Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
Title: Comp~itions, Concentrates, Lubricant Compositions and Methods
for Improv;ng~ Fuel Economy of Internal Combustion Engines
BACK(3ROUND OF THE INVENTION
Thîs invention relates to compositions and methods for improving
the operation of internal combustion engines, speeifically by reducing the
amount of fuel consumed by such engines. More particularly, the invention
5 comprises lubricating compositions which may be used in such engines to
decrease fuel consumption, and a method of using such lubricating
compositions to accomplish this purpose.
Efforts to reduce the amount of fuel consumed by internal
combustion engines such ~s automobile engines have increased in recent
10 years as a result of the petroleum shortage, the increas2d cost of petroleum
products, and the desire for conservation of natural resources such as
petroleum. It is recognized that a situation under which fuel consumption is
minimized is desirable, both because of the conservation factor and because
such a situation is economical for the user o~ the engine.
Many OI the proposed solultions to the ~uel consewation problem
have been mechanical, as for example, adjusting the engine for a leaner burn
or simply building smaller cars and smaller engines. Other efforts have
related to developing lubricants that reduce the overall friction of the
engine thereby reduci~ energy requirements. Some synthetie lubricants
20 have been developed and compounded for use in the automobile engine to
reduce fuel consumption. A considerable amount of effort has been
expended toward developing additives for use in mineral lubricating oils and
greases to reduce the friction properties of the oils and greases.
Oil-soluble aliphatic polycarboxylic acids including those wherein
25 the aliphaffe group contains one or more hydroxyl groups have been
suggested as additives for use in mineral lubricating oils and motor fuels to
improve the perIormance OI the oils and motor fuels. U~S. Patents 2,370,299
and 2,37Q,300 describe compounded lubricants comprising lubricating oil
containing organic esters which comprise an aliphatic alcohol of from 10 to
30 30 carbon atoms esterified with a hydroxy aliphatic acid having at least one
hydroxyl group. The presence of the organic ester decreases the coefficient
of friction between metal frictional surfaees at low rubbing speeds.
~3~ S
Lubricating oils and motor fllels ContAinirlg derivatives of tartaric
acid with various amines and amino alcohols are described in U.S. Patents
23977,309; 2~865,723; 2,811,~29; 3,183,069 and 4~237,022~ In general, the rust
inhibition and anti-oxidation properties of the lubricants and fuels are
improved by these amino derivatives.
U.~. Patent 2,715,108 describes a lubricating oil useful particularly
as a turbine oil which contains an additive amount o~ a mixture of an aliphatic
polycarbcxylic acid or partial ester thereoI, and oil-soluble phenolic compound
or its thio or seleno analogs, and an aromatic carboxylic acid. This mixture
added to a turbine oil results in improved rust and corrosion inhibition and
improved resistance to emulsification in the presence of water. Mineral oils
containing a small amount of an ester of a trialkylammonium acid salt of a
hydroxy aliphatic dicarboxylic acid and a primary, aliphatie, monohydric
alcohol are described in U.S. Patent 2,585,877. In addition to the beneficial
effects on rust inhibition, the additive improves the arlti-wear properties and
cutting ef~iciencies of mineral oilsO Extreme pressure lubricants containing
compounds obtained by reacting aliphatic hydroxy carboxylic acids and lower
aliphatic polyhydric alcohols are described in U.S. Patent 2,755,250. Mineral
transformer oils are described in U.S. Patent 2,397,332 which include a small
amount of a tartaric di~acid ester of a eyclic alcohol. The extreme pressure
properties of lubricants are reported to be improved in U.S. Patent 2,628,941
by incorporating into lubricatin~ compositiolls a reaction product obtained by
reacting a polyacidic compound containing from 1 to 3 free carboxylic acid
groups and at least one hydroxy group with an alkylene oxide, an alkylene
sulfide or an alkylene imine.
SUMMARY OF TH~ INVENTION
In its broadest sense, the present invention provides a multi-
component composition comprising
A. at least one tartrate of the formula
HO-CHCO R
HO-CHCo2 R
wherein each R is independen~ly a hydrocarbon-based group and the sum of
carbon atoms in both the R groups is at least about 8; and
B. àt least one oil soluble detergent and dispersant;
3~S
and the use of such compositions in lubricating oils for internal eombustion
engines. Lubricating oils containing the compositions of the invention are
effective in reducing the amount of fuel consumed by internal combustion
engines. The invention also relates to a method of reducing the amount of
S fuel consumed by an intern&l combustion engine. The lubricants also can
contain other additives such as corrosion- and oxidation-inhibiting agents,
pour point depressing agents, viscosity-improving components, color stabi
lizers snd anti-îoam ~ents.
D~SCD PIION O- ~IID Pr~l8ERRFD EMBO131MENTS
As mentioned above, the multi-component compositions of the
invention comprise, in the broadest sense, component A which is at least one
tartrate and component B which is an oil-soluble detergent or dispersant, or
mixtures thereof.
~a~
Component A of the compositions OI the invention is at least one
tartrate of the formula
H~}CHC02R
H~CHC02R
wherein each R is independently a hydrocarbon-based group, and the sum of
the carbon atoms in both R groups is at least about 8.
One method of preparing the tartrates represented by the above
formula involves esterification of tartaric acid with an alcohol or mixture of
alcohols which are preferably monohydric alcohols.
The monohydric alcohols which can be employed to provide the
tartrate compounds with the desired R groups are well known and can
compriset for example, primary and secondary aliphatic aleohols. The
preferred monohydric alcohols, however, are primary aliphatic alcc hols,
especially 1iphatic hydrocarbon alcohols such as alkenols and alkanols of
from about 4 to about 40 carbon atoms, and preferably from about 8 to
about 40 carbon ~toms. Mixtures of alcohols can be utilized provided that
the total number of carbon atoms in the two R groups is at least about 8.
More preferably, each R group is derived from a monohydric alcohol
containing at least 8 carbon atomsO Accordingly, examples of the preferred
monohydric alcohols from which the R group is derived include l-octanol, l-
decanol, l-dodec~mol, l-tetradecanol, l-hexadecanol, l-octadecanol, oleyl
alcohol, linoleyl alcohol, linolenyl alcohol, phytol, myricyl alcohol, lauryl
alcohol, myristyl alcohol, cetyl alcohol, stearyl aleohol and behenyl alcohol.
C)f course, commerci~l alcohols (mixtures) are contemplated
herein9 and these commercial alcohols may comprise minor amount~s of
5 alcohols which9 although not specified herein, do not detract from the major
purposes of this invention. Higher synthetic monohydric alcohols of the type
formed by the Oxo process (e.g., 2-ethylhexyl), the aldol condensation, or by
organoaluminum-catalyzed oligomerization of alpha-olefins (especially
ethylene), followsd by oxidation~ also are useful.
,~ 10 Examples of some preferred monohydric alcohols and alcohol
mixtures suitable for forming the tartrates useful in the compositions of the
invention include commercially available "Alfol" ~alcohols marketed by
Continental Oil Corporation. Alfol 810 is a mixture containing alcohols
consisting essentially of straight chain, primary alcohols having from 8 to 10
carbon atoms. The Alfol 20+ alcohols are mixtures of C18-C28 primary
alcohols having mostly, on an alcohol basis, C20 alcohols as determined by
GLC (gas-liquid-chromatography). The Alfol 22~ alcohols are C18-C28
primary alcohols having mostly, on an alcohol basis, C22 alcohols. These
Alfol alcohols can contain a fairly large percentage (up to 40% by weight) of
paraffinic compounds which can be removed before the esterification
rea¢ffon if desired.
Another example of a commercially available alcohol mixture is
Adol 6~ which comprises about 75% by weight of a straight chain C2~
primary alcohol, about 15% of a C20 primary alcohol and about 8% of C18
and C2a,L alcohols. Adol 60 is marketed by Ashland Chemical.
A variety of mixtures of monohydric fatty alcohols derived from
naturally occurring triglycerides and ranging in chain length of from C8 to
G18 are available from Procter ~c Gamble Company. These mixtures contain
various amounts of fatty alcohols containing mainly 12,14,16, or 18 carbon
atoms. For example, CO-1214 is a fatty alcohol mixture containing 0.5% of
Clo alcohol, 66.0% of C12 alcohol, 26.0% of C14 alcohol and 6.596 of C16
alcohol.
Another group of commercially available mixtures include the
"Neodol" products available from Shell Chemical Co. For example, Neodol
tr.l61~ Ma~ I<s
--5--
23 is a mixture of C12 and C13 alcohols; Neodol 2S is a mixture of C12 and
C15 alcohols; and Neodol 45 is a mixture of C14 and C15 alcohols.
Fatty vicinal diols also are useful and these include those
available from Ashland Oil under the general trade designation Adol 114L and
5 Adol 15û. The former is derived from a straight chain ~pha olefin fraction
of Cll-C14, and the latter is derived from a C15-Cl~ fraction.
~ a~amples of preferred branched chain monohydric alcohols suit-
able for formir~ the tartrates useful in the present invention include, for
example, commercial tridecyl alcohol corresponding in large part substan-
10 tially to the formula
CH3CH2CH(CH3)CH(CH3)CH(CH3)CH(CH3)CH2CH2CH20H
prepared by the Oxo process and which is available from Exxon Corporation,hexadecyl alcohol prepared by the Oxo process, 12-methylpentadecyl alcohol,
6-methyldecyl alcohol, 8-ethyltetradecyl alcohol, 5,6-dipropyldecyl alcohol
15 as well as mixtures of these alcohols. Branched chain alcohols of from 12 to
14 carbon atoms with one or more methyl branches are the more preferred.
The tartrates represented by the above formula can be obtained
by esterification of tartaric acid with one or more of the above described
alcohols under conditions whi¢h are typical for effecting esterification.
20 Such conditions include, for example, a temperature of up to the reflux
temperature of the mixture provided that the temperature is maintained at
a level below the decomposition of the reaction mixture or any products
thereof. Water normally is removed as the esterifi¢ation proceeds. These
conditions option~lly may include the use of ~n excess amount of alcohol
25 over the stoichiometric requirements for complete esterification with the
alcohols in order to facilitate the esterification reaction~
Generally, the esterification reaction is conducted in a substan-
tially inert, normally liquid, organic solvent or diluent such as minerAl oil,
toluene, benzene, xylene and the like. Esterification catalysts are included
3n in the mixtuPe, and these catalysts include toluene sulfonic acid, sulfuric
acid, aluminum chloride, boron trifluorîde~triethylamine, methane sulfonic
acid, hydrochlor;c acid, ammonium sulfate, phosphoric acid, sodium methox-
ide, etc.
The followin~ examples illustrate the procedure for preparing the
35 tartrates useful RS component A in the compositions of the invention.
Unless otherwise indicated, all parts and percentages are by weight.
6-
~e~
A mixture of 153 parts of DL tartaric acid hydrate, 400 parts of
Procter & Gamble's CO-1214~ an alcohol mixture containing principally C12
and C14 aliphatic alcohols, one part of toluene sulfonic acid and 500 parts of
5 toluene is heated to the reflux temperature of the mi~cture. Nitrogen is
blown below the surface of the liquid and water is rernoved as the
temperature re~ches 1~0 C. A total of 35 parts of water are collected. The
residue i5 filtered through a filter aid, and the filtrate is the desired
product.
10 ~
A mixture of 95 parts of meso-tartaric acid, 226 parts of the
alcohol mixture used in Example 1, and 0.5 part of toluene sulfonic acid is
heated to reflux with nitrogen blowing. At a temperature of 160 C, 25 parts
of water are eollected. The mixture is cooled to 145-155C and heated for
lS an additional two hours. The reaction mixture is filtered through a filter
aid~ and the filtrate is the desired product.
E~
A mixture of 800 parts of the alcohol mixture of Example 1 and 14
parts of water is heated to 50 C whereupon sulfuric acid (107 parts~ is added
20 dropwise over a pePiod of two hours and the temperature of the mixture
reaches 60C. Potassium bitartrate t376 parts) is added over ten minutes
using high speed stirring followed by heating to a temperature of about 94 C
for one hour. Xylene (500 ml.~ is added and the mixture is heated to reflux
while collecting water. The temperature of the reaction mixture reaches
25 165C near the end of the esterification. 85 parts of water are collected.
The residue is stripped at 140C and 30 mm. Hg. This residue is filtered
through a filter aid, and the filtrate is the desired product.
~e~
A mixture of 150 parts of tartaric acid, 288 parts of Alfol 8-10 (a
30 commercial mixture of C8 and C10 aliphatic alcohols~, 1.12 parts of para-
toluene sulfonic acid and 400 parts of toluene is heated to reflux while
collecting water in a sidearm trap. A total of 34 parts of water was
collected. The mixture is stripped to 150C/25mm Hg. Calcium hydroxide
(0.44 parts~ is added with stirring for ten minutes at 80 C, and the mixture
35 is filtered through a filter aid. The filtrate is the desired product.
~3~
A mixture of 7S parts of tartaric acid, 468 parts of Alfol 22+ S.P.
and 1 part of para-toluene sulfonic acid is prepared and 400 parts of toluene
is added. The mixture is heated to reflux for a total of thirteen hours and a
total of 16 parts of water is collectedO The residue is stripped at 120C/Z5
mm. llg. and filtered through a filter aid. The filtrate is the desired product
having a saponification number of 96.3 (t!heory is 107).
~e~
A mixture of 199 parts of tartaric acid, 718 parts of commercial
alcohol mixture available flom Procter & Gamble under the general desig-
nation "(~01895F" containing about 2% C16 and 96% C1~3 fatty aleohols, and
1.1 part OI para~toluene sulfonic acid is prepared and 500 parts of toluene is
added. This mixture is heated to reflux for a total heating time of about
thirteen hours, and 47 parts of water is collected in a sidearm trap. The
mixture is stripped at 135 C/25 mm. Hg. The residue is filtered through a
filter aid, and the filtrate is the desired product having a saponification
number of 171 (theory is 172) and a melting point of 80-81 C.
_7 A
A mixture of 150 parts o~ tartaric acid, 590 parts of Aldol 158 (a
commercial diol mixture available from Ashland Chemicals)9 500 parts of
toluene and 1.1 part of para-toluene sulfonic acid is heated to reflux while
collecting 33 parts OI water in a sidearm trap. The reaction mixture is
stripped to 100C/25 mm. Hg, and the residue is filtered through a filter
aid. The filtrate is the desired product having a saponification number OI
1$8 (repeat 157; theory is 159).
A mixture of 150 parts of tartaric acid5 414 parts of Neodol 23 (a
commercial mixture of C12 and C13 alcohols), 1 part of para-toluene sulfonic
acid and 500 parts of toluene is prepared and heated to reflux. Water (36
parts) is collected in a sidearm trap. The mixture then is stripped at
135C/27 mm. Hg. and filtered through a filter aid. The filtrate is the
desired product having a saponification number of 218 (theory is 212) and a
melting point of 5S-56 C.
Example 9-A
A mixture of 150 parts of tartaric acid, 436 parts of Neodol 45 (a
tr~lt ~.rl~ '
2S
commercial mixture of C14 and C15 alcohols)~ 1 part of para-toluene sulfonic
acid and 500 parts of toluene is heated to reflux. Water (35 parts) is
collected in a sidearm trap. The reaction mixture then is stripped at
110 C/21 mm. Hg. and filtered through a filter aid. The filtrate is the
S desired product having a saponification mlmber of 189 (theory is 204).
Example 10-A
A rnixture of 112.5 parts of tartaric acid, 480 parts of Adol 60 (a
commercially available alcohol containing about 75% by weight of a straight
chain C22 primary alkanolJ about 15% of a C20 alcohol and about 8% of a
mixture of C18 and C24 alcohols), 400 parts of toluene and 1 part of para-
toluene sulfonic acid is heated to reflux. Water (25.5 parts) is collected in A
sidearm trap. The mixture is stripped At 115C122 mm. Hg. and filtered
through a filter aid. The filtrate is the desired product having a
saponification number of 139 (theory is 149).
15 ~
A rnixture is prepared comprising 163 parts (2.2 moles) of n-
butanol, 400 parts (2 moles) of the commercial mixture of alcohols OI
Example 1, 150 parts of tartaric acid (2 moles), 1 part of para-toluene
sulfonic acid and 1000 parts of toluene. This mixture is heated to reflux
20 while collecting water (7B parts) in a sidearm trap. The mixture is stripped
at 100C/17 mm. EIg. and filtered through a filter aid. The filtrate is the
desired product having a saponification number of 260 (theory is 283).
A mixture of 1500 parts of tartaric acid, 4000 parts o the
2S commercial alcohol mixture of Example 17 2000 parts of toluene and 10 parts
of para-toluene sulfonic acid is heated to reflux while removing 36û parts of
water (theory is 360 parts). The reaction mixture is stripped at 105 C/23
mm. Hgo Calcium hydroxide ~4 parti) is added at 100C with stirring for
fiIteen minutes. The reaction mixture is filtered through a filter aid, and
30 the filtrate is the desired product.
A mixture of 150 parts of tartaric acid, 484 parts of an alcohol
mixture available from Procter & Gamble under the trade designation CO-
~- 1418 (comprising 1-4% C12; 35-47% C14; 15-27% C16 and 30~ 40% Cl~ alcohols),
35 400 parts of toluene and 2 parts of para-toluene sulfonic acid is prepared and
tr~J~ K
~3~
heRted to reflux while removing water through a sidearm trap. The mixture
then is stripped to 122C at 16 mm. Hg. The residue is filtered while hot
through a filter aid, and the filtrate is the desired produet.
ExamJ?le 14-A
A mixture of 102Q parts of potassium bitartrate and 200û parts of
the alcohol mixture of Example 1 is prepared3 and 737 parts of hydrochloric
aci* (37%) are added dropwise over a period of about twenty minutes. The
mixture is heated while purging with nitrogen, and water is collected over a
period o one hour of heating at about 105-115C. EIeating is continued to
140C over a period of seven hours while removing additional water. After
cooling overnight9 the mixture is reheated to about 155 C and maintained at
this temperature for about two hours while removing additional water~ The
mixture then is filterecl at about 90 C through a filter aid, and the filtrate
is the desired product.
E_~
To a mixture of 2000 parts of the alcohol mixture of Example 1
and 49 parts of water there is ~dded 383 parts OI sulfuric acid (969~) over a
period of ~wenty minutes, followed by the addition of 1020 parts of
potassium bitartrate over a period of ten minutes. This mixture is heated
while purging with nitrogen, and water is removed beginning at about 120 C
and up to a temperature of about 155 C. After cooling overnight, the
mixture is reheated to a temperature of about 155 165C while removing
additional water. The total heating time at esterification temperature is
seven hours. The mixture is filtered at about 90 C through a filter aid, and
the filtrate is the desired product~
A mixture of 882 parts of maleic anhydride, 819 parts of water and
21.78 parts of anhydrolls sodium molybdate is prepared and warmed gently
until the maleic anhydride dissolves. The mixture is heated to about 75 C
under a vacuum of about 20 inches of mercury to allow gentle reflux. While
maintaining the vacuum at about 19-21 inches of mercury, 1525 parts of 30%
aqueous hydrogerl peroxide is added over a period of 3.75 hours at 73-78C
with external heating appliecl only as necessary to maintain this temperature
range~ The yellow solution becomes orange-red indicating the absence of
peroxide and the conversion of the maleic anhydride to tartari~ acid.
3~
-10-
A mixture of 2828 parts of ~he tartaric acid solution prepared
above, 2994 parts of the alcohol mixture of Exarnple 1, and 41 parts of
phosphoric acid (85%) is prepared and heated under a nitrogen flow to 165 C
over several hours while removing water by distillation. The mixture is held
at 165 C for R total of twelYe hours9 anld after cooling to 50 C, 30 parts of
calcium hydroxide is added ~t once. Vacuum is applied, and the mixture is
heated to 145~ C at 20 mm. EIg. The reaction mixture is filtered through a
filter aid, and the filtrate is the desired product.
COMPONENT 13 - THE DETER~5ENT OR DISPERSANT
The terms "detergent" and "di~;persant" as used in the lubricant art
generally mean, respectively, a composition which is capable OI removing
deposits from engine parts and a composition which is capable of retaining
such deposits in suspension in the oil once they are removed. Eor the most
part, detergents comprise basic metal salts or complexes of various organic
compositions (normally acidic~ containing both a polar and a non-polar group,
while dispersants comprise compositions also containi~ag a polar and a non-
polar group but which are metal-free or, if they contain metal~ contain at
most about 1.1 equivalents thereof per equivalent of acidic moieties. Both
detergents and dispersants will be more fully characterized hereinafter,
although their general nature is well known to the skilled lubricant chemist.
Detergents
As noted above, most detergents are basic metal salts or com-
plexes of a phenol, sulfonic acid, carboxylic acid or phosphorus acid. The
metals are usually alkali metals or alkaline earth metals; that is~ they are
members respectively of (:roup lA and Group IIA of the Periodic Table. For
the purpose of the present invention, alkaline earth metal salts are
preferred. The preferred alkaline earth metals are magnesium, calcium,
strontium and b~rium, particularly calcium or barium and still more
particularly calciurn.
The non-metalllc moiety of the salt or complex is ordinarily the
anion of an organic acidic compound. Examples of such compounds are
phenoLs, sulfonic acids, carboxylic acids and phosphorus acids.
The word "phenol", as used herein, denotes any hydroxyaromatic
compound inclucling hydroxy compou~ds derived from fused-ring hydr~
35 carbons (e.g., naphthols and the like). Especially preferred in the
3~
preparation of component B are phenols substituted with aliphatic or cycl~
aliphatic groups having at least about 6 carbon atoms and up to as many as
7000 carbon atoms. Examples of such groups are hexyl, cyclohexyl, heptyl,
decyl, eicosyl, and groups derived from the polymerization of olefins such as
5 ethyleneg propylene, 1-butene, 2-butene, isobutene and the like. Groups
derived from polymers of propylene and commercial mixtures of butenes
(comprising predominantly isobutene) ar~e preferred, especially those having
a number average molecular weight (as determined, for example, by gel
permeation chromatography) of about 150-1750 (containing about 10-125
10 aliphatic carbon atoms). The substituent and the aryl nucleus of the phenol
may eontain other groups such as hydroxy, nitro, nitroso and sulfo groups.
Introduetion of the aliphatic or cycloaliphatic substituent onto the
phenol can be effected by mixing the hydrocarbon (or a halogenated
clerivative thereof, or the like~ and the phenol at a temperature of about 50-
15 200 C in the presen~e of a suitable cat~lyst, such as aluminum trichloride,boron trifluoride, zine chloride or the like~ The substituent can also be
introduced by other alkylation processes known in the art lt is irrelevant
which position on the phenolic ring is substituted; any single isomer, or a
mixture of isomers, may be used. Polysubstituted materials such as dialkyl
20 and trialkyl phenols may also be present9 either alone or in admixture with
monoalkyl phenols.
Additional suitable phenols are polyphenols containing sulfur or
alkylene bridges, typieally prepared by reaction of a simple phenol with
sulfur, a sulfur halide such as sulfur monochloride or dichloride, or a lower
25 aliphatic aldehyde (preferably formaldehyde). Polyphenols containing both
sulfur and alkylene bridges are also suitable.
The equivalent weight of a phenol for the purpose of this invention
is its molecular weight divided by the number of phenolic hydroxy groups
therein. Thus, the equivalent weight of an alkylated phenol is equal to its
30 molecular weight and that of an alkylated resorcinol is half its molecular
weight.
The phosphorus acids useful in the preparation of component B
may eontain pentavalent or trivalent phosphorus. The pentavalent phos-
phorus acids, which are preferred, may be represented by the ~ormula
-12
Rl~X)a \
P(X) XH
R~
wherein each Rl is independently hydrogen or a hydrocarbon-based group, at
least one thereof being hydrocarbon based; each ~ is independently oxygen
or sulfur; and each a is independently Cl or 1. Thus, it will be appreciated
5 that the phosphorus acid may be an organophosphoric, phosphonic or
phosphinic acid, or a thio analog of any of these.
The term "hydrocarbon-based" as used herein denotes a group
having a carbon atom directly attached to the remainder of the molecule
and having predominantly hydrocarbon character within the context OI this
10 invention. ~uch groups include the following:
(1~ Hydrocarbon groups; that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic ~e.g., cycloPlkyl or cycloalkenyl), aromatic, aliphati~ and al!i-
cyclic-substituted aromatic? aromatic-substituted aliphatic and alicyclic
groups, and the like, as well as cyclic groups wherein the ring is completed
15 ~hrough another portion of the molecule (that is, any two indicated
substituents may together form an alicyclic group).
(2~ Substituted hydrocarbon groups; that is, hydrocarbon based
groups as defined above also containing non-hydrocarbon substituents which,
in the context of this invention3 do not alter the predominantly hydrocarbon
20 ch~acter of the group. Those skilled in t~le ar~ will be aware of suitable
substituents; examples include halo, nitro, hydroxy, alkoxy, alkylthio7
carbalkoxy and acyl groups.
(3) Hetero groups; that isg groups which, while predominantly
hydrocarbon in character within the context of this invention, contain atoms
25 other than carbon present in a chain or ring otherwise composed of carbon
atoms. Suitable hetero atoms will be apparent to those skilled in the art and
include, for example, nitrogen~ oxygen and sul~r.
In general, no more than about three substitu0nts or hetero atoms,
and preferably no more than one, will be present for each 10 carbon atoms in
30 the hydrocarbon-based group.
Included among the suitable phosphorus acids are those prepared
by the treatment of an ole~in polymer (e~g., a polybutene having a molecular
weight of about 1000) with a phosphorizing agent such as phosphorus
3~25
--13--
trichloride9 phosphorus heptasulfide~ phosphorus pentasulfide, phosphorus
trichloride and sulfur, white phosphorus and a sulfur halide, or phosphoro-
thioic chloride.
The equivalent weight of a phosphorus acid is its molecular weight
5 divided by the number of hydroxy groups bonded to phosphorus therein.
Carboxylic acids suitable for use in the preparation of comporlent
El include aliph~tic, cycloaliphatic and aromatic mono- and polybasic
carboxylic acids free from acetylenic unsaturation, including naphthenic
acids, alkyl- or alkenyl-substituted cyclopentanoic acids, ~lkyl- or alkenyl-
10 substituted cyclohexanoic acids9 and alkyl- or alkenyl-substituted aromatic
carboxylic acids (including salicylic acids). The aliphatic acids generally
contain at least 8 and preferably at least 12 carbon atomsO The
cycloaliphatic and aliphatic carboxylic aeic1s ean be saturated or un-
saturated. Specific examples include 2-ethylhexanoic acid, linolenic acid,
15 propylene tetrame~substituted maleic acid, behenic acid, isostearic acid,
pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic
acid7 ricinoleic acid, undecylic acid, dioctylcyclopentanecarboxylic acid,
myristic acid, dilauryldecahydronaphthalenecarboxylic acid, stearyl-octa-
hydroindenecarboxylic acid, palmitic acid, acids formed by oxidation of
2n petrolatum or of hydrocarbon waxes9 and commercially available mixtures of
two or more carboxylic acids such as tall oil acids, rosin acids, and the like.
The equivalent weight of any sueh acid is its molecular weight divided by the
number of carboxy groups present therein.
The sulfonie acids useful in the preparation of detergents suitable
25 for use as component B include mahogany sulfonic acids, petrolatwn sulfonic
acicls, mon~ and polywax-substituted naphthalene sulfonic acids, cetyl-
chlorobenzene sulfonic acids~ cetylphenol sulfonic acids, cetylphenol di-
sulfide sulfonic acids, cetoxycapryl benzene sulfonic acids, dicetyl thi-
anthrene sulfonic acids, di-lauryl beta-naphthol sulfonic acids, dicapryl
30 nitr~naphthalene sulfonic acids9 paraffin wax sulfonic acids, unsaturated
paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids,
tetraisobutylene sulfonic acids, tetraamylene sulfonic acids, chloro-substi-
tuted paraffin wax sulfonic acids, nitros~substituted parafIin wax sulfonic
acids, petroleum naphthene sulfonic acids, cetylcyclopentyl sulfonic acids,
35 lauryl cyclohexyl sulfonic acids, mono- and polywax-substituted cyclohexyl
sulfonic acids, postdodecylbenzene sulfonic acids, "dimer alkylate" sulfonic
~3~
- 14 -
acids, and -the likeO These sulfonic acids are well known in the
art and require no further discussion herein.
For the purpose of this invention, the equivalent weight of a
sulfonic acid or derivative thereof is its molecular weight
divided by the num~er of sulfonic acid groups or sulfonic acid
derivative groups present therein. Thus, for a monosulfonic acid
the equivalent weight is equal -to the molecular weight.
The basic salts and complexes useful as component B are well
known in the art and are disclosed in many United States patents
of which the following are exemplary:
2,616,904 3,031~28~ 3,410,671
2,616,905 3,256,186 3,437,465
2,695,910 3,312,618 31629rlO9
2,723,234 3,342,733 3,746,643
2,777,~74 3,350,308 3,764,533
2,781,403 3,410,670
as well as in German published application 1,243,915. The salts
and complexes useful in the present invention are those disclosed
in said patents and application both generically and in the
working examples, and include those disclosed merely as
intermediates for conversion into more highly basic salts and
complexes.
The commonly employed method for the preparation of these basic
salts and complexes involves heating a solution of the organic acid
compound in a substantially inert, normally liquid organic diluent
such as mineral oil with a stoichiometric excess of a metal
neutraliæiing agent such as the oxide, hydroxide, carbonate,
bicarbonate or sulfide at a temperature above 50C and filtering
the resulting mass. A "promoter" is often used in the
neutralization step to ald the incorporation of a large excess of
metal. Examples of compounds useful as promoters include phenolic
compounds such as phenol, naphthol, alkylphenols, thiophenols,
sulfurized alkylphenols, and condensation products of phenols with
formaldehyde; alcohols such as methanol, 2-propanol r actyl alcohol,
Cellosolve*, Carbitol*, ethylene glycol, stearyl alcohol and
* trade marks
3~5
- 14a -
cyclohexyl alcohol; and amines such as aniline, phenylene diamine,
phenothiazine, phenyl-beta-naphthylamine and dodecylamine. It is
also frequently preferred to further treat the basic compound
prepared as .....
3~lY~5
--15--
described above w;th an acidic gas, especially carbon dioxide. This
treatment may be intermittent and followed by successive treatments with
the metal neutralizing agent, and often enables the incorporation of still
larger amounts of basic metal in the complexO
S The preferred organic acidic s~ompounds for use in the preparation
of the detePgent are the abov~described sulfonic and carboxylic acids,
especially those having an equivalent weight of about 300 500. The sulfonic
acids are most often used, and a particulQr preference is expre~ssed for
alkylaromatic sulfonic acids and more particularly or alkylbenzene sulfonie
acids.
The preferred detergents are the basic alkali or alkaline earth
metal salts of carboxylic and sulfonic acids. Particul~ly useful as
detergents are the oil soluble basic c~lcium sulfonates.
~?~
Oil dispersible dispersants are particularly useful as component B
in the present invention. As previously noted, these dispersants are
generally metal-Iree or contain relatively small amounts of metal in
comparison to the detergents described above. Their characterizing feature7
with respect to molecular structure, is the presence of an oil-solubilizing
aliphatic hydrocarbon-based group containing at least about 40 aliphatic
carbon atoms bonded directly to a polar group. The dispersant may contain
more than one of either of such groups per molecule, as will be apparent
from the description hereinafter.
M~ny dispersants of this type are known in the art and are
described in various patents. Any of such dispersants are suitable for use in
the compositions and methods OI this invention. The foLlowing are
illustrative:
(1~ Reaction products of carboxylic acids ~or derivatives ther~
of~ containing at least about 44 and preferably at least about 54 aliphatic
carbsn atoms with nitrogen-containing compounds having at least one ~NH
group such as amines, ureRs and hydrazines, with organic hydroxy compounds
such as phenols and alcohols, and/or with reactive basic inorganic materials.
Examples o these products, referred to herein as "carboxylic dispersants",
are described in British Patent 1,306,529 and in many U.S. patents including
the following:
~3~
-16-
3,163,603 37351,552 3,S41,012
3~1~4,47~ 3,381,0~2 3,5~2,~78
3,215,707 3,399,141 3,542~B80
3,219,666 3,415,750 3,5679637
3,271,310 3,433,744 3,57~,101
3,272,746 3,4~4,17 0 3,576,743
3,281,357 3,448,04~ 3,630,~04
3,306,908 3,448,0~9 3,632,510
3,311,558 3,451,9~3 3,632,511
3,316,177 3,454,607 3,897,~28
3,3~0,281 3,467,668 3,725~441
3,341,542 3,501,405 Re 2~,433
3,3~6,493 3,~2~,179
(2) Reaction products of aliphati~ or alicyclic halides containing
lS at least about 40 carbon atoms with amines, preferably polyalkylene
polyamines. These may be characterized as "amine dispersants" and
example~ reof ~re described, for example, in the following U.S. patents~
3,275,554 3,454,~55
3,438,757 3956~,804
(3) R~action products of alkyl phenols in which the alkyl group
contains at lea~t about 40 carbon atoms with aliphatic aldehyde~ containing
at most about 7 carbon atoms (especially ~ormaldehyde) and amines
(especi~lly alkylene polyamines), which may be characterized as 'IManni~h
dispersants". The materials des~ribed in the following U.S. patents are
illustrativ~:
29459,112 35442,808 3~591,598
2,962,442 3,448,047 3,600,372
2,984,550 ~9454,497 3,634,S15
3~03~,003 3,459,661 3,649,229
3,1669516 3,461,172 3,697,574
3,23~,770 3,4~3,520 3,725,277
3,355,270 3,~39,633 3y725,480
39368,972 3,558,743 3,726,8~2
3,413,347 3,586,629 3,980,563
11 3~
(4) Polymers containing an oil-solubilizing group (e.g., a
p~ndant alkyl group having at least about 8 carbon a~oms) and a
polar groupO Illustrative are interpolymers of decyl methacrylate,
vinyl decyl ether or a rela-tively high molecular weight olefin with
aminoalkyl acrylates, aminoalkyl acrylamides or poly-(oxyalkylene)-
substituted alkyl acrylates, as well as copolymers of styrene, alkyl
maleates and maleic acid amides or imides. These may be
characterized as "polymeric dispersants" and examples thereof are
disclosed in the following U.S. patents:
3,329,658 3,6~6,730
3,449,?50 3,687,849
3,519,565 3,702,300
(5) Products obtained by post-treating the carboxylic, amine,
Mannich or polymeric dispersants with such reagents as sulfur, urea,
thiourea, guanidine, carbon disulfide, aldehydes, ketones,
carboxylic acids, h~drocarbon-substituted succinic anhydrides,
nitriles, epoxides, boron compounds, phosphorus compounds or the
like. Products of these types are described in Canadian patent
1,064,479 and in the following U.S. patents:
3,036,003 3,282,955 3,493,520 3,639,242
3,087,936 3,312,619 3,502,677 3,64g,229
3,200,107 3,366,56~ 3,513,093 3,649,659
3,216,936 3,367,943 3,533,9~5 3,658,836
3,254,025 3,373,111 3,539,633 3,697,574
3,256,185 3,403,102 3,573,010 3,702,757
3,278,550 3,442,808 3,579,450 3,703,536
3,280,234 3,455,831 3,591,598 3,704,308
3,281,428 3,455,832 3,600,372 3,708,522
4~161,475
The carboxylic and Mannich dispersants are preferred.
Carboxylic dispersants may be most conveniently and accurately
described in terms of the groups (B-l and s-2) present therein.
Group B 1 is usually an acyl, acyloxy or acylimidoyl yroup
containing at least about 44 carbon atoms. The structures of
these yroups, as defined by the International Union of Pure and
~L183~ AJSj
--18-
Applied Chemistry, are as foLlows ~each R2 individually representing a
hydrocarbon or similar group):
o
Acyl: R2 -C-
2 11
Acyloxy: R C-0-
N~2
2 11
Acylimidoyl: R -C~
Group B-2 is preferably at least one group in which a nitrogen or
oxygen atom is attached directly to sQid acyl, acyloxy or acylimidoyl
radical, said nitrogen or oxygen atom also being attached to 2 hydrocarbon-
based group. The carboxylic dispersants are conveniently classified as
la "nitrogen-bridged dispersants" and "oxygen-bridged dispersants" wherein the
atom attached directly to radical B 1 is nitrogen or oxygen respectively.
The nitrogen-bridged carboxylic dispersants, which will be de-
scribed first, are those diselosed (for example) in the above-mentioned U.~.
Patents 3~219,666 and 3,~72,746 which also describe a large number oE
15 methods for their preparationO
The source of group B-l in the nitrogen bridged dispersants is an
acylating agent comprising a earbo2cylic aci~producing compound containing
a hydrocarbon or substituted hydrocarbon substituent which has at least
about 40 and preferably at least about 50 carbon atoms. By "carboxylic
20 acid-producing compound" is meant an acid, anhydride, a~id halide, ester,
amide, imide, amidine or the like; the acids and anhydrides are preferred.
The carboxylic acid producing compound is usually prepared by
the reaction (more fully described hereinafter~ of a relatively low mole~ular
weight carboxylic acid such as maleic acid, fumaric acid, maleic anhydride,
25 etc., or derivative thereof with a hydroearbon source containing at least
about 4û and preferably at least about 5û carbon atoms. The hydrocarbon
source i9 usually aliphatic and should be substantially saturated, i.e., at least
about 95% of the total number of carbon-to-carbon covalent linkages should
be saturated. It should also be substantially free from pendant groups
30 containing more than about six aliphatic carbon atoms. It rnay be a
- l9 -
substituted hydrocarbon source; by "substituted" is meant sources cont~ining
substituents which do not alter significalltly their character or reactivity.
Examples are halide, hydroxy, ether, keto, carboxy, ester (especially lower
carbalkoxy~, amide~ nitro, cyano, sulfoxy and sulfone radicals. The
S substituents, if present, generally comprise no more than about 10% by
weight of the hydrocarbon source.
The preferred hydrocarbon sources are those derived from
substantially saturated petroleum fractions and olefin polymers, particularly
polymers of monoolefins having from 2 to about 30 carbon atoms and more
10 particu~arly frorn 216 carbon a~oms. Thus, the hydrocarbon source may be
derived from a polymer of ethylene, propene, l-butene, isobutene, l-octene,
3-cyclohexyl-1-butene, 2-butene, 3-pentene or the like. Also useful are
interpolymers of olefins such as those illustrated above with other
polymerizable olefinic substanees such as styrene, chloroprene, isoprene, p-
15 methylstyrene, piperylene and dienes such as 1,3-hexadiene, isoprene, 1~4-
hexadiene ~nd 1,4-cyclohexadiene. In general, these interpolymers should
contain at least about 80%, preferably at least about 95%, on a weight basis
OI units derived from the aliphatic monoolefins.
Another suitable hydrocarbon source comprises saturated aliphatic
20 hydrocarbolls such as highly refined high molecular weight white oiLs or
synthetic alkanes.
In many instances, the hydrocarbon source should contain an
activating polar group to facilitate its reaction with the low mdecular
weight aeid-producing compound. The preferred activating groups are
25 halogen atoms, especially chlorine, but other suitable groups include sulfide,
disulfide, nitro, mercaptan9 ketone and ~ldehyde group~.
As already pointed out, the hydrocarbon sources generally contain
at least about 4a and prePerably at least about 50 carbon atoms. Among the
olefin polymers those having a number average molecular weight above
30 about 600 ar~ useful and those between about 1300 and about 50ûO (as deter-
mined by gel permeation chromatography) are preferred, although higher
polyrners having moleclllar weights from absut 10,000 to about 100,000 or
higher may sometimes be used. The ratio o~ weight average to number
average molecular weight (Mw/Mn) may be about 1.5-6.0 ~d is usually L5-
35 4Ø
2~;
--20--
A first preferred class of polymers comprises those of terminalolefins such as propylene, l-butene, isobutene and l-hexene. Especially
preferred within this class are polybutenes comprlsing predominantly
isobutene units. A second preferred class comprises terpolymers of
5 ethylene, a C3-8 alpha-monoolefin and a polyene selected from the group
~;, consisting of non-conjugated dienes (which are especially pref erred) and
trienes. Illustrative of these terpolymer~ is "Ortholeum 2052" m~nufactured
by E~ I. duPont de Nemours dc Company, which is a terpolymer containing
about 48 mole percent ethylene groups, 48 mole percent propylene groups
10 and 4 mole percent 1,4-hexadiene groups and having an inherent viscosity of
1.35 (8.2 grams of polymer in lU0 rnl. of carbon tetrachloride at 30 C).
Any one of a number of known reactions may be employed for the
preparation of the carboxylic acid producing compound. Thus, an alcohol o
the desired molecular weight may be oxidized with potassium permanganate,
15 nitric acid or a similar oxidizing agent; a halogenated olefin polymer may bereaeted with a ketone; an ester of an active hydrogen-containing acid, such
as acetoacetic acid, may be converted to its sodium derivative and the
sodium derivative reacted with a halogenated high molecular weight
hydrocarbon such as brominated wax or brominated polyisobutene; a high
20 molecular weight olefin may be ozonized; a methyl ketone of the desired
molecular weight may be oxidized by means of the haloform reaction; an
organometallic derivative of a halogenated hydrocarbon or olefin polymer
may be converted to a nitrile, which is subsequently hydrolized; or an olefin
polymer or its halogenated derivative may undergo a reaction with an
25 unsaturated carboxylic acid or derivative thereof such as acrylic acid,
methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid7
itaconis~ anhydride, citraconic acid, citraconic anhydride5 mesaconic acid,
glutaconic acid, chlorQmaleic acid, aconitic acid, crotonic acid, methyl-
crotonic acid, sorbic acid, 3-hexenoic acid, 10-decenoic acid, 2-pentene-
30 1,3,5-tricarboxylic acid, and the like, or with a halogen~ubstituted car-
boxylic acid or derivative thereof. This latter reaction is preferred,
especially when the acid-producing compound is unsaturated and preferably
when it is maleic acid or anhydride. The resulting product is then a
hydrocarbon-substîtuted succinic acid or deriva~ive thereof. The reaction
35 leading to its formation involves merely heating the two reactants at a
* ~r~ e~r~
3~ AJS
-21-
temperature from about 100 to about 20U C. The mole ratio of the
polymer to the maleic acid or anhydri-3e may be equal to, greater than or
less than 1, depending on the type of dispersant product desired. It is often
preferred, however, to employ proportions such that the dispersant will
5 contain an average of at least 1.3 succinic rnoities per polymeric moiety;
such dispersants are termed "polysuccinated dispersants". Especially
preferred are polysuccinated dispersants containing about 1.4-3.5 succinic
groups and most desirably about 1.5-2.5 succinic groups per polymer group.
The substituted succirlic acid or anhydride thus obtained, may, if desired, be
10 converted to the corresponding acid halide by reaction with known
halogenating agents sueh as phosphorus trichloride, phosphorus pentachloride
or thionyl chloride.
The nitrogen-bridged carboxylic dispersants are prepared by
reacting the acylating agent such as the substituted succinic acids or
15 anhydrides with at least one nitrogen compound preferably having the
structure~NH wherein the two remaining valences of nitrogen are satisfied
by hydrogen9 amino or organic radicals bonded to said nitrogen atom through
direct carbon-t~nitrogen linkages. These eompounds include aliphatic,
aromatic, heterocyclic and carbocyclic amines as well as substituted ureas,
20 thiorueas, hydrazines, guanidines, amidines, amides, thioamides, eyanamides
and the like.
Arnong the amines useful in preparing the nitrogen-hridged
dispersant are rnonoarnines. These monoamines can be secondary, i.e., those
eontaining only one hydrogen atom bonded directly to an amino nitrogen
25 a~om. Preferably, however, they contain at least one primary amino group,
i.e., a group wherein an amino nitrogen atom is directly bonded to two
hydrogen atoms. The monoamines are generally substituted with Cl 30
hydrocarbon-based groups. Preferably these hydrocarbon-based groups are
aliphatic in nature and free from acetylenic unsaturation and contain from
30 about 1 to about 10 carbon atoms. Saturated aliphatic hydrocarbon groups
are particularly preferred.
Among the preferred monoamines are those' of the general
formula HNR3R4, wherein R3 is an alkyl group of up to ten carbon atoms
and R4 is hydrogen or an alkyl group of up to ten carbon atoms. C)ther
35 preferred monoarnines are arornatic monoamines of the general formula
~L83~
--2~--
HNR5R6 wherein R5 is a phenyl, alkylated phenyl, naphthyl or alkylated
naphthyl group of up to 10 carbon atoms and R6 Ig a hydro~en atom, an alkyl
group of up to 10 carbon atoms, or a group similar to R5. Examples of
suitable monoamines are ethylamine, diethylamine, n-butylamine, di-n-
S butylamine~ allylamine, isobutylamine, cocoamine, stearylamine, lauryl-amine, methyl laurylamine, oleylamine, aniline, methylaniline, N-methyl-
aniline, diphenylamine, benzylamine, tolylamine and methyl-2-cyclohexyl-
amine.
Hydroxy amines are also included in the class of useful mono-
10 amines. Such compounds are the hydroxyhydrocarbyl-substituted analogs of
the afore-described monoamines. Preferred hydroxy monoamines have the
formulas HNR7R8 and HNR9R10, wherein R7 is an alkyl or hydroxy-
substituted alkyl group of up to 10 carbon atoms, R8 is hydrogen or a group
simil~r to R7, R9 is a hydroxy-substituted phenyl, alkylated phenyl, naphthyl
15 or alkylated naphthyl group of up to 10 carbon atoms, and R10 is hydrogen or
A group similar to R9, at least one of R7 and R8 and at least one of R9 and
R10 being hydroxy-substituted.
Suitable hydroxy~substituted monoamines include ethanolamine,
di-3-propanolamine, 4-hydroxybutylamine, diethanolamine, N-methyl-2-
20 propylamine, 3-hydroxyaniline, N-hydroxyethylethylene diamine, N,N-di-
(hydroxypropyl~propylene diamine and tris(hydroxymethyl)methylamine.
While in general, hydroxy amines containing only one hydroxy group will be
employed as reactants, those containing more can also be used.
Heterocy~lic amines are also useful in making the nitrogen-
25 bridged dispersant, provided they contain a primary or secondary aminegroupO The heterocyclic ring can also incorporate unsaturation and can be
substituted with hydrocarbon groups such as alkyl~ alkenyl, aryl, alkaryl or
aralkyl. In addition, lhe ring can also contain o~her hetero atoms such as
oxygen, sulfur, or other ni$rogen atoms including those not having hydrogen
30 atoms bonded to them. Generally, these rings have from about 3 to about 10,
preferably 5 or 6, ring members. Among such heterycydes are aziridines,
azetidines, azolidines, pyridines, pyrroles, piperidines, imidazoles, indoles,
piperazines,isoindoles, purines, morpholines, thiamorpholines, N-aminoalkyl
morpholines, N-aminoalkyl thiamorpholines, azepines7 azocines, azonines,
35 azecines and tetrahydro-, dihydr~ and perhydro- derivatives of each of the
~3~
-23-
above. Preferred heterocyclic amines are the saturated ones with 5- and 6-
membered rings, especially the piperidines, piperazines and morpholines
described above.
Polyamines are preferred for preparing the nitrogen-bridged
5 dispersant. Among the polyamines are alkylene polyamines (and mixtures
thereof) including those having the formula
A ~ N~RIl- N~jH
A A
wherein n is an integer between about 1 and about 10, preferably between 2
and 8; each A is independently hydrogen or a hydrocarbon or hydroxy-
10 substituted hydrocarbon group having up to about 30 atoms; and Rll is adivalent hydrocarborl group having from about 1 to about 18 carbons.
Preferably A is an sliphatic group of up to about 10 carbon atoms which may
be substituted with one or two hydroxy groups, and Rll is a lower alkylene
group having 1-10, preferably 2-6 carbon atoms. Rspecially preferred are the
15 alkylene polyamines wherein each A is hydrogen. Such alkylene polyamines
include methylene polyamines, ethylene polyaminesS butylene polyamines,
propylene polyamines, pentylene polyamines3 hexylene polyamines and
heptylene polyamines. The higher homologs of such ~mines and related
aminoalkyl-substituted piperaæines are also included. Specific examples of
20 such polyamines include ethylene diamine, triethylene tetramine, tris(2-
aminoethyl)amine, prowlene diamine, trimethylene diamine9 hexamethylene
diamine9 decamethylene diamine, octamethylene diamine, di(hepta-
methylene)triamine, tripropylene tetramine, tetraethylene pentamine9 tri-
methylene diamine, pentaethylene hexamirle, di(trimethylene) triamine, 2-
25 heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis-(2-aminoethyl)imidazoline, 1-(2-aminopropyl)-piperazine, 1,4-bis(2-aminoethyl)piperazine ~nd 2-methyl-1-(2-
aminobutyl~piperazine. Higher homologs, obtained by condensing two or
more o~ the abov~illustrated alkylene amines, are also useful, as are the
.~ polyoxyalkylene polyamines (e.g., "Jeffamines" available from Jefferson
30 Chemical Co.).
The ethylene polyamines, examples of which are mentioned abo~e,
are especially us~eful for reasons of cost and effectiveness. Such polyamines
are described in detail under the heading "I)iamines and Higher Amines" in
E~irk-Othmer, ~lopedia o~ ~,, Second Edition, Vol. 7,
-~r~J~ ma~
33~
-24--
pp. 22-39. They are prepared most conveniently by the reaction of an
alkylene chloride with ammonia or by reaction of an ethylene imine with a
ring-opening reagent such as ammonia. These reactions result in the
production of the somewhat complex mixtures of alkylene polyamines,
including cyclic condensation products such as piperazines. Bec~use of their
availabllity, these mixtures are parti~ularly useful in preparing the nitrogen-
bridged dispersant. Satisfsctory products can also be obtained by the use of
pure alkylene polyamines.
Hydroxy polyamines, e.g., alkylene polyamines having one or more
hydroxyallcyl substituents on the nitrogen atoms, are also useful in preparing
the nitrogen-bridged dispersant. Preferred hydroxyalkyl-substituted alkyl-
ene polyamines are those in which the hydroxyalkyl group has less than about
10 carbon atoms. Examples of such hydroxyalkyl-substitllted polyamines
include N-(2-hydroxyethyl)ethylene diamine, N,N'-bis(2-hydroxyethyl)-
ethylene diamine, 1~(2-hydroxyethyl~p;perazine, monohydroxypropyl-substi-
tuted diethylene triamine, dihydroxypropyltetraethylene pentamine and N-
(3-hydroxybutyl)tetramethylene diamine. Higher homologs obtained by
condensation of the above-illustrated hydroxyalkyl~ubstituted alkylene
amines through amino groups or through hydroxy groups are likewise useful.
The dispersant can also be prepared from hydrazine or an organo-
substituted hydrazine of the general formula
R12 R12
/N-N \
R12 R12
wherein each R12 is independently hydrogen or a Cl 30 hydrocarbon radical,
at least one R radical being hydrogen. Pre~erably, the others are Cl 10
aliphatic groups. More preferably at least two R radicals are hydroges~,
and most preferably at least two such groups bonded to the same nitrogen
atom are hydrogen and the remaining ones are alkyl groups of up to 10
carbon atoms. Examples of suitable substituted hydrazines are m ethyl-
hydrazine, N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenyl-
hydra7ine, N-phenyl-N'-ethylhydrazine, N-(p-tolyl)-N'-(n-butyl)hydrazine, N-
(p-nitrophenyl}N-methylhydrazine9 N,N'-di~chlorophenyl)hydrazine and
N-phenyl-N' cyclohexylhydrazine.
~3 ,~
-25-
For the forma~ion of the nitrogen-bridged dispersant, the hydro-
earbon-substituted succinic anhydride or acid, or other carboxylic acid-
producing compound, and the alkylene polyamine or other nitrogen-
containing reagent are heated to a temperature above about 80 C,
preferably from about 100 tc about ~250C. The product thus obtained has
predominantly amide, imide and/or amidine linkages (containing acyl or
acylamidoyl groups). The process may in some instances be carried out at a
temperature below 80C to produce a product having predominantly salt
linkages (containing acyloxy groups)~ The use of a diluent such as mineral
lD oil, benzene, toluene, naphtha or the like is often desirable to facilitate
control of the reaction temperature.
The relative proportions of the carboxylic acid-producing com
pound and the alkylene polyamine or the like are such that at least about
one-half the stoichiometrically equivalent amount of polyamine is used for
each eguivalent of carboxylic acid-producing compound. In this regard it
will be noted that the equivalent weight of the alkylene polyamine is based
upon the number of amine radicals therein, and the equivalent weight OI the
earboxylic acid-producing compound is based on the number of acidic or
potentially acidic radicals. (Thus, the equivalent weight of a hydrocarbon-
substituted succinic acid or anhydride is one-half its molecular weight.)
Although a minimum of on~half equivalent of polyamine per equivalent of
acylating agent should be used, there does not appear to be an upper limit
for the amount of polyamine. If an excess is used, it merely remains in the
product unreacted without any apparellt adverse effects. Ordinarily, about
1-2 equiv~ents of polyamine are used per equivalent of acylating agent.
In an alternative method for producing the nitrogen-bridged
dispersant, the alkylene polyamine is first reacted with a low moleculai
weight, unsaturated or halogen-substituted carboxylic acid or derivative
thereof lsuch as maleic anhydride or one OI the others previously mentioned)
and tSle resulting intermediate is subsequently reacted with the hydrocarbon
source as previously described.
Oxygen-bridged carboxylic dispersants comprise the esters of the
abov~described carboxylic acids9 as described (for example) in the afore-
mentioned U.S. Patents 3,381,022 and 3,5427678. As such, they contain acyl
35 or, occasionally, acylimidoyl groups as group B-l. (An oxygen-bridged
-26-
dispersant containing an acyloxy group as group B-l would be a peroxide,
which is unlikely to be stable under all conditions of use of the compositions
of this invention.~ These esters are preferably prepared by conventional
methods, usually the reaction (frequently in the presence of an acidic
5 catalyst~ of the cnrboxylic acid-producing compound with a monohydric or
polyhydric hydrocarbon-based alcohol or with an aromatic hydroxy compound
such as a phenol or naphthol. The hyd]roxy compounds are usually alcohols
containing up to about 4a aliphatic carbon atoms. These may be monohydric
alcohols such as methanol, ethanol, the propanols, butanols, pentanols,
10 isooctanol, dodecanol, cyclohexanol, neopentyl alcohol, monomethyl ether of
ethylene glycol as well as the so called fatty alcohols such as lauryl
myristyl, cetyl, stearyl and behenyl alcohols and their mixtures, or
polyhydric alcohols includil~ ethylene glycol, diethylene glycol, dipropylene
glycol, tetramethylene glycol, pentaerythritol, glycerol and the like. ~atty
15 alcohols containing minor arnolmts of unsaturated (e.g., no more than about
two earbon-t~carbon unsaturated bonds per molecule) also are usefuL
These are exemplified by palmitoleyl (C~6H30O), oleyl (C18H36O) and
eicosenyl (C2oH4oO3 alcohols-
A further class of useful hydroxy compounds comprises the
20 polyoxyalkylene compounds of the type commonly sold as deml]lsifiers.These include the "Ethomeens~ "~thoduomeens'i, "Pluronics", "Tergitols",
"Tetronics", "Dow Polyglycols", etc. Carbohydrates (e.g~, sugars, starches9
cellulose) are also suitable as are partially esterified derivatives of
polyhydric alcohols having at least three hydroxy radicalsO Aliphatic polyols
25 containing up to 10 carbon atoms and at least 3 hydroxy groups, especially
those with up to 6 carbon atoms and 3-6 hydroxy groups, are preferred.
The esterification reaction is usually effected at a temperature
above about 100C and typically from about 150 to about 3û0C. The
esters may be neutral or acidic; or may contain unesterified hydroxy groups,
30 according as the ratio of equivalents of acid-producing compound to hydroxy
compound is equal to, greater than or less than 1:1.
It is possible to prqpare mixed oxygen- and nitrogen-bridged
dispersants by reacting the acylating agent simultaneously or, preferably,
sequentially with nitrogen-containing and hydroxy reagents such as those
35 described above. The relative amounts of the nitrogen-containing and
tra le ~n~r Ks
3 ~
-27-
hydroxy reagents may be between about 10:1 and 1:10, on an equivalent weight
basis. The methods of preparation of the mixed oxygen- and nitrogen-
bridged dispersants are generally the same as for the individual dispersants
described, except that two sources of group B-2 are used. Mixtures of
S independently prepared dispersants are slso suitable. Mixed dispersants of
these types are frequently preferred for the purposes of this invention.
Illustrative reactive metal compounds which may be reacted with
the carboxylic acids described above to produce dispersants include lithium
oxide, lithium hydroxide, lithium carbonate, lithium pentyloxide, sodium
10 oxide, sodium hydroxide, sodium carbonate, sodium methoxide, sodium
propoxide, potassium oxide, potassiwn hydroxide, potassium carbonate,
potassium methoxide, magnesium oxide, magnesium hydroxide, magnesium
carbonate, ma~nesium methoxide, magnesium propoxide, magnesium salt of
ethylene glycol monomethyl ether, calcium oxide, calcium hydroxide,
15 calcium carbonate, calcium methoxide, calcium propoxide~ calcium pentyl-
oxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc propoxide, strontium
oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmium
carbonate, cadmium ethoxide, barium oxide, barium hydroxide, barium
carbonate, barium ethoxide, barium pentyloxide, aluminum oxide, aluminum
20 isopropoxide, cupric acetate~ lead oxide, lead hydroxide, lead carbonate, tino~ide, tin butoxide, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt
pentyloxide, nickel oxide, nickel hydroxide~ nickel chloride, nickel carbonate
and chromium (II~ acetate.
Typical carboxylic dispersants suitable for use as component B are
~5 listed in Table I. "Reagent B-l" and "Reagent B-2" are, respectively, the
sources of groups B-l and B-2 as previously defined.
~1~83~5
C .~ .~ .o .~
3 ~ a
~ ~ c
~ 3
.~ ~ ~ U~
E~
.
.0 ~ ~ d~ O
3 ~ o o o
*. :~c a~
¢¦ q c E a E ~ 1 E
V ~ c 2 ~ E : ~ ;~ , E
C~ Z
o ~ ~ tq 0
~ 3 U F~l 3 ~ ~_ ~ 3
a~ ~ .~, D ~ Q 3 m ~ ~
~ ~ X 7 E o 7 ~ ~ x ~ 7
~ ~ ~ .~ F~ D ~ 'g,D ~ p,.D ~ a~
7 m m ~
~ , ~ c ~
3~ ~
~ I ~o .~ .~
C
C
~ ~
a~
C 5
~ E 3 3 ~
o Z C~
'~ ~ ~ o ~ ~ ~ o
a~
~i ~J = ~I~c~ o ~ E
S ~ ~ _ ~ ~ S ~
c ~ ra e
~D o X C ~ ~ e~ ~; X ~ ~ '~.
.~0 Q~
O ~
E E E E = E o ~ o c~ 3 E
0 '~ 0 ~ C~ V7 ~ ~o ~ 3 5; ~ .Q 3
a~
a~ q m a: m
CO ~ o ~
21
~ ~3
C .~
oC _ o C~ ", o
,,, ~i3 ~ ~ X 00 ~ Q ~ ~ O
~ m O O O O
a~
3 ~ c ~;
~ ~ e
o~
n~
m a~ m
~I l ~ ~ N
3~
.~ .~
d
.~ X
o ~
C~ ~ c) ~ ~ , ~
U~
o ~ ~ ol ~ o ~ '
~o
m
E c E E o 1
a~
e~
~1
-32-
In the preparation of carboxylie dispersants such as those
described in Examples lB-24B, reagent B-1 is normally prepared by reacting
approximately equimolar amounts of the hydrocarbon source and the low
molecular weight carboxylic acid or derivative thereof. It is also within the
5 scope of the invention, however, to u~se as component B a nitrogen- or
oxygen-bridged, or mixed nitrogen- and oxygen-bri~ged, dispersant prepared
by initially reacting substantially more than one mole of acid or acid
derivative with one mole OI hydrocarbon source. In the preferred dispersants
of this type, as in those previously described herein, the hydrocarbon source
0 i5 an olefin polymer such as polybutene and the carboxylic acid derivative is
maleic anhydride. Dispersants of this type usually contain up to about 3.5
and most often from about 1.5 to about 2.5 succinic groups for each ~roup
derived from the hydrocarbon source.
The method of preparation of dispersants of this type is basically
15 the same as for the carboxylic dispersants already described. Reagent B-1,
in particular, may be prepared by a one step procedure in which the
hydrocarbon source i5 reacted with maleic anhydride; by a tw~step
procedure in which the hydrocarhon source is chlorinated and the chlorinated
intermediate is reacted with maleic anhydride; or by various combinations of
20 the two procedures.
The following examples illustrate typical methods for the prepara-
tion of suitable dispersants of this type~
Exam~_5-B
A mixture of 1000 parts (0.495 mole) of a polybutene comprising
25 principally isobutene units and having a number average molecular weight of
2020 and a weight average molecular weight of 6049 and 115 parts (1.17
moles) of maleic anhydride is heated to 184 C over 6 hours as 85 parts (1.2
moles) of chlorine is added beneath the surface. At 184-189 C an additional
59 parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture
30 is stripped by blowing with nitrogen at 186-190C for 26 hours to yield a
polybutene substituted succinic anhydride having a saponification number o
87 as determined by ASTM Procedure D94.
To 893 parts (1.38 equivalents) of this substituted succinic
anhydride is added lOG7 parts of mineral oil and 57 parts (1.38 equivalents) of
35 a commercial ethylene polyamine mixture containing from about 3 to about
33~
-33--
10 nitrogen atoms per molecule. The mixture is heated to 140-155 C for 3
hours and is then stripped by blowing with nitrogen. The stripped liquid is
filtered and the filtrate is the desired dispersant (approximately 50%
solution in oil).
Example 26-B
A mixture of 334 parts (0.52 equivalent) of the polybutenyl
succinic anhydride of Example 25-B, 548 parts of mineral oil, 30 parts (0.88
equivalent) of pentaerythritol and 8.6 parts (0.0057 equivalent) of Polyglycol
112-2 demulsifier from Dow Chemical Company is heated at 150-21()C for
1() about 11 hours. The mixture is cooled to 190 C and 8.5 parts (0.2 equivalent)
of the ethylene polyamine mixture of Example 25-B is added. The mixture is
stripped by blowin~ with nitrogen for 3 hours at 205C and is filtered to
yield the desired dispersant as an approximately 40% solution in oil.
Example 27-B
A substituted succinic anhydride is prepared by the procedure o
Example 26-B, using a similar polybutene with a Mn of 1457 and a Mw of
5808. A mixture of 550û parts OI this anhydride, 3000 parts of mineral oil
and 236 parts of the ethylene polyamine mixture of Example 26-B is heated
at 155-165C for 2 hours, stripped by blowing with nitrogen at 165C for 1
20 hour, and filtered to yield an oil solution of the desired dispersant.
Example 28-B
.
A product is prepared by the procedure of Example 26-B from 1
equivalent of the substituted succinic anhydride of Example 25-B, 1-8
equivalents OI pentaerythritol, 0.2 equivalent of the ethylene polyamine
25 mixture of Example 26-B, and mineral oil in an amount to afford a 30%
solution of the product in oil.
~e~
A product is prepared by the procedure of Example 25-B using a
substituted succinic anhydride prepared by the reaction of 98 parts of maleic
3n anhydride with 5670 parts of a 10% solution of "Ortholeum 2052l' in mineral
oil.
Oil~soluble metal salts of substituted succinic acid acylated
aliphatic polyamines also are useful as detergents in the compositions of the
invention. These are exemplified by the alkali, alkaline earth, lead,
35 cadmium, zinc, nickel and cobalt salts of hydrocarbon-substituted succinic
31 ~
-3~--
acid acylated alkylene polyamines. The prineipal sources of the hydrocarbon
substituent incluAe the higll molecular weight petroleum fraction and olefin
polymers as described above, and the substituent should be substantially
saturated, that is, at least about 95% of the total number of carbon-to-
5 carbon covalent linkages are saturated linkages.
The si7e of the hydrocarbon substituent of the succinic compoundappears to determine the effectiveness of the additive as a dispersant. It is
important, therefore, that the substituent be large, that is, that it have at
least about 50 aliphatic carbon atoms. The molecular weight of the
10 hydrocarbon substituent should be within the range of from 70Q to about
100,000. The most common sources of the substantially aliphatic hydro-
carbon substituents are the polyolefins such as polyethylene, polypropylene,
polybutene, etc. A particularly preferred polyolefin is polyisobutene having
a molecular weight of about 1000.
The basic metal reactant can be an alkali metal, alk~line earth
metal, lead, cadmium and zinc oxides, hydroxides, - carbonates and lower
alcoholates and a combination of all of an alkali metal hydroxide and an
inorganic metal salt selected from the group consisting of alkaline earth
metal, lead, cadmium, zinc, nickel and eobalt halides and nitrates.
20 Illustrative examples of the basic metal compounds include sodium oxide,
sodium methylate9 potassium hydroxide, potassium carbonate, lithium
hydroxide, calcium hydroxide, calcium carbonate, calcium chloride, barium
oxide, barium fluoride, magnesium ethylate, magnesium bromide, magnesium
phenoxide, zinc hydroxide, ~ine nitrate trihydrate, cadmium oxide, lead
25 oxide, lead chloride, nickel hydroxide, nickel carbonate, cobalt hydroxide,
cobaltous bromide, etc.
The amines which are useful in the preparation of these
detergents inelude alkaline polyamines and hydroxyalkyl-substituted alkaline
polyamines of the types described above with respect to the carboxylate
30 disper~ants.
These metal salts of substituted succinic acid acylated aliphatic
polyamines can be prepared by either (1) first preparing the acylated amine
of the hydrocarbon-substituted succinic compound and then reacting the
acylated amine with the basic metal compound, or (2) first preparing the
35 mono-metal salt of the hydrocarbon-substituted succinic compound and then
3~ ~
- 35 -
reactlng said mono-metal salt wlth an alkaline polyamine or
hydroxyalkyl-substituted alkallne polyamine. In the first method,
it is preEerred -that the succinic compound be the succinic anhydride
and that trace amounts of water, that is, up to about 2.5% by weight,
be present when the basic metal compound is an oxide. In the
second method, it is preferred that the succinic compound be the
succinic acid. In all cases, it is preferred that nitrogen or some
inert gas be bubbled through the reaction mixtures to remove any
water formed as a result of the acylation reaction.
The oil-soluble metal salts of subs-tituted succinic acid
acylated aliphatic polyamines and processes for their preparation
are described in detail in U.S. Patent Re 26,433. The following
examples illustrate the preparation o:E the oil-soluble metal salts
of substituted succinic acid acylated aliphatic polyamines.
~ 30-B
A polyisobutenyl succinlc anhydride is prepared by the
reaction of a chlorinated polyisobutylene (having an average
chlorine content of 4.3 weight percent and an average of 70 carbon
atoms) with maleic anhydride at about 200C. The resulting
polyisobutenyl succinic anhydride has an acid number of 103. To a
mixture of 3,264 grams (6 equivalents) of this polyisobutenyl
succinic anhydride, 2,420 grams of mineral oil and 75 grams of
water, there is added at 80 to 100C, 122.1 grams (3 equivalents)
of zinc oxide. The addition is made portionwise over a period of
30 minutesO The mixture is maintained at a temperature of 90-
100C for a period of 3 hours. Thereupon, the mixture is heated
to 150C and maintained at this temperature until it is essentially
dry. The mixture is cooled to 100C and there is added 245 grams
(6 equivalents) of an ethylene polyamine mixture having an average
compositi.on corxesponding to that of tetraethylene pentamine and
an equivalent weight of 40.8. The addition is made portionwise
over a period of 30 minutes whereupon the mixture is heated to a
temperature of 150-160C and maintained at this temperature for 5
hours. Throughout the 5-hour period, nitrogen is bubbled through
the mixture to remove water formed as a result of acylation. The
residue is filtered. The resulting filtra-te has a zinc content of
1.63% and a nitrogen content of 1.39%.
~3~
-36-
To a mixture of 3,750 grams (6 equivalents) of a polyisobutenyl
suceinic anhydride (having an acid number of 89.8 and prepared, as in
Example 30-B~ from maleic anhydride and chlorinated polyisobutylene having
an average chlorine content of 4.3 weight percent and an average of 81
carbon atoms), 2,632 grams of mineral oil and 75 grams of water, th~re is
added, at 80-100C, 60 grams (3 equivalents) of magnesium oxide. The
addition is m~de portionwise over a lO~minute period. The mixture is
maintained ~t a temperature of 100-105C for 3 hours. During the first
part of this 3-hour period, 50 grams of water is adcled. Thereupon, 113 grams
~3 equivalents) of an amine mixture such as described in Example 30-B tbut
with an equivalent weight of 3~.8) is aclded portionwise over a period of 30
minutes while the temperature of the mixture is maintained at 98-100C.
The mixture is heated at 210-215 C and maintained at this temperature for
4 hours. Throughout the 4-hour period, nitrogen is bubbled through the
mixture to remove water resulting from acylation. The residue is filtered.
The filtrate has a magnesium content of 0.S5%, based on sulfate ash, and a
nitrogen content of 0.64%.
To a mixture of 1,028 grams (2 equivalents) of a polyisobutenyl
succinic anhydride (having an acid number of 109 and prepared, as in
Example 30~B, from maleic anhydride and a chlorinated polyisooutylene
having an average chlorine content of 4.3 weight percent and an average of
65 carbon atoms), 707 grams of mineral oil and 1,5()0 grams of benzene,
~here is added at 60 C, 41 grams (1 equivalent) of an amine mixture such as
described in Example 30-B (but with an equivalent weight of 41). The
addition is made portionwise over a 3û-minute period. The mixture is
maintained at a temperature of 85-90C for 7 hours. Throughout this 7-
hour period, nitrogen is bubbled through the mixture to remove water
resulting from acylation. To 1,034 grams of the above mixture and 52 grams
of water, there is added 80-90C, 52 grams (0.67 equivalent) of barium
oxide. The addition is made portionwise over a 30-minute period. The
mixture is maintained at a temperature of 80-90 C for 2 hours~
Thereupon, the rnixture is heated to 150 C and stripped of the last traces of
water. The residue is filtered. The filtrate has a barium content of 3.9%
and a nitrogen content of 0~76%.
-37-
Rxample 33-B
To a mixture of 4,200 grams (6 equivalents) of a polyisobutenyl
succinic anhydride (having an acid number of 80 and prepared, as in Example
30-B, from m~leic anhydride and chlorinated polyisobutylene having an
5 average chlorine content of 4.3 weight percent and an average of 92 carbon
atoms) and 2,930 grams of mineral oil, there i9 added at 80C, 390 grarns of
1-(2-hydroxyethyl)piperazine. The addition is made portionwise over a 30-
minute period and the resulting mixture is maintained at a temperature of
180-205C for 5 hours. Throughout tlhe 5-hour period, nitrogen is bubbled
10 through the mixture to remove wal:er resulting from acylation. To the above
mixture, combined with 35 grams of water, there is added nt 30C, 159
grams (3 equi-ralents) of sodium carbonate. The addition is made portionwise
over a 45-minute period. The temperature is maintained at 70-80C for 3
hours whereupon the mixture is heated to 150C and stripped of the last
15 traces of water. The residue is filtered. The filtrate has a sodium content
of 0.88 percent and a nitrogen content of 1.1 percent.
Example 34-B
To a mixture of 1,245 grams (2 equivalents) of a polyisobutenyl
succinic anhydride (having an acid number of 90 and prepared, as in Example
20 30-B3 from maleic anhydride and chlorinated polyisobutylene having an
average chlorine content OI 4.3 weight percent and an average OI 81 carbon
atoms), 871 grams of mineral oil and 25 grams of water, there is added at
80~ C, 56 grams (1 equivalent) of potassium hydroxide. The addition is made
porffonwise over a 30-minute period, after whieh the mixture is held at 85-
25 95C for 1 hour, then dried by heating at 135S'-140C for 1 hour. Thereupon,
104.2 grams (I equivalent) of barium chloride is added portionwise over a
pelqod of 30 minutes, with the temperature at 80-90 C. The mixture then
is heated at 130-140 C for 9 hours, and filtered. To the filtrate there is
added 41 grams (1 equivalent) of an amine mixture such as described in
30 Example 30-B (but with an equivalent weight of 413. The addition is made
portionwise over a 30-mimJte period, with the temperature at 110-140C.
The mixture then is heated at 160-165C for 4 hours, throughout which
period nitrogen is bubbled into the mixture to remove wa~er resulting from
acylation. The residue is filtered. The filtrate has a barium content of 2.7%
35 and a nitrogen content OI 0.61%.
~3~
--38 -
Also preferred for use as component B, as an alternative to the
carboxylic dispersAnts hereinabo7re described, are the Manrlich dispersants.
These are, as previously noted, reaction products of certain alky] phenols
with aldehydes (usually lower aliphatic aldehydes and especially formalde-
5 hyde) and amino compounds. The StrUCtllre of the alkyl substituent on thephenol is subject to the same preferene~es as to source, structure, molecular
weight and the lilce expressed hereinabove with respect to the carboxylic
dispersant. The amino compounds ar~e the snme as those described with
reference to nitrogen-bridged carboxylic dispersants and are subject to the
10 same preferellces.
Suitable Mannich dispersants for use as component B are illus-
trated in the workin~ examples of the aforementioned U.S0 Patent 3,980,569
/~ Ca.q~ an p~ 06~J~ ~q
and ~e ~. The following examples also are
illustrative.
~
A mixture of 3~40 parts (2 equivalents) of a polybutenyl phenol in
which the polybutene substituent comprises principally isobutene units and
has a molecular weight of abcut 160û, 1250 parts of textile spirits and 2000
parts of isopropyl alcohol is stirred as 352 parts (2.2 equivalents) of 50%
aqueous sodium hydroxide is added, followed by 480 parts (6 equiv~lents~ of
389S aqueous formaldehyde solution. The mixture is stirred for 2 hours,
~llowed ~o stand for 2 days and then stirred again for 17 hours. Acetic acid,
150 parts (2.5 equivalents~, is added and the mixture is stripped of volatile
materials under vacuunn. The remaining water is removed by adding benzene
and distilling azeotropicaily; during the distillation, 1000 parts of mineral oil
is added in two portions. The distillation residue is filtered.
To 430 parts (0.115 equivalent) of the filtrate is added with
stirring, at 90C, 14.1 parts (0.345 equivalent) of the polyethylene amine
mixture containing about 3 to 7 amino groups per rnolecule. The mixture is
heated at 90-120~C for 2 hours and then at 150-160C for 4 hours, with
nitrogen blowing to rsmove volatiles. The resulting solution is filtered to
yield the desired Mannich dispersant (52% solution in mineral oil) which
contains 1.03% nitrogen~
A mi~.~ture of 564 parts (0.25 equivalent) of polybutenyl phenol in
which the polybutene substituent comprises principally isobutene units and
.2~
-39-
has a rnolecular weight of about 2020, 400 parts of mineral oil and 16.5 parts
of isobutyl alcohol is heated to 65C, with stirring, and 2.15 parts ~0.025
equivalent) of 50% aqueous sodium hydroxide solution is added, ïollowed by
16.5 parts (0.5 equivalent) of paraformaldehyde. The mixture is stirred at
80 88C for 6 hours and then 5 parts (00025 equivalent) of 18.5% aqueous
hydro~hloric acid is added slowly~ with continued stirring, ~ollowed by 36
parts (0.875 equivalent) of a polyethylene amine mixture containing about 3
to 7 amino groups per molecule~ at 88C. Mixing is continu~d at 88-91C
for 30 minutes. The mixture is then heated to about lS8C with nitrogen
blowing to remove volatiles.
Sul~ur, 16 parts (0.5 mole), and 25 parts of a filter aid material are
added slowly at 150C, with stirring, after which the mixture is blown with
nitrogen at 150-155 C for 3 hours. The mixture is then cooled to 132 C and
filtered to yield the desired sulfurized Mannich product as a 6D% solution in
mineral oil; it contains about 0.63% sulfur.
In general, the compositions of this invention comprise about 0.2-
3.0 parts by weight of component A per part of component B. These
proportions are of active chemicals; that is, they disregard any diluent such
as mineral oil. The preferred proportions are about 0.3-1.0 part of
component A per part OI component B.
Specific examples of the multi-component compositions of the
invention comprising mixtures of components A and B are as follows:
TABLE II
25Composition
Exame~ ~ ~ Weight Ratio
A l-A 3-B 1:2
B 12-A 26-B 0.3:1
C 12-A2-B:4-B 0.3:0.5:0.5
D 13-A 30-B 0.4-1
30 E 6-A3-B:32-B 0.3:0.4:0.4
F 8-A 3B-B 1:1
As previously indicated, the compositions of this invention are
also useful as additives for lubricants. They are particularly useful for
lubricating machinery which operates at relatively high temperatures, and
3~"S
-40-
are effective over a wide range of concentrations. Moreover, they
frequently result in a decrease in the amount of oxidation inhibiting
additives (examples of which are listed hereinafter) which rnust be
incorporated in the lubricant and in a decrease in fuel consumption.
The compositions c~n be employed in a variety of lubricants based
on diverse oils of lubricatin~ viscosity, including natural and synthetic
lubricating oils and mixtures thereof. These lubricants include crankcase
lubricating oils for spark-ignited and compression-ignited internal com-
bustion engines, including automobile ~d truclc engines, tw~cycle engines7
aviation piston engines, marine and railroad diesel engines, and the like.
They can ~lso be used in gas engines, stationary power engines and turbines
and the like. Automatic transmission fluids, transaxle lubricants, gear
lubricants, metal-working lubricants, hydraulic fluids and other lubricating
oil and grease compositions can also benefit from the ineorporation therein
lS of the compositions of the present invention.
Natural oils include snimal oils and vegetable oils (e.g., castor oil,
lard oil) as well as mineral lubricating oil such as liquid petroleum oils and
solvent-refined or acid-refined mineral lubricating oils of the paraffinic,
naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating vis-
eosity derived from coal or shale are also useful base oils. Synthetic lubri-
cating oils include hydrocarbon oils and halosubstituted hydrocarbon oils
such as polymerized and interpolymerized olefins (e.g., polybutylenes, poly-
propylenes, propylene-isobutylene copolymers, chlorinated polybutylenes,
poly(l-hexenes), poly(l-octenes, poly(l decenes)l etcO and mixtuPeS thereof),
alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes9 dinonylbenzenes,
di~2-ethylhexyl)benzenes, etc.3; polyphenyls (e.g., biphenyls, terphenyls,
etc.); alkylated diphenyl ethers and alkylated diphenyl sulfides and the
derivatives, analogs and homologs thereof, etc.
Alkylene o~ide polymers and interpolymers and derivatives there-
of where the terminal hydroxyl groups have been modified by esterification,
etherification, etc., constitute another elass of kr;own synthetic lubricating
oils. These are exemplified by the oils prepared through polymeriæation of
ethylene oxide or propylene oxide, the alkyl and aryl ethers of these
polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having
an average mo]ecular weight of lUOQ, diphenyl ether of polyethylene glycol
~ !33~'~S
having a molecular weight of 500-1000, diethyl ether of polypropylene glycol
hRving a molecular weight of 1000-1500, etc) or rnono- and polycarboxylic
esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid
esters, or the C13Oxo acid diester of tetraethylene glycol.
Another suitable elass of synthetic lubricating oils comprises the
esters of dlcarboxylic acids (e~g., phthalic acid, succinic acid, rnaleic acid,
azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic
acid dimer, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl
alcohol, dodecyl ~lcohol9 2-ethylhexyl alcohol, ethylene glycol, etc.).
Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl~
sebELcate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diis~
decyl azelate, dioctyl phthalate, didecyl phthalate~ dieicosyl sebacate, the
2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by
reacting one mole of seba~ic acid with two moles of tetraethylene glycol
and two moles of 2-ethylhexanoic acid and the like.
Esters useful as synthetic oils also include those made from C5 to
C12 monocarboxylic acids and polyols flnd polyol athers such as trimethylol
propane, pentaery~hritol, dipentaerythritol, etc.
Silicorl-based oils such as the polyalkyl-, polyaryl-polyalkoxy-, or
polyarylo2~y-siloxane oils and siliG~te oils comprise another useful ~lass of
synthetic lubri~ants ~e.g., tetraethyl silicate~ tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-tetraethyl)silicate, tetra-(p-tert-
butylphenyl)silicate, hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(methyl~
siloxanes, poly(methylphenyl)-siloxanes, etc.). Other synthetic lubricating
oils include liquid esters of phosphorus-containing acids (e.gO, tricresyl
phosphate trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.),
polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils, either natural or synthetic
(as well as mixtllres of two or more of any of these) of the type disclosed
hereinabove can be used in the lubricant eompositions of the present
invention. Unrefined oils are those obtained directly from a natur~l or
synthetic source without further purification treatment. For example, a
shale oil obtained directly from retorting operatiorls, a petroleum oil
obtained directly from distillation or ester oil obtained directly from an
esterification process and used without further treatment would be an
3i~
-42
unrefined oil. Refined oils are similar to the unrefined oils except they have
been further treated in one or more purification steps to improve one or
more properties. Many such purification techniques are known to those of
skill in the art such as sol-rent extraction, second~ry distillation, acid or base
5 extraction, filtration9 percolation, el c. Rerefined oils are obtained by
proeesses similar to those used to obtain refined oils applied to refined oils
which have been already used in service. Such rerefined oils are also known
as reclaimed or reprocessed oils and often are additionally processed by
techniques directed to removal of spent additives and oil breakdown
10 products.
Generally, the lubricants oP this invention will cont~in an amount
of the composition of the invention which is e~fective to reduce fuel
consumption of engines lubricated with the lubricants OI the invention.
Normally this amount will be in the range of from about Ooû5% to about 10%
15 although amounts of 0.1 to 5% per lOa parts of the total finished lubricant
weight are preIerred.
The compositions of the present invention can contain, in addition
to components A and B, other additives that are normally used in lubrieants.
Such additi~es include, for example, auxiliary detergents oî the ash-forming
20 and of the ashless type, viscosity index improving agents7 pour-point
depre~sants, anti-foam agents, extreme pressure agents7 rust inhibiting
agents, oxidation and corrosion inhibiting agents.
l[he ash-producing detergents are exemplified by oil-soluble
neutrP1 and basic salts of alkali or alkaline earth metals with sulfonic acids,
25 carboxylic acids, or organic phosphorus acids characterized by at least one
direct carbon-t~phosphorus linkage such as those prepared by the treatment
of an olefin polymer (e.g., polyisobutene h~ving a molecular weight of 1000)
with a phosphorizing agent such as phosphorus trichloride, phosphorus
heptasulfide, phosphorus pentasulfide9 phosphorus trichloride and sulfur,
30 white phosphorus and a sulIur halide7 or phosphorothioic chloride. The most
commonly used salts of such acids are those of sodium, potassium, lithium,
calcium, magnesium, strontium and barium.
The term "basic salt" is used to designate metal salts wherein the
metal is present in stoichiometrically larger amounts than the organic acid
35 radical. The commonly employed methods for preparing the basic salts
.
3~ t3
-~3-
involve heating a mineral oil solution of an acid with a stoichiometric excess
of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate,
bicarbonate, or sulfide at a temperature above 50 C and filtering the
resulting mass. The use of a "promoter" in the neutralization step to aid the
incorporation o~ a large excess of mletal likewise is known. ExalTIples of
compounds useful as the promoter include phenolic substances such as
phenoll naphthol, ~Ikylphenol, thiophenol, sulfurized alkylphenol, and con-
dens~tion products of formaldehyde with a phenolic subst~nce; ~lcohols such
AS methanol, 2-propanol, octyl alcoholr cellosolve, carbitol, ethylene glycol~
stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline,
phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, and dodecyl-
amineO A particularly effective method for preparing the basic salts
comprises mixing an acid with an excess oi a basic alkaline earth metal
neutralizing agent and at least one alcohol promoter, and carbonatir~ the
mixture at an elevated temperature such as 60-20û C.
Auxiliary ashless detergents and dispersants are so called despite
the fact that~ depending on its constitution, the dispersant may upon
combustion yield a non-volatile material such as boric oxide or phosphorus
pentoxide; however, it does not ordinarily contain metal and therefore does
not yield a metal-containing ash on combustion. Many types are known in
the art and are disclosed in patents induding those listed hereinabove with
respect to component B. Also useful as auxiliary dispersants al e
interpolymers OI oil-solubilizing monomers such as decyl methacrylate, vinyl
deeyl ether and high molecular weight olefins with monomers containing
polar substi~uents, e.g., aminoalkyl acrylates or acrylamides and poly-
(oxyethylene~substituted acrylates. These may be characterized as "poly-
,~ meric dispersants" arld examples thereof are disclosed in the following U.S.
k~ patents ~_:
3,329,658 3,666,730
3,449~2S0 3,687,849
3,519,565 3,702,300
Extreme pressure agents and corrosion- and oxidation inhibiting
agents are exemplified by chlorinated aliphatic hydrocarbons such as
chlorînated wax; organic sldfides and polysulfides such as benzyl disulfide,
bis~chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized Islethyl ester of
~33~h~5
-4~l-
oleic acid, sul:t`urized dipentene, and sulfurized terpene; phosphosulfurized
hydrocarbons such as the reaction product of a phosphorus sulfide with
turpentine or methyl oleate; phosphorus esters including principally dihydro-
carbon and trihydrocarbon phosphite~ such as dibutyl phosphite, diheptyl
phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl
phosphite9 tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phos-
phite, oleyl 4-pentylphenyl phosphite, polypropylene ~molecular weight 500)-
substitu~ed phenyl phosphite, diisobutyl~substituted phenyl phosphite; methl
thiocarbamates, such as zinc dioctyldithiocarbamate, and barium h~ptyl-
0 phenyl dithiocarbamate; Group II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithio~te, zinc dioctylphosphorodithioate, barium ~i-
(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, and
the zinc salt of a phosphorodithioic acid produced by the reaction of
phosphorus pentasulfide with an equimolar mixture of isopropylalcohol and
n-hexyl alcohol.
The compositions of this invention also can contain at least one
viscosity improving component; that is~ at least one component capable of
substantiRlly improving the viscosity properties thereof. For the purposes oP
this invention, a substance is considered to substantially improve the
viscosity properties of a composition if its incorporation in the composition
in operative amounts causes an increase in its viscosity index (as determined
by ASTM procedure D2270) of at least 6 unitsO
A number of types OI viscosity improvers are known in the art,
and many of these are described in Ranney, ~iv~ (Noyes Data
Corporation, 1973)7 pp. 93-119. Illustrative viscosity improvers include
various olefin polymers such as polybutene (especially containing predomi-
nantly isobutene units); ethylen~propylene copolymers; copolymers of
ethylene and other low molecular weight olefin.q (especially alpha-olefins);
terpolym ers of ethylene, propylene and various dienes (especially non-
conjugated dienes); polybutadiene; hydrogenated styrene-butadiene co
polymers; alkylated polystyrenes; polymers of alkyl methacrylates; alkylene
polyethers; and polyesters prepared from polyols, short-chain dicarboxylic
acids and monobasic carboxylic acid terminators (useful predominantly in
lubricants in which the lubrieating oil is a synthetic ester).
It is also within the scope of this invention to use as component B
- ~5 ~ 3~2S
a composition which improves viscosity properties as well as
serving as a dispersant or detergent. When component B also
improves viscosity propertiesl it may be possible to decrease the
amount of auxiliary viscosity improver used or to eliminate it
entirely~
The present invention contemplates two materials as being
particularly useful as combination viscosity improvers and
detergents or dispersants. The first comprises the dispersants
containing more than one succinic moiety per molecule,
particularly those prepared from a hydrocarbon source having a
number average molecular weight (Mn~ of at least about 1300 and
usually about 1300-5000 as determined by gel permeation
chromatography. Examples 25~-29B hereinabove illu,strate suitable
dispersants of this type which also have viscosity improving
properties.
The second type of preferred viscosity improver having
dispersant or detergent properties comprises interpolymers being
substantially free of titratable acidity and containing carboxylic
ester groups in which part of the alcohol moieties have at least
8 aliphatic carbon atoms and another part have no more than 7
aliphatic carbon atoms, and also containing carbonyl-polyamino
groups in which the polyamino group is derived from a compound
having one primary or secondary amino group. These polymers are
described in U.S. Patent 3,702,300. Preferred are interpolymers
prepared by first copolymerizing styrene with maleic anhydride and
subsequently esterifying a portion of the carboxylic acid groups
with a mixture of primary alcohols having the numbers of carbon
atoms noted above, and neutralizing the remaining carboxylic acid
groups with a suitable amine. The working examples of U.S. Patent
30 3,702,300 illustrate specific suitable polymers.
A further component in -the phosphorus acid salt compositions
of this invention can be at least one compound of the formula
R130 11
P-SM
R140 /
~.
3~
- 45a -
wherein each of R13 and Rl is independently a hydrocarbon-based
group having from about 3 -to about 20 carbon atoms and M is a
Group I metal, a Group II metal, aluminum, -tin, iron, cobalt,
lead, arsenic, molybdenum, ....
,~'
-46~
manganese, nickel, or a mixture of any of said metals. These phosphorus
acid salts~ when present9 provide load c~rryir4~ and oxidation inhibiting
properties to the lubricant.
Each of R13 and R14 is preferably an alkyl group, although it may
5 be an aryl or substituted aryl group (e.g., phenyl, tolyl, chlorophenyl).
Suitable alkyl groups include propylJ butyl, octyl, decyl, hexadecyl, octa
decyl, eicosyl and mixtures thereof. Most often, each of R13 and R14 is an
allcyl group containing from about 6 to about 20 and preferably from about 6
to about 10 c~rbon atoms. Branched groups (e.g., isooctyl, 2 ethylhexyl) are
10 especially pref erred.
The metal ~M) of the phosphorus acid salt is preferably 2inc or
molybdenum and especially zinc. As previously noted, it is within the scope
of the invention to use salts of more than one metal or to use a mixed salt of
two or more metals (e.g., zinc and arsenic, zinc and nickel, molybdenum and
15 manganese).
The compositions OI this invention can be added directly to the
lubricant. Preferably, however, they are diluted with a substantially inert,
normally liquid organic diluent such as mineral oil, naphtha, benzene,
toluene or xylene, to form an additive ~oncentrate. These concentrates
20 usually contain about 20~90% by weight of the composition of this inven$ion
and may contain, in addition, one or more other additives known in the art or
described hereinabove.
Illustrative concentrates of this invention are listed in Table III
and illustrative lubricants of this invention are listed in Table IVo All
25 amounts except ~hose for the products of Examples are exclusive of diluents
such as mineral oil.
I o I I I o I I I o~
I I I o o I ~ ~ I I I o
~c
)
¢ ~ ¢ I 1 ~1~1 1 1 1 1 1
V O r~
o ~
E ~ ~, v ~D
~ ~ ~ p o,~
'` ~ ¢ ¢ ~ .g C
.~ , ' ~ U~ E ~ E E :~ ~ o, r
._ o ~o ~ ~ o o ~a o ~ Y,~ ~
~
~t 7
3~
~ 1~1~ 11111 1111111
a ~ ~ I ~,, I I I I I I I I I I I I I
3 ~ o I c~ I
~ ~ ~4 ~ o _, ~ I o I I I o o
:~ E~
E~ .= ~ n c ~ I o I I to U~ X I ~ I I I O I o
C g.
E ~ 3 ~ c = E 3 ~ ~ ~ , s
~ E E = E o. ~ E ~ ;, ~ ~ E
& ~ S 0 e ~ ~ 4 ;~
C ~ o o o O ~ ~ ~ 3
v ~ c~ c~ .~ '' ,, ~ E ~ , o o .N Y ~
,, " e S ~ ~ 3 0
33~
-49-
The fuel consumption of internE~l combustion engines is reduced
when the engines are lubricated with the compositions OI this invention.
This can be shuwn by the Pinto Friction Horsepower Test, in which a ~ord
Pinto engine is driven by a dynamometer at constant temperature while
5 engine r.p.m. and torque are measured by a digital tachometer and a
precision dial manometer, respectively. Friction horsepower, as calculated
from these values9 is roughly proportional to fuel consumed and thus
decreases with improved fuel economy.
