Note: Descriptions are shown in the official language in which they were submitted.
~C~3~
ORGANO TRANSITION METAL SALT/ASHLESS
DETERGENT-DISPERSANT COMBINATIONS
Field o~ the Invention
This invention relates to hydrocarbon~soluble com~
positions containing a transition metal salt of an organic
acid and a hydrocarbon-soluble ashless dispersant. Typi
cally, it relates to such compositions wherein the organic
acid is a carboxylic, sulfonic or phosphorus acid and the
10 ashless dispersant is a nitrogen or non-nitrogen containing
ester dispersant. It also relates to hydrocarbon systems
containing the aforesaid compositions, such as lubricants
based on oils of lubricating viscosi~y and hydrocarbon
fuels.
15 Prior ~rt
The treatment of hydrocarbon systems such as
lubricants based on lubricating oils of lubricating vis-
cosity (e.g., greases, lubricating oils and the like) and
hydrocarbon fuels of both the solid and normally liquid type
20 with transition metals and transition metal-containing
compounds, both organic and inorganic, is well known to the
art. Such treatments are used to increase the systems'
resistance to oxidative deterioration, promote ~.heir con-
version to cohesive films in the case of paints and lac-
25 quers, and improve theix combustion as, for example, fuelsD
Among the organic transition metal compounds thathave been used for such purposes are carboxylate and sul-
333
-- 2fonate salts and mixtures of such salts. For example, U.S.
Patent 4,162,986 to ~lkaitis et al. describes transition
metal salts of mixed organic carboxylic and sulfonic or
second carboxylic acids and their use as catalysts, anti-
5 knock agents, combustion improvers, smoke suppressants,curing agents, driers, micronutrient sources, lubricant
additives, and the like.
U.S Patent 3,762,~90 to Collins describes hydro-
lyzable manganese soaps, stablilized by the inclusion of
10 proprionic acid and the use of such materials as siccatives
for paints, varnishes and inks, stabilizers in various
plastics and additives for greases and lubricating oils as
well as smoke-suppressing and anti-corrosion additives for
fuel and fuel oils.
U.S. Patent 3,723,152 to Alkaitis et al. des-
c:ribes basic cobalt salts of carboxylic acids and their
use as drier compos-itions for oil vehicles.
Other patents such as U.S. Patent 4,202,671 to
Diehl et al. describe the use of organic magnesium compounds
20 as fuel conditioners for the reduction of fuel requirements
and emissions.
Increasing concern with pollution and the rising
cost of hydrocarbon-based fuels and luhricants has promoted
continued interest in the use of transition metal compounds
25 in such systems. It has been found, however, that such uses
sometimes causes deliterious as well as beneficial effects.
~nong the deliterious effects are promotion of sediment and
sludge, particularly in lubricants and fuel oils. Such de-
posits can interfere with storage and transport of the oil
30 by promoting corrosion and interferring with pumps, meters
and associated equipment.
Therefore, it is an object of the present inven-
tlon to provide hydrocarbon-soluble compositions containing
organic transition metal salts in combination with ashless
35 dispersants, which provide an optimum balance between bene-
ficial and deliterious effects. Other objects will be
apparent to those of skill in the ar~ upon reading this
di~closure.
Su~ary of the Invention
It has now been found that useful hydrocarbon-
soluble compositions comprise (A) one or more transition
metal salts of at least one or~anic acid; and (B) at least
5 one hydrocarbon-soluble ashless dispersant.
Hydrocarbon systems such as lubricant and fuel
compositions (such as distillate fuel compositions com-
prising a major amount of hydrocarbon fuel and a minor
amount of the aforedescribed salt/dispersant compositions),
10 as well as additive concentrate compositions, are also
within the scope of the invention.
Detailed Description of the Invention
(A) The transition metal salts.
The transition metals in the organic salts of this
15 invention are chosen from the group consisting of copper,
scandium, titanium, vanadium, chromium, manganese, iron,
cobalt, nic]cel and mixtures of two or more of these. Man-
ganese salts and salts containing manganese in admixture
with other metals are most commonly used. Often salts
20containing only manganese are used. Lead salts can also be
used.
The organic acids used to make the transition
metal salts used in this invention contain carbon atoms and
include carboxylic acids, particularly those containing from
251 to 30 carbon atoms, sulfonic acids, particularly those
containing an aromatic ring structure (e.g., benzene ring)
substituted with one or more alkyl groups of 4 to about 22
carbon atoms, and phosphorus acids, containing within their
structures one or more organic groups of 1 to about 30 or
30more carbon atoms.
Such carboxylic, sulfonic and phosphorus acids are
well known to the art. The carboxylic acids can be mono- or
polycarboxylic acids (if the latter, typically they are di-
or tricarboxylic acids). Monocarboxylic acids include Cl- 7
35lower acids (acetic, proprionic, etc.) and higher C8+
acids (e.g., octanoic, decanoic, etc.) as well as the well
known fatty acids of about 12-30 carbon atoms. The fatty
acids are often mixtures or straight and branched chain
acids containing, for example, from 5 to about 30% s-traight chain
acids and about 70 to about 95% (mole) branched chain acids.
Other commercially available fatty acid mixtures containing mueh
higher proportions of s-traight chain acids are also useful.
Mixtures produeed from dimerization of unsaturated Eat-ty acids
can also be used.
Higher carboxylic acids include the well known dicarboxylic
acids made by alkylating maleic anhydride or its derivatives.
The products of sueh reactions are hydrocarbon substituted
succinic aeids, anhydrides, and the like. Lower molecular weight
dicarboxylic acids, such as the polymethylene bridged aeids
(glutaric, adipie, and the like), can also be used to make the
salts of -this invention as well as the lower molecular weight
substituted succinic acids such as tetrapropenyl succinic acid
and its analogs of to about C30 substituted acids.
Higher molecular weight substituted sueeinie anhydrides,
aeids, and analogs useful in making the salts of this invention
have been described in a number of patents, partieularly those
dealing with aeylated compounds useful as dispersants. ~ypical
high molecular weight acids are those made by reaeting a
poly(isobutene) fraction having between 30 and 400 (usually 50-
250) earbon atoms with maleic anhydride. Such materials are
described in U.S. Patents 3,172,892, 3,219,666 and 3,272,746.
Other monocarboxylic acids of similar moleeular weight ean be
made by alkylating aerylie aeid and its analogs. Mixtures of
sueh aeids can also be used.
Useful salts ean also be made from earboeyclie carboxylic
aeid and even aeidic hydroxy compounds such as alkylated
phenols. Such materials are diselosed in U.S. Patent 4,100,082,
particularly eolumns 15-17.
_c . .
33
The '082 pa-tent just identified also describes a number of
sulfonic acids which are useful in making the salts of this
invention, particularly in columns 12-14.
Transition metal salts made from phosphorus acids are also
useEul in this invention. Such phosphorus acids have been
disclosed in a number of U.S. patents and other literature.
Exemplary of -the former is U.S. Patent 4,191,658 which discloses
phosphorus acid salts of the formula
X3
R ¦X )a ll
P-X M
R (X )b
wherein M is a transition metal as described above; each Rl and
R is a hydrocarbon radical; each of Xl, X2, X3 and X4 is oxygen
or sulfur; and each of a and b is 0 or l.
Typically, the organic acids used to make the salts of this
invention are carboxylic acid, sulfonic acid, or mixtures thereof.
A particularly useful group of such salts are those described in
U.S. Patent 4,162,986 to Alkaitis et al.
It should be noted that the transition metal salts used in
this invention are often overbased; that is, they contain more
than sufficient metal to neutralize the acid present. In other
words, they contain in excess of one equivalent of metal per
equivalent of acid derived moiety. Such salts are known to the
25 art. See, for example, the just cited 4,162,986 patent as well
as the following U.S. Patents: 3,827,979 to Piotrowski et al.,
3,312,618 to LeSuer et al., 3,616,904 and 3,616,905 to Asseff et
al., 2,595,790 to Norman et al., and 3,725,441 to Murphy et al.
.. ..~.
333
-- 6
(B) The ashless dispersants.
The ashless dispersants useful in the present invention are
}cnown to the art and are those dispersants commonly used in
]ubricants based on oils of lubricating viscosity and hydrocarbon
fuels such as normally liquid hydrocarbon fuels. Ashless
dispersants are those which leave little or no (metallic)
residue or ash on combustion. Generally, this means that they
are substantially metal free though they may contain, in
addition to carbon, oxygen, hydrogen and, often, nitrogen
elements such as phosphorus, sulfur, boron, etc.
Generally, the ashless dispersants of the present invention
contain only C, H, O, and N. Occassionally, ester -type
dispersants (see below~ can contain only C, H, and O. More
complex ashless dispersants, while still metal free, may also
contain other elements, such as sulfur, boron, phosphorus, and
the like. Typically, however, the ashless dispersan-ts used in
this invention are of the nitrogen-containing or nitrogen-free
ester type.
Many types of ashless dispersants are known; see, for
example, the descriptions in "Lubricant Additives - Recent
Developments", the earlier "Lubricant Additives", both by
M.W. Ranney, published by Noyes Data Corporation, Park Ridge,
New Jersey, 1978 and 1973, respectively, and U.S. Patent
4,136,043.
Among the more commonly available and, therefore, useful
hydrocarbon-soluble ashless dispersants are:
(1) Acylated nitrogen-containing dispersants such as
those described in U.S. Pa-tent 4,100,082, particularly those
at columns 18-20.
i33
-- 7 --
These dispersants are made by reaction of an acyla-ting
agent (e.g., carboxylic acid or anhydride) with an amino
compound such as an amine, polyamine, or other compound
containing an -NH- group. Typical acylating agents include the
substituted succinic acids descri.bed above and in the '082
patent. Other useful acylating agents have been described in
detail in many other patents, such as U.S. Patent 4,234,435
which describes in detail both acylating agents and amino-
containing and non-amino-containing compounds which can be used
to prepare ashless dispersants.
The acylated ashless dispersants useful in the present
invention can be of either the high or low molecular weight
type. In addition to portions from amino compounds, they may
also incorporate portions from mono- and poly- alcohols,
including amino hydroxy compound groups such as the well known
amino alcohols. Typical ashless dispersants include those made
from alkylene polyamines having 2 to 7 amino groups and 1 to 6
alkylene groups, each containing 2 to 4 carbon atoms. The
commercially available ethylene polyamines are useful reagents
in this regard.
Lower molecular weight acylated nitrogen containing
compounds are also useful as dispersants in the compositions of
this invention. Such compounds are made from the aforedescribed
amino compounds and mono- and dicarboxylic acid acylating agents
containing about 12 to about 20 carbon atoms. Such dispersants
often contain imidazoline groups and are known to the art; see,
for example, U.S. Patents 3,405,064 and 3,240,575.
High molecular weight acylated nitrogen-containing ashless
dispersants wherein an amino and alcohol compound (or amino-
alcohol~ both are acylated are also known and useful in thecompositions of this invention; these are described in U.S.
Patent 4,136,043.
(2) ~igh molecular weight nitrogen-free esters.
These esters, as indicated above, are made by reacting the
aforedescribed acylating agents (e.g., poly(isobutene)) succinic
anhydride with polyols and monoalcohols and are well known; see,
for example, U.S. Patent 3,522,179.
(3) Hydrocarbyl substituted amines.
Hydrocarbyl substituted amines useful as ashless
dispersants are known in the art; see, for example, U.S.
Patents 3,275,554, 3,438,757, 3,454,555, and 3,565,804. A
discussion of such materials also appears in the aforementioned
'082 patent.
(4) Nitrogen-containing condensates of phenols, aldehydes
and amino compounds.
Condensates made from reacting a phenol, aldehyde (such as
formaldehyde) and amino compounds (such as those described above)
are useful as ashless dispersants in the compositions of this
invention. These materials are often generically known as
Mannich condensatesO Generally, they are made from reacting
a hydrocarbon substituted phenol (e.g., an alkylated phenol
20 having an alkyl group of about 34-400 carbon atoms), formalde-
hyde and an amino or polyamino compound having at least one
-NH- group. A number of such materials are known to the art;
see, for example, the aforementioned '082 patent, particularly
columns 21-22, and the references cited therein.
33
The hydrocarbon-soluble compositions of this in-
vention are made by combining (A) one or more of the afore-
described transition metal salts of organic acids with ~B)
at least one of the aforedescribed hydrocarbon-soluble
5 ashless dispersants. It should be noted that "hydrocarbon
soluble" in describing this invention means that the ma-
terial in question has a solubility at 25C of at least
0.001 parts by weight in the hydrocarbon system in which it
is to function. The combination of the materials (A) and
10 (B) can be effected in any convenient mannerO Usually, it
ls advantageous to avoid combining the salt and the dis
persant directly since precipitation problems can thus be
avoided. Therefore, it is common to combine either the
dispersant or the salt with an inert, solvent diluent and
15 then combine this material with the other and/or auxiliary
agents. The solvent/diluents used in the composition of
this inven~ion are usually hydrocarbyl in nature although
they may contain small amounts of other hetero elements and
are often highly aromatic to promote solubilityO Auxiliary
20 agents used in the compositions of this invention include
dyes, anti-oxidants, metal deactivators, and, paxticularly,
demulsifying agents which inhibit the tendency of the dis-
persant and/or the salt to promote emulsion formations in
the vehicles it is used to treat, such as fuel oils, lu-
25 bricants and the like. Many such demulsifying agents areknown; see, for example, Encyclopedia of Chemical Tech-
nology - Kir~-Othmer, Volume ~, pages 151 et seq. and
Volume 19, pages 507 et seq. (1965). Typical demulsifying
agents are surface active agents containing hydrophilic and
30 lipophilic portions in the molecule. Such agents are often
made by reacting a hydroxy compound, such as a phenol or
alcohol, with materials such as ethylene oxide and propylene
oxide and their mixtures in various propor~ions.
As indicated above, the compositions of this
35 invention are used to treat lubricants based on lubricating
33
-- 10 --
oils of lubricating viscosity and hydrocarbon fuels. The
lubricating oils are typically hydrocarbon in nature al-
though they may contain non-hydrocarbyl portions, such as
synthetic ester, ether, and similar oils.
The fuels treated with the composi~ions of this
invention include both solid and normally liquid fuels.
Among the solid fuels are coal, shale, peat, wood, organic
refuse, charcoal and the like. Liquid fuels encompass the
lighter petroleum fractions such as gasoline, kerosene, and
10 the like, as well as other fractions such as middle dis-
tillate fuel oils. Typical middle distillate fuel oils
which can be treated with the compo~sitions in this invention
include No. 1, 2, and 4 fuel oils as defined by ANSI/ASTM
Standard D-396-97 and other such materials. ~ombinations of
15 such fuel oils with straight run, vacuum run, and other
specially treated residual oils can also be advantageously
treated with the combinations of the present invention.
The concentration of the compositions of this
invention in the treated lubricant or oil compositions is
20 such that the treated lubricant or sil composition~ contain
about 1-500, preferably 5-350 ppm (b~ weight) transition
metal* and about 5-1000, preferably 10-800 ppm (by weight)
ashless dispersant. In fuel oils, particularly, the com-
position is used to produce a transition metal concentration
25 at about 10-200 ppm (by weight) and ashless dispersant
concentration of about 15-~50 ppm (by weight).
EXAMP~ES
Example 1
A known ashless acylated nitrogen-containing
30 dispersant is prepared by reacting a mixture of poly(iso-
butene) substituted succinic anhydride acylating agent
(having a substituent with an Mn equal to about 1,000) with
a commercial mixture of ethylene polyamines averaging in
composition triethylene tetra-amine. The reaction is
35 carried out in aromatic solvent/diluent and the proportion
* The concentration of salt is expressed in terms o~
metal alone.
33
of acid to polyamine, by weight, is approximately 100 to 9;
water and other low-boiling products and impurities are
removed by heating to give the desired ashless dispersant
having a nitrogen content of about 2% (by weight).
5 Example 2
A hydrocarbon-soluble composition is prepared by
combining by weight the following: an overbased magnesium
carboxylate* (containing 40% by weight Mn) - 10.82 parts,
the ashless dispersant of Example 1 - 14.43 parts, a first
10 demulsifier** - 0.18 parts, a second demulsifier (3) - 0.14
parts, and aromatic solvent (4) - 74.43 parts. * Sold by the
Mooney Chemical Company as Mooney 910. ** An Ethoxylated/
Propylated Hydroxy Compound available as TOLAD 285 from The
Treatolite Division of Petroli~e Corporation, St. I,ouis,
15 Missouri. (3) An Ethoxylated Propoxylated Pentaerythritol
available as NALCO 5RD-648 from the Nalco Chemical Company
of Houston, Texas. (4) HI-SOL Aromatic Solvent having a
Kauri Gum-Butanol Value of 95. The above combination is
made by using the aromatic solvent in such a way as to avoid
20 direct combination of the concentrated carboxylate and
ashless dispersant. The combination has a specific gravity
at 15.6 o 0.94, a pour point of -57C., and a manganese
content of 4.3 4.6 percent by weight~
Example 3
The composition of Example 2 was used to treat a
typical commercially available No. 2 middle distillate fuel
oil. The treatment level is 1 part composition to 4600
parts by weight of fuel oil. This treatment level is
equivalent to 10.7 parts per million manganese per part of
30 fuel. The treated fuel was used to operate a commercial
boiler and compared with use of untreated fuel in the same
boiler under comparable conditions. It was found that use
of the compositions of this invention in the fuel, as des-
cribed above, produced a 1.7 percent efficiency improvement
35 as reflected by reduced fuel consumption.
