Note: Descriptions are shown in the official language in which they were submitted.
case EI-6311
- 1 20~9~
LUBRICATING OIL CONPOSITIONS
AND CONCEN~RATES ~ND THE USE THEREOF
This invention relates to oleaginous compositions of
enhanced performance characteristics, to additive concen-
trates for enhancing the performance characteristics of ole-
aginous base fluids (e.g., lubricants and functional flu-
ids), and to methods of achieving such enhanced performance
- characteristics.
Over the years the demand for performance improvements
in lubricating oils and functional fluids has persisted and,
if anything, progressively increased. For example, lubri-
cating oils for use in internal combustion engines, and in
particular, in spark-ignition and diesel engines, are con-
stantly being modified and improved to provide improved per-
formance. Various organizations including the ~AE (Society
of Automotive Engineers), the ASTM (formerly the American
Society for Testing Materials) and the API (American Petro-
leum Institute) as well as the automotive manufacturers con-
tinually seek to improve the performance of lubricatingoils. Various standards have been established and modified
over the years through the efforts of these organizations.
As engines have increased in power output and complexity,
and in many cases decreased in size, the performance re-
quirements have been increased to provide lubricating oilsthat will exhibit a reduced tendency to deteriorate under
conditions of use and thereby to reduce wear and the forma-
tion of such undesirable deposits as varnish, sludge, car-
bonaceous materials and resinous materials which tend to
adhere to various engine parts and reduce t~e operational
efficiency of the engine.
Current objectives include the development of additive
formulations and lubricant compositions, especially crank-
case lubricants and crankcase lubricant additive packages,
capable of achieving these stringent performance require-
ments without requiring use of increased amounts of metal-
Case EI~6311
~ - 2 - 2~5~
containing components, such as zinc dihydrocarbyl dithio-
phosphates. Indeed, if possible, it is desired to achieve
these stringent performance requirements with reduced
amounts of such metal-containing components. Still another
desirable objective is to provide additive formulations and
lubricant compositions which exhibit good compatibility with
elastomeric substances utilized in the manufacture of seals,
gaskets, clutch plate facings, diaphragms, and like parts.
Unfortunately, commonly used additives containing basic ni-
trogen cons~ituents tend to cause excessive degradation ofsuch elastomers when oils containing such additives come in
contact with such elastomers during actual service condi-
tions.
There are literally hundreds, if not thousands, of pat-
ent disclosures describing attempts (some more successfulthan others) to improve the performance characteristics of
oils of lubricating viscosity. The following is but a small
selection from this vast body of literature: U.S. Pat. Nos.
3,087,936; 3,184,411; 3,185,645; 3,235,497; 3,254,025;
20 3,265,618; 3,281,428; 3,282,955; 3,284,410; 3,324,032;3,325,567; 3,33~,832; 3,344,069; 3,403,102; 3,502,677;
3,511,780; 3,513,093; 3,533,945; 3,623,985; 3,718,663;
3,865,740; 3,950,341; 3,991,056; 4,097,389; 4,234,435;
4,338,205; 4,428,849; 4,554,086; 4,615,826; 4,634,543;
25 4,~48,980; 4,747,971; 4,857,214; and 4,873,004.
This invention provides additive systems capable of im-
parting enhanced performance characteristics to natural and
synthetic oils of lubricating viscosity. In addition, this
invention makes it possible to achieve such enhanced per-
formance with additive systems containing reduced amounts ofmetal-containing performance enhancers such as metal dithio-
phosphates (e.g., zinc dialkyldithiophosphates) and/or metal
dithiocarbamates.
In accordance with this invention there is provided in
3~ one of its embodiments a composition comprising a major pro-
portion of at least one oil of lubricating viscosity and a
minor proportion of at least the following components: a)
one or more oil-soluble metal hydrocarbyl dithiophosphates
Case EI-6311 2~94~
-- 3
or dithiocarbamates; and b) one or more oil-soluble boron-
free additive co~positions formed by heating (i) at least
one boron-free oil-soluble ashless dispersant containing ba-
sic nitrogen and/or at least one hydroxyl group, with (ii)
at least one inorganic phosphorus acid such that a liquid
boron-free phosphorus-containing composition is formed. The
cooperation between components a) and b) of such composi-
tions makes it possible to achieve performance levels
(reduction in sludge formation and/or deposition and
reduction in wear in gears and/or other relatively moveable
metal surfaces in contact with each other) normally
achieved, if at all, by higher concentrations of component
a). Moreover, these performance levels can be maintained
for long periods of time despite the well-known relatively
low thermal stability of compounds such as the zinc
dihydrocarbyl dithiophosphates.
Another advantage of this invention is that certain
preferred combinations of components a) and b) can exhibit
good compatibility toward elastomers commonly employed in
the manufacture of seals or gaskets, clutch plate facings,
diaphragms, etc., such as nitrile rubbers, fluoroelastomers,
and silicone-type elastomers. In other words, such elasto-
mers are not subjected to excessive degradation when in con-
tact under actual service conditions with a preferred lubri-
cant or functional ~luid composition of this invention con-
taining particular combinations of components a) and b),
which combinations are thus preferred because of this advan-
tageous property which they possess and exhibit in the base
oil. To realize these beneficial properties, component b)
should be formed from one or more sulfur-free inorganic
phosphorus acids and the overall sulfur content of the
finished lubricant or functional fluid composition should be
kept below 1% and most preferably below 0.3% based on the
total weight of the finished lubricant or functional fluid
composition.
Another embodiment of this invention involves the dis-
covery, inter alia, that basic alkali metal-containing and/
or basic alXaline earth metal-containing detergents of the
case EI-6311
- 4 ~ 2~
types generally known to be useful in oleaginous fluids
(e.g., overbased sulfonates, overbased phenates, overbased
sulfurized phenates, overbased salicylates, overbased sul-
furized salicylates, etc.) can serve a dual role in the com-
positions of this invention. Besides contributing detergen-
cy to the compositions, such metal compounds can serve to
reduce corrosive attack on so-called "yellow metals" such as
copper, bronze, and the like. Detergents of the foregoing
types having a total base number (TBN) of at least 50 are
utilized in the practice of this embodiment of the inven-
tion. TBN is determined in accordance with ASTM D 2896-88.
Accordingly, another embodiment of this invention is a
composition comprising a major proportion of at least one
oil of lubricating viscosity and a minor proportion of at
least the following components:
a) one or more oil-soluble metal hydrocarbyl dithiophos-
phates or dithiocarbamates;
b) one or more oil-soluble boron-free additive composi-
tions formed by heating (i) at least one boron-free
oil-soluble ashless dispersant containing basic ni-
trogen and/or at least one hydroxyl group, with (ii) at
least one inorganic phosphorus acid such that a liquid
boron-free phosphorus-containing composition is formed;
and
c) one or more oil-soluble alkali or alkaline earth metal-
containing detergents having a TBN of at least 50.
Additive concentrates comprising at least components a)and b) above, and preferably additionally containing compo-
nent c), i.e., one or more suitably basic, oil-soluble alka-
li metal-containing and/or alkaline earth metal-containing
detergents, constitute additional embodiments of this in~en-
tion. Such concentrates contain a minor proportion of at
least one diluent oil of lubricating viscosity (usually a
process oil) and a major proportion of the active ingredi-
ents or components utilized in forming the additive concen-
trate.
It has been found, quite surprisingly, that in order to
achieve optimum performance as regards minimal corrosive at-
case EI-6311
- 5 2
tack on yellow metals such as copper, the order in 7~hich
components a), b) and c) are blended together should be pro-
perly seguenced. In particular, in order to achieve minimal
copper corrosivity, components a) and b) should not be pre-
mixed in the absence of component c). Thus in situationswhere optimum compatibility with copper is necessary or de-
sirable, it is preferable, in forming any additive concen-
trate in which components a), b) and c) are used, to pre-
blend components b) and c) before mixing with component a).
Likewise, in forming a lubricant or functional fluid by add-
ing the components separately into the oil (rather than
blending into the oil an additive concentrate of this inven-
tion formed in the manner specified in this paragraph --
which is most preferred~, it is preferable to either add a
preblend of components b) and c) to the oil before blending
component a) in the oil, or to separately blend components
b) and c) into the oil (in either order) before blending
component a) into the oil. Accordingly, the blending pro-
cedures and modes of addition set forth in this paragraph
constitute still additional preferred embodiments of this
invention.
Still another embodiment of this invention is a compo-
sition comprising a major proportion of at least one oil of
lubricating viscosity and a minor proportion of at least the
following components:
a) one or more oil-soluble metal hydrocarbyl dithiophos-
phates or dithiocarbamates;
b) one or more oil-soluble boron-free additive composi-
tions formed by heating (i) at least one boron-free
oil-soluble ashless dispersant containing basic nitro-
gen and/or at least one hydroxyl group, wi~h (ii) at
least one inorganic phosphorus acid such that a liquid
boron-free phosphorus-containing composition is formed;
c) one or more oil-soluble alkali or alkaline earth metal-
containing detergents having a TBN of at least 50; and
d) one or more oil-soluble or oil-dispersible boron-con-
taining additive components.
Such compositions are of particular effectiveness under con-
case EI-6311
o ~ 4 ~
ditions wh~re scuffing wear is likely to be encounter~d.
Although it is preferable to include component c) in these
compositions, it is possible to achieve satisfactory results
with compositions comprising components a), b), and d), and
devoid of component c). Thus these latter compositions form
yet another embodiment of this invention.
Likewise, additive concentrates which comprise the
abo~e components a), b), c), and d), and additive concen-
trates which comprise the above components a), b) and d)
form still additional embodiments of this invention.
Among the preferred embodiments of this invention are
oleaginous compositions and additive concentrates in which
component a) is at least one oil-soluble metal hydrocarbyl
dithiophosphate (preferably a zinc hydrocarbyl dithiophos-
phate and most preferably a zinc dialkyl dithiophosphate),and in which the relative proportions of components a) and
b) are such that the atom ratio of phosphorus in the form of
component a) to phosphorus in the form of component b), re-
spectively, falls in the range of lO:l to 0.01:1 (and more
preferably in the range of 5:1 to 0.1:1 and most preferably
in the range of 4:1 to 1:1). Particularly preferred are
compositions of these types which additionally contain com-
ponent c) in an amount such that the atom ratio of total
metal in the form of component a) to total metal in the form
of component c), respectively, falls in the range of 0.01:1
to 10:1 (and more preferably in the range of 0.1:1 to 4:1).
Especially preferred are lubricants and functional fluids
containing components a), b), and c) proportioned as speci-
fied in this paragraph wherein the total content of metals
in the form of components a) and c) is in the range of 0.01
to 3, preferably in the range of 0.05 to 1.8, and most pre-
ferably in the range of 0.1 to 1.0 weight percent of metals
based on the total weight of the lubricant composition or
functional fluid composition. Despite their low level of
"ash" or metal-containing components, such lubricant and
functional fluid compositions can provide a high level of
performance.
In order to satisfy the stringent specification
case EI-6311 2 ~
xequirements to qualify for top-grade crankcase lubricating
oils, a combination of antioxidant and corros7On inhibitor
is preferably included in the compositions of this
invention. In this way, the enhanced performance (e.g.,
effective control of sludge, deposit and varnish formation
and of wear of contacting metal parts) made possible by this
invention can be maintained while at the same time
satisfying specification requirements associated with
oxidation and corrosion inhibition. Thus in another
preferred embodiment of this invention, there is provided a
crankcase lubricant composition which comprises a major
proportion of at least one oil of lubricating viscosity and
a minor proportion of at least the following components:
a) one or more oil-soluble metal hydrocarbyl dithiophos-
phates or dithiocarbamates;
b) one or more oil-soluble boron-free additive composi-
tions formed by heating (i) at least one boron-free
oil-soluble ashless dispersant containing basic nitro-
gen and/or at least one hydroxyl group, with (ii) at
least one inorganic phosphorus acid -- preferably one
or more sulfur-free inorganic phosphorus acids, most
preferably phosphorous acid (H3P03) -- such that a
liquid boron-free phosphorus-containing composition is
formed;
c) optionally but preferably, one or more oil-soluble al-
kali or alkaline earth metal-containing detergents hav-
ing a TBN of at least 50, preferably above 100, more
preferably above 200, and most preferably above 300;
d) optionally but preferably, one or more oil-soluble or
oil-dispersible boron-containing additive components;
e) one or more oilsoluble antioxidants; and
f) one or more oil-soluble corrosion inhibitors;
such that said lubricant composition satisfies (1) the re-
quirements of the Sequence IID, Sequence IIIE, and Sequence
VE procedures of the American Petroleum Institute; and/or
(2) the requirements of the L-38 Test Procedure of the
American Petroleum Institute; and/or (3) the requirements of
the Caterpillar~ lG(2) and/or the 1~(2) Test Procedure. The
.
case
- 8 - 2~
Sequence IID procedure is as set forth in ASTM STP 315~ Part
1, including any and all amendments detailed by the Informa-
tion Letter System (up to November 1, 1990). The Sequence
IIIE procedure is as set forth in ASTM Research Report:
D-2:1225 of April 1, 1988 including any and all amendments
detailed by the Information Letter System (up to November 1,
1990). The Sequence VE procedure is as set forth in ASTM
Sequence VE Test Procedure, Seventh Draft, May 19, 1988,
including an~ and all amendments detailed by the Information
Letter System (up to November 1, 1990). The L-38 procedure
is as set forth in ASTM D-5119, including any and all amend-
ments detailed by the Information Letter System (up to
November 1, 1990). The Caterpillar~ lG(2) procedure is as
set forth in ASTM STP 509A, Part 1, including any and all
amendments detailed by the Information Letter System (up to
November 1, 1990). The Caterpillar3 lH(2) procedure is as
set forth in ASTM STP 509A, Part 2, including any and all
amendments detailed by the Information Letter Systam (up to
November 1, 1990). Additive concentrates which comprise at
least components a), b), c), d) and e) as set forth above,
and which when blended with a base oil of lubricating visco~
sity provide a lu~ricant satisfying the foregoing Sequence
IID, IIIE, and VE procedures; and/or the L-38 procedure;
and/or at least one of the Caterpillar~ lG(2) and Caterpil-
lar~ lH(2) procedures constitute still additional especiallypreferred embodiments of this invention. The most preferred
embodiments are lubricant compositions and additive concen-
trates which satisfy the requirements of all of the Sequence
IID, Sequence IIIE, Sequence VE, L-38, Caterpillar~ lG(2)
and Caterpillar~ lH~2) procedures.
Additional preferred embodiments of this invention in-
volve providing oleaginous compositions and additive compo-
sitions in which component a) is one or more oil-soluble me-
tal hydrocarbyl dithiophosphates and the amount of phospho-
rus present in the form of component b) is equal to or inexcess of the amount of phosphorus present in the form of
component a). Thus for example, in accordance with this
embodiment, preferred are compositions in which the atom
case ~
_ 9 _ 2~
ratio of phosphorus in the form of component a) to phospho-
rus in the form of component b), respectively, falls in the
range of 0.001:1 to 1:1, more preferably in the range of
0.01:1 to 0.99:1, and most preferably in the range of 0.1:1
to 0.95:1.
Among the most preferred embodiments of this invention
are oleaginous fluids wherein component a) is composed of
one or more oil-soluble zinc dihydrocarbyl dithiophosphates,
wherein components a) and b) are proportioned such that the
atom ratio of phosphorus in the form of component a) to
phosphorus in the form of component b), respectively, falls
in the range of 4:1 to 1:1, and wherein the phosphorus con-
tent of such fluids is in the range of 0.05 to 0.15% by
weight of the total composition, especially where such
fluids additionally contain at least one oil-soluble alkali
or alkaline earth metal-containing detergent having a TBN of
at least 50, pre~erably abo~e 100, more preferably above
200, and most preferably above 300.
Other embodiments of this invention include the provi-
sion of methods for inhibiting sludge formation and/or depo-
sition in oils normally tending to occur during actual ser-
vice conditions, and methods for imparting antiwear and/or
extreme pressure properties to oils of lubricating visco-
sity.
Component a)
In essence, there are two general categories of addi-
tives which may be used singly or in combination with each
other as component a) in the practice of this invention.
One type is comprised of oil-soluble metal hydrocarbyl di-
thiophosphates. The other is comprised of oil-soluble metal
hydrocarbyl dithiocarbamates.
Type 1 - Metal hydrocarbyl dithiophosphates. As is
well known, metal hydrocarbyl dithiophosphates are usually
prepared by reacting phosphorus pentasulfide with one or
more alcohols or phenolic compounds or diols to produce a
hydrocarbyl dithiophosphoric acid which is then neutralized
with one or more metal-containing bases. When a monohydric
alcohol or phenol is used in this reaction, the final pro-
Case EI-6311
"` - lo 2~94~
duct is a metal dihydrocarbyl dithiophosphate. On the other
hand, ~hen a suitable diol (e.g., 2,4-pentanediol) is used
in this reaction, the final product is a metal salt of a cy-
clic hydrocarbyl dithiophosphoric acid. See, far example,
U.S. Pat. No. 3,089,850. Thus typical oil-soluble metal
hydrocarbyl dithiophosphates used as component a) may be
represented by the ~ormula
R ~ ~1 1
~P--S M
R 2
x
where R1 and R2 are, independently, hydrocarbyl groups or
taken together are a single hydrocarbyl group forming a
cyclic structure with the phosphorus and two oxygen atoms,
preferably a hydrocarbyl-substituted trimethylene group of
sufficient carbon content to render the compound oil solu-
ble, M is a metal, and x is an integer corresponding to thevalence of M. The preferred compounds are those in which R1
and R2 are separate hydrocarbyl groups (i.e., the metal di-
hydrocarbyl dithiophosphates). Usually the hydrocarbyl
groups of the metal dihydrocarbyl dithiophosphates will con-
tain no more than 50 carbon atoms each although e~en highermolecular weight hydrocarbyl groups can be present in the
compound. The hydrocarbyl groups include cyclic and acyclic
groups, both saturated and unsaturated, such as alkyl, cy-
cloalkyl, alkenyl, cycloalkenyl, aryl, cycloalkylalkyl,
aralkyl, and the like. It will be understood that the
hydrocarbyl groups may contain elements other than carbon
and hydrogen provided such other elements do not detract
from the predominantly hydrocarbonaceous character of the
hydrocarbyl group. Thus the hydrocarbyl groups may contain
ether oxygen atoms, thioether sulfur atoms, secondary or
tertiary amino nitrogen atoms, and/or inert functional
groups such as esterified carboxylic groups, keto groups,
thioketo groups, and the like.
Case EI-6311
11- 2~9~5
The metals present in the oil-soluble metal dihydro-
carbyl dithiophosphates and oil-soluble metal cyclic hy-
drocarbyl dithiophosphates include such metals as lithium,
sodium, potassium, copper, magnesium, calcium, zinc, stron-
tium, cadmium, barium, mercury, aluminum, tin, lead, chro-
mium, molybdenum, tungsten, manganese, iron, cobalt, nickel,
ruthenium, etc., as well as combinations of two or more such
metals. Of the foregoing, the salts containing group II
metals, aluminum, lead, tin, molybdenum, manganese, cobalt,
and/or nickel, are preferred. The dihydrocarbyl dithiophos-
phates of zinc and copper are particularly preferred, with
the zinc salts being the most preferred type of compound for
use as component a).
The phosphorodithioic acids from which the metal salts
are formed can be prepared by the reaction of 4 moles of one
or mor~ alcohols (cyclic or acyclic) or one or more phenols
or mixture of one or more alcohols and one or more phenols
(or 2 moles of one or more diols) per mole of phosphorus
pentasulfide, and the reaction may be carried out within a
temperature range of from 50 to 200C. The reaction gener-
ally is completed in 1 to 10 hours. Hydrogen sulfide is
liberated during the reaction.
Another method for the preparation of the phosphoro-
dithioic acids involves reaction of one or more alcohols
and/or one or more phenols with phosphorus sesquisulfide in
the presence of sulfur such as is described in PCT Interna-
tional Publication No. WO 90/07512. This reaction is con-
ducted at an elevated temperature, preferably in the range
of 85-150C with an overall atomic P:S ratio of at least
2.5:1.
The alcohols used in forming the phosphorodithioic
acids by either of the above methods are preferably primary
alcohols, or secondary alcohols. Mixtures thereof are also
suitable. The primary alcohols include propanol, butanol,
isobutyl alcohol, pentanol, 2-ethyl-1-hexanol, isooctyl
alcohol, nonanol, decanol, undecanol, dodecanol, tridecanol,
tetradecanol, octadecanol, eicosanol, and the like. The
primary alcohols may contain various substituent groups such
Case EI-6311
- 12 - 2~
as halogen atoms, nitro groups, etc., which do not interfere
with the desired reaction. Among suitable secondary alco-
hols are included 2-butanol, 2-pentanol, 3-pentanol, 2-
hexanol, 5-methyl-2-hexanol, and the like. In some cases,
it is preferable to utilize mixtures of various alcohols,
such as mixtures of 2-propanol with one or more higher
molecular weight primary alcohols, especially primary
alcohols having from 4 to 13 carbon atoms in the molecule.
Such mixtures preferably contain at least 10 mole percent of
2-propanol, and usually will contain from 20 to 90 mole per-
cent of 2-propanol. In one preferred embodiment, the alco-
hol comprises 30 to 50 mole percent of 2-propanol, 30 to 50
mole percent isobutyl alcohol and 10 to 30 mole percent of
2-ethyl-1-hexanol.
Other suitable mixtures of alcohols include 2-propa-
nol/butanol; 2-propanol/2-butanol; 2-propanol/2-ethyl-1-
hexanol; butanol/2-ethyl-1-hexanol, isobutyl alcohol/2-
ethyl-l-hexanol; and 2-propanol/tridecanol.
Cycloaliphatic alcohols suitable for use in the pro-
duction of the phosphorodithioic acids include cyclopen-
tanol, cyclohexanol, methylcyclohexanol, cyclooctanol, bor-
neol and the like. Preferably, such alcohols are used in
combination with one or more primary alkanols such as buta-
nol, isobutyl alcohol, or the like.
Illustrative phenols which can be employed in forming
the phosphorodithioic acids include phenol, o-cresol, m-
cresol, p-cresol, 4-ethylphenol, ~,4-xylenol, and the lika.
It is desirable to employ phenolic compounds in combination
with primary alkanols such propanol, butanol, hexanol, or
the like.
Other alcohols which can be employed include benzyl
alcohol, cyclohexenol, and their ring-alkylated analogs.
When mixtures of two or more alcohols and/or phenols
are employed in forming the phosphorodithioic acid, the
resultant product will normally comprise a mixture of three
or more different dihydrocarbyl phosphorodithioic acids,
usually in the form of a statistical distribution in rela-
tion to the number and proportions of alcohols and/or phe-
Case EI-6311
~ - 13 - 2~
nols used.
Illustrative diols which can be used in forming the
phosphorodithioic acids include 2,4-pentanediol, 2,4-hex-
anediol, 3,5-heptanediol, 7-methyl-2,4-octanediol, neopentyl
glycol, 2-butyl-1,3-propanediol, 2,2-diethyl-1,3-propanedi-
ol, and the like. The preparation of the metal salts of
the dihydrocarbyl dithiophosphoric acids or the cyclic hy-
drocarbyl dithiophosphoric acids is usually effected by re-
acting the acid product with a suitable metal compound such
as a metal carbonate, metal hydroxide, metal alkoxide, metal
oxide, or other appropriate metal salt. Simply mixing and
heating such reactants is normally sufficient to cause the
reaction to occur and the resulting product is usually of
sufficient purity for use in the practice of this invention.
Typically, the salts are formed in the presence of a diluent
such as an alcohol, water or a light mineral oil. Neutral
salts are prepared by reacting one equivalent of metal oxide
or hydroxide with one equivalent of the acid. Basic metal
salts are prepared by adding an excess (i.e., more than one
equivalent) of the metal oxide or hydroxide with one equiva-
lent of the dihydrocarbyl phosphorodithioic acid or cyclic
hydrocarbyl phosphorodithioic acid.
Illustrative metal compounds which may be used in such
reactions include calcium oxide, calcium hydroxide, silver
oxide, silver carbonate, magnesium oxide, magnesium hydrox-
ide, magnesium carbonate, magnesium ethoxide, zinc oxide,
zinc hydroxide, strontium oxide, strontium hydroxide, cad-
mium oxide, cadmium hydroxide, cadmium carbonate, barium
oxide, aluminum oxide, aluminum propoxide, iron carbonate,
copper hydroxide, lead oxide, tin butoxide, cobalt oxide,
nickel hydroxide, manganese oxide, and the like.
In some cases, incorporation of certain ingredients
such as small amounts of metal acetate or acetic acid in
conjunction with the metal reactant will facilitate the
r~action and provide an improved product. For example, use
of up to 5~ of zinc acetate in combination with the required
amount of zinc oxide tends to facilitate the formation of
zinc dihydrocarbyl dithiophosphates.
case EI-6311
- 14 - 2 a ~
Examples of useful metal salts of dihydrocarbyl dithio-
phosphoric acids, and methods for preparing such salts are
found in the prior art such as for example, U.S. Pat. Nos.
4,263,150; 4,289,635; 4,308,154; 4,322,479; 4,417,990; and
4,466,895.
Generally speaking, the preferred types of metal salts
of dihydrocarbyl dithiophosphoric acids are the oil-soluble
metal salts of dialkyl dithiophosphoric acids. Such com-
pounds generally contain alkyl groups having at least three
carbon atoms, and preferably the alkyl groups contain up to
10 carbon atoms although as noted above, even higher mole-
cular weight alkyl groups are entirely feasible. A few il-
lustrative zinc dialkyl dithiophosphates include zinc diiso-
propyl dithiophosphate, zinc dibutyl dithiophosphate, zinc
diisobutyl dithiophosphate, zinc di-sec-butyl dithiophos-
phate, the zinc dipentyl dithiophosphates, the zinc dihexyl
dithiophGsphates, th~ zinc diheptyl dithiophosphates, the
zinc dioctyl dithiophosphates, the zinc dinonyl dithiophos-
phates, the zinc didecyl dithiophosphates, and the higher
homologs thereof. Mixtures of two or more such metal com-
pounds are often preferred for use such as metal salts of
dithiophosphoric acids formed from mixtures of isopropyl
alcohol and secondary butyl alcohol; isopropyl alcohol, iso-
butyl alcohol, and 2-ethylhexyl alcohol; isopropyl alcohol,
butyl alcohol, and pentyl alcohol; isobutyl alcohol and oc-
tyl alcohol; and the like. If desired, the metal dihydro-
carbyl dithiophosphate additives of the type described above
may be treated with an epoxide to form an adduct. In gener-
al, the most suitable metal dihydrocarbyl dithiophosphates
use~ul in forming such adducts are the zinc dihydrocarbyl
dithiophosphates. The epoxides comprise alkylene oxides and
arylalkylene oxides. Typical alkylene oxides which may be
used include alkylene oxides having up to 8 carbon atoms in
the molecule, such as ethylene oxide, propylene oxide, 1,2-
butene oxide, trimethylene oxide, tetramethylene oxide, bu-
tadiene monoepoxide, 1,2-hexene oxide, epichlorohydrin, and
the like. The arylalkylene oxides are exemplified by sty-
rene oxide. Other suitable epoxides include, for example,
Case EI-6311
- 15 - 2 a ~
butyl 9,10-epoxystearate, epoxidized soybean oil, epoxidized
tung oil, and epoxidized styrene-butadiene copolymer.
Procedures for preparing epoxide adducts are known and are
reported, for example, in U. S. Pat. No. 3,390,082.
The adduct may be obtained by simply mixing the metal
phosphorodithioate and the epoxide. The reaction is usually
exothermic and may be carri~d out within wide temperature
limits from 0C to 300C. Because the reaction is exother-
mic, it is best carried out by adding one reactant, usually
the epoxide, in small increments to the other reactant in
order to obtain convenient control of the temperature of the
reaction. The reaction may be carried out in a solvent such
as benzene, mineral oil, naphtha, or n-hexene.
The chemical structure of the adduct is not known. Th~
adducts obtained by the reaction of one mole of the phos-
phorodithioate with from 0.25 mole to 5 moles, usually up to
0.75 mole or 0.5 mole of a lower alkylene oxide, particular-
ly ethylene oxide and propylene oxide, are the preferred ad-
ducts.
Another type of metal dihydrocarbyl phosphorodithioate
additives contemplated as useful as component a) in the com-
positions of this invention comprises mixed-acid metal salts
of a combination of (a) at least one phosphorodithioic acid
of the formula (RO)(R'O)PSSH, as exemplified above (R and R'
being, independently, hydrocarbyl groups (or taken together,
a single hydrocarbyl group ~orming a cyclic moiety with the
two oxygen atoms and the phosphorus atom) of sufficient car-
bon content to render the salt soluble in lubricating oil),
and (b) at least one aliphatic or alicyclic carboxylic acid.
The carboxylic acid may be a monocarboxylic or polycarboxy-
lic acid, usually containing from 1 to 3 carboxy groups and
preferably only one. It may contain from 2 to 40, prefer-
ably from 2 to 20 carbon atoms, and advantageously 5 to 20
carbon atoms. The preferred carboxylic acids are those hav-
ing the formula R3CooH~ wherein R3 is an aliphatic or alicy-
clic hydrocarbon-based radical preferably free from acety-
lenic unsaturation. Suitable acids include the butanoic,
pentanoic, hexanoic, octanoic, nonanoic, decanoic, dodecano-
case EI-6311
- 16 - 2~
ic, octadecanoic and eicosanoic acids, as well as olef inic
acids such as oleic, linoleic, and linolenic acids and lino-
leic acid dimer. For the most part, R3 is a saturated ali-
phatic group and especially a branched alkyl group such as
the isopropyl or 3-heptyl group. Illustrative polycarbox-
ylic acids are succinic, alkyl- and alkenylsuccinic, adipic,
sebacic and citric acids.
The mixed-acid metal salts may be prepared by merely
blending a metal salt of a phosphorodithioic acid with a
metal salt of a carboxylic acid in the desired ratio. The
ratio of equivalents of phosphorodithioic to carboxylic acid
salts is between 0.5:1 and 200:1. Advantageously, the ratio
can be from 0.5:1 to 100:1, preferably from 0.5:1 to 50:1,
and more preferably from 0.5:1 to 20:1. Further, the ratio
15 can be from 0.5:1 to 4.5:1, preferably 2.5:1 to 4.25:1. For
this purpose, the equivalent weight of a phosphorodithioic
acid is its molecular weight divided by the number of -PSSH
groups therein, and that of a carboxylic acid is its molecu-
lar weight divided by the number of carboxy groups therein.
A second and preferred method for preparing the mixed-
acid metal salts useful in this invention is to prepare a
mixture of the acids in the desired ratio and to react the
acid mixture with a suitable metal base. When this method
of preparation is used, it is frequently possible to prepare
a salt containing an excess of metal with respect to the
number of equivalents of acid present; thus, mixed-acid
metal salts containing as many as two equivalents and
especially up to 1.5 equivalents of metal per e~uivalent of
acid may be prepared. The equivalent of a metal for this
purpose is its atomic weight divided by its valence.
Variants of the above-described methods may also be
used to prepare the mixed-acid metal salts useful in this
invention. For example, a metal salt of either acid may be
blended with an acid of the other, and the resulting blend
reacted with additional metal base.
Suitable metal bases for the preparation of the mixed-
acid metal salts include the oxides, hydroxides, alkoxides
and other basic salts of the metals previously enumerated,
Case EI-6311 - 17 - 2 ~ 4 ~
and in some cases the free metals themselves. Examples are
sodium hydroxide, potassium hydroxide, magnesium oxide, cal-
cium hydroxide, zinc oxide, lead oxide, nickel oxide and the
like.
The temperature at which the mixed-acid metal salts are
prepared is generally between 30C and 150C, preferably up
to 125C. If the mixed-acid salts are prepared by neutral-
ization of a mixture of acids with a metal base, it is pre-
ferred to employ temperatures above 50C and especially
above 75C. It is frequently advantageous to conduct the
reaction in the presence of a substantially inert, normally
liquid organic diluent such as naphtha, benzene, xylene,
mineral oil and the like. If the diluent is mineral oil, it
frequently need not be removed before using the mixed-acid
metal salt as an additive for lubricants or functional
fluids.
U. S. Patents 4,308,154 and 4,417,970 describe proce-
dures for preparing these mixed-acid metal salts and dis-
close a number of examples of such mixed salts.
Tvpe 2 - Metal hydrocarbyl dithiocarbamates. The se-
cond type of oil-soluble metal salts used as component a) in
the compositions of this invention are salts of one or more
dithiocarbamic acids of the formula RR'N-CSSH wherein R and
R' are each independently hydrocarbyl groups in which the
total number of carbon atoms in R and R' is sufficient to
render the metal salt oil-soluble. R and R' taken together
may represent a polymethylene or alkyl substituted poly-
methylene group thereby forming a cyclic compound with the
nitrogen atom (i.e., a monocyclic hydrocarbyl dithiocarbam-
ate). Gener~lly the hydrocarbyl groups will each contain at
least two carbon atoms and may contain 50 or more carbon
atoms. The metal component present in the dihydrocarbyl ~or
monocyclic hydrocarbyl) dithiocarbamate salts may be a mono-
valent metal or a polyvalent metal, although polyvalent
3S metals are preferred as the salts of the polyvalent metals
tend to possess better solubility in oils of lubricating
viscosity. Thus although the alkali metal monocyclic hydro-
carbyl or dihydrocarbyl dithiocarbamates may be used if oil-
Case EI-6311
~ - 18 -
soluble, the preferred salts include, for example, salts of
one or more of the alkaline earth metals, zinc, cadmi~m,
magnesium, tin, molybdenum, iron, copper, nickel, cobalt,
chromium, lead, etc. The Group II metal dihydrocarbyl
dithiocarbamates are preferred.
In selecting a metal salt of a dithiocarbamic acid to
be used in the compositions of this invention, R, R', and
the metal may be varied so long as the metal salt is ade-
quately oil-soluble. The nature and type of the mineral
base stock, and the type of service contemplated for the
treated lubricating oil should be taken into consideration
in the choice of metal salt.
The metal constituent of the metal dihydrocarbyl
dithiocarbamate is usually a simple metal cation. However
in the case o~ certain polyvalent metal derivatives such as
the tin and lead compounds, the metal constituent itself may
be hydrocarbyl substituted (e.g., (RRIN-CSS-~XMR1R2, where M
is a polyvalent metal, R, R', Rl and R2 are, independently,
hydrocarbyl groups (and, optionally ~ and R' taken together
are a single cyclic hydrocarbyl group) in which the total
number of carbon atoms is sufficient to render the compound
oil-soluble, and x is an integer sufficient to satisfy the
remaining valence(s) of M. Techniques described for example
in U.S. Pat. No. 2,786,814 may be employed for preparing
such hydrocarbyl-substituted metal dithiocarbamates.
Mixtures of metal salts of dithiocarbamic acids also
are contemplated as being useful in the present invention.
Such mixtures can be prepared by first preparing mixtures of
dithiocarbamic acids and thereafter converting said acid
mixtures to metal salts, or alternatively, metal salts of
various dithiocarbamic acids can be prepared and thereafter
mixed to give the desired product. Thus, the mixtures which
can be incorporated in the compositions of the invention may
be merely the physical mixture o* the different metallic di-
thiocarbamic compounds, or compounds having different di-
thiocarbamate groupings attached to the same polyvalent
metal atoms.
Examples of alkyl groups are ethyl, propyl, butyl,
Case EI 6311
- 19
amyl, hexyl, heptyl, octyl, decyl, dodecyl, tridec-yl,
pentadecyl and hexadecyl groups including isomeric forms
thereof. Examples of cycloalkyl groups include cyclohexyl
and cycloheptyl groups, and examples of aralkyl groups
include benzyl and phenethyl. Examples of polymethylene
groups include penta- and hexamethylene groups, and examples
of alkyl-substituted polymethylene groups include methyl
pentamethylene, dimethyl pentamethylene, etc.
Speci~ic examples of the metal dithiocarbamates useful
lo as component a) in the compositions of this invention in-
clude zinc dibutyldithiocarbamate, zinc diamyldithiocarbam-
ate, zinc di(2-ethylhexyl)dithiocarbamate, cadmium dibutyl-
dithiocarbamate, cadmium dioctyldithiocarbamate, cadmium oc-
tylbutyldithiocarbamate, magnesium dibutyldithiocarbamate,
magnesium dioctyldithiocarbamate, cadmium dicetyldithiocar-
bamate, copper diamyldithiocarbamate, sodium dioctadecyl
dithiocarbamate, lead dioctyldithiocarbamate, nickel di-
heptyldithiocarbamate, calcium di-2-ethylhexyldithiocar
bamate, etc.
The various metal salts of dithiocarbamic acids uti-
lized in the compositions of this invention are well known
in the art and can be prepared by known techniques. See for
example Ullmann, Encyklo~die der technischen Chemie, Band
10, Verlag Chemie, Weinheim, copyright 1975, pages 167-170
(and references cited therein); Thorn and Ludwig, The
Dithiocarbamates and Related Compounds, Elsevier Publishin~
Company, 1962, pages 12 to 37 (and references cited there-
in); Delepine, ComPt. Rend., 144, 1125 (1907); Whitby et al,
Proceedinqs and Transactions of The Royal Society of Canada,
XVIII, 111-114 (1924~ (a~d references cited therein),
Chabrier et al, Bulletin de la Societe Chimique De France,
1950, pages 43 et seq. (and references cited therein), and
U. S. Pat. Nos. 1,622,534; 1,921,091; 2,046,875; 2,046,876;
2,258,847; 2,406,960; 2,~43,160; 2,450,633; 2,492,314;
2,580,274; 3,513,094; 3,630,897; 4,178,258; and 4,226,733.
While boron is not a metallic element, boron tris(dihy-
drocarbyl dithiocarbamates) can be used as compone~t a) of
the compositions of this invention, either individually or
-
case EI-6311
- 20 -
2 ~
in combination with one or more metal dihydrocarbyl dithio-
carbamates. Methods suitable for the production of such
boron dithiocarbamates are set forth in U.S. Pat. No.
4,879,071.
Derivatives of metal dihydrocarhyl dithiocarbamates may
be used in addition to or in lieu of the metal dihydrocarbyl
dithiocarbamates. Such derivatives include dithiocarbamate-
derived phosphates such as are described in U.S. Pat. No.
4,919,830, reaction products of N,N-diorganodithiocarbamates
with thionyl chloride such as are described in U.S. Pat. No.
4,867,893,N,N-diorganodithiocarbamate-alkylthiosulfinylha-
lide reaction products such as are described in U.S. Pat.
No. 4,859,356, reaction products of halogenated EPDM ter-
polymers and alkali metal dialkyldithiocarbamate such as are
described in U.S. Pat. No. 4,502,972, and sulfurized metal
dihydrocarbyl dithiocarbamates such as are described in U.S.
Pat. No. 4,360,438, among others. In addition, the metal
dihydrocarbyl dithiocarbamates may be used in combination
with other carbamate compounds such as for example, a 1,2-
dicarbethoxyethyl dialkyldithiocarbamate such as is dis-
closed in U.S. Pat. No. 4,479,883; or a mercaptoalkanoic
acid dithiocarbamate of the type described in U.S. Pat. No.
3,890,363. ~ixtures of different metal dihydrocarbyl di-
thiocarbamates as well as combinations of (1) one or more
metal dihydrocarbyl dithiophosphates and (2) one or more
metal dihydrocarbyl dithiocarbamates can be used as compo-
nent a) in the practice of this invention.
Comp~nent b)
The other indispensable additive ingredient of the
compositions of this invention is comprised of one or more
oil-soluble additive compositions formed by heating (i) at
least one boron-free oil-soluble ashless dispersant con-
taining basic nitrogen and/or at least one hydroxyl group,
with (ii) at least one inorganic phosphorus acid such that
a liquid boron-free phosphorus-containing composition is
formed.
The ashless dispersant which is used in the process is
preferably a preformed ashless dispersant containing basic
Case EI-6311
- 21 - 2~
nitrogen and/or at least one hydroxyl group. Thus, for
example, any suitable horon-free ashless dispersant formed
in the customary manner can be heated with one or more
inorganic phosphorus acids to cause phosphorylation to
occur. The resulting liquid product composition when sub-
jected to chemical analysis reveals the presence of phos-
phorus.
Rather than utilizing a preformed ashless dispersant
containing basic nitrogen and/or at least one hydroxyl
10 group, it is possible to produce component b) by: -
1) forming the ashless dispersant in the presence of one
or more suitable inorganic phosphorus acids; or
2) heating one or more inorganic phosphorus acids with a
basic nitroyen-containing and/or hydroxyl group-con-
taining reactant used in forming the ashless disper-
sant, and using the resultant phosphorylated reactant
to form the ashless dispersant.
In all such cases, the final product composition [component
b)] should be a liquid that on analysis reveals the presence
of phosphorus. Such product composition should also exhibit
dispersant properties. In any case wherein an ashless dis-
persant used in forming component b) is not a liquid but ra-
ther is in whole or in part in the solid state of aggrega-
tion at room temperature (e.g., 25c), it is preferable to
dissolve such dispersant in a suitable solvent or diluent
(polar or non-polar, as may be required to dissolve the dis-
persant) before the dispersant is subjected to phosphoryla-
tion in forming component b). In this connection, the
phrase "such that a liquid boron-free phosphorus-containing
composition is formed" as used herein in connection with
such solid state dispersants means that compon~nt b), in-
cluding such solvent or diluent, is in the liquid state of
aggregation at room temperature ~e.g., 25C), even though at
a lower temperature the dispersant may revert in whole or in
part to the solid state. Of course in any case, component
b) must be oil-soluble within the meaning of such term as
set forth hereinafter.
Irrespective of the method used in forming component
case EI-6311
- - 22 - 2~
b), in any instance wherein macro (i.e., non-dispersible)
solids are formed or remain in the liquid composition after
it has been formed, such solids should be removed, and can
be readily removed, by any of a variety of conventional
separation techniques such as filtration, centrifugation,
decantation, or the like.
The actual chemical structures of the final product
compositions used as component b) in the practice of this
invention, however prepared, are not known with absolute
certainty. While it is believed that phosphorus-containing
moieties are chemically bonded to the ashless dispersant, it
is possible that component b) is in whole or in part a mi-
cellar structure containing phosphorus-containing species or
moieties. Thus, this invention is not limited to, and
should not be construed as being limited to, any specific
strùctural configurations with respect to component b). As
noted above, all that is required is that component b) is a
liquid that is oil soluble and that if subjected to analysis
reveals the presence of phosphorus. In addition, component
b) should possess dispersant properties.
Although any of a variety of standard methods can be
used to analyze the phosphorylated dispersant for the pre-
sence of phosphorus therein, it is desirable to use the ana-
lytical procedure set forth in ASTM D-4951. In this proce-
dure it is convenient to use a Perkin-Elmer Plasma 40 Emis-
sion Spectrometer. The analyzing wavelength for acceptable
measurements for phosphorus is 213.618 nm.
It is to be understood and appreciated that component
b) may contain chemical species and/or moieties besides the
phosphorus-containing species or moieties such as, for
example, nitrogen- and/or oxygen- and/or sulfur-containing
species or moieties over and above the basic nitrogen and/or
hydroxyl group(s) forming an essential part of the initial
ashless dispersant itself. The only qualification to the
foregoing is that component b) is itself boron-free. It is
also to be understood and appreciated that organic phos-
phorus-containing compounds may be used along with inorganic
phosphorus acids in making component b). Further, the inor-
case EI-6311
- 23 - 2~
ganic phosphorus acid or acids can be formed in situ, as,
for example, by heating a mixture of an inorganic phosphorus
oxide and water to form a phosphorus acid.
As used herein, the term "phosphorylated" means that
the ashless dispersant has been heated with one or more
inorganic phosphorus acids such that the resultant product,
on analysis, reveals the presence of phosphorus. As noted
hereinabove, the precise chemical makeup of the phosphory-
lated dispersant compositions is not known with absolute
certainty. Thus the term "phosphorylated" is not to be
construed as requiring that the resultant composition con-
tain chemically bound phosphorus. While it is believed that
chemical reactions do occur to produce a composition con-
taining at least some chemically bound phosphorus moieties,
moieties or species of phosphorus conceiYably could be pre-
sent, at least in part, in the form of micellar structures.
Any of a variety of ashless dispersants can be utilized
in forming component b) of the compositions of this inven-
tion. These include the following types:
TyPe A - Carboxylic ~shless DisPersants. These are re-
action products of an acylating agent such as a monocarboxy-
lic acid, dicarboxylic acid, polycarboxylic acid, or deriva-
tives thereof which contain amine groups and/or hydroxyl
groups (and optionally, other groups). These products,
herein referred to as carboxylic ashless dispersants, ar~
described in many patents, including British patent speci-
fication No. 1,306,529 and the following U. S. Patents:
3,163,603; 3,184,474; 3,215,707; 3,219,666; 3,~71,310;
3,272,746; 3,281,357; 3,306,908; 3,311,558; 3,316,177;
3,340,281; 3,341,542; 3,346,493; 3,381,022; 3,399,141;
3,415,750; 3,433,744; 3,444,170; 3,448,048; 3,448,049;
3,451,933; 3,454,607; 3,467,668; 3,522,179; 3,541,012;
3,542,678; 3,574,101; 3,576,743; 3,630,904; 3,632,510;
3,632,511; 3,697,4~8; 3,725,4~1; 3,86~,330; 3,94~,800;
4,234,435; and Re. 26,433.
There are a number of sub-categories of carboxylic ash-
less dispersants. One such sub-category which constitutes
a preferred type for use in the formation of component b) is
.
,
Case EI-6311
- 24 - 20~
composed of the polyamine succinamides and more preferably
the polyamine succinimides in which the succinic group con-
tains a hydrocarbyl substituent containing at least 30 car-
bon atoms. The polyamine used in forming such compounds
contains at least one primary amino group capable of forming
an imide group on reaction with a hydrocarbon-substituted
succinic acid or acid derivative thereof such an anhydride,
lower alkyl ester, acid halide, or acid-ester. Representa-
tive examples of such dispersants are given in U.S. Pat.
Nos. 3,172,892; 3,202,678; 3,216,936; 3,219,666; 3,254,025;
3,272,746; and 4,234,435. The alkenyl succinimides may be
formed by conventional methods such as by heating an alkenyl
succinic anhydride, acid, acid-ester, acid halide, or lower
alkyl ester with a polyamine containing at least one primary
amino group. The alkenyl succinic anhydride may be made
readily by heating a mixtllre of olefin and maleic anhydride
to 180-220C. The olefin is preferably a polymer or co-
polymer of a lower monoolefin such as ethylene, propylene,
1-butene, isobutene and the like. The more preferred source
of alkenyl group is from polyisobutene having a number aver-
age molecular weight of up to 100,000 or higher. In a still
more preferred embodiment the alkenyl group is a polyiso-
butenyl group having a number average molecular weight (de-
termined using the method described in detail hereinafter)
of 500-5,000, and preferably 700-2,500, more preferably 700-
1,400, and especially 800-1,200. The isobutene used in mak-
ing the polyisobutene is usually (but not necessarily) a
mixture of isobutene and other C4 isomers such as l-butene.
Thus, strictly speaking, the acylating agent ~ormed from
maleic anhydride and "polyisobutene" made from such mixtures
of isobutene and other C4 isomers such as 1-butene, can be
termed a 'Ipolybutenyl succinic anhydride" and a succinimide
made therewith can be termed a "polybutenyl succinimide".
However, it is common to refer to such substances as "poly-
isobutenyl succinic anhydride" and "polyisobutenyl succin-
imide", respectively. As used herein "polyisobutenyl" is
used to denote the alkenyl moiety whether made from a highly
pure isobutene or a more impure mixture of isobutene and
~ase EI-6311
- 25 - ~ 9~
other C4 isomers such as 1-butene.
Polyamines which may be employed in forming the ashless
dispersant include any that have at least one primary amino
group which can react to form an imide group. A few repre-
sentative examples include branched-chain alkanes containing
two or more primary amino gxoups such as tetraaminoneopen-
tane, etc.; polyaminoalkanols such as 2-(2-aminoethylamino)-
ethanol and 2-[2-(2-aminoethylamino)-ethylamino]-ethanol;
heterocyclic compounds containing two or more amino groups
at least one of which is a primary amino group such as 1-(B-
aminoethyl)-2-imidazolidone, 2-(2-aminoethylamino)-5-nitro-
pyridine, 3-amino-N-ethylpiperidine, 2-(2-aminoethyl)-pyri-
dine, 5-aminoindole, 3-amino-5-mercapto-1,2,~-triazole, and
4-(aminomethyl)-piperidine; and the alkylene polyamines such
as propylene diamine, dipropylene triamine, di-(1,2-buty-
lene)triamine, N-(2-aminoethyl)-1,3-propanediamine, hexa-
methylenediamine and tetra-(1,2-propylene)pentamine.
The most preferred amines are the ethylene polyamines
which can be depicted by the formula
H2N(CH2CH2NH)nH
wherein n is an integer from one to ten. Th~se include:
ethylene diamine, diethylene triamine, triethylene tetra-
mine, tetraethylene pentamine, pentaethylene hexamine, and
the like, including mixtures thereof in which case n is the
average value of the mixture. These ethylene polyamines
have a primary amine group at each end so can form mono-
alkenylsuccinimides and bis-alkenylsuccinimides. Commer-
cially available ethylene polyamine mixtures usually contain
minor amounts of branched species and cyclic species such as
N-aminoethyl piperazine, N,N'-bis(aminoethyl)piperazine,
N,N'-bis(piperazinyl)ethane, and like compounds. The pre-
ferred commercial mixtures have approximate overall com-
positions falling in the range corresponding to diethylene
triamine to pentaethylene hexamine, mixtures generally cor-
responding in overall makeup to tetraethylene pentamine be-
ing most preferred.
Thus especially preferred ashless dispersants for use
in the present invention are the products of reaction OI a
case EI-6311 2
- - 26 -
polyethylene polyamine, e.g. triethylene tetramine or tetra-
ethylene pentamine, with a hydrocarbon-substituted carboxy-
lic acid or anhydride (or other suitable acid derivative)
made by reaction of a polyolefin, pre~erably polyisobutene,
having a number average molecular weight of 500 to 5,000,
preferably 700 to 2,500, more preferably 700 to 1,400 and
especially 800 to 1,200, with an unsaturated polycarboxylic
acid or anhydride, e.g., maleic anhydride, maleic acid, fu-
maric acid, or the like, including mixtures of two or more
such substances.
As used herein the term "succinimide" is meant to en-
compass the completed reaction product ~rom reaction between
the amine reactant(s) and the hydrocarbon-substituted car-
boxylic acid or anhydride (or like acid derivative) reac-
tant(s), and is intended to encompass compounds wherein the
product may have amide, amidine, and/or salt linkages in
addition to the imide linkage of the type that results from
the reaction of a primary amino group and an anhydride moi-
ety.
Residual unsaturation in the alkenyl group of the alke-
nyl succinimide may be used as a reaction site, if desired.
For example the alkenyl substituent may be hydrogenated to
form an alkyl substituent. Similarly the olefinic bond(s)
~n the alkenyl substituent may be sulfurized, halogenated,
hydrohalo~enated or the like. Ordinarily, there is little
to be gained by use of such techniques, and thus the use of
alkenyl succinimides as the precursor of component b) is
preferred.
Another sub-category of carboxylic ashless dispersants
which can be used in forming component b) includes alkenyl
succinic acid esters and diesters of alcohols containing
1-20 carbon atoms and 1-6 hydroxyl groups. Representative
examples are described in U.S. Pat. Nos. 3,331,776;
3,381,022; and 3,522,179. The alkenyl succinic portion of
these esters corresponds to the alkenyl succinic portion of
the succinimides described above including the same pre-
ferred and most pref~rred subgenus, e.g., alkenyl succinic
acids and anhydrides, etc., where the alkenyl group contains
case EI-6311
` - 27 - 2~9~
at least 30 carbon atoms and notably, polyisobutenyl suc-
cinic acids and anhydrides wherein the polyisobutenyl group
has a number average molecular weight of 500 to 5,000, pre-
ferably 700 to 2,500, more preferably 700 to 1,400, and es-
pecially 800 to 1,200. As in the case of the succinimides,the alkenyl group can be hydrogenated or subjected to other
reactions involving olefinic double bonds.
Alcohols useful in preparing the esters include metha-
nol, ethanol, 2-methylpropanol, octadecanol, eicosanol,
ethylene glycol, diethylene glycol, tetraethylene glycol,
diethylene glycol monoethylether, propylene glycol, tri-
propylene glycol, glycerol, sorbitol, 1,1,1-trimethylol
ethane, 1,1,1-trimethylol propane, l,l,1-trimethylol butane,
pentaerythritol, dipentaerythritol, and the like.
The succinic esters are readily made by merely heating
a mixture of alkenyl succinic acid, anhydride or lower alkyl
(e.g., C1-C~) ester with the alcohol while distilling out
water or lower alkanol. In the case of acid-esters less
alcohol is used. In fact, acid-esters made from alkenyl
succinic anhydrides do not evolve water. In another method
the alkenyl succinic acid or anhydrides can be merely re-
acted with an appropriate alkylene oxide such as ethylene
oxide, propylene oxide, and the like, including mixtures
thereof.
Still another sub-category of carboxylic ashless
dispersants useful in forming component b) comprises an
alkenyl succinic ester-amide mixture. These may ~e made by
heating the above-described alkenyl succinic acids, anhy-
drides or lower alkyl esters or etc. with an alcohol and an
amine either sequentially or in a mixture. The alcohols and
amines described above are also useful in this embodiment.
Alternatively, amino alcohols can be used alone or with the
alcohol and/or amine to form the ester-amide mixtures. The
amino alcohol can contain 1-20 carbon atoms, 1-6 hydroxy
groups and 1-4 amine nitrogen atoms. Examples are ethanol-
amine, diethanolamine, N-ethanol-diethylene triamine, a~d
trimethylol aminomethane.
Here again, the alkenyl group of the succinic ester-
Case EI-6311
- 28 - 2~ 4~
amide can be hydrogenated or subjected to other reactions
involving olefinic double bonds.
Representative examples of suitable ester-amide
mixtures are described in U.S. Pat. Nos. 3,184,474;
3,576,743; 3,632,511; 3,804,763; 3,836,471; 3,862,981;
3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855;
3,991,098; 4,071,548; and 4,173,540.
Yet another sub-category of carboxylic ashless disper-
sants use~ul in forming component b) comprises the Mannich-
based derivatives of hydroxyaryl succinimides. Such com-
pounds can be made by reacting a polyalkenyl succinic anhy-
dride with an aminophenol to produce an N-(hydroxyaryl)
hydrocarbyl succinimide which is then reacted with an
alkylene diamine or polyalkylene polyamine and an aldehyde
(e.g., formaldehyde), in a Mannich-base reaction. Details
of such synthesis are set forth in U.S. Pat. No. 4,354,950.
As in the case of the other carboxylic ashless dispersants
discussed above, the alkenyl succinic anhydride or like
acylating agent is derived from a polyolefin, preferably a
polyisobutene, having a number average molecular weight of
500 to 5,000, preferably 700 to 2,500, more preferably 700
to 1,400, and especially 800 to 1,200. Likewise, residual
unsaturation in the polyalkenyl substituent group can be
used as a reaction site as for example, by hydrogenation,
sulfurization, or the like.
~ ype B - Hydrocarbyl_Polvamine Dispersants. This cate-
gory of ashless dispersants which can be used in forming
component b) is likewise well known to those skilled in the
art and ~ully described in the literature. The hydrocarbyl
polyamine dispersants are generally produced by reacting an
aliphatic or alicyclic halide (or mixture thereof) contain-
ing an average of at least 40 carbon atoms with one or more
amines, preferably polyalkylene polyamines. Examples of
such hydrocarbyl polyamine ashless dispersants are described
in U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555;
3,565,804; 3,671,511; 3,821,302; 3,394,~76; and in European
Patent Publication No. 382,405.
In general, the hydrocarbyl-substituted polyamines are
case EI-6311
2 ~
- 29 -
high molecular weight hydrocarbyl-N-substituted polyamines
containing basic nitrogen in the molecule. The hydrocarbyl
group typically has a number averags molecular weight in the
range of 750-lO,Ooo, more usually in the range of 1,000-
5,000.
The hydrocarbyl radical may be aliphatic or alicyclic
andl except for adventitious amounts of aromatic components
in petroleum mineral oils, will be free of aromatic un-
saturation. The hydrocarbyl groups will normally be
branched chain aliphatic, having 0-2 sites of unsaturation,
and preferably from 0-1 site of ethylene unsaturation. The
hydrocarbyl groups are preferably derived from petroleum
mineral oil, or polyolefins, either homo-polymers or higher-
order polymers, or l-olefins of from 2-6 carbon atoms.
Ethylene is preferably copolymerized with a higher olefin to
insure oil solubility.
Illustrative polymers include polypropylene, polyiso-
butylene, poly-1-butene, etc. The polyolefin yroup will
normally have at least one branch per six carbon atoms along
the chain, preferably at least one branch per four carbon
atoms along the chain. These branched-chain hydrocarbons
are readily prepared by the polymerization of olefins of
from 3-6 carbon atoms and preferably from olefins 5f from 3-
4 carbon atoms.
In preparing the hydrocarbyl polyamine dispersants,
rarely will a single compound having a defined structure be
employed. With both polymers and petroleum-derived hy-
drocarbon groups, the composition is a mixture of materials
having various structures and molecular weights. Therefore,
in referring to molecular weight, number average molecular
weights are intended. Furthermore, when speaking of a par-
ticular hydrocarbon group, it is intended that the group
include the mixture that is normally contained within ma-
terials which are commercially available. For example,
polyisobutylene is known to have a range of molecular
weights and may include small amounts of very high molecular
weight materials.
Particularly preferred hydrocarbyl-substituted amines
Case EI-6311
_ 30 _ 2~9~
or polyamines are prepared from polyisobutenyl chloride.
The polyamine employed to prepare the hydrocarbyl-
substituted polyamine is preferably a polyamine having from
2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms.
The polyamine is reacted with a hydrocarbyl halide (e.g.,
chloride) to produce the hydrocarbyl-substituted polyamine.
The polyamine preferably has a carbon-to-nitrogen ratio of
from 1:1 to 10:1.
The amine portion of the hydrocarbyl-substituted amine
may be substituted with substituents selected from (A) hy-
drogen, and (B) hydrocarbyl groups of from 1 to 10 carbon
atoms.
The polyamine portion of the hydrocarbyl-substituted
polyamine may be substituted with substituents selected from
(A) hydrogen, (B) hydrocarbyl groups of from 1 to 10 carbon
atoms, (C) acyl groups of from 2 to 10 carbon atoms, and (D)
monoketo, monohydroxy; mononitro, monocyano, lower alkyl and
lower alkoxy derivatives of (B) and (C). "Lower" as used in
terms like lower alkyl or lower alkoxy, means a group con-
taining from 1 to 6 carbon atoms.
At least one of the nitrogens in the hydrocarbyl-
substituted amine or polyamine is a basic nitrogen atom,
i.e., one titratable by a strong acid.
Hydrocarbyl, as used in describing the substituents in
the amine or polyamine used in forming the dispersants, de-
notes an organic radical composed of carbon and hydrogen
which may be aliphatic, alicyclic, aromatic or combinations
thereof, e.g., aralkyl. Preferably, the hydrocarbyl group
will be relatively free of aliphatic unsaturation, i.e.,
ethylenic and acetylenic, particularly acetylenic unsatur-
ation. The hydrocarbyl substituted polyamines used in
forming the dispersants are generally, but not necessarily,
N-substituted polyamines. Exemplary hydrocarbyl groups and
substituted hydrocarbyl groups which may be present in the
amine portion of the dispersant include alkyls such as
methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, oc-
tyl, etc., alkenyls such as propenyl, isobutenyl, he~enyl,
octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-hy-
Case EI-6311 - 31 -
droxypropyl, hydroxyisopropyl, 4-hydroxybutyl, etc., ke'co-
alkyls, such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and
lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropyl,
propoxyethyl, propoxypropyl, 2-~2-ethoxyethoxy)ethyl, 2-(2-
(2-ethoxyethoxy)ethoxy)ethyl, 3,6,9,12-tetraoxytetradecyl,
2-(2-ethoxyethoxy)hexyl, etc.
Typical amines useful in preparing the hydrocarbyl-
substituted amines include methylamine, dimethylamine,
ethylamine, diethylamine, n-propylamine, di-n-propylamine,
etc. Such amines are either commercially available or are
prepared by art recognized procedures.
The polyamine component may also contain heterocyclic
polyamines, heterocyclic substituted amines and substituted
heterocyclic compounds, wherein the heterocyclic comprises
one or more 5-6 membered rings containing oxygen and/or
nitrogen. Such heterocyclics may be saturated or unsatur-
ated and substituted with groups selected from the afore-
mentioned (A), (B), (C), and (D~. The heterocyclics are
exemplified by piperazines, such as 2-methylpiperazine, 1,2-
bis(N-piperazinyl-ethane),andN,N'-bis(N-piperazinyl)piper-
azine, 2-methylimidazoline, 3~aminopiperidine, 2-aminopyri-
dine, 2-(~-aminoethyl)-3-pyrroline, 3-aminopyrrolidine, N-
(3-aminopropyl)morpholine, etc. Among the heterocyclic com-
pounds, the piperazines are preferred.
Typical polyamines that can be used to form the hydro-
carbyl polyamine dispersants include the following: ethylene
diamine, 1,2-propylene diamine, 1,3-propylene diamine, di-
ethylene triamine, triethylene tetramine, hexamethylene di-
amine, tetraethylene pentamine, methylaminopropylene dia-
mine, N-(~-aminoethyl)piperazine, N,N'-di(~-aminoethyl)pip-
erazine, N,N'-di(B-aminoethyl)imidazolidone-2, N~ cyano-
ethyl)ethane-1,2-diamine, 1,3,6,9-tetraaminooctadecane,
1,3,6-triamino-9-oxadecane, N-methyl-1,2-propanediamine, 2-
(2-aminoethylamino)ethanol, and the like.
Another group of suitable polyamines are the polyalky-
lene amines in which the al~ylene groups differ in carbon
content, such as for example bis(aminopropyl)ethylenedia-
mine. Such compounds are prepared by the reaction of
Case EI-6311 - 32 ~ 5 9 4 5
acrylonitrile with an ethyleneamlne, for example, an ethyl-
eneamine having the formula H2H(CHzCH2NH)nH wherein n is an
integer from 1 to 5, followed by hydrogenation of the re-
sultant intermediate. Thus, the product prepared from
ethylene diamine and acrylonitrile has the formula
H2N(CH2)3NH(CX2)2NH(C~2)3NH2.
In many instances th~ polyamine used as a reactant in
the productian of the hydrocarbyl-substituted polyamine is
not a single compound but a mixture in which one or sev~ral
compounds predominate with the average composition indicat-
ed. For example, tetraethylene pentamine prepared by the
polymerization of aziridine or the reaction of 1,2-dichlo-
roethane and ammonia will have both lower and higher amine
members, e.g., triethylene tetramine, substituted pipera-
zines and pentaethylene hexamine, but the composition willbe largely tetraethylene pentamine and the empirical formula
of the total amine composition will closely approximate that
of tetraethylene pentamine. Finally, in preparing the hy-
drocarbyl-substituted polyamines for use in this invention,
where the various nitrogen atoms of the polyamin~ are not
geometrically equivalent, several substitutional isomers are
possible and are encompassad with the final product. Meth-
ods of preparation of polyamines and their reactions are
detailed in Sidgewick, The Orqanic Chemistrv of Nitroqen,
Clarendon Press, Oxford, 1966; Noller, Chemistry of Orqanic
Compounds, Saunders Philadelphia, 2nd Ed., 1957; and Kirk~
Othmer, EncYclo~edia of Chemical Technology, 2nd Edition,
especially volume 2, pp. 99-116.
The preferred hydrocarbyl-substituted polyalkylene
polyamines may be represented by the formula
RlNH-(-R2-NH-)a-H
wherein R1 is hydrocarbyl having an average molecular weight
of from 750 to 10,000; R2 is alkylene of from 2 to 6 carbon
atoms; and ~ is an integer of from 0 to 10.
Preferably, R1 ls hydrocarbyl having an average mole-
cular weight of from 1,000 to 10,000. Preferably, R2 is
alkylene of from 2 to 3 carbon atoms and ~ is preferably an
integer of from 1 to 6.
Case EI-6311
_ 33 _ 29~ 4~
Type C - Mannich polYamine disPersants. This category
of ashless dispersant which can be utilized in the formation
of component b) is comprised of reaction products of an al-
kyl phenol, with one or more aliphatic aldehydes containing
from 1 to 7 carbon atoms (especially formaldehyde and deri-
vatives thereof), and polyamines (especially polyalkylene
polyamines of the type described hereinabove). Examples of
these Mannich polyamine dispersants are described in the
following U.S. Patents: 2,459,112; 2,962,442; 2,984,550;
3,036,003; 3,166,516; 3,236,770; 3,368,972; 3,413,347;
3,442,808; 3,448,047; 3,454,497; 3,459,661; 3,493,520;
3,539,633; 3,558,743; 3,586,629; 3,591,5g8; 3,600,372;
3,634,515; 3,649,229; 3,697,574; 3,703,536; 3,704,308;
3,725,277; 3,725,480; 3,726,882; 3,736,357; 3,751,365;
3,756,953; 3,793,202; 3,798,165; 3,798,247; 3,803,039;
3,872,019; 3,980,569; and 4,011,380.
The polyamine group of the Mannich polyamine disper-
sants is derived from polyamine compounds characterized by
containing a group of the structure ~NH- wherein the two
remaining valances of the nit~ogen are satisfied by hydro-
gen, amino, or organic radicals bonded to said nitrogen
atom. These compounds include aliphatic, aromatic, heter-
ocyclic and carbocyclic polyamines. The source of the oil-
soluble hydrocarbyl group in the Mannich polyamine disper-
sant is a hydrocarbyl-substituted hydroxy aromatic compound
comprising the reaction product of a hydroxy aromatic com-
pound, according to well known procedures, with a hydro-
carbyl donating agent or hydrorarbon source. The hydro-
carbyl substituent provides substantial oil solubility to
the hvdroxy aromatic compound and, preferably, is substan-
tially aliphatic in character. Commonly, the hydrocarbyl
substituent is derived from a polyolefin having at least 40
carbon atoms. The hydrocarbon source should be substantial-
ly free from pendant groups which render the hydrocarbyl
group oil insoluble. Examples of acceptable substituent
groups are halide, hydroxy, ether, carboxy, ester, amide,
nitro and cyano. ~owever, these substituent groups prefer-
ably comprise no more than 10 weight percent of the hydro-
Case EI-6311
_ 34 _ 2~
carbon source.
The preferred hydrocarbon sources for preparation of
the Mannich polyamine dispersants are those derived from
substantially saturated petroleum fractions and olefin poly-
mers, preferably polymers of mono-olefins having from 2 to
30 carbon atoms. The hydrocarbon course can be derived, for
example, from polymers of olefins such as ethylene, propene,
1-butene, isobutene, 1-octene, 1-methylcyclohexene, 2-butene
and 3-pentene. Also useful are copolymers of such olefins
with other polymerizable olefinic substances such as sty-
reneO In general, these copolymers should contain at least
80 percent and preferably 95 percent, on a weight basis, of
units derived from the aliphatic mono-olefins to preserve
oil solubility. The hydrocarbon source generally contains
at least 40 and preferably at least 50 carbon atoms to pro-
vide substantial oil solubility to the dispersant. The ole-
fin polymers having a number average molecular weight be-
tween 600 and 5,000 are preferred for reasons of easy reac-
tivity and low cost. However, polymers of higher molecular
weight can also be used. Especially suitable hydrocarbon
sources are isobutylene polymers.
The Mannich polyamine dispersants are generally pre-
pared by reacting a hydrocarbyl-substituted hydroxy aromatic
compound with an aldehyde and a polyamine. Typically, the
substituted hydroxy aromatic compound is contacted with from
0.1 to 10 moles of polyamine and 0.1 to 10 moles of aldehyde
per mole of substituted hydroxy aromatic compound. The re-
actants are mixed and heated to a temperature above ~0C. to
initiate the reaction. Preferably, the reaction is carried
out at a temperature from 100 to 250C. The resulting Man-
nich product has a predominantly benzylamine linkage between
the aromatic compound and the polyamine. The reaction can
be carried out in an inert diluent such as mineral oil, ben-
zene, toluene, naphtha, ligroin, or other inert solvents to
facilitate control of viscosity, temperature and reaction
rate.
Polyamines are preferred for use in preparing the Man-
nich polyamine dispersants, and suitable polyamines include,
.
Case EI-631~
- 35 - 2~
but are not limited to, alkylene diamines and polyalkylene
polyamines (and mixtures thereof) of the formula:
A-7-(-R-N-)n-H
A A
wherein n is an integer from 1 to 10, R is a divalent hydro-
carbyl group of from 1 to 18 carbon atoms, and each A is in-
dependently selected from the group consisting of hydrogen
and monovalent aliphatic groups containing up to 10 carbon
atoms which can be substituted with one or two hydroxyl
groups. Most preferably, R is a lower alkylene group of
from 2 to 6 carbon atoms and A is hydrogen.
Suitable polyamines for use in preparation of the
Mannich polyamine dispersants include, but are not limited
to, methylene polyamines, ethylene polyamines, butylene
polyamines, propylene polyamines, pentylene polyamines,
hexylene polyamines and heptylene polyamines. The higher
homologs of such amines and related aminoalkyl-substituted
piperazines are also included. Specific examples of such
polyamines include ethylene diamine, triethylene tetramine,
tris(2-aminoethyl)amine, propylene diamine, pentamethylene
diamine, hexamethylene diamine, heptamethylene diamine,
octamethylene diamine, decamethylene diamine, di(hepta-
2S methylene) triamine, pentaethylene hexamine, di(trimethyl-
ene) triamine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-
bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)piperazine,
1,4-bis(2-aminoethyl)piperazine and 2-methyl-1-(2-aminobu-
tyl)piperazine. Higher homologs, obtained by condensing two
or more of the above mentioned amines, are also useful, as
are the polyoxyalkylene polyamines.
The polyalkylene polyamines, examples of which are set
forth above, are especially useful in preparing the Mannich
polyamine dispersants for reasons of cost and effectiveness.
Such polyamines are described in detail under the heading
"Diamines and Higher Amines" in Kirk-Othmer, Encyclopedia of
Chemical Technoloqy, Second Edition, Vol. 7, pp. 22-39.
They are prepared most conveniently by the reaction of an
,
Case EI 6311 - 36 - 2 ~ ~ ~ 9 ~ ~
ethylene imine with a ring-opening reagent such as ammonia.
These reactions result in the production of somewhat complex
mixtures of polyalkylene polyamines which include cyclic
condensation products such as piperazines. Because of their
availability, these mixtures are particularly useful in
preparing the Mannich polyamine dispersants. Howaver, it
will be appreciated that satisfactory dispersants can also
be obtained by use of pure polyalkylene polyamines.
Alkylene diamines and polyalkylene polyamines having
one or more hydroxyalkyl substituents on the nitrogen atom
are also useful in preparing the Mannich polyamine disper-
sants. These materials are typically obtained by reaction
of the corresponding polyamine with an epoxide such as
ethylene oxide or propylene oxide. Preferred hydroxyalkyl-
substituted diamines and polyamines are those in which thehydroxyalkyl groups have less than 10 carbon atoms. Exam-
ples of suitable hydroxyalkyl-substituted diamines and
polyamines include, but are not limited to, N-(2-hydroxy-
ethyl)ethylenediamine, N,N'-bis(2-hydroxyethyl)ethylene-
diamine,mono(hydroxypropyl)diethylenetriamine,(di(hydroxy~propyl)tetraethylenepentamine and N-(3-hydroxybutyl)tetra-
methylenediamine. Higher homologs obtained by condensation
of the above mentioned hydroxyalkyl-substituted diamines and
polyamines through amine groups or through ether groups are
also useful.
Any conventional formaldehyde yielding reagent is use-
ful for the preparation of the Mannich polyamine disper-
santsO Examples of such formaldehyde yielding reagents are
trioxane, paraformaldehyde, trioxymethylene, aqueous forma-
lin and gaseous formaldehyde.
Tv~e D - Polymeric polYamine dispersants. Also suit-
able for preparing component b) are polymers containing
basic amine groups and oil solubilizing groups (for example,
pendant alkyl groups having at least 8 carbon atoms)~ Such
polymeric dispersants are herein referred to as polymeric
polyamine dispersants. Such materials include, but are not
limited to, interpolymers of decyl methacrylate, vinyl decyl
ether or a relatively high molecular weight olefin with
case EI-6311
- 37 - 2~3~
aminoalkyl acrylates and aminoalkyl acrylamides. Examples
of polymeric polyamine dispersants are set forth in the
following U.S. patents: 3,316,177; 3,326,804; 3,329,658;
3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849;
5 3,702,300; 4,089,794; 4,632,769.
Type E - Post-treated basic nitroqen-containinq and/or
hydroxYl-containina ashless dis~ersants. As is well known
in the art, any of the ashless dispersants referred to above
as types A-D can be subjected to post-treatment with one or
more suitable reagents such as urea, thiourea, carbon disul-
fide, aldehydes, ketones, carboxylic acids, anhydrides of
low molecular weight dibasic acids, nitriles, epoxides, and
the like. Suoh posk-treated ashless dispersants can be used
in forming component b) of the compositions of this inven-
tion provided that the post-treated dispersant is boron-free
and contains residual basic nitrogen and/or one or more
residual hydroxyl groups. Alternatively, the phosphorylated
dispersant can be subjected to post-treatment with such rea-
gents. Examples of post-treatment procedures and post-
treated ashless dispersants are set forth in the followingU.S. Patents: 3,036,003; 3,200,107; 3,216,936;
3,256,185; 3,278,550; 3,312,619; 3,366,569; 3,367,943;
3,373,111; 3,403,102; 3,442,808; 3,455,831; 3,455,832;
3,493,520; 3,502,677; 3,513,033; 3,573,010; 3,579,450;
3,591,598; 3,600,372; 3,639,242; 3,649,229; 3,64g,659;
3,702,757; and 3,708,522; and 4,971,598.
Mannich-based derivatives of hydroxyaryl succinimides
that have been post-treated with ~5-C9 lactones such as ~-
caprolactone and optionally with other post-treating agents
(except boronating agents) as described for example in U.S.
4,971,711 can also be utilized in forming component b) for
use in this invention, provided that such post-treated
Mannich-based derivatives of hydroxyaryl succinimides con-
tain basic nitrogen, and/or at least one hydroxyl group.
See also U.S. Patents 4,820,432; 4,828,742; 4,866,135;
4,866,139; 4,866,140; 4,866,141; 4,866,142; 4,906,394; and
4,913,830 as regards additional suitable boron-free basic
nitrogen-containing and/or hydroxyl group-containing ashless
Case EI-6311
- - 38 - 2~6~4~
dispersants which may be utilized in forming component b).
One preferred category of post-treated ashless disper-
sants is comprised of basic nitrogen-containing and/or hy-
droxyl group-containing ashless dispersants which have been
heated with a phosphorus compound such that they contain
phosphorus with the proviso that such post-treated products
contain residual basic nitrogen and/or one or more residual
hydroxyl groups. Numerous examples of such dispersants and
methods for their production are described in U.S. Patents
3,184,411; 3,185,645; 3,235,497; 3,265,618; 3,324,032;
3,325,567; 3,403,102; 3,502,677; 3,513,093; 3,511,780;
3,623,985; 3,865,740; 3,950,341; 3,991,056; ~,097,389;
4,234,435; 4,338,205; 4,4~8,849; 4,615,826; 4,648,980;
4,747,971; and 4,873,004. The phosphorus-containing post-
treated ashless dispersants of the prior art type can beconverted into a material suitable for use as component b)
simply by conducting a phosphorylation in the manner de-
scribed herein, whereby additional phosphorus from the inor-
ganic phosphorylating agent of the type used herein is in-
corporated into a prior art type post-treated phosphorus-
containing ashless dispersant.
It is also possible after using the phosphorylation
procedures described herein to post-treat the phosphorylated
ashless dispersant using any prior art-type post-treating
procedure (except borGnation), again provided that the re-
sultant post-treated ashless dispersant is boron-free and
contains at least some residual basic nitrogen and/or at
least some residual hydroxyl substitution.
The ashless dispersant(s) used in forming component b)
can be any mixture containing any two or more ashless dis-
persants containing basic nitrogen and/or at least one hy-
droxyl group.
Because of environmental and conservational concerns it
is desirable to employ ashless dispersants which contain
little, if any, halogen atoms such as chlorine atoms. Thus,
in order to satisfy such concerns, it is desirable (although
in many cases not necessary from a performance standpoint)
to select ashless dispersants (as well as the other compo-
-- , .
Case EI-6311
39 _ 2~
nents used in the compositions of this invention) such that
the total halogen content, if any, of the overall lubricant
or functional fluid composition does not exceed 100 ppm.
Indeed, the lower the better. Likewise, it is preferable in
accordance with this invention, to provide additive concen-
trates which, when dissolved in a halogen-free base oil, at
a concentration of 10% by weight, yield an oleaginous com-
position in which the total halogen content, if any, is 100
ppm or less.
Typical procedures for producing the phosphorylated
ashless dispersants involve heating one or more ashless
dispersants of the types described above with at least one
inorganic phosphorus acid under conditions yielding a liquid
phosphorus-containing composition. Examples of inorganic
phosphorus acids which are useful in forming such products
include phosphGrous acid (H3PO3, sometimes depicted as
H2(HPO3), and sometimes called ortho-phosphorous acid),
phosphoric acid (H3PO4, sometimes called orthophosphoric
acid), hypophosphoric acid (H4P2O6), metaphosphoric acid
20 (HPO3), pyrophosphoric acid (H4Pz07), hypophosphorous acid
(H3PO2, sometimes called phosphinic acid), pyrophosphorous
acid (H4P2Os, sometimes called pyrophosphonic acid),
phosphinous acid (H3PO), tripolyphosphoric acid (HsP301o),
tetrapolyphosphoric acid (H6P4013), trimetaphosphoric acid
25 (H3P309), phosphoramidic acid (H2O3PNH2), phosphoramidous acid
(H4N02P), and the like. Partial or total sulfur analogs such
as phosphorotetrathioic acid (H3PS4), phosphoromonothioic
acid (H3P03S ), phosphorodithioic acid (H3P02S2), phosph~ro-
trithioic acid (H3POS3), can also be used in forming products
suitable for use as component b) in the practice of this in-
vention. The preferred phosphorus reagent is phosphorous
acid, (H3PO3).
The form or composition of the inorganic acid(s) as
charged into the mixture to be heated or being heated may be
altered in situ. For example, the action of heat and/or
water can transform certain inorganic phosphorus compounds
into other inorganic phosphorus compounds or species. ~ny
such in situ transformations that may occur are within the
case EI-6311
- 40 - 2~9~5
purview of this invention provided that the liquid phos-
phorylated ashless dispersant reveals on analysis the pre-
sence therein of phosphorus.
Optionally, additional sources of basic nitrogen can be
included in the inorganic phosphorus compound-ashless dis-
persant mixture so as to provide a molar amount (atomic pro-
portion) of basic nitrogen up to that equal to the molar
amount of basic nitrogen contributed by the ashless disper-
sant. Preferred auxiliary nitrogen compounds are long chain
primary, secondary and tertiary alkyl amines containing from
12 to 24 carbon atoms, including their hydroxyalkyl and
aminoalkyl derivatives. The long chain alkyl group may
optionally contain one or more ether groups. E~amples of
suitable compounds are oleyl amine, N-oleyltrimethylene dia-
mine, N-tallow diethanolamine, N,N-dimethyl oleylamine, and
myristyloxapropyl amine.
Other materials normally used in lubricant additives
which do not interfere with the process may also be added,
for example, a benzotriazole, including lower (C1-C4) alkyl-
substituted benzotriazoles, which function to protect coppersurfaces.
The heating step is conducted at temperatures suffi-
cient to produce a liquid composition which contains phos-
phorus. The heating can be carried out in the absence of a
solvent by heating a mixture Gf the ashless dispersant and
one or more suitable inorganic phosphorus compounds. The
temperatures used will vary somewhat depending upon the na-
ture of the ashless dispersant and the inorganic phosphorus
reagent being utilized. Generally speaking however, the
temperature will usually fall within the range of 4~ to
200~C. The duration of the heating is likewise susceptible
to variation, but ordinarily will fall in the range of l to
3 hours. When conducting the heating in bulk, it is impor-
tant to thoroughly agitate the components to insure intimate
contact therebetween. When utilizing the preferred phospho-
rus reagent (solid phosphorous acid), it is convenient to
apply heat to the mixture until a clear liquid composition
is formed. Alternatively, the phosphorous acid may be uti-
Case EI-6311
- 41 - ~ ~6~
lized in the form of an aqueous solution. Water formed in
the process and any added water is preferably removed from
the heated mixture by vacuum distillation at temperatures of
from 100 to 140C. The heating may be conducted in more
than one stage if desired. Preferably the heating step or
steps will be conducted in a diluent oil or other inert liq-
uid medium such as light mineral oils, and the like.
The amount of inorganic phosphorus acid employed in the
heating process preferably ranges from 0.001 mole to 0.999
mole per mole of basic nitrogen and free hydroxyl in the
mixture being heated, up to one half of which may be contri-
buted by an auxiliary nitrogen compound. It is possible
however to use the inorganic phosphorus acid(s) in excess of
the amount of basic nitrogen and/or hydroxyl groups in the
dispersant being heated.
When used, the amount of diluent usually ranges from 10
to 50% by weight of the mixture being subjected to heating.
Water can be added to the mixture, before and/or during the
heating, if desired.
Usually the phosphorylated dispersants utilized as com-
ponent b) in the compositions of this invention when in
their undiluted state will have on a weight basis a phospho-
rus content of at least 5,000 parts per million (ppm) (pre-
ferably at least 6,000 ppm and more preferably at least
7,000 ppm). ~hen forming component b) in part by use of one
or more organic phosphorus compounds such as one or more or-
ganic phosphates ~e.g., trihydrocarbyl phosphates, dihydro-
carbyl monoacid phosphates, monohydrocarbyl diacid phos-
phates, or mixtures thereof), phosphites (e.g., trihydro-
carbyl phosphites, dihydrocarbyl hydrogen phosphites, hydro-
carbyl diacid phosphites, or mixtures thereof), phosphonates
(e.g., hydrocarbyl phosphonic acids, mono- and/or dihydro-
carbyl esters of phosphonic acids, or mixtures thereof),
phosphonites (e.g., hydrocarbyl phosphinic acids, mono-
and/or dihydrocarbyl esters of phosphinic acids, or mixturesthereof), etc., or the partial or total sulfur analogs
thereof, and in part by use of one or more inorganic phos-
phorus acids, the latter should be used in an amount suffi-
.
case EI-6311
- - 42 -
cient to provide at least 25% (preferably at least 50% and
more preferably at least 75%) of the total content of phos-
phorus in the phosphorylated dispersant.
The preparation of phosphorylated ashless dispersants
suitable for use as component b) in the compositions of this
invention is illustrated by the following examples in which
all parts and percentages are by weight unless otherwise
clearly specified.
EXAMPLE B~l
A mixture is formed from ~60 parts of a polyisobutenyl
succinimide ashless dispersant (derived from polybutene hav-
ing a number average molecular weight of about 950 and a
mixture of a polyethylene polyamines having an average over-
all composition approximating that of tetraethylene penta-
mine), 100 parts of a 100 Solvent Neutral refined mineral
oil diluent, 8 parts of solid phosphorous acid, and 3.5
parts of tolutriazole. The mixture is heated at 110C for
two hours. A vacuum of 40 mm Hg is gradually drawn on the
product to remove traces of water while the temperature is
maintained at 110C. A clear solution or composition is ob-
tained which is soluble in oil and suitable for use as
component b).
EXAMPLE B-2
The procedure of Example B-l is repeated except that
the succinimide ashless dispersant used is derived from
polybutene having a number average molecular weight o~
1,150. The average number of succinic groups per alkenyl
group in the succinimide is approximately 1.2.
EXAMPLE B-3
The procedure of Example B-l is repeated except that
the succinimide ashless dispersant used is derived from
polybutene ha~ing a number average molecular weight of
2,100.
EXAMPLE B-4
The procedure of Example B-l is repeated except that
the succinimide ashless dispersant is replaced by an equal
amount of a boron-free Mannich polyamine dispersant made
from tetraethylene pentamine, polyisobutenyl phenol (made
-
case EI-6311
- 43 -
9 ~ 5
from polyisobutene having a number average molecular weight
of about 1710 and formalin) having a nitrogen content of
1.1%.
EXAMPLE B-5
The procedure of Example B-1 is repeated except that
the succinimide ashless dispersant is replaced by an equal
amount of an ashless dispersant of the pentaerythritol
succinic ester type. EXAMPLE B-6
The procedure of Example B-l is repeated except that
9.6 parts of orthophosphoric acid is used in place of the
phosphorous acid, and the mixture is heated for three hours
at 110C to provide a clear, oil-soluble composition suit-
able for use as component b).
EXAMPLE B-7
The procedure of Example B-l is repeated except that
the phosphorous acid is replaced by 6.4 parts of hypophos-
phorous acid.
EXAMPLE B-8
The procedures of Examples B-l through B-7 are repeated
except that the tolutriazole is omitted from the initial
mixtures subjected to the thermal processes.
EXAMPLE B-9
To 2,500 parts of a polyisobutenyl succinimide (derived
from polyisobutene having a number average molecular weight
of 950 and a mixture of polyethylene polyamines having ~n
overall average composition appro~imating that of tetra-
ethylene pentamine) warmed to 28C are added 54.31 parts of
phosphorous acid, 20.27 parts of tolutriazole and 23.91
parts of water. This mixture is heated at llO~C for 1.5
hours. Then the reflux cond~nser is replaced by a distil-
lation column and water is removed under vacuum for 2.25
hours at 110C to form a homogeneous liquid composition
suitable for use as component b) in the practice of this in-
vention.
EXAMPLE B-lo
A mixture of 7300 parts of a polyisobutenyl succinimide
(derived from polybutene having a number average molecular
weight of about 1,300 and a mixture of polyethylene poly-
Case EI-6311
` - - 44 - 2~
amines having an average overall composition approximating
that of tetraethylene pentamine), and 2500 parts of 100
Solvent Neutral mineral oil is heated to 90-100C. To this
mixture is added 200 parts of phosphorous acid and the re-
sultant mixture is heated at 90-100C for 2 hours. The re-
sultant homogeneous liquid composition is suitable for use
as component b) in the practice of this invention.
EX~MPLE B-11
A mixture of 58,415.5 parts of a polyisobutenyl succin-
imide (derived from polyisobutene having a number averagemolecular weight of 1300 and a mixture of polyethylene poly-
amines having an overall average composition approximating
that of tetraethylene pentamine), and 12,661.6 parts of 100
Solvent Neutral mineral oil is heated to 80C. To this mix-
ture is added lS42.28 parts of phosphorous acid and the re-
sultant mixture is heated at 110C for 2 hours. The resul-
tant homogeneous liquid composition is suitable for use as
component b) in the practice of this invention.
EXAMPLE B-12
The procedure of Example B-ll is repeated using 45,600
parts of the ashless dispersant, 8983.2 parts of the mineral
oil diluent, and 2415.~ parts of the phosphorous acid.
EXAMPLE B-13
A mixture of 14,400 parts of a polyisobutenyl succin-
imide (derived from polyisobutene having a number average
molecular weight of 950 and a mixture of polyethylene poly-
amines having an overall average composition approximating
that of tetraethylene pentamine), and 3121.2 parts of 100
Solvent Neutral mineral oil is heated to 80C. To this
mixture is added 478.8 parts of phosphorous acid and the
resultant mixture is heated at 110C for 2 hours. The
resultant homogsneous liquid composition contains about
1.04% of phosphorus and is suitable for use as component b)
in the practice of this invention.
E~AMPLE B-14
A mixture of 7300 parts of ashless dispersant as used
in Example B-10, 2500 parts of 100 Solvent Neutral mineral
oil, and 200 parts of phosphorous acid is formed at room
case EI-6311 2
- 45 -
temperature and heated to 110C for two hours. The res~l-
tant homogeneous liquid composition is suitable for use as
component b) in the practice of this invention.
EXAMPLE B-15
A mixture of 4680 parts of phosphorylated dispersant
formed as in Example B-14 and 2340 parts of a commercial
boronated succinimide ashless dispersant (HiTEC~ 648 disper-
sant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum
Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.) is formed.
The resultant homogeneous liquid composition is suitable for
use in the practice of this invention. A portion of the
resultant mixture can be heated to 110C for two hours, and
this resultant homogeneous liquid composition is also suit-
able for use as component b) in the practice of this inven-
tion.
EXAMPLE B-16
(a) A mixture of 1,000 parts (0.495 mole) of polyiso-
butene (Nn = 2020; Mw = 6049, both determined using the
methodology of U.S. Pat. No. 4,234,435) and 115 parts (1.17
moles) of maleic anhydride is heated to 110C. This mixture
is heated to 184C in 6 hours during which 85 parts (1.2
moles) of gaseous chlorine is added beneath the surface. At
184-189C, an additional 59 parts (0.83 mole) of chlorine is
added over 4 hours. The reaction mixture is stripped by
heating at 186-190C with nitrogen purged for 26 hours. The
residue is predominately polyisobutenyl succinic anhydride
acylating agent.
(b) A mixture is prepared by the addition of 57 parts
(1.38 equivalents) o~ a commercial mixture of ethylene poly-
amines having the approximate overall composition of tetra-
ethylene pentamine to 1,067 parts of mineral oil and 893
paxts (1.38 equivalents) of substituted succinic acylating
agent prepared as in (a) while maintaining the temperature
at 140-145C. The reaction mixture is then heated to 155C
over a three hour period and stripped by blowing with ni-
trogen. The reaction mixture is filtered to yield the fil-
trate as an oil solution of the desired product composed
predominately of polyisobutenyl succinimides.
case EI-6311
- 46 - 2~9~3
(c) A mixture is formed from 250 parts of the polyiso-
butenyl succinimide product solution formed as in (b), 8
parts of phosphorous acid, and 3.5 parts of tolutriazole.
The mixture is heated at 100C for two hours. A clear solu-
tion or composition is obtained which is soluble in oil andsuitable for use as component b).
EXAMPLE B-17
The procedure of Example B-16 is repeated except that
the tolutriazole is eliminated from the reaction mixture of
10 (c).
EXAMPLE B-18
The procedure of Example B-17 is repeated except that
the phosphorous acid is replaced by 11.1 parts of phosphoro-
monothioic acid (H3PO3S).
EXAMPLE B-l9
(a) A mixture of 1,000 parts (0.495 mole) of polyiso-
butene (Mn = 2020; Mw = 6049, both determined using the
methodology of U.S. Pat. No. ~,234,435) and 115 parts (1.17
moles) of maleic anhydride is heated to 110C. This mixture
is heated to 184C in 6 hours during which 85 parts (1.2
moles) of gaseous chlorine is added beneath the surface. At
184-189C, an additional 59 parts (0.83 mole) of chlorine is
added over 4 hours. The reaction mixture is stripped by
heating at 186-190C with nitrogen purged for 26 hours. The
residue is predominately polyisobutenyl succinic anhydride
acylating agent.
(b) A mixture is prepared by the addition of 18.2
parts (0.433 equivalents) of a commercial mixture of ethy-
lene polyamines having the approximate overall composition
of tetraethylene pentamine to 392 parts of mineral oil and
348 parts (0.52 equivalent) of substituted succinic acylat-
ing agent prepared as in (a) while maintaining the tempera-
ture at 140C. The reaction mixture is then heated to 150C
in 1.8 hours and stripped by blowing with nitrogen. The
reaction mixture is filtered to yield the filtrate as an oil
solution of the desired product composed predominately of
polyisobutenyl succinimides.
(c) A mixture is formed from 250 parts of the polyiso-
,
Case EI-6311
- 47 - 2~
bukenyl succinimide product solution formed as in (b), 8
parts of phosphorous acid, and 3.5 parts of tolutriazole.
The mixture is heated at 100C for two hours. A clear solu-
tion or composition is obtained which is soluble in oil and
suitable for use as component b).
EXAMPLE B-20
The procedure of Example B-19 is repeated except that
the tolutriazole is eliminated from the reaction mixture of
(c) .
EXAMPLE B-21
The procedure of Example B 20 is repeated except that
the phosphorous acid is replaced by 13.7 parts of phosphor-
amidic acid, (HO)2PONH2.
EXAMPLE B-22
(a) A mixture of 1,000 parts (0.495 mole) of polyiso-
butene (Mn = 2020; Mw = 6049, both determined using the
methodology of U.S. Pat. No. 4,234,435) and 115 parts (1.17
moles) of maleic anhydride is heated to 110C. This mixture
is heated to 184C in 6 hours during which 85 parts (1.2
moles) of gaseous chlorine is added beneath the surface. At
184-189C, an additional 59 parts (0.83 mole) of chlorine is
added over 4 hours. The reaction mixture is stripped by
heating at 186-190C with nitrogen purged for 26 hours. The
residue is predominately polyisobutenyl succinic anhydride
2~ acylating agent.
(b) A mixture of 334 parts (0.52 equivalents~ of the
polyisobutene substituted succinic acylating agent prepared
as in (a), 548 parts of mineral oil, 30 parts (0.88 equi-
valent) of pentaerythritol and 8.6 parts (0.0057 equivalent)
of Polyglycol 112-2 demulsifier ~Dow Chemical Company) is
heated at 150C for 2.5 hours. The reaction mixture is then
heated to 210C over a period of 5 hours and then held at
210C for an additional 3.2 hours. The reaction mixture is
cooled to 190C and 8.5 parts (O.2 equivalent) of a commer-
cial mixture of ethylene polyamines having an overall compo-
sition approximating that of tetraethylene penkamine is
added. The reaction mixture is stripped by heating at 205C
with nitrogen blowing for 3 hours, and then filtered to
Case EI-6311 2
- ~8 -
yield the filtrate as an oil solution of the desired ashless
dispersant product.
(c) A mixture is formed from 300 parts of the ashless
dispersant product solution formed as in (b), 8 parts of
phosphorous acid, and 3.5 parts of tolutriazole. The mix-
ture is heated at 100C for two hours. A clear solution or
composition is obtained which is soluble in oil and suitable
for use as component b).
EX~MPLE B-23
The procedure of Example B-22 is repeated except that
the tolutriazole is eliminated from the reaction mixture of
(c) .
EXAMPLE B-24
The procedure of Example B-23 is repeated except that
the phosphorous acid is replaced by 9.6 parts of orthophos-
phoric acid.
EXAMPLE B-25
(a) A mixture of 1,000 parts (0.495 mole) of polyiso~
butene (Mn = 2020; Mw = 6049, both determined using the
methodology of U.S. Pat. No. 4,234,435) and 115 par~s (1.17
moles) of maleic anhydride is heated to 110C. This mixture
is heated to 184C in 6 hours during which 85 parts (1.2
moles) of gaseous chlorine is added beneath the surface. At
184-189DC, an additional 59 parts (0.83 mole) of chlorine is
added over 4 hours. The reaction mixture is stripped by
heating at 186-190C with nitrogen purged for 26 hours. The
residue is predominately polyisobutenyl succinic anhydride
acylating agent.
(b) A mixture of 3225 parts (5.0 equivalents) of the
polyisobutene-substituted succinic acylating agent prepared
as in (a), 289 parts (8.5 equivalents) of pentaerythritol
and 5204 parts of mineral oil is heated at 225-235~C for 5.5
hours. The reaction mixture is filtered at 130~C to yield
an oil solution of the desired ashless disp~rsant product.
(c) A mixture is formed from 300 parts of the ashless
dispersant product solution formed as in (b), 8 parts of
phosphorous acid, and 3.5 parts of tolutriazole. The
Case ~I - 6 311
_ 49 ~ 9 ~ ~
mixture is heated at 100C for two hours. A clear solution
or composition is obtained which is soluble in oil and
suitable for use as component b).
EXAMPLE B-26
The procedure of Example B-25 is repeated except that
the tolutriazole is eliminated from the reaction mixture of
(c) .
EXAMPLE B-27
The procedure of Example B-26 is repeated except that
11 parts of phosphoric acid is used in place of the phos-
phorous acid to provide a clear, oil-soluble composition
suitable for use as component b).
EXAMPLE B-28
The procedure of Example B-27 is repeated except that
10 parts of an equimolar mixture of phosphoric acid and
phosphorous acid is used.
EXAMPLE B-29
(a) A mixture of 1,000 parts (0.495 mole) of polyiso-
butene (Mn = 2020; Mw = 6049, both determined using the
methodology of U.S. Pat. No. 4,234,435) and 115 parts (1.17
moles) of maleic anhydride is heated to 110C. This mixture
is heated to 184C in 6 hours during which 85 parts (1.2
moles) of gaseous chlorine is added beneath the surface. At
184-189C, an additional 59 parts ~0.83 mole) of chlorine is
added over 4 hours. The reaction mixture is stripped by
heating at 186-190C with nitrogen purged for 26 hours. Ths
residu~ is predominately polyisobutenyl succinic anhydride
acylating agent.
(b) A mixture of 322 parts (0.5 equivalent) of the
polyisobutene-substituted succinic acylating agent prepared
as in (a), 68 parts (2.0 equivalents) of pentaerythritol and
508 parts of mineral oil is heated at 204-227C for 5 hours.
The reaction mixture is cooled to 162C and 5.3 parts (0.13
equivalent) of a commercial ethylene polyamine mixture
having an overall composition approximating that of te-
traethylene pentamine is added. The reaction mixture is
heated at 162-163C for 1 hour, then cooled to 130~C and
filtered. The filtrate is an oil solution of the dPsired
case EI-6311 2
- - 50 -
ashless dispersant product.
(c) A mixture is formed from 350 parts of the ashless
dispersant product solution formed as in (b), 8 parts of
phosphorous acid, and 3.5 parts of tolutriazole. The mix-
ture is heated at 100C for two hours. A clear solution orcomposition is obtained which is soluble in oil and suitable
for use as ~omponent b).
EXAMPLE B-30
The procedure of Example B-29 is repeated except that
the tolutriazole is eliminated from the reaction mixture of
(c) .
EX~MPLE B-31
The procedure of Example B-30 is repeated except that
15.8 parts of phosphorotetrathioic acid (H3PS4) is used in
place of the phosphorous acid.
EXAMPLE B-32
(a) A mixture of 510 parts (0.28 mole) of polysobutene
(Mn - 1845; Mw = 5325, both determined using the methodology
of U.S. Pat. No. 4,234,435) and 59 parts (0.59 mole) of
maleic anhydride is heated to 110C. This mixture is heated
to 190C in 7 hours during which 43 parts (0.6 mole) of
gaseous chlorine is added beneath the surface. At 190-
192C, an additional 11 parts (0.16 mole) of chlorine is
added over 3.5 hours. The reaction mixture is stripped by
heating at 190-193C with nitrogen blowin~ for 10 hours.
The residue is predominately polyisobutenyl succinic
anhydride acylating agent.
(b) A mixture of 334 parts (0.52 equivalents) of the
polyisobutene substituted succinic acylating agent prepared
as in (a), 548 parts of mineral oil, 30 parts (0.88 equiva-
lent) of pentaerythritol and 8.6 parts (O.0057 equivalent~
of Polyglycol 112-2 demulsifier (Dow Chemical Company) is
heated at 150C for 2.5 hours. The reaction mixture is then
heated to 210C o-~er a period of 5 hours and then held at
210C for an additional 3.2 hours. The reaction mixture is
cooled to 190C and 8.5 parts (0.2 equivalent) of a commer-
cial mixture of ethylene polyamines having an overall com-
position approximating that of tetraethylene pentamine is
case EI-6311
- - 51 ~
added. The reaction mixture is stripped by heating at 20~C
with nitrogen blowing for 3 hours, and then filtered to
yield the filtrate as an oil solution of the desired ashless
dispersant product.
(c) A mixture is Pormed ~rom 260 parts of the ashless
dispersant product solution formed as in (b), 8 parts of
phosphorous acid, and 3.5 parts of tolutriazole. The mix-
ture is heated at 100C for two hours. A clear solution or
composition is obtained which is soluble in oil and suitable
for use as component b).
EXAMPLE B-33
The procedure of Example B-32 is repeated except that
the tolutriazole is eliminated from the reaction mixture of
(c) .
EXAMPLE B-34
The procedure of Example B-36 is repeated except that
6.4 parts of hypophosphorous acid (H3PO2) is used in place of
the phosphorous acid.
EXAMPLE B-35
(a) A mixture of 510 parts (0.28 mole) of polyisobu-
tene (Mn = 1845; Mw = 5325, both determined using the
methodology of U.S. Pat. No. 4,234,435) and 59 parts (0.59
mole) of maleic anhydride is heated to 110C. This mixture
is heated to 190C in 7 hours during which 43 parts (0.6
mole) of gaseous chlorine is added beneath the surface. At
190-192C, an additional 11 parts (0.16 mole) of chlorine is
added over 3.5 hours. The reaction mixture is stripped by
heating at 190-193C with nitrogen blowing for 10 hours.
The residue is predominately polyisobutenyl succinic anhy-
dride acylating agent.
~ b) A mixture is prepared by the addition of 10.2
parts (0.25 equivalent) of a commercial mixture of ethylene
polyamines having the approximate overall composition of
tetraethylene pentamine. ~o 113 parts of mineral oil and 161
parts (0.25 equivalent) of the substituted succinic acyla-
ting agent prepared as in (a) while maintaining the tem-
perature at 138C. The reaction mixture is heated to 150C
over a 2 hour period and stripped by blowing with nitrogen.
Case ~I~6311
- 52 - 2~
The reaction mixture is filtered to yield th~ filtrate as an
oil solution o~ the desired ashless dispersant product.
(c) A mixture is formed from 125 parts of the polyiso-
butenyl succinimide product solution formed as in (b), 8
parts of phosphorous acid, and 3.5 parts of tolutriazole.
The mixture is heated at 100C. to form a composition which
is soluble in oil and suitable for use as component b).
EXAMPLE B-36
The procedure of E~ample B-35 is repeated except that
the tolutriazole is eliminated from the reaction mixture of
(c) .
EXAMPLE B-37
The procedure of Example B-36 is repeated except that
9.6 parts of orthophosphoric acid is used instead of the
phosphorous acid.
EXAMPLE B-38
To a reactor are charged under a nitrogen atmosphere
67.98 parts of a commercially-available polyisobutenyl suc-
cinimide of a mixture of polyethylene polyamines having the
approximate overall composition of tetraethylene pentamine
(the polyisobutenyl group derived from polyisobutene having
a number average molecular weight of about 950; the suc-
cinimide product having a ratio of about 1.15 su~.cinic
groups per alkenyl group) and 26.14 parts of a 100 Solvent
Neutral refined mineral oil. After raising the temperature
of the resulting solution to 100-105C, 2.09 parts of phos-
phorous acid are introduced into the reactor, followed by
0.92 part of tolutriazole (Cobratec TT-100; PMC Specialties
Group, Cincinnati, Ohio). The resultant mixture is heated
at 100-105C for two hours. Then the temperature is gra-
dually raised to 115C with the application of a vacuum to
40 mm Hg. Stripping is continued for 90 minutes and until
120C/40 mm Hg has been reached. A flow of dry nitrogen is
then applied to the system and the product mixture is
allowed to cool. The product mixture is suitable for use as
component b) in the compositions of this invention.
Case EI 6311
_ 53 _ ~ ~6
EXAMPLE B-39
The procedure of Example B-38 is repeated except that
the tolutriazole is omitted from the reaction mixture.
EXAMPLE B-40
The procedure of Example B-13 is repeated except that
763.2 parts of phosphorous acid (H3P03) and 2,836.8 parts of
100 Solvent Neutral mineral oil are used. The phosphorus
content of the final product i5 about 1.66%.
EXAMPLE B-41
(a) A mixture of 322 parts of the polyisobutene-
substituted succinic acylating agent prepared as in Example
B-35(a), 68 parts of pentaerythritol and 508 parts of
mineral oil is heated at 204-227C for 5 hours. The
reaction mixture is cooled to 162C and 5.3 parts of a
commercial ethylene polyamine mixture having the approximate
overall composition corresponding to tetraethylene pentamine
is added. The reaction mixture is heated at 162-163C for
1 hour, then cooled to 130C and filtered. The filtrate is
an oil solution of the desired product.
(b) A mixture is formed from 275 parts of the product
solution formed as in (a), 8 parts of phosphorous acid, and
3.5 parts of tolutriazole. The mixture is heated at 100C
for two hours. A clear solution or composition is obtained
which is soluble in oil and suitable for use as component
b).
EXAMPLE B-42
The procedures of Examples B-l through B-5 and B-9
through B-14 are repeated except that in each case the phos-
phorylating agent consists of a chemically equivalent amount
of a mixture consisting of an equimolar mixture of phospho-
rous acid and dibutyl hydrogen phosphite.
EXAMPLE B-43
(a) To 120 part~ of chlorinated polyisobutylene having
a number average molecular weight of about 1,300 and
containing about 2.8 weight percent chlorine are added 21.7
parts of pentaethylene hexamine and 5.6 parts of sodium
carbonate. The reaction mixture is heated to about 205C
and maintained at this temperature for about 5 hours. A
case ~I-6311
~ 54 ~ 2~6~
stream of nitrogen is passed through the reaction mixture to
remove the water of reaction. The reaction mixture is
diluted with 60 parts of light mineral oil and hexane,
filtered and extracted with methanol to remove excess
pentaethylene hexamine. The hexane is stripped from the
product by heating the mixture to 120C under a suitable
vacuum. The product should have a nitrogen content of
approximately 1.0 to 1.5 weight percent.
(b) A mixture is formed from 80 parts of a diluted re-
10 action product formed as in (a), 20 parts of a 100 Solvent
Neutral refined mineral oil diluent, and 2.1 parts of phos-
phorous acid. The resultant mixture is heated at 100-105C
for 2 hours and then the temperature is gradually raised to
115C with the application of a vacuum to 40 mm Hg. Stri-
15 pping is continued for 90 minutes and until 120C/40 mm Hg
has been reached. A flow of dry nitrogen is then applied to
the system and the product mixture is allowed to cool. The
product mixture is suitable for use as component b) in the
compositions of this invention.
EXAMPL,E B-44
(a) Into a reactor are placed 220 parts of p-nonyl-
phenol and 465 parts of diethylenetriamine. The mixture is
heated to 80C and 152 parts of 37~ formalin is added drop-
wise over a period of about 30 minutes. The mixture is then
heated to 125C for several hours until the evolution of
water has ceased. The resultant product should contain
approximately 16-20% nitrogen.
(b) Into a reactor are placed 202 parts of styrene-
maleic anhydride resin (having a number average molecular
weight in the range of 600-700 and a mole ratio of styrene
to maleic anhydride of 1:1), 202.5 parts of octadecyl amine
and 472 parts of a 95 VI lubricating oil having a viscosity
at 37.8C (100F) of 150 SUS. The mixture is heated to
225C for several hours. To this mixture is added dropwise
over a period of about 30 minutes, 85 parts of the product
formed as in (a). The resulting mixture is heated for 6
hours at 210-230C while collecting the water formed during
reaction. The polymeric product so formed should have a
case ~I-6311
- 55 ~ 2~9~a
nitrogen content of about 2.1 weight percent.
(c) To a reactor are charged 200 parts of the basic
nitrogen polymer produced as in (b) and 50 parts of a 100
Solvent Neutral refined mineral oil. ~fter raising the
temperature of the resulting mixture to 100-105C, 4.0 parts
of phosphorous acid is added. The resultant mixture is
heated at 100-105C for two hours and then the temperature
is gradually raised to 115C with the application of a
vacuum to 40 mm Hg. Stripping is continued for 90 minutes
and until 120C/40 mm Hg has been reached. A flow of dry
nitrogen is then applied to the system and the product
mixture is allowed to cool. The product mixture is suitable
for use as component b) in the compositions of this inven-
tionO
EXAMPLE B-45
The procedure of Example B-13 is repeated except that
the proportions of the reaction components are 14,400 parts
of the succinimide, 3409.2 parts of the mineral oil, and
190.8 parts of phosphorous acid (H3PO3). This produc~ con-
0 tains approximately 0.40% of phosphorus.EXAMPLE B-46
The procedure of Example B-11 is repeated except that
the proportions of the reaction components are 45,600 parts
of the succinimide, 10,795.8 parts of the process oil, and
604.2 parts OL phosphorous acid (H3P03). This product con-
tains approximately 0.41% of phosphorus.
A particularly preferred embodiment of this invention
involves using as component b) a phosphorylated alkenyl
succinimide of a polyethylene polyamine or mixture of
polyethylene polyamines, wherein the succinimide is formed
from (i) an alkenyl succinic acylating agent having a suc-
cination ratio (i.e., the ratio of the average number of
chemically bound succinic groups per alkenyl group in the
molecular structure of the succinic acylating agent) in the
range of 1 to about 1.3, the alkenyl group being derived
rom a polyolefin (most preferably a polyisobutene) having
a number average molecular weight in the range of about 600
to about 1,300 (more preferably in the range of 700 to 1,250
Case EI-6311 2
- 56 -
and most preferably in the range of 800 to 1,200).
The number average molecular weight (Mn) of the polyalkene
from which the substituent is derived is determined by use
of either of two methods, namely, vapor pressure osmometry
(VPO) or gel permeation chromatography (GPC). VPO determi-
nation should be conducted in accordance with ASTM D-2503-82
using high purity toluene as the measuring solvent. Alter-
natively, a GPC procedure can be employed. As is well
known, the GPC technique involves separating molecules
according to their size in solution. For this purpose
liquid chromatographic columns are packed with a styrene-
divinyl ben2ene copolymer of controlled particle and pore
sizes. When the polyalkene molecules from which the sub-
stituent is derived are transported through the GPC columns
by a solvent (tetrahydrofuran), the polyalkene molecules
small enough to penetrate into the pores of the column
packing are retarded in their progress through the columns.
On the other hand, the polyalkene molecules which are larger
either penetrate the pores only slightly or are totally ex-
cluded from the pores. As a consequence, these larger poly-
alkene molecules are retarded in their progress through the
columns to a lesser extent. Thus a velocity separation oc-
curs according to the size of the respective polyalkene
molecules. In order to define the relationship between
polyalkene molecular weight and elution time, the GPC system
to be used is calibrated using known molecular weight poly-
alkene standards and an internal standard method. Details
concerning such GPC procedures and methods for column cali-
bration are extensively reported in the literature. See for
example, W. W. Yau, J. J. Kirkland, and D. D. Bly, Modern
Size-Exclusion Liquid Chr_matoqraphy, John Wiley ~ Sons,
1979, Chapter 9 (pages 285-341), and references cited
therein.
ComDonent c)
The metal-containing detergents which preferably are
employed in conjunction with components a) and b) of the
compositions of this invention are exemplified by oil-
soluble basic salts of alkali or alkaline earth metals with
Case EI-6311
- 57 - 2~5~
one or more of the following acidic substances (or mixtures
thereof): (1) sulfonic acids, (2) carboxylic acids, (3)
salicylic acids, (4) alkylphenols, (5) sulfurized alkylphe-
nols, (6) organic phosphorus acids characterized by at least
one direct carbon-to-phosphorus linkage. Such organic phos-
phorus acids include those prepared by the treatment of an
olefin polymer (e.g., polyisobutene having a molecular
weight of 1,000) with a phosphorizing agent such as phos-
phorus trichloride, phosphorus heptasulfide, phosphorus pen-
tasulfide, phosphorus trichloride and sulfur, white phos-
phorus and a sulfur halide, or phosphorothioic chloride.
The most commonly used salts of such acids are those of
sodium, potassium, lithium, calcium, magnesium, strontium
and barium. The salts for use as component c) should be
basic salts having a TBN of at least 50, preferably above
200, more preferably above 250, and still more preferably
300 or above.
The term "basic salt" is used to designate metal salts
wherein the metal is present in stoichiometrically larger
amounts than the organic acid radical. The commonly em-
ployed methods for preparing the basic salts involve heating
a mineral oil solution of an acid with a stoichiometric ex-
cess of a metal neutralizing agent such as the metal oxide,
hydroxide, carbonate, bicarbonate, or sulfide at a tempera-
ture of about 50C, and filtering the resulting mass. Theuse of a "promoter" in the neutralization step to aid the
incorporation of a large excess of metal likewise is known.
Examples of compounds usefuI as the promoter include phe-
nolic substances such as phenol, naphthol, alkylphenol,
thiophenol, sulfurized alkylphenol, and condensation pro-
ducts of formaldehyde with a phenolic substance; alcohols
such as methanol, 2-propanol, octyl alcohol, Cellosolve
alcohol, Carbitol alcohol, ethylene glycol, stearyl alcohol,
and cyclohexyl alcohol; and amines such as aniline, phenyl-
enediamine, phenothiazine, phenyl-beta-naphthylamine, and
dodecylamine. A particularly ef~ective method for preparing
the basic salts comprises mixing an acid with an excess of
a basic alkaline earth metal neutralizing agent and at least
Case EI-6311 2~945
- 58 -
one alcohol promoter, and carbonating the mixture at an ele-
vated temperature such as 60-200C.
Examples of suitable metal-containing detergents in-
clude, but are not limited to, the basic or overbased salts
of such substances as lithium phenates, sodium phenates,
potassium phenates, calcium phenates, magnesium phenates,
sulfurized lithium phenates, sulfurized sodium phenates,
sulfurized potassium phenates, sulfurized calcium phenates,
and sulfurized magnesium phenates wherein each aromatic
group has one or more aliphatic groups to impart hydrocarbon
solubility; lithium sulfonates, sodium sulfonates, potassium
sulfonates, calcium sulfonates, and magnesium sulfonates
wherein each sulfonic acid moiety is attached to an aromatic
nucleus which in turn usually contains one or more aliphatic
substituents to impart hydrocarbon solubility; lithium
salicylates, sodium salicylates, potassium salicylates,
calcium salicylates, and magnesium salicylates wherein the
aromatic moiety is usually substituted by one or more
aliphatic substituents to impart hydrocarbon solubility; the
lithium, sodium, potassium, calcium and magnesium salts of
hydrolysed phosphosulfurized olefins having 10 to 2000
carbon atoms or of hydrolyzed phosphosulfurized alcohols
and/or aliphatic-substituted phenolic compounds having 10 to
2000 carbon atoms; lithium, sodium, potassium, calcium and
magnesium salts of aliphatic carboxylic acids and ali-
phatic-substituted cycloaliphatic carboxylic acids; and many
other similar alkali and alkaline earth metal salts of
oil-soluble organic acids. Mixtures of basic or overbased
salts of two or more different alkali and/or alkaline earth
metals can be used. Likewise, basic or overbased salts of
mixtures of two or more different acids or two or more
different types of acids (e.g., one or more calcium phenates
with one or more calcium sulfonates) can also be used.
While rubidium, cesium and strontium salts are feasible,
3~ their expense renders them impractical for most uses.
Likewise, while barium salts are effective, the status of
barium as a heavy metal under a toxicological cloud renders
barium salts less preferred for present-day usage.
Case EI-6311 2
- 59 -
As is well known, overbased metal detergents are gene-
rally regarded as containing overbasing quantities of inor-
ganic bases, probably in the form of micro dispersions or
colloidal suspensions. Thus the term "oil-soluble" as
applied to component c) materials is intended to include
metal detergents wherein inorganic bases are present that
are not necessarily completely or truly oil-soluble in the
strict sense of the term, inasmuch as such detergents when
mixed into base oils behave in much the same way as if they
were fully and totally dissolved in the oil.
Collectively, the various basic or overbased detergents
referred to hereinabove, have sometimes been called, quite
simply, basic alkali metal or alkaline earth metal-contain-
ing organic acid salts.
Methods for the production of oil-soluble basic and
overbased alkali and alkaline earth metal-containing de-
tergents are well known to those skilled in the art and are
extensively reported in the patent literature. See for
example, U.S. Pat. Nos. 2,451,345; 2,451,346; 2,485,861;
2,501,731; 2,501,732; 2,585,520; 2,671,758; 2,616,904;
2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925;
2,617,049; 2,695,910; 3,178,368; 3,367,867; 3,496,105;
3,629,109; 3,865,737; 3,907,6gl; 4,100,085; 4,129,589;
4,137,184; 4,148,740; 4,212,752; 4,617,135; 4,647,387;
4,880,550; GB Published Patent Application 2,082,619 A, and
European Patent Application Publication Nos. 121,024 Bl and
259,974 A2.
The basic or overbased metal detergents utilized as
component c) can, if desired, be oil-soluble boronated
alkali or alkaline earth metal~containing detergents.
Methods for preparing boronated, overbased metal dPtergents
are described, for e~ample, in U.S. Pat. Nos. 3,480,548;
3,679,584; 3,829,381; 3,909,691; 4,965,003; and 4,965,004.
Particularly preferred metal detergents for use as com-
ponent c) are one or more calcium sulfonates, one or moremagnesium sulfonates, or combinations of one or more calcium
sulfonates and one or more magnesium sulfonates. Most pre-
ferred are one or more overbased calcium sulfonates, one or
Case EI-6311
~ - 60 - 2~
more overbased magnesium sulfonates, and combinations of one
or more overbased calcium sulfonates and one or more over-
based magnesium sulfonates.
Component d)
As noted above, in situations where scuffing wear is
likely to be encountered, it is desirable to combine one or
more boron-containing additive components with components a)
and b) or with components a), b), and c). The boron-con-
taining additive components are preferably oil-soluble
additive components, but effective use can be made of boron-
containing components which are sufficiently finely divided
as to form stable dispersions in the base oil. Examples of
the latter type of boron-containing components include the
finely-divided inorganic orthoborate salts such as lithium
borate, sodium borate, potassium borate, magnesium borate,
calcium borate, ammonium borate and the like.
The oil-soluble boron-containing components include
boronated ashless dispersants (often referred to as borated
ashless dispersants) and esters of acids of boron. Examples
of boronated ashless dispersants and descriptions of methods
by which they can be prepared are well-documented in the
literature. See for example U.S. Pat. Nos. 3,087,936;
3,254,025; 3,281,428; 3,282,955; 3,533,945; 3,539,633;
3,658,836; 3,697,574; 3,703,536; 3,704,308; 4,025,445; and
4,857,214. Likewise the literature is replete with examples
of oil-soluble esters of boron acids and methods for their
production. See for example the disclosures of U.S. Pat.
Nos. 2,866,811; 2,931,774; 3,009,797; 3,009,798; 3,009,7g9;
3,014,061; and 3,092,586.
Other Addltive Components
The lubricant and lubricant concentrates of this inven-
tion can and preferably will contain additional components
in order to partake of the properties which can be conferred
to the overall composition by such additional components.
The nature of such components will, to a large extent, be
governed by the particular use to which the ultimate olea-
ginous composition (lubricant or functional fluid3 is to be
subjected.
case EI-6311 2 ~ 4 ~
- 61 -
Antioxidants. Most oleaginous compositions will con-
tain a conventional quantity of one or more antioxidants in
order to protect the composition from premature degradation
in the presence of air, especially at elevated temperatures.
Typical antioxidants include hindered phenolic antioxidants,
secondary aromatic amine antioxidants, sulfurized phenolic
antioxidants, oil-soluble copper compounds, phosphorus-
containing antio~idants, and the like.
Illustrative sterically hindered phenolic antioxidants
include ortho-alkylated phenolic compounds such as 2,6-di-
tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol,
2,4,6-tri-tert-butylphenol, 2-tert-butylphenol, 2,6-di-
isopropylphenol, 2-methyl-6-tert-butylphenol, 2,4-di-
methyl-6-tert-butylphenol, ~-(N,N-dimethylaminomethyl)-
2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol,
2-methyl-6-styrylphenol, 2,6-di-styryl-4-nonylphenol, and
their analogs and homologs. Mixtures of two or more such
mononuclear phenolic compounds are also suitable.
The preferred antioxidants for use in the compositions
of this invention are methylene-bridged alkylphenols, and
these can be used singly or in combinations with each other,
or in combinations with sterically-hindered unbridged phe-
nolic compounds. Illustrative methylene bridged compounds
include 4,4'-methylenebis(6-tert-butyl-o-cresol), 4,4l_
methylenebis(2-tert-amyl-o cresol), 2,2'-methylenebis(4-
methyl-6-tert-butylphenol), 4,4'-methylene-bis(2,6-di-
tert-butylphenol), and similar compounds. Particularly
preferred are mixtures of methylene-bridged alkylphenols
such as are described in U.S. Pat. No. 3,211,652.
Amine antioxidantsj especially oil-soluble aromatic
secondary amines can also be used in the compositions of
this invention. Whilst aromatic secondary monoamines are
preferred, aromatic secondary polyamines are also suitable.
Illustrative aromatic secondary monoamines include di-
phenylamine, alkyl diphenylamines containing 1 or 2 alkyl
substituents each having up to 16 carbon atoms, phenyl-~-
naphthylamine, phenyl-~-naphthylamine, alkyl- or aralkyl-
substituted phenyl-~-naphthylamine containing one or two
Case EI-6311
~ - 62 - 2~9~
alkyl or aralkyl groups each having up to 16 carbon atoms,
alkyl- or aralkyl-substituted phenyl-~naphthylamine con-
taining one or two alkyl or aralkyl groups each having up to
16 carbon atoms, and similar compounds.
~ preferred type of aromatic amine antioxidant is an
alkylated diphenylamine of the general formula
R l C NH~ R2
wherein R1 is an alkyl group (preferably a branched alkyl
group) having 8 to 12 carbon atoms, (more preferably 8 or 9
carbon atoms) and R2 is a hydrogen atom or an alkyl group
(preferably a branched alkyl group) having 8 to 12 car~on
atoms, (more preferably 8 or 9 carbon atoms). Most prefer-
ably, R1 and R2 are the same. One such preferred compound is
available commercially as Naugalube 438L, a material which
is understood to be predominately a 4,4'-dinonyldiphenyl-
amine (i.e., bis(4-nonylphenyl)amine) wherein the nonyl
groups are branched.
Another useful type of antioxidant for inclusion in ~he
compositions of this invention is comprised to one or more
liquid, partially sulfurized phenolic compounds such as are
prepared by reacting sulfur monochloride with a liquid
mixture of phenols -- at least 50 weight percent of which
mixture of phenols is composed of one or more reactive,
hindered phenols -- in proportions to provide from 0.3 to
0.7 gram atoms of sulfur monochloride per mole of reactive,
hindered phenol 50 as to produce a liquid product. Typical
phenol mixtures useful in making such liquid product com-
positions include a mixture containing by weight about 75%
of 2,6-di-tert-butylphenol, about 10% of 2-tert-butylphenol,
about 13% of 2,4,6-tri-tert-butylphenol, and about 2% of
2,4-di-tert-butylphenol. The reaction is exothermic and
thus is preferabl~ kept within the range of 15C to 70C,
most preferably between 40C to 60C.
Mixtures of different antioxidants can also be used.
One suitable mixture is comprised of a combination of (i) an
Case EI-6311
- 63 ~ 4 ~
oil-soluble mixture of at least three different sterically-
hindered tertiary butylated monohydric phenols which is in
the liquid state at 25OC, (ii) an oil-soluble mixture of at
least three different sterically-hindered tertiary butylated
methylene-bridged polyphenols, and (iii) at least one bis(4-
alkylphenyl)amine wherein the alkyl group is a branched al-
kyl group having 8 to 12 carbon atoms, the proportions of
(i), (i.i) and (iii) on a weight basis falling in the range
of 3.5 to 5.0 parts of component (i) and 0.9 to 1.2 parts of
component (ii) per part by weight of component (iii).
The lubricating compositions of this invention prefer-
ably contain 0.01 to 1.0% by weight, more preferably 0.05 to
0.7% by weight, of one or more sterically-hindered phenolic
antioxidants of the types described above. Alternatively or
additionally the lubricants of this invention may contain
0.01 to 1.0~ by weight, more preferably 0.05 to 0.7% by
weight of one or more aromatic amine antioxidants of the
types described above.
Corrosion Inhibitors. It is also preferred pursuant to
this invention to employ in the lubricant compositions and
additive concentrates a suitable quantity of a corrosion
inhibitor. This may be a single compound or a mixture of
compounds having the property of inhibiting corrosion o~
metallic surfaces.
One type of such additives are inhibitors of copper
corrosion. Such compounds include thiazoles, triazoles and
thiadiazoles. Examples of such compounds include benzo-
triazole, tolyltriazole, octyltriazole, decyltriazole, do-
decyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto-
30 1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thi-
adiazoles, 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadia-
zoles, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and
2,5-(bis)hydrocarbyldithio)-1,3,4-thiadiazoles. The pre-
ferred compounds are the 1,3,4-thiadiazoles, a number of
which ar~ available as articles of commerce. For synthesis
procedures, see for example U.S. Pat. Nos. 2,765,289;
2,749,311; 2,760,933; 2,850,453; 2,910,439; 3,663,561;
3,862,798; and 3,840,549.
Case EI-6311
- 64 - 2~&~9~
Other types of corrosion inhibitors suitable for use in
the compositions of this invention include dimer and trimer
acids, such as are produced from tall oil fatty acids, oleic
acid, linoleic acid, or the like. Products of this type are
currently a~ailable from various commercial sources, such
as, for example, the dimer and trimer acids sold under the
H~STRENE trademark by the Humco Chemical Division of Witco
Chemical Corporation and under the EMPOL trademark by Emery
Chemicals. Another useful type of corrosion inhibitor for
use in the practice of this invention are the alkenyl suc-
cinic acid and alkenyl succinic anhydride corrosion inhi-
bitors such as, for example, tetrapropenylsuccinic acid,
tetrapropenylsuccinic anhydride, tetradecenylsuccinic acid,
tetradecenylsuccinic anhydride, hexadecenylsuccinic acid,
hexadecenylsuccinic anhydride, and the like. Also useful
are the half esters of alkenyl succinic acids having 8 to 24
carbon atoms in the alkenyl group with alcohols such as the
polyglycols. Other suitable corrosion inhibitors include
ether amines; acid phosphates; amines; polyethoxylated com-
pounds such as ethoxylated amines, etho~ylated phenols, and
ethoxylated alcohols; imidazolines; and the like. Materials
of these types are well known to those skilled in the art
and a number of such materials are available as articles of
commerce.
Other useful corrosion inhibitors are aminosuccinic
acids or derivatives thereof represented by the formula-
R6 o
11
R 7-- C -- C -- o R 5
3~N -- C -- C -- O R
11
R2 o
wherein each of R1, R2, Rs, R6 and R7 is, independently, a
hydrogen atom or a hydrocarbyl group containing 1 to 30
carbon atoms, and wherein each of R3 and R4 is, indepen-
dently, a hydrogen atom, a hydrocarbyl group containing 1 to
Case EI-6311
~ - 65 - 2 ~ ~3
30 carbon atoms, or an acyl group containing from 1 to 3~
carbon atoms. The groups R , R , R , R , R , R and R , when
in the form of hydrocarhyl groups, can be, for example,
alkyl, cycloalkyl or aromatic containing groups. Preferably
Rl and Rs are the same or different straight-chain or
branched-chain hydrocarbon radicals containing 1-20 carbon
atoms. Most preferably, R1 and Rs are saturated hydrocarbon
radicals containing 3-6 carbon atoms~ R2, either R3 or R4,
R6 and R7, when in the form of hydrocarbyl ~roups, are
preferably the same or different s~raight-chain or branched-
chain saturated hydrocarbon radicals. Preferably a dialkyl
ester of an aminosuccinic acid is used in which R1 and Rs are
the same or different alkyl groups containing 3-6 carbon
atoms, R2 is a hydrogen at:om, and either R3 or R4 is an alkyl
group containing 15-20 carbon atoms or an acyl group which
is derived from a saturated or unsaturated carboxylic acid
containing 2-10 carbon atoms.
Most preferred of the aminosuccinic acid derivatives is
a dialkylester of an aminosuccinic acid of the above formula
wherein Rl and R5 are isobutyl, R2 is a hydrogen atom, R3 is
octadecyl and/or octadecenyl and R4 is 3-carboxy-1-oxo-2-pro-
penyl. In such ester R6 and R7 are most preferably hydrogen
atoms.
The lubricant compositions of this invention most pre-
ferably contain from 0.005 to 0.5~ by weight, and especiallyfrom 0.01 to 0.2% by weight, of one or more corrosion inhi-
bitors and/or metal deactivators of the type described
above.
Antifoam ~qents. Suitable antifoam agents include
silicones and organic polymers such as acrylate polymers.
Various antifoam agents are described in Foam Control Aaents
by H. T. Kerner (Noyes Data Corporation, 1976, pages 125-
176). Mixtures of silicone-type antifoam agents such as the
liquid dialkyl silicone polymers with various other
substances are also effective. Typical of such mixtures are
silicones mixed with an acrylate polymer, silicones mixed
with one or more amines, and silicones mixed with one or
more amine carboxylates.
case EI-6311
- 66 -
Neutral Metal-Containinq Deterqents. For some applica-
tions such as crankcase lubricants for diesel engines, it is
desirable to include an oil-soluble neutral metal-containing
detergent in which the metal is an alkali metal or an al-
kaline earth metal. Combinations of such detergents canalso be employed. The neutral detergents of this type are
those which contain an essentially stoichiometric equivalent
quantity of metal in relation to the amount of acidic moi-
eties present in the detergent. Thus in general, the neu-
tral detergents will have a TBN of up to about 50.
The acidic materials utilized in forming such deter-
gents include carbo~ylic acids, salicylic acids, alkylphe-
nols, sulfonic acids, sulfurized alkylphenols, and the like.
Typical detergents of this t~pe and/or methods for their
preparation are known and reported in the literature. See
for example U.S. Pat. Nos. 2,001,108; 2,081,075; 2,095,538;
2,144,078; 2,163,622; 2,180,697; 2,180,698; 2,180,699;
2,211,972; 2,223,127; 2,~28,654; 2,228,661; 2,~49,626;
2,252,793; 2,270,183; 2,281,824; 2,289,795; 2,292,205;
2,294,1~5; 2,321,463; 2,322,307; 2,335,017; 2,336,074;
2,339,692; 2,356,013; 2,360,302; 2,362,291; 2,399,877;
2,399,878; 2,409,687; and 2,416,281. A number of such com-
pounds are available as articles of commerce, such as for
example, HiTEC~ 614 additive (Ethyl Petroleum Additives,
Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
Supplemental Antiwear and/or Extreme Pressure
Additives For certain applications such as use as gear
oils, the compositions of this invention will preferably
contain one or more oil-soluble supplemental antiwear and/or
extreme pressure additives. These comprise a number of well
known classes of materials including, for example, sulfur-
containing additives, esters of boron acids, esters of phos-
phorus acids, amine salts of phosphorus acids and acid es-
ters, higher carboxylic acids and derivatives thereof, chlo-
rine-containinq additives, and the like.
Typical sulfur-containing antiwear and/or extreme pres-
sure additives include dihydrocarbyl polysulfides; sulfur-
.
, -
Case EI 6311
- 67 - 2~
ized olefins; sulfurized fatty acid esters of both natural
(e.g. sperm oil) and synthetic origins; trithiones; thienyl
derivatives; sulfurized terpenes; sulfurized oligomers of C2-
C8 monoolefins; xanthates of alkanols and other organo-hy-
droxy compounds such as phenols; thiocarbamates made fromalkyl amines and other organo amines; and sulfurized Diels-
Alder adducts such as those disclosed in U.S. reissue patent
Re 27,331. Specific examples include sulfurized polyiso-
butene of Mn 1,150, sulfurized isobutylene, sulfurized tri-
isobutene, dicyclohexyl disulfide, diphenyl and dibenzyl di-
sulfide, di-tert-butyl trisulfide, and dinonyl trisulfide,
among others.
Esters of boron acids which may be used include borate,
metaborate, pyroborate and bikorate esters of monohydric
and/or polyhydric alcohols and/or phenols, such as trioctyl
borate, tridecyl borate, 2-ethylhexyl pyroborate, isoamyl
metaborate, trixylyl borate, (butyl)(2,4-hexanediyl)borate,
and the like.
Typical esters of phosphorus acids which may be used as
antiwear and/or extreme pressure additives include trihydro-
carbyl phosphites, phosphonates and phosphates, and dihydro-
carbyl phosphites; such as tricresyl phosphate, tributyl
phosphite, tris(2-chloroethyl) phosphate and phosphite, di-
butyl trichloromethyl phosphonates, di(n-butyl)pho~phite,
triphenyl phosphite, tris(tridecyl) phosphite, and tolyl
phosphinic acid dipropyl ester.
Among the amine salts of phosphorus acids and phospho-
rus acid-esters which can be employed are amine salts of
partially esterified phosphoric, phosphorous, phosphonic,
and phosphinic acids and their partial or total thio analogs
such as partially esterified monothiophosphoric, dithi-
ophosphoric, trithiophosphoric and tetrathiophosphoric
acids; amine salts of phosphonic acids and their thio ana-
logs; and the like. Specific examples include the dihexyl-
ammonium salt of dodecylphosphoric acid, the diethyl hexylammonium salt of dioctyl dithiophosphoric acid, the octa-
decylammonium salt of dibutyl thiophosphoric acid, the
dilaurylammonium salt of 2-ethylhexylphosphoric acid, the
case EI-6311
2 ~
- 68 -
dioleyl ammonium salt of butane phosphonic acid, and ana-
logous compounds.
Higher carboxylic acids and derivatives which can be
used as antiwear and/or extreme pressure additives are il-
lustrated by fatty acids, dimerized and trimerized unsatur-
ated natural acids (e.g., linoleic) and esters, amine, am-
monia, and metal (particularly lead) salts thereof, and
amides and imidazoline salt and condensation products
thereof, oxazolines, and esters of fatty acids, such as
ammonium di-(linoleic) acid, lard oil, oleic acid, animal
glycerides, lead staarate, etc.
Suitable chlorine-containing additives include chlori-
nated waxes of both the paraffinic and microcrystalline
type, polyhaloaromatics such as di- and trichlorobenzene,
trifluoromethyl naphthalenes, perchlorobenzene, pentachloro-
phenol and dichloro diphenyl trichloroethane. Also useful
are chlorosulfurized olefins and olefinic waxes and sulfur-
ized chlorophenyl methyl chlorides and chloroxanthates.
Specific examples include chlorodibenzyl disulfide, chloro-
sulfurized polyisobutene of Mn 600, chlorosulfurized pineneand chlorosulfurized lard oil.
Supplemental Ashless Dispersants~ If desired, the com-
positions of this invention can include one or more supple-
mental ashless dispersants in order to supplement the dis-
persancy contributed by component b) (and optional componentd) when used). The supplemental ashless dispersant(s) dif-
fer from component b) and component d) in that the supple-
mental ashless dispersant(s) are not phosphorylated in the
manner of component b) or boronated (and optionally addi-
tionally phosphorylated) in the manner of component d).
Thus, the supplemental ashless dispersant(s) which maybe used in the compositions of this invention can be any of
the basic nitrogen-containing and/or hydroxyl group-contain-
ing ashless dispersants of the type referred to hereinabove
in connection with the preparation of component b). Use can
therefore be mad~ of any of the carboxylic ashless disper-
sants and/or any of the hydrocarbyl polyamine dispersants
and/or any ~f the Mannich polyamine dispersants and/or any
Case EI-6311 2
- 69 -
of the polymeric polyamine dispersants referred to herein-
above. Other ashless dispersants which can be included in
the compositions of this invention are imidazoline disper-
sants which can be represented by the formula:
H 2 C N R 2
\ N~
wherein R1 represents a hydrocarbon group having 1 to 30 car-
bon atoms, e.~. an alkyl or alkenyl group having 7 to 22
carbon atoms, and R2 represents a hydrogen atoms or a hydro-
carbon radical of 1 to 22 carbon atoms, or an aminoal~yl,
acylaminoalkyl or hydroxyalkyl radical having 2 to 50 carbon
lo atoms. Such long- chain alkyl (or long-chain alkenyl)
imidazoline compounds may be made by reaction of a corres-
ponding long-chain fatty acid (of formula R1-COOH), for exam-
ple oleic acid, with an appropriate polyamine. The imidazo-
line formed is then ordinarily called, for example, oleyl-
imidazoline where the radical R1 represents the oleyl residueof oleic acid. Other suitable alkyl substituents in the 2-
position of these imidazolines include undecyl, heptadecyl,
lauryl and erucyl. Suitable N-substituents of the imida-
zolines (i.e. radicals R2) include hydrocarbyl groups, hy-
droxyalkyl groups, aminoalkyl groups, and acylaminoalkyl
groups. Examples of these various groups include methyl,
butyl, decyl, cyclohexyl, phenyl, benzyl, tolyl,
hydroxyethyl, aminoethyl, oleylaminoethyl and
stearylaminoethyl.
Another class of ashless dispersant which can be incor-
porated in the compositions of this invention are the pro-
ducts of reaction of an ethoxylated amine made by reaction
of ammonia with ethylene oxide with a carboxylic acid of 8
to 30 carbon atoms. The ethoxylated amine may be, for exam-
ple, mono-, di- or tri- ethanolamine or a polyethoxylated
derivative thereof, and the carboxylic acid may be, for
Case EI-6311 2~9~
- 70 -
example, a straight or branched chain fatty acid of 10 to 2Z
car~on atoms, a naphthenic acid, a resinic acid or an alkyl
aryl carboxylic acid.
Still another type of ashless dispersants which can be
used in the practice of this invention are the ~-olefin-ma-
leimide copolymers such as are described in U.S. Pat. No.
3,909,215. Such copolymers are alternating copolymers of
N-substituted maleimides and aliphatic ~-olefins of from 8
to 30 carbon atoms. The copolymers may have an average of
lo 4 to 20 maleimide groups per molecule. The substituents on
the nitrogen of the maleimide may be the same or different
and are organic radicals composed essentially of carbon,
hydrogen and nitrogen having a total of 3 to 60 carbon
atoms. A commercially available material which is highly
suitable for use in this invention is Chevron OFA 425B, and
this material is believed to be or comprise an ~-olefin
maleimide copolymer of the type describ~d in U.S. Pat. No.
3,909,215.
The above and many other types of ashless dispersants
can be utilized either singly or in combination in the
compositions of this invention, provided of course that they
are compatible with the other additive components being
employed and are suitably soluble in the base oil selected
for use.
Pour Point Depressants. Another us~ful type of addi-
tive included in compositions of this invention is one or
more pour point depressants. The use of pour point depres-
sants in oil base compositions to improve the low tempera-
ture properties of the compositions is well known to the
art. See, for example, the books Lubricant Additive_ by C.
V. Smalheer and R. Kennedy Smith (Lezius-Hiles Co. Pub-
lishers, Cleveland, Ohio, 1967); Gear and Transmission
Lubricants by C. T. Boner (Reinhold Publishing Corp., New
York, 1964); and Lubricant Additives by M. W. Ranney (Noyes
Data Corporation, New Jersey, 1973). ~mong the types of
compounds which function satisfactorily as pour point de-
pressants in the compositions of this invention are poly-
methacrylates, polyacrylates, condensation products of halo-
Case EI-6311 2
- 71 -
paraffin waxes and aromatic compounds, and vinyl carboxylate
polymers. Also useful as pour point depressants are ter-
polymers made by polymerizing a dialkyl fumarate, vinyl
ester of a fatty acid and a vinyl alkyl ether. Techniques
for preparing such polymers and their uses are disclosed in
U.S. Pat. No. 3,250,715. Generally, ~hen they are present
in the compositions of this invention, the pour point
depressants (on an active content basis) are present in
amounts within the range of 0.01 to 5, and more often ~ithin
lo the range of o.Ol to 1, weight percent of the total
composition.
Viscosity Index Improvers. Depending upon the
viscosity grade required, the lubricant compositions can
contain up to 15 weight percent of one or more viscosity
index improvers (excluding the weight of solvent or carrier
fluid with which viscosity index improvers are often asso-
ciated as supplied). Among the numerous types of materials
known for such use are hydrocarbon polymers grafted with,
for example, nitrogen-containing polymers, olefin polymers
such as polybutene, ethylene-propylene copolymers, hydro-
genated polymers and copolymers and terpolymers of styrene
with isoprene and/or butadiene, polymers of alkyl acrylates
or alkyl methacrylates, copolymers of alkyl methacrylates
with N-vinyl pyrrolidone or dimethylaminoalkyl methacrylate;
2S post grafted polymers of ethylene-propylene with an active
monomer such as maleic anhydride which may be further re-
acted with an alcohol or an alkylene polyamine; styrene/
maleic anhydride polymers post-treated with alcohols and/or
amines, and the like.
Dispersant viscosity index improvers, which combine the
activity of dispersants and viscosity index improvers, suit-
able for use in the compositions of this invention are de-
scribed, for example, in U.S. Pat. Nos. 3,702,300;
4,068,056; 4,068,058; 4,089,794; 4,137,185; 4,146,489;
35 4,149,984; 4,160,739; and 4,519,929.
Friction Modifiers These materials, sometimes known
-
as fuel economy additivesl include such substances as the
alkyl phosphonates as disclosed in U.S. Pat. No. 4,356,097,
Case EI-6311 ~ 9 ~ ~
- 72 -
aliphatic hydrocarbyl-substituted succinimides derived from
ammonia or alkyl monoamines as disclosed in E~ropean Patent
Publication No. 20037, dimer acid esters as disclosed in
U.S. Pat. No. 4,105,571, oleamide, and the like. Such addi-
tives, when used are generally present in amounts of 0.1 to5 weight percent. Glycerol oleates are another example of
fuel economy additives and these are usually present in very
small amounts, such as 0.05 to 0.2 weight percent based on
the weight of the formulated oil.
Other suitable friction modifiers include aliphatic
amines or ethoxylated aliphatic amines, aliphatic fatty acid
amides, aliphatic carboxylic acids, aliphatic carboxylic es-
ters, aliphatic carboxylic ester-amides, aliphatic phos-
phates, aliphatic thiophosphonates, aliphatic thiophos-
phates, etc., wherein the aliphatic group usually contains
above eight carbon atoms so as to render the compound suit-
ably oil soluble.
A desirable friction modifier additive combination
which may be used in the practice of this invention is
described in European Patent Publication No. 389,237. This
combination involves use of a long chain succinimide deri-
vative and a long chain amide.
Seal Swell A~ents. Additives may be introduced into
the compositions of this invention in order to improve the
seal perfor~ance (elastomer compatibility) of the compo-
sitions. Known materials of this type include dialkyl
diesters such as dioctyl sebacate, aromatic hydrocarbons of
suitable viscosity such as Panasol AN-3N, products such as
Lubrizol 730, polyol esters such as Emery 2935, 2936, and
2939 esters from the Emery Group of Henkel Corporation and
Hatcol 2352, 2962, 2925, 2938, 2939, 2970, 3178, and 4322
polyol esters from Hatco Corporation. Generally speaking
the most suitable diesters include the adipates, azelates,
and sebacates of C8-C13 alkanols (or mixtures thereof), and
the phthalates of C4-C13 alkanols (or mixtures thereof).
Mixtures of two or more different types of diesters (e.g.,
dialkyl adipates and dialkyl azelates, etc.) can also be
used. Examples of such materials include the n-octyl,
Case EI-6311
2 ~ 5
2-ethylhexyl, isodecyl, and tridecyl diesters of adipic
acid, azelaic acid, and sebacic acid, and the n-butyl,
isobutyl, pentyl, haxyl, heptyl, octyl, nonyl, decyl, un-
decyl, dodecyl, and tridecyl diesters of phthalic acid.
Base Oils.
The additive combinations of this invention can be
incorporated in a wide variety of lubricants and functional
fluids in effective amounts to provide suitable active in-
gredient concentrations. The base oils not only can be
hydrocarbon oils of lubricating viscosity derived from
petroleum (or tar sands, coal, shale, etc.), but also can be
natural oils of suitable viscosities such as rapeseed oil,
etc., and synthetic oils such as hydrogenated polyolefin
oils; poly--olefins (e.g., hydrogenated or unhydrogenated
a-olefin oligomers such as hydrogenated poly-l-decene);
alkyl esters of dicarboxylic acids; complex esters of di-
carboxylic acid, polyglycol and alcohol; alkyl esters of
carbonic or phosphoric acids; polysilicones; fluorohydro-
carbon oils; and mixtures of mineral, natural and/or syn-
thetic oils in any proportion, etc. The term "base oil" forthis disclosure includes all the foregoing.
The additive combinations of this invention can thus be
used in lubricating oil and functional fluid compositions,
such as automotive crankcase lubricating oils, automatic
transmission fluids, gear oils, hydraulic oils, cutting
oils, etc., in which the base oil of lubricating viscosity
is a mineral oil, a synthetic oil, a natural oil such as a
vegetable oil, or a mixture thereof, e.g~ a mixture of a
mineral oil and a synthetic oil.
Suitable mineral oils include those of appropriate Vi5-
cosity refined from crude oil of any source including Gulf
Coast, Midcontinent, Pennsylvania, California, Alaska,
Middle East, North Sea and the like. Standard refinery
operations may be used in processing the mineral oil. Among
the general types of petroleum oils useful in the composi-
tions of this invention are solvent neutrals, bright stocks,
cylinder stocks, residual oils, hydrocracked base stocks~
paraffin oils lncluding pale oils, and solvent extracted
case EI-6311 2 ~
naphthenic oils. Such oils and blends of them are produced
by a number of conventional techniques which are widely
known by those skilled in the art.
As is noted above, the base oil can consist essentially
of or comprise a portion of one or more synthetic oils.
Among the suitable synthetic oils are homo- and inter-
polymers of C2-C12 olefins, carboxylic acid esters of both
monoalcohols and polyols, polyethers, silicones, polygly-
cols, silicates, alkylated aromatics, carbonates, thio-
carbonates, orthoformates, phosphates and phosphites, bor-
ates and halogenated hydrocarbons. Representative of such
oils are homo- and interpolymers of C2-C12 monoolafinic
hydrocarbons, alkylated benzenes (e.g., dodecyl benzenes,
didodecyl benzenes, tetradecyl benzenes, dinonyl benzenes,
di-(2-ethylhexyl)benzenes, wax-alkylated naphthalenes); and
polyphenyls (e.g., biphenyls, terphenyls).
Al~ylene oxide polymers and interpolymers and deri-
vatives thereof where the terminal hydroxyl groups have been
modified by esterification, etherification, etc., constitute
another class of synthetic oils. These are exemplified by
the oils prepared through polymerization of alkylene oxides
such as ethylene oxide or propylene oxide, and the alkyl and
aryl ethers of these polyoxyalkylene polymers (e.g., methyl
polyisopropylene glycol ether having an average molecular
weight of 1,000, diphenyl ether of polyethylene glycol hav-
ing a molecular weight of 500-1,000, diethyl ether of poly-
propylene glycol having a molecular weight of 1,000-1,500)
or mono- and poly-carboxylic esters thereof, for example,
the acetic acid ester, mixed C3-C6 fatty acid esters, or the
C~3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic oils comprises the
esters of dicarboxylic acids (e.g., phthalic acid, succinic
acid, maleic acid, azelaic acid, suberic acid, sebacic acid,
fumaric acid, adipic acid, linoleic acid dimer) with a var-
iety of alcohols (e.g., butyl alcohol, hexyl alcohol, do-
decyl alcohol, 2-ethylhexyl alcohol, ethylene glycol). Spe-
cific examples of these esters include dibutyl adipate,
di(2-ethylhexyl) adipate, didodecyl adipate, di(tridecyl)
case EI-6311
- 75 - 2~9~
adipate, di(2-ethylhexyl) sebacate, dilauryl sebacate, di-n-
hexyl fumarate, dioctyl sebacate, diisooctyl azelate, di-
isodecyl azelate, dioctyl phthalate, didecyl ph~halat~,
di(eicosyl) sebacate, the 2-ethylhexyl diester of linoleic
acid dimer, and the complex ester formed by reacting one
mole of sebacic acid with two moles of tetraethylene glycol
and two moles of 2-ethylhexanoic acid.
Esters which may be used as synthetic oils also include
those made from C3-C18 monocarboxylic acids and polyols and
polyol ethers such as neopentyl glycol, trimethylolpropane,
pentaerythritol and dipentaerythritol. Trimethylol propane
tripelargonate and pentaerythritol tetracaproate, the ester
formed from trimethylolpropane, caprylic acid and sebacic
acid, and the polyesters derived from a C4-C~4 dicarboxylic
acid and one or more aliphatic dihydric C3-C12 alcohols such
as derived from azelaic acid or sebacic acid and 2,2,4-
trimethyl-1,6-hexanediol serve as examples. Silicon-based
oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or
polyaryloxy-siloxane oils and silicate oils comprise another
class of synthetic lubricants (e.g., tetraethyl silicate,
tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate,
tetra-(p-tert-butylphenyl) silicate, poly(methyl)siloxanes,
and poly(methylphenyl)siloxanes. Other synthetic lubricat-
ing oils include liquid esters of phosphorus-containing
acids (e.g., tricresyl phosphate, trioctyl phosphate,
triphenyl phosphite, and diethyl ester of decane phosphonic
acid.
Also useful as base oils or as components of base oils
are hydrogenated or unhydrogenated liquid oligomers of C6-C16
alphaolefins, such as hydrogenated or unhydrogenated oligo-
mers formed from l-decene. Methods for the production of
such liquid oligomeric 1-alkene hydrocarbons are known and
reported in the literature. See for example U.S. Pat. Nos.
3,749,560; 3,763,244; 3,780,128; 4,172,855; 4,218,330;
4,902,846; 4,906,798; 4,910,355; 4,911,758; 4,935,570;
4,950,822; 4,956,513; and 4,981,578. Additionally,
hydrogenated l-alkene oligomers of this type are available
as articles of commerce, for example, under the trade desig-
Case EI-6311
76 - 2~9~
nations ~THYLFLO 162, ETHYLFLO 164, ETHYLFLO 166, ETHYLFLO
168, ETHYLFLO 170, ETHYLFLO 174, and ETHYLFLO 180 poly-~-
olefin oils (Ethyl Corporation; Ethyl Canada Ltd.; Ethyl
S.A.). Blends of such materials can also be used in order
to adjust the viscometrics of the given base oil. Suitable
l-alkene oligomers are also available from other suppliers.
As is well known, hydrogenated oligomers of this type con-
tain little, if any, residual ethylenic unsaturation.
Preferred oligomers are formed by use of a Friedel-
Crafts catalyst (especially boron trifluoride promoted withwater or a C120 alkanol) followed by catalytic hydrogenation
of the oligomer so formed using procedures such as are de-
scribed in the foregoing U.S. patents.
Other catalyst systems which can be used to form oligo-
mers of l-alkene hydrocarbons, which, on hydrogenation, pro-
vide suitable oleaginous liquids include Ziegler catalysts
such as ethyl aluminum sesquichloride with titanium tetra-
chloride, aluminum alkyl catalysts, chromium oxide catalysts
on silica or alumina supports and a system in which a boron
trifluoride catalyzed oligomerization is followed by
treatment with an organic peroxide.
It is also possible in accordance with this invention
to utilize blends of one or more liquid hydrogenated l-al-
kene oligomers in combination with other oleaginous mater-
ials having suitable viscosities, provided that the resul-
tant blend has suitable compatibility and possesses the phy-
sical properties desired.
Typical natural oils that may be used as base oils or
as components of the base oils include castor oil, olive
oil, peanut oil, rapeseed oil, corn oil, sesame oil, cotton-
seed oil, soybean oil, sunflower oil, safflower oil, hemp
oil, linseed oil, tung oil, oiticica oil, jojoba oil, and
the like. Such oils may be partially or fully hydrogenated,
if desired.
The fact that the base oils used in the compositions of
this invention may be composed of (i) one or more mineral
oils, (ii) one or more synthetic oils, (iii) one or more
natural oils, or (iv) a blend of (i) and (ii), or (i) and
Case EI-6311
- 77 - 2~
(iii), or (ii) and (iii), or (i), (ii) and (iii) does not
mean that these various types of oils are necessarily equi-
valents of each other. Certain types of base oils may be
used in certain compositions for the specific properties
they possess such as high temperature stability, non-
flammability or lack of corrosivity towards specific metals
(e.g. silver or cadmium). In other compositions, other
types of base oils may be preferred for reasons of avail-
ability or low cost. Thus, the skilled artisan will recog-
nize that while the various types of base oils discussedabove may be used in the compositions of this invention,
they are not necessarily functional equivalents of each
other in every instance.
Proportions and Concentrations
In general, the components of the additive compositions
of this invention are employed in the oleaginous liquids
(e.g., lubricating oils and functional fluids) in minor
amounts sufficient to improve the performance character-
istics and properties of the base oil or fluid. The amounts
will thus vary in accordance with such factors as the vis-
cosity characteristics of the base oil or fluid employed,
the viscosity characteristics desired in the finished pro-
duct, the service conditions for which the finished product
is intended, and the performance characteristics desired in
the finished product. However, generally speaking, the
following concentrations (weight percent) of the components
(active ingredients) in the base oils or fluids are
illustrative:
MoreParticularly
3 O GeneralPreferred Preferred Preferred
Ran~e Ran~ Ran e Ran~e
Component a) 0.1- 5 0.2 - 20.3 -1.4 0.35 -1.35
Component b) 0.01- 20 0.1-150.5 -10 1- 8
Component c) 0 - 20 0.01-100.1- 6 0.5 - 3
Component d) û - 20 0.1- 150.5 - 10 1- 8
The relative proportions of components a), b), c) and
d) in the finished oleaginous liquids and in the additive
Case EI-6311
concentrates of this invention generally are such that per
atom of phosphorus in component b), there are from 0.05 to
100 atoms (and preferably from 0.15 to 10 atoms) of metal as
component a); from 0 to 1,000 atoms (and prefera~ly from
0.05 to 150 atoms) of metal as component c); and from 0 to
600 atoms (and preferably from 0.15 to 200 atoms) of boron
as component d).
In order to achieve optimum performance, the base oil
should contain at least 0.03%, preferably at least 0.04%,
more preferably at least 0.05%, and most preferably at least
0.06% by weight of phosphorus as component b). For this
reason it is desirable to proportion the components in the
additive concentrates to yield such concentrations of phos-
phorus as component b) at the treat level recommended for
any given additive concentrate. A wide variety of component
proportions in the additive concentrates can of course be
used to achieve these use concentrations in the finished
oil. Nevertheless, and without in any way limiting the
scope of this invention, preferred additive concentrates of
this invention will typically contain at least 0.3% by
weight of phosphorus as component b), and may contain as
much as 3% or more of phosphorus as component b).
The concentrations (weight percent of active ingre-
dient) of typical optional ingredients in the oleaginous
liquid compositions of this invention are gen~rally as
follows:
Case EI-6311 2~9~
- 79 -
Typical Preferred
Ranqe Ranqe
Antioxidant 0 - 4 0.05 - 2
Corrosion inhibitor 0 - 3 0.02 - 1
Foam inhibitor 0 - 0.30.0002 - 0.1
Neutral metal detergent 0 - 3 0 - 2.5
Supp~emental antiwear/EP agent 0 - 5 0 - 2
Supplemental ashless dispersant 0 - 100 - 5
10 Pour point depressant 0 - 5 0 - 2
Viscosity index improver 0 - 15 0 - 5
Friction modifier 0 - 3 0 - 1
Seal swell agent 0 - 20 0 - 10
Dye 0 - 0.10 - 0.05
The individual components a) and b), preferably compo-
nent c) and/or component d) as well, and also any and all
auxiliary components employed, can be separately blended
into the base oil or fluid or can be blended therein in var-
ious subcombinations, if desired. Moreover, such components
can be blended in the form of separate solutions in a dil-
uent. Except for viscosity index improvers and/or pour
point depressants (which are usually blended apart from
other components), it is preferable to blend the components
used in the form of an additive concentrate of this inven-
tion, as this simplifies the blending operations, reduces~he likelihood of blending errors, and takes advantage of
the compatibility and solubility characteristics afforded by
the overall concentrate. In this connection, in order to
minimize corrosive attack on yellow metals, it is desirable
to employ component c) and to arrange the blending order
such that components b) and c) are premixed prior to mixing
with component a).
The additive concentrates of this invention will
contain components a) and b), and preferably components c)
Case EI-6311 2 ~ 5
- 80 -
and/or d), in amounts proportioned to yield finished oil or
fluid blends consistent with the concentrations tabulated
above. In most cases, the additive concentrate will contain
one or more diluents such as light mineral oils, to facil-
itate handling and blending of the concentrate. Thusconcentrates containing up to 50% by weight of one or more
diluents or solvents can be used.
The oleaginous liquids provided by this invention can
be used in a variety of applications. For example, they can
be employed as crankcase lubricants, gear oils, hydraulic
fluids, manual transmission fluids, automatic transmission
fluids, cutting and machining fluids, brake fluids, shock
absorber fluids, heat transfer fluids, quenching oils,
transformer oils, and the like. The compositions are par-
ticularly suitable for use as crankcase lubricants for sparkignition (gasoline) engines, and compression ignition (die-
sel) engines.
Blendinq
The formulation or blending operations are relatively
simple and involve mixing together in a suitable container
or vessel, using a dry, inert atmosphere where necessary or
desirable, appropriate proportions of the selected ingre-
dients. Those skilled in the art are cognizant of and fami-
liar with the procedures suitable for formulating and blend-
ing additive concentrates and lubricant compositions. Whileit is usually possible to blend the components in various
sequences, it is distinctly preferable when forming the con-
centrates of this invention which are to contain components
a), b) and c~, to form the concentrate by preblending compo-
nents b) and c) prior to blending component a) therewith.In this way, the resultant product (whether an additive
concentrate or a finished lubricant) is substantially less
corrosive to yellow metals, such as copper, than material
formed by blending components a) and b) together prior to
addition of component c). Similarly, when utilizing a sul-
furized fatty ester polyalkanol amide type product such as
SUL-PERM 60-93 as a component, this type of ingredient is
preferably introduced into the additive concentrate or into
Case EI-6311 2~?~
81 -
the lubricating oil composition after inclusion therein of
at least components a) and b), and, if used, components c)
and/or d). In addition, when forming compositions of this
invention which are to contain a sulfurized antioxidant or
stabilizer and a sulfurized fatty ester-polyalkanol amide
type product such as SUL-PERM 60-93, it is preferable to
combine the sulfurized antioxidant or stabilizer with the
ashless dispersant component(s) prior to mixing with the
sulfurized fatty ester-polyalkanol amide type product. It
will be appreciated that in any blending operation, the
components being blended at any given time should not be
irreconcilably incompatible with each other.
Agitation such as with mechanical stirring equipment is
desirable to facilitate the blending operation. Frequently
it is helpful to apply sufficient heat to the blending
vessel during or after the introduction of the ingredients
thereto, so as to maintain the temperature at, say, 40-60C.
Similarly, it is sometimes helpful to preheat highly viscous
components to a suitable temperature even before they are
introduced into the blending vessel in order to render them
more fluid and thereby facilitate their introduction into
the blending vessel and render the resultant mixture easier
to stir or blend. Naturally the temperatures used during
the blending operations should b~ controlled so as not to
cause any significant amount of thermal degradation or un-
wanted chemical interactions.
When forming the lubricant compositions of this inven-
tion, it is usually desirable to introduce the additive
ingredients into the base oil with stirring and application
of mildly elevated temperatures, as this facilitates the
dissolution of the components in the oil and achievement of
product uniformity.
The practice and advantages of this invention are still
further illustrated by the following examples in which all
parts and percentages are by weight unless otherwise speci-
fically indicated. In these examples, the weights of the
various ingredients are on an "as received" basis -- i.e.,
the weights include solvents or diluents which are in the
Case EI-6311 2
- 82 ~
products as supplied. In forming the compositions described
in the ensuing examples, the preferred order of ~ddition is
to add component a) to a preblend of components b) and c),
and in those instances where a sulfurized fatty ester such
as SUL~PERM 60-93 is employed, to introduce this component
as the final component.
A particularly preferred method of forming such com-
positions is to form a mixture of components b) and c), or
a mixture of components b) and c) plus oil, and heat such
mixture for about 15 minutes at 50-60C. Thereupon all of
the other in~redients specified in the examples (except for
a sulfurized fatty ester such as SUL-PERM 60-93, if used)
can be added in any desired order and the resultant mixture
is heated at 50-60OC for about 45 minutes. When a fatty
ester such as SUL-PERM 60-93 is used, it is most preferably
added as the last component and the resulting composition is
heated at 50-60C for about 10 to 15 minutes. In these
operations the mixtures should be stirred throughout.
EXAMPLE I
A crankcase lubricating oil of this invention is formed
by blending together the following components:
Compo~ent a)1 1.20%
Component b) 2 5.00%
Component c)3 1.40%
25 Nonylphenol sulfide4 0.25%
Bis(p-nonylphenyl)amine5 0.05%
Antifoam agent6 0.04%
Process oil diluent 1.11%
Viscosity index improver7 5.40%
30 Sulfurized fatty ester~ 0.30%
Neutral calcium sulfonate9 0.25%
Base oil10 85.00%
100 . 00%
_
(1) Zinc dialkyl dithiophosphate (HiTEC~ 685 additive;
Ethyl Petroleum Additives, Inc.; Ethyl Petroleum
Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.; a
product having a mixture of alkyl groups formed from 40
mole % 2-propanol, 40 mole % isobutyl alcohol, and 20
Case EI-6311
- 83 ~ 2~9~
mole % 2-ethyl 1-hexanol).
(2) A product formed as in Example B-10.
(3) Overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl
Petroleum Additives, Inc.; Ethyl Petroleum Additives,
Ltd.; Ethyl S.A.; Ethyl Canada Ltd.; a product having
a nominal TBN of 300).
(4) HiTEC~ 619 additive; Ethyl Petroleum Additives, Inc;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.
(5) Naugalube 438L antioxidant; Uniroyal Chemical Company,
Inc.
(6) Dow Corning Fluid 200; 60,000 cSt, an 8% dimethyl sili-
cone solution from Dow Corning Company.
(7) Polymethylmethacrylate (Acryloid 954 polymer; Rohm &
Haas Chemical Company).
(8) SUL-PERM 60-93 (Keil Chemical Division of Ferro
Corporation).
~9) HiTEC~ 614 additive; Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.; a product having a nominal TBN of 30).
(10) A blend of 51% solvent refined mineral oil (Mobil MTN
736A) and 34% solvent refined mineral oil (Mobil M~N
737).
EXAMPLE II
Using the same ingredients as in Example I except where
otherwise indicated, a crankcase lubricating oil of this
invention is formed by blending together the following
components:
Component a) 0.82%
30 Component b)1 4.00%
Component c) 1.90%
Component d)2 2.00%
Phenolic antioxidant mixture3 1.00%
Antifoam agent 0.01%
35 Pour point depressant4 0.20%
Neutral calcium sulfonateS 1.25~
Process oil diluent 1~29%
Viscosity index improver 5.30%
Case EI-6311
- 8~ - 2~
Base oil6 82.23%
100.000%
(l) A product formed as in Example B-13.
(2) Boronated succinimide dispersant (HiTEC0 648 additive;
Ethyl Petroleum Additives, Inc.; Ethyl Petroleum
Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.)
(3) Ethyl~ antioxidant 738 diluted to a 50% solution with
process oil (Ethyl Corporation; Ethyl Canada Ltd.;
Ethyl S.A.).
(4) HiTEC~ 672 additive; (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
(5) HiTEC~ 614 additive; (Ethyl Petroleum Additives, Inc.;
15 Ethyl Petroleum Additives, Ltd.; Ethyl S.~.; Ethyl
Canada Ltd.)
(6) A blend of 65.50% Amoco SX-10 and 16.73% Amoco SX-20.
EXAMPLE III
The following components are blended together in the
amounts indicated:
Component a) 1.200%
Component b)1 6.000%
Component c) 1.310%
Nonylphenol sulfide 0.260%
25 Bis(p-nonylphenyl) amine 0.050%
Antifoam agent 0.005%
Process oil diluent 0.355%
Rust inhibitor 0.450%
Viscosity index improver2 10.200%
30 Neutral calcium sulfonate 0.320%
Base oil3 79.850%
100.000%
_
(1) A product formed as in Example B-l.
(2) Texas TLA 555 additive (Texaco, Inc., a dispersant-VII
copolymer).
(3) Exxon 100 Neutral Low Pour Point oil.
Case EI-6311
- 85 - 2~
EXAMPLE IV
Using the same ingredients as in Example II except
where otherwise indicated, a crankcase lubricating oil of
this invention is formed by blending together the following
components:
Component a) 0.650%
Component b)1 5.360%
Component c) 1.900%
Component d) 2.000%
Neutral calcium sulfonate1.250%
Phenolic antioxidant mixture1.000%
Antifoam agent 0.013%
Pour point depressant 0.200%
Viscosity index improver 5.300%
Process oil diluent 1.287%
Base oil2 81.040%
100.000%
_
(1) A product formed as in Example B-ll.
20 (2) A blend of 64.56% of Amoco SX-10 and 16.48% of Amoco
SX-20 oils.
EXAMPLE V
Using the same ingredients as in Example IV except
where otherwise indicated, a crankcase lubricating oil of
this invention is formed by blending together the following
components: -
Component a) 0.820%
Component b)1 ~.000%
Component c) 1.900%
Component d) 2.000%
Phenolic antioxidant mixture1.000%
Antifoam agent 0.013%
Pour point depressant 0.200%
Viscosi~y index improver 5.300%
Process oil diluent 2.537%
Base oil2 82.230%
Case EI-6311
- 86 - 2~
100.000%
(1) A product formed as in Example B-13.
(2) A blend of 65.50% of Amoco SX-10 and 16.73% of Amoco
SX-20 oils.
EXAMPLE VI
The procedures of Examples IV and V are repeated except
that in each case the phenolic antioxidant mixture is
eliminated and replaced by 0.5% of a partially sulfurized
mixture of tert-butyl phenols made by reacting EthylD
antioxidant 733 with sulfur monochloride, for example, as in
U.S. Pat. No. 4,946,610, and 0.5% of additional process oil.
EXAMPLE VII
The procedure of Example V is repeated using the same
ingredients as therein specified except where otherwise
indicated below:
Component a) 1.250%
Component b)1 4.690%
Component c) 1.500
20 Component d) 2.310%
Nonylphenol sulfide 0.500%
Neutral calcium sulfonate I.000%
Antifoam agent 0.037%
: Sulfurized fatty ester2 0.500%
25 Viscosity index improver3 8.500%
Pour point depressant 0.400%
Process oil diluent 1.583%
Antirust additive4 0.120%
Base oilS 77.610%
100.000%
_
(1) A product formed as in Example B-10.
(2) SUL-PERM 60-93 (Keil Chemical Division of Ferro
Corporation).
(3) Texaco TLA 656 additive (Texaco, Inc., a dispersant VII
Case EI-6311 2
- 87 -
olefin copolymer).
(~) Sterox ND (Monsanto Company), belived to be ~-
(nonylphenyl)-~-hydroxy-poly(oxy-1,2-ethanediyl).
(5) A blend of 50.45% of Mobil MTN 737B and 27.16% of Mobil
MTN 736A oils.
EXAMPLE VIII
The procedure of Example VII is repeated using the same
ingredients as therein specified except where otherwise
indicated below:
Component a) 0.820%
Component b)1 3.750%
Component c) 1.860%
Component d) 2.000%
Nonylphenol sulfide 0.520%
Neutral calcium sulfonate 1.150%
Antifoam agent 0.037%
Viscosity index improver2 0.150%
Antirust additive 0.120%
Process oil diluent 1.573%
Base oil3 88.020%
100.000%
_
(1) A product formed as in Example B-13.
(2) Paramins ECA 7955 additive (Exxon Chemicals, a division
of Exxon Corporation).
(3) A blend of 73.06% of Ashland lOON and 14.96~ of Ashland
330 N solvent refined oils.
EXAMPLE IX
The procedures of Examples VII and VIII are repeated
except that in each case the nonyl phenol sulfide is
eliminated and replaced by a corresponding amount of a
partially sulfurized mixture of tert-butyl phenols described
in Example VI.
Case EI-6311
- ~38 -
EXAMPLE X
A synthetic lubricant of this invention is formed by
blending together the follo~ling components in the amounts
specified:
Component a)l 0.500%
Component b) 2 6.000%
Component c) 3 1 . 500%
Neutral calcium sulfonate4 0.500%
Partially sulfurized tert-butyl phenols5 0.500%
Antifoam agent6 0.010%
Antirust additive7 0.150%
Pour point depressant8 0.300%
Process oil diluent 0.710%
Viscosity index improver9 4.200%
Base oil10 85.630%
100.000%
_
(1) Zinc dialkyl dithiophosphate (HiTEC~ 685 additive;
Ethyl Petroleum Additives, Inc.; Ethyl Petroleum
Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.; a
product having a mixture of alkyl groups formed from 40
mole % 2-propanol, 40 mole % isobutyl alcohol, and 20
mole % 2-ethyl-1-hexanol).
(2) A product formed as in Example B-13.
(3) Overbased calcium sulfonate (HiTEC~ 611 additive; Ethyl
Petroleum Additives, Inc.; Ethyl Petroleum Additives,
Ltd.; Ethyl S.A.; Ethyl Canada Ltd.; a product having
a nominal TBN of 300).
(4) Neutral calcium sulfonate (HiTEC~ 614 additive; Ethyl
Petroleum Additives, Inc.; Ethyl Petroleum Additives,
Ltd.; Ethyl S.A~; Ethyl Canada Ltd.; a product having
a nominal TBN of 30).
(5) A product formed by reacting ETHYL~ Antioxidant 733
with sulfur monochloride, for example as in U.S. Pat.
No. 4,946,610.
(6) Dow Corning Fluid 200; 60,000 cSt, an 8% dimethyl sili-
cone solution from Dow Corning Company.
(7) Sterox ND (Monsanto Company), believed to be ~-(nonyl-
phenyl)-~-hydroxy-poly(oxy~1,2-ethanediyl).
(8) Santolube C (Monsanto Company).
Case EI-6311 2~9~
- 89 -
(9) Texaco TLA 347A additive, (Texaco Inc.).
(10) A blend of 77.26% 8 cSt poly-~-olefin oil (ETHYLFL0 168
oil; Ethyl Corporation; Ethyl Canada Ltd.; Ethyl S.A.)
and 8.37% 4 cSt poly-~-olefin oil (Emery 2921 oil;
Emery Group of Henkel Corporation).
EXAMPLE XI
The procedure of Example X is repeated except that
compon~nt b) is prepared as in Example B-1 and is employed
at a concentration of 5.940% and the amount of process oil
used is 0.770%.
EXAMPLE XII
The procedure of Example X is repeated using the same
ingredients except as otherwise specified:
Component a) 0.500%
15 Component b) 6.000%
Component c) 1.900%
Neutral calcium sulfonate 1.250%
Partially sul~urized tert-butyl phenols 0.750%
Bis(p-nonylphenyl)amine1 0.050%
20 Antifoam agent 0.010%
Antirust additive 0.~50%
Process oil diluent 2.050%
Base oil2 87.340%
100.000%
- - - - _ _ _
(1) Naugalube 438L antioxidant; Uniroyal Chemical Company,
Inc.
(2) A blend of 78.806% 8 cSt poly-~-olefin oil ~ETHYLFL0
168 oil; Ethyl Corporation; Ethyl Canada Ltd.; Ethyl
S.A.) and 8.534% 40 cSt poly-~-olefin oil (ETHYLFL0 174
oil; Ethyl Corporation; Ethyl Canada Ltd.; Ethyl S.A.).
Case EI-6311 2 0 ~
- 90 -
EXAMPLE XIII
The procedure of Example XII is repeated using the same
ingredients except where otherwise specified:
Component a) 0-500%
Component b) 6.000~
Component c) 1.900%
Neutral calcium sulfonate 1.250%
Partially sulfurized tert-butyl phenols 0.750%
Bis(p-nonylphenyl)amine 0.050%
10 Antifoam agent 0.010%
Viscosity index improver1 7.200%
Process oil diluent 0.260%
Base oilZ 82.080%
100.000%
- - - _ _ _ _
(1) Paratone 715 (Exxon Chemical Company).
(2) A blend of 69.77% 8 cSt poly-a-olefin oil (ETHYLFL0 168
oil; Ethyl Corporation; Ethyl Canada Ltd.; Ethyl S.A.)
and 12.31% 40 cSt poly-~-olefin oil (ETHYLFL0 174 oil;
Ethyl Corporation; Ethyl Canada Ltd.; Ethyl S.A.).
EXAMPLE_XIV
An additive concent1ate of this invention is formed by
blending together the following components as identified in
~xample I:
25 Component a) 12.50%
Component b) 52.08%
Component c) 14.58%
Neutral calcium sulfonate 2.60%
Nonylphenol sulfide 2.60%
30 Bis(p-nonylphenyl)amine 0.52%
Antifoam agent 0.42%
Sulfurized fatty ester 3.13%
Process oil diluent 11.57%
100. 00%
Case EI-6311
-- 91 --
EXAMPLE XV
An additive concentrate of this invention is formed by
blending together the following components as identified in
Example II:
Component a) 6.11%
Component b) 38.33%
Component c) 14.17%
Component d) 14.91%
Phenolic antioxidant mixture7.46%
Neutral calcium sulfonate 9.32%
Antifoam agent 0.07%
Process oil diluent 9.63%
100. 00%
EXAMPLE XVI
15 An additive concentrate of this invention is formed by
blending together the following components as identified in
Example IV:
Component a) 4.83%
Component b) 39.82%
Component c) 14.12%
Component d) 1~.86%
Neutral calcium sulfonate 9.29%
Phenolic antioxidant mixture7.43%
Antifoam agent 0.10%
Process oil diluent 9.55%
100.00%
EXAMPLE XVII
An additive concentrate of this invention is formed by
blending together the following components as identified in
Example V:
Component a) 6.68%
Component b) 32.60%
Component c) 15.48%
Component d) 16.30%
Phenolic antioxidant mixture8.15%
Antifoam agent 0.11%
Case EI-6311
- 92 - 2~
Process oil diluent 20.68%
100.00%
EXAMPLE XVIII
An additive concentrate of this invention is formed by
blending together the following components as identified in
Example VII:
Component a) 9.27%
Component b) 34.77%
Component c) 11.12%
Component d) 17.12%
Nonyl phenol sulfide 3.71%
Neutral calcium sulfonate 7.41%
Antifoam agent 0.27%
Sulfurized fatty ester 3.71%
Antirust additive 0.89%
Process oil diluent 11.73%
1~0.00%
EXAMPLE XIX
An additive concentrate of this invention i5 formed by
blending together the following components as identified in
Example VIII:
Component a) 6.93%
Component b) 31.70%
Component c) 15.72%
Component d) 16.91%
Nonyl phenol sulfide 4O40%
Neutral calcium sulfonate ~ 9.72%
Antifoam agent 0.31%
Antirust additive 1.01%
Process oil diluent 13.30%
100. 00%
EXAMPLE XX
An additive concentrate of this invention is formed by
blending together the following components:
Component a)l 5.81%
2 ~
Case EI-6311
- 93 -
Component b)2 75.60%
Component c) 3 14.43%
Nonyl phenol sulfide 2.81%
Bis(p~nonylphenyl)amines 0.50%
Antifoam agent6 0.05%
Process oil diluent 0.80%
100.00%
_
(1) Zinc dialkyl dithiophosphate (HiTEC~ 685 additive;
Ethyl Petroleum Additives, Inc.; Ethyl Petroleum
Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.; a
product having a mixture of alkyl groups formed from 40
mole % 2~propanol, 40 mole % isobutyl alcohol, and 20
mole % 2-ethyl-1-hexanol).
(2) A product formed as in Example B-9.
(3) Overbased calcium sulfonate (HiTEC0 611 additive; Ethyl
Petroleum Additives, Inc.; Ethyl Petroleum Additives,
Ltd.; Ethyl S.A.; Ethyl Canada Ltd., a product having
a nominal TBN of 300).
(4) HiTEC~ 619 additive; (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
(5) Naugalube 438L antioxidant; Uniroyal Chemical Company,
Inc.
(6) Dow Corning Fluid 200; 60,000 cSt, an 8% dimethyl sili-
cone solution from Dow Corning Company.
A lubricant composition of this invention is formed by
blending the above concentrate and a viscosity index
improver in a base oil as follows:
Case EI-6311 9 4
- 94 -
Above additive concentrate 9.979%
Viscosity index improver1 7.000%
Base oil2 83.021%
100.000%
- - - ~ _ _
(1) Polymethylmethacrylate viscosity index improver
(Acryloid 953 polymer; Rohm ~ Haas Chemical Company).
(2) A blend of 62.05% Turbine 5 oil (a 100 Solvent Neutral
refined mineral oil) and 20.97i% Esso Canada MCT-10 oil
(a 150 Solvent Neutral refined mineral oil).
EXAMPLE XXI
An additive concentrate of this invention is formed by
blending together the components as identified in Example
XX, except as otherwise indicated, in the following
proportions:
Component a) 6.68%
Component b)l 32.60%
Component c) 15.48%
Component d) 2 16.30%
Antifoam agent 0.11%
Phenolic antioxidant mixture3 8.15%
Process oil diluent 20.68%
100. 00%
(1) A product formed as in Example B-13.
(2) HiTEC~ 648 additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
(3) Ethyl~ Antioxidant 738 (Ethyl Corporation; Ethyl Canada
Ltd.; Ethyl S.A.) diluted to a 50% solution in process
oil.
A lubricant composition of this invention is formPd by
blending the above concentrate, a viscosity index improver,
and a pour point depressant in a base oil described below:
Case EI-6311
- 95 -
Above additive concentrate 12.270%
Viscosity index improver1 5.300%
Pour point depressant2 0.200%
Base oil3 82.230%
100.000%
(1) Polymethacrylate viscosity index improver (Acryloid 954
polymer; Rohm & Haas Chemical Company).
(2) Sterox ND (Monsanto Company), believed to be ~-(nonyl-
10 phenyl)-~-hydroxy-poly(oxy-1,2-ethanediyl).
(3) A blend of 65.504% of Amoco SX-lo and 16.726% o~ Amoco
SX-20 oils.
EXAMPLE ~XII
A lubricant of this invention is formed by blending
together the components as identified in Example XXI, except
as otherwise indicated, in the following proportions:
Component a) 0.880%
Component b)1 3-000%
Component c) l.gO0%
20 Component d) 2 2.330%
Component d)3 0.670
Neutral calcium sulfonate4 1.250%
Antifoam agent 0.013%
Bis(p-nonylphenyl)amineS 0.050%
25 Phenolic antioxidant mixture 1.000%
Process oil diluent 1.287%
Pour point depressant6 0.200%
Viscosity index improver7 10.700%
Base oil8 76.720%
100.00%
_
(1) A product formed as in Example B-10.
(2) A product formed as in Example D-8.
(3) HiTEC~ 648 additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
Case EI~6311 ~ 4
- 96
(4) HiTEC~ 614 additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
(5) Naugalube 438L antioxidant; Uniroyal Chemical Company,
Inc.
(6) Sterox ND (Monsanto Company), believed to be ~-(nonyl-
phenyl)-~-hydroxy-poly(oxy-1,2-ethanediyl).
(7) Amoco 6565 viscosity index improver.
(8) A blend of 56.006% of Amoco SX-10 and 20.714% of Amoco
SX-20 oils.
The lubricating oil compositions of Examples I and II
were subjected to the standard Sequence VE engine test
procedure. The results of this evaluation are summarized in
the following table, which also shows the American Petroleum
Institute SG passing limits for the various parameters.
Table - Seguence VE Test Results
Passing
20 Ratin~: This Invention API SG Limits
En~ine Cleanliness Example I Example II
Average Sludge 9.32 9.40 9.0 min.
Average Varnish 6.56 6.95 5.0 min.
25 Rocker Arm Cover Sludge 8.65 8.70 7.0 min.
Piston Skirt ~arnish 6.91 7.04 6.5 min.
En~ine Wear
Average Cam Lobe Wear, mils 2.14 0.52 5.0 max.
Maximum Cam Lobe Wear, mils 6.40 0.70 15.0 max.
The antiwear advantages that can be achieved by the
practice of this invention were further illustrated by a
series of standard 4-Ball wear tests (40 kg load, 1800 rpm,
54.4C (130F), 30 minute test length~ on three lubricating
oil compositions having the same total concentration of
phosphorus therein. The compositions were identical to each
other except that one such composition (Oil A) contained
Case EI-6311 2 ~ 5
- 97 -
only zinc dialkyldithiophosphate as the phosphorus-contain-
ing component whereas another such composition (Oil B)
contained a phosphorylated succinimide of this invention as
the sole source of phosphorus. Oil C, a representative com-
position of this invention, contained the combination ofboth the same zinc dialkyldithiophosphate and the same phos-
phorylated succinimide dispersant. All compositions con-
tained in addition the same concentration of overbased cal-
cium sulfonate having a nominal TBN of 300. The makeup of
these compositions was as follows:
Oil A
1.18 grams of zinc dialkyldithiophosphate1
1.23 grams of overbased calcium sulfonate2
97.59 grams of mineral oil3
15 Oil B
10.2g ~rams of phosphorylated succinimide4
1.23 grams of overbased calcium sulfonateZ
8~.48 grams of mineral oil3
Oil C
0.59 grams of zinc dialkyldithiophosphate
5.14 grams of phosphorylated succinimide4
1~23 grams of overbased calcium sulfonate2
93.04 grams of mineral oil3
(1) HiTEC~ 685 Additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.)
(2) HiTEC~ 611 Additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.)
(3) Turbine 5 oil, a 100 Solvent Neutral refined mineral
oll .
(4) Prepared as in Example B-13~
The results of these 4-Ball tests were as follows:
Composition Scar Diameter, mm
Oil A 0.433
Oil B 0.608
Oil C 0.416
.
2~9~
Case EI-6311
- 98 -
In another pair of 4-Ball Tests, two blends were formed
from the same base oil. Blend A contained the following:
1.2% of zinc dialkyldithiophosphate1
1.3% of overbased calcium sulfonate2
0.5~ of sulfurized fatty ester3
6.0% of non-phosphorylated, non-boronated succinimide4
Blend B contained the following:
1.2% of zinc dialkyldithiophosphate1
1.3~ of overbased calcium sulfonate2
0.5% of sulfurized fatty ester3
7.5% of phosphorylated, non-boronated succinimide5
_
(1) HiTEC~ 685 Additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
(2) HiTEC~ 611 Additive (Ethyl Petroleum Additives, Inc.;
~thyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
(3) SUL-PERM 60-93 (Keil Chemical Division of Ferro
Corporation).
(4) Polyisobutenyl succinimide derived from polyisobutene
with Mn of 1300 and a mixture of polyethylene
poIyamines with an overall composition approximating
that of tetraethylene pentamine).
(5) Product formed as in E~ample B-ll.
The results of these 4-Ball tests were as follows:
Composition Scar Diameter mm
Blend A 0.437
Blend B 0.372
The ability of overbased alkali or alkaline earth
metal-containing detergents to suppress copper corrosion was
demonstrated by a pair of tests employing a base oil
(Turbine 5 oil) containing in one instance components a), b)
and c) and in another instance omitting component c) from
the composition. These tests were conducted according to
ASTM D-130 but under more severe conditions, viz., operation
at 121C rather than at the standard temperature of 100C.
Case EI~6311 2 ~
99
In these tests component a) was HiTEC~ 685 additive (a zinc
dialkyl dithiophosphate described above), component b) was
formed as in Example B-ll, and component c) was HiTEC~ 611
additive (an overbased calcium sulfonate). The compositions
tested (weight percentages) and the results obtained
therewith are tabulated below:
Com~ositions Run 1 Run 2
Component a) 0.65 0.65
Component b) 5.36 5.36
Component c) -- 1.90
Base oil 93.99 92.09
Results: 4b lb/2a with
trace of 2d
Another pair of D-130 tests was conducted as above
using the same materials as components a), b) and in one
instance, c). The makeup of the compositions tested and the
test results were as follows:
CoTnositions Run 1Run 2
Component a) 0.77 0.77
20 Component b~ 3.00 3.00
Component c~ -- 1.40
Component d)1 2.00 2.00
Neutral calcium sulfonate2 0.30 0.30
Antifoam agent3 0.01 0.01
25 Process oil 0.62 0.62
Base oil4 93.3091.gO
Results: 4a la
Case EI-6311
- 100 -
_
(1) HiTEC~ 648 Additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
~2) HiTEC~ 614 Additive (Ethyl Petroleum Additives, Inc.;
Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada Ltd.).
(3) Dow Corning Fluid 200; 60,000 cSt, an 8~ dimethyl sili-
cone solution from Dow Corning Company.
(4) Turbine 5 oil.
Still another series of D-130 Tests conducted as above
using the same materials as above for components a), b) and
c), demonstrated the fact that the beneficial effects on
reduced copper corrosivity engendered by use of a metal-
containing detergent of relatively high TBN are realizedover a wide range of proportions. The makeup of the test
compositions and the results obtained are summarized in the
following table:
com~ositionsun 1Run 2 Run 3 Run 4
20 Component a)0.77 0.77 0.77 0.77
Component b)5.00 4.00 3.00 2.00
Component c)1.40 1.40 1.40 1.40
Base oil92.83 93.83 94.83 95.83
Results: lb la la la
Another feature of this invention is that the particu-
larly preferred phosphorylated alkenyl succinimides of
polyethylene polyamines made from alkenyl succinic
anhydrides (or like succinic acylating agents, such as the
acid, acid halide, lower alkyl ester, lower alkyl-acid
ester) in which the succination ratio (i.e., ratio of the
average number of succinic groups per alkenyl group chemi-
cally bound in the acylating agent) is in the range of 1:1
to 1.3:1 and in which the alkenyl group is derived from a
polyolefin having a number average molecular weight in the
range of 600 to 1,300 (preferably 700 to 1,200, and most
preferably 800 to 1,100) when utilized in accordance with
this invention can provide greater dispersancy than the same
Case EI-6311 2 ~ ~ ~ 9 ~ ~
-- 101 --
concentration or an even higher concentration of an analo-
gous succinimide not containing phosphorus or an analo~ous
boronated succinimide not containing phosphorus.
For example, a group of lubricant compositions made
from different succinimide dispersants were subjected to a
bench test simulating sludge performance in the Sequence VE
engine tests. This test involves subjecting each lubricant
to standard Hot Oil Oxidation Test (HOOT) conditions and
determining the change in dielectric constant of the lubri-
cants before and after the oxidation. On completion of theoxidation, the oxidized oil is mixed with a known amount of
standard oxidized oil (a laboratory preparation) and diluted
with a hydrotreated base stock. Turbidity measurements are
then taken and then dielectric constant measurement, HOOT
time and turbidity data, are combined into a single number
for reporting and comparison purposes. A lower number
indicates better anti-sludge properties.
The lubricant compositions subjected to this test were
as described in Example III except that component b) was
varied as indicated in the following table. The results of
these tests were as follows:
case EI-6311 2~9~5
- 102 -
Bench Test
Run No. Succinimide Dispersant Used Sludqe Factor
1 Phosphorylated (Mn = 950)1 62.6
2 Phosphorylated (Mn = 950) 2 290.0
3 Phosphorylated (Mn = 950) 3 68.9
4 Phosphorylated (Mn = 1300) 4 65.8
Phosphorylated (Mn = 1300)5 492.0
6 Phosphorylated (Mn = 1300) 6 71.2
_
(1) Produced as in Example B-13.
(2) Produced as in Example B-45.
(3) Produced as in Example B-40.
(4) Produced as in Example B-11.
(5) Produced as in Example B-46.
(6) Produced as in Example B-12.
The results tabulated above indicate, among other things,
that when the finished oil contained significantly less than
than 0.03% by weight of phosphorus as component b) in the
particular formulation tested (Run Nos. 2 and 5), optimum
results were not achieved. Putting the matter a different
way, these results indicate that on an equal weight basis
the component b) materials produced as in Examples B-11, B-
25 12, B-13, and B-40 were substantially more effective than
those produced as in Examples B-45 and B-46.
Data further illustrating the effectiveness of various
embodiments of this invention under various test conditions
are summarized below.
An SAE 15W40 lubricant of this invention formulated as
-in Example V was subjected to the Toyota 3AU test procedure
to assess valve train wear. After 100 hours a rocker arm
demerit rating of 22.2 was obtained.
An SAE 15W40 lubricant of this invention formulated as
case EI-~311 2 ~ 3
- 103 -
in Example XXII was subjected to the Sequence VE test
procedure. The results were as follows:
Ratinq
Average Sludge 9.29
5 Average Varnish 6.27
Rocker Arm Cover Sludge 8.68
Piston Skirt Varnish 6.82
Engine Wear
Average Cam Lobe Wear, mils 0.98
10 Maximum Cam Lobe Wear, mils 2.10
This same composition was subjected to the L-38 test
and gave a bearing weight loss of only 14.8 mg. The limit
for passing the test is 40 mg.
Rendering the results achievable by the practice of
this invention all the more remarkable is the fact that in
U.S. Pat. No. 4,873,004 it is pointed out that to achieve
improved dispersancy properties it is necessary to have a
molar ratio of succinic groups to alkenyl groups (sometimes
referred to as the "succination ratio") of at least 1.4 when
~0 using succinimides made from polyamines such as tetra-
ethylene pentamine and polyisobutenyl succinic anhydrides
having number average molecular weights in the range of 600
to 1,300. For example the patent shows in its Tables 3 and
4 that with succinimide derived from polyisobutylene of num-
ber average molecular weight of 95Q, maleic anhydride andtetraethylene pentamine, products having a succination ratio
of 1.0 gave inferior results on dispersancy and varnish
formation than corresponding succinimides in which the
succination ratio was 1.8. Yet as shown by some of the
results presented above, phosphorylated polyisobutenyl
succinimides with a succination ratio of 1.18 made from
polyisobutene of number average molecular weight of about
950, gave excellent results both on dispersancy and on wear
prevention.
As used in the foregoing description, the term "oil-
soluble" is used in the sense that the component in question
has sufficient solubility in the selected base oil in order
Case EI~6311 ~ 3 d, 5
- 104 -
to dissolve therein at ordinary temperatures to a concentra-
tion at least equivalent to the minimum concentration speci-
fied herein for use of such component. Preferably, however,
the solubility of such component in the selected base oil
will be in excess of such minimum concentration, although
there is no requirement that the component be soluble in the
base oil in all proportions. As is well known to those
skilled in the art, certain useful additives do not com-
pletely dissolve in base oils but rather are used in the
form of stable suspensions or dispersions. Additives of
this type can be employed in the compositions of this in-
vention, provided they do not significantly interfere with
the performance or usefulness of the composition in which
they are employed.
2 ~
Case EI-6311
- 105 -
Some additional embodiments of this invention are:
A. Lubricant or functional fluid compositions of the in-
vention wherein the total halogen content, if any, of
the overall composition does not exceed 100 ppm.
B. Additive concentrates of the invention which, if dis-
solved in a halogen-free base oil, at a concentration
of 10% b~ weight, yields an oleaginous composition in
which the total halogen content, if any, is 100 ppm or
less.
C. Lubricant or functional fluid compositions of the in-
vention wherein the composition contains at least about
0.03% of phosphorus, preferably at least about 0.04% of
phosphorus, more preferably at least about 0.05% of
phosphorus, and most preferably at least about 0.06% of
phosphorus, as component b).
D. A mechanical mechanism in which an elastomeric material
is in contact with a lubricant or functional fluid of
the invention.
E. A mechanical mechanism in accordance with D wherein
said elastomeric material comprises a fluoroelastomer.
F. Apparatus in accordance with D or E wherein said
mechanical mechanism is an internal combustion engine.
G. Apparatus in accordance with D or E wherein said me-
chanical mechanism is a spark-ignition (gasoline)
engine.
H. Apparatus in accordance with D or E wherein said me-
chanical mechanism is a compression-ignition (diesel)
engine.
I. Apparatus in accordance with D or E wherein said me-
chanical mechanism is a vehicular transmission.
J. Apparatus in accordance with D or E wherein said me-
chanical mechanism is a vehicular automatic transmis-
sion.
K. Apparatus in accordance with D or E wherein said me-
chanical mechanism is a vehicular manual transmis ion.
L. Apparatus in accordance with D or E wherein said me-
chanical mechanism is a gear box.
