizing process to
aid in the incorporation of the large excess of metal.
These promoters are presently known and include such
compounds as the phenolic substances, e.g., phenol,
naphthol, alkylphenol, thiophenol, sulfurized alkyl
phenol and the various conderlsation products of
formaldehyde with a phenolic substance, e.g., alcohols
such as methanol, 2-propanol, octyl alcohol, cellosolve
carbitol, ethylene, glycol, stearyl alcohol, and
cyclohexyl alcohol; amines such as aniline, phenylene-
diamine, phenothiazine, phenyl-beta~naphthylamine, and
dodecyl amine, etc. A particularly effective process
for preparing the basic salts comprises mixing the acid
with an excess of the basic alkaline earth metal in the
presence of the phenolic promo~er and a smal} amount o
water and carbonating the mixtu~e at an elevated
temperature, e.g., 60C to about 200C.
.:
,~
. , ': -
. .
.
. ' : :
-90-
As mentioned above, the acidic organic
compound from which the salt of component (C) is
derived may be at least one sulfur acid, carboxylic
acid, phosphorus acid, or phenol or mixtures thereo~.
Such acidic organic compounds previously have been
described above with respect to the preparation of the
alkali metal salts 5component (B)), and all o the
acidic organic compounds described above can be
utilized in the preparation of the alkaline earth metal
salts useful as component (C~ by techniques known in
the art. The amount of component (C) included in the
diesel lubricants of the present invention also may be
varied over a wide range, and useful amounts can be
readily determined by one skilled in the art.
Component ~C) functions as an auxiliary or supplemental
detergent. The amount of component (C) contained in a
diesel lubricant of the invention may vary from about
0~ to about 5% or more.
The following examples illustrate the
preparation of neutral and basic alkaline earth metal
salts useful as component (C).
Example C-l
A mixture of 906 parts of an oil solution of
an alkyl phenyl sulfonic acid (having an average
molecular weight of 450, vapor phase osmometry), 56~
parts mineral oil, 600 parts toluene, 9807 parts
magnesium oxide and 120 parts water is blown with
carbon dioxide at a temperature of 78-85~C for 7
hours at a rate of about 3 cubic feet of carbon dioxide
per hour. The reaction mixture is constantly agitated
throughout the carbonation. After carbonationl the
reaction mixture is stripped to 165/20 tor and the
residue filteredO The filtrate is an oil solution of
,
.
3L;2~4~5
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the desired overbased magnesium sulfonate having a
metal ratio of about 3.
Example C-2
A polyisobutenyl succinic anhydride is
prepared by reacting a chlorinated polytisobutene)
(having an average chlorine content of 4.3% and an
average of 8~ carbon atoms) with maleic anhydride at
about 200C. The resulting polyisobutenyl succinic
anhydride has a saponification number of 90~ To a
mixture of 1246 parts of this succinic anhydride and
1000 parts of toluene there is added at 25C, 76 6
parts of barium oxide. ~he mixture is heated to
115C and 125 parts of water i5 added drop-wise over
a period of one hour. The mix~ure is then allowed to
reflux at 150C until all the barium oxide is
reacted. Stripping and filtration provides a filtrate
having a barium content of 4.71%.
Example C-3
A basic calcium sulfonate having a metal ratio
of about 15 is prepared by carbonation, in increments~
of a mixture of calcium hydroxide, a neutral sodium
petroleum sulfonate, calcium chloride, methanol and an
alkyl phenol.
Example C-4
A mixture of 3~3 parts of mineral oil, 4.8
parts of water, 0.74 parts of calcium chloride, 79
parts of lime, and 128 parts o methyl alcohol is
prepared, and warmed to a tempera~ure of about 50C.
To this mixture there is added 1000 parts of an alkyl
phenyl sulfonic acid having an average molecular weight
(vapor phase osmometry) of 500 with mixing. The
mixture then is blown with carbon dioxide at a
temperature of about 50C at the rate of about 5 D 4
~za~
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pounds per hour for ahout 2.5 hours. A~ter
carbonation, 102 additional parts of oil are added and
the mixture is stripped of volatile materials at a
temperature o~ about 150-155C at 55 mm. pressure.
The residue is f iltered and the filtrate is the desired
oil solution of the overbased calcium sulfonate having
calcium content of about 3.7% and a metal ratio of
about 1.70
The present invention also contemplates the
use of other additives in the diesel lubricant
compositions of the present invention. These other
additives include such conventional additive types as
anti-oxidants, extreme pressure agents, corrosion-
inhibiting agents, pour point depressants, color
stabilizing agents, anti-foam agents, and other such
additive materials known generally to ~hose skilled in
the art of formulating diesel lubricants.
Extreme pressure agents and corrosion- and
oxidation-inhibiting agents are exemplified by
chlorinated aliphatic hydrocarbons such as chlorinated
wa~; organic sulf ides and polysulfides such as benzyl
disulfide, bis~chlorobenzyl)disulfide, dibutyl tetra-
sulfide, sulfurized methyl estPr of oleic acid,
sulfurized alkylphenol, sulfurized dipentene, and
sulfurized terpcne; phosphosulfurized hydrocarbons such
as the reaction product of a phosphorus sulf ide with
turpentine or methyl oleate; phosphorus esters
including principally dihydrocarbon and trihydrocarbon
phosphites such as dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphi~e, pen~yl phenyl
phosphite, dipentyl phenyl phosphite, tridecyl
phosphite, distearyl phosphi~e, dimethyl naphthyl
phosphite, oleyl 4-pentylphenyl phosphite~ polypro
34~
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pylene (molecular weight 500)-substituted phenyl
phosphite, diisobutyl-substituted phenyl phosphite;
metal thiocarbamates, such as zinc dioctyldithiocarba-
mate, and barium heptylphenyl dithiocarbamate; Group II
metal phosphorodithioates such as zinc dicyclohexyl-
phosphorodithioate, zinc dioctylphosphorodithioate;
barium di(heptylphenyl)-phosphorodithioate, cadmium
dinonylphosphorodithioate, and the zinc salt of a
phosphorodithioic acid produced by ~he reaction of
phosphorus pen~asulfide with an equimolàr mixture of
isopropyl alcohol and n-hexyl alcohol.
Many of the above-mentioned auxiliary extreme
pressure agents and corrosion-oxidation inhibitors also
serve as antiwear agents. Zinc dialkylphosphoro-
dithioates are a well known example~
Pour point depressants ar~ a particularly
useful type of additive often included in the
lubricating oils described herein. The use of such
pour point depressants in oil-based compositions to
improve low temperature properties of oil-based
compositions is well known in the art. See, for
example, page 8 of "Lubricant Additives" by C.V.
Smalheer and R. Kennedy Smith (Lezius-Hiles Co~
publishers, Cleveland, Ohio, 1967).
Examples of useful pour point depressants are
polymetha~rylates; polyacrylates; polyacrylamides;
condensation products of haloparaffin waxes and
aromatic compounds; vinyl carboxylate polymers; and
terpolymers of dialkylfumarates, vinyl esters of fatty
acids and alkyl vinyl ethers. Pour point depressants
useful for the purposes o this inven~ion, techniques
for their preparation and their uses are described in
U.S. Patents 2,387,501, 2,015,748, 2,655,479,
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' ,," ~;
~LZ8~
1,815,022; 2,191,498; 2,666,746; ~,721,877; 2,721,878; and
3,250,715.
Anti-~oam agents are used to reduce or prevert
the formation of stable Eoam. Typical anti-foam agents
include silicones or organic polymers. Additional
anti-foam compositions are described in "Foam Control
Agents", by H~nry T. Kerner (Noy~s Data Corporation,
1976), pages 125-162.
The present invention will be further
understood by a consideration of the following examples
which are intended to be purely exemplary of the
invention. Other embodiments of the invention will be
apparent to those skilled in the art from a
consideration of the following examples.
Parts by
Product of Example A-ll 2
Product of Example B-2 0.5
Lubricating Oil 97.5
~h~ .
Product of Example A-12 l.O
Product of Example B-2 0~4
Product of Example C-3 0.25
Lubricating Oil 98.35
- ' ,. . . ., . . ' , . - , . . .~
. :
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Parts by Weigh~
Lubrican~s III-V III 1~ V Control
Product of Example A-ll .47 ~47 .47 .47
Product of Example B-~, .45 .33
Product of Example C-3 - .12
Product of Example B-13 - - .25
Hydrogenated copolymer of
isoprene-styrene .60 .60 .60 .60
Reaction product of maleic
anhydride-st~rene copolymer
with alcohol and amine .08 ,08 .08 .08
Polybutenyl succinic anhy-
dride-ethylene polyamine 1 97
reaction product 1.97 1.97 1.97
Basic calcium salt of a
sulfurized tetrapropenyl
phenol 1.18 1.118 1.121.11
Zinc salt of m:ixed isobutyl-
and primary amyl-phosphoro
dithioic acid .39 .39 .3~ .39
Zinc salt of mixed isooctyl
phosphorodithioic acid1.04 1.04 1.04 1.04
Alkylated aryl amine .08 .08 .06 .06
Bas c magnesium petroleu50 .50 ~4~ .49
sulfonate .27 .27 .25 .25
Silicone anti-foam agent lOppm lOppm lOppm lOppm
Mineral oil balance ~
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The diesel lubricants of the present invention
are useful in the operation of diesel engines, and when
the diesel lubricants of the present invention are so
utilized, the diesel engines can be operated ~or longer
periods of time without undergoing undesirable
viscosi~y increases. Furthermore, the diesel
lubricants of the present invention are capable of
passing the Caterpillar l-G-2 and the Caterpillar 1-H-2
test procedures.
The advantages of the diesel lubricants of the
present invention is demonstrated by subjecting the
diesel lubricants o~ lubricant Examples III~V to the
Mack Truck ~echnical Services Standard Test Procedure
No. 5GT 57 entitled "Mack T-7: Diesel Engine Oil
Viscosity Evaluation", dated August 31, 1984. This
test has been designed to correlate with field
experience. In this test, a Mack EM6-285 engine is
operated under low speed, high torque, steady-state
conditions. l'he engine is a direct injection, in-line,
six-cylinder, four-stroke, turbo-charged series charge
air-cooled compression ignition engine containing
keystone rings. The rated power iC 283 bhp at 2300 rpm
governed speed.
The test operation consists of an initial
break-in-period (after major rebuild only) a test oil
flush, and 150 hours of steady sta~e operation at 1200
rpm and 1080 ft/lb. of torque. No oil changes or
additions are made, although eight 4 oz. oil samples
are taken periodically from the oil pan drain valve
during the test for analysis. Sixteen ounces of oil
are taken at the oil pan drain valve before each 4 oz.
sample is taken to purge the drain line. This purge
sample is then returned to the engine after sampling.
No make-up oil is added to the engine to replace the 4
oz. samples.
.
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: . ' ' . ' ' ,. ' ~ ~ '' ,- ,
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The kinematic viscosity at 210F is measured
at 100 and 150 hours into the test, and the "viscosity
slope" is calculated. The "viscosity slope" is defined
as the difference between the 100 and 150~hour
viscosity divided by 50. It is desirable that the
viscosity slope should be as small a number as
possible, reflecting a minimum viscosity increase as
the test progresses.
The kinematic viscosity at 210F can be
measured by two procedures. In both procedures, the
sample is passed through a No. ~00 sieve before it is
loaded into the Cannon reverse flow viscometer. In the
ASTM D-445 method, the viscometer is chosen to result
in flow times equal to or greater than 200 seconds. In
the method described in the Mack T-7 specification, a
Cannon 300 viscometer is used for all viscosity
determinations. Flow times for the latter procedure
are typically 50-100 seconds or fully formulated
15~-40 diesel lubricants.
The results of the Mack T 7 test using three
of the diesel lubricants of the invention are
summarized in the following table.
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, '~. . .
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~ck T-7 Resul~
- Sulfated Ash
Lubricant of DetergentSupplement ~iscosiky
Exam~le ~s~1~m~n~ (Wt.~ lo~e*
Control - 0.16
III Sodium 0.33 0.01
IV Sodium ~ 0.33 0.02
Calcium
Potassium 0.09 0.11
-
* cst @ 210F per hour.
Other embodiments of the invention will be
apparent to those skilled in the art from a
consideration of this specification or practice of the
invention disclosed herein. It is intended that the
specification and examples be considered as exemplary
only, with the true scope and spirit of the invention
being indicated by the following claims.
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