Note: Descriptions are shown in the official language in which they were submitted.
Case EI-b214 +
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OIL ADDITIVE CONCENTRATES AND LUBRICANTS
OF ENHANCED PERFORIyIANCE CAPABILITIES
This invention relates to additive concentrates and oleaginous compositions
(i.e., lubricating oils and f<mctional fluids) having enhanced performance
properties.
Heretofore a number of additive concentrates containing, inter alia, sulfur-
containing antiwear and/or extreme pressure additives, phosphorus-containing
antiwear and/or extreme pressure additives, and other additive components have
been proposed and used. Among such other additive components are acidic
components such as carboxylic acids, hydrocarbyl phosphoric acids, and
hydrocarbyl
thiophosphoric acids; basic components such as amines; and ashless dispersants
such a.S boronated succinimides.
In order to qualify for premium automotive gear oil usage, the finished
lubricating oil composition and additive concentrate from which it is made
must
be formulated to meet the American Petroleum Institute GL-5 requirements. This
involves passing a battery of standard tests. In addition, the provision of
clean gears
in the L-60 test is an important consideration in the marketplace. So far as
is
known, only a very limited number of lubricant additive packages have received
GL-5 approval. Thus there is a need for additional automotive gear oil
packages
which give good performance in the GL-S qualification tests, and especially
for
packages capable of satisfying the GL-S requirements.
There is, additionally, a need for automotive gear oil formulations which
not only meet the GL-S requirements but which afford superior results in the
standard planetary spur gear test.
Still another need is for an ashless or low-ash lubricant additive package
affording high dispersancy and high wear resistance to lubricants, such as
crankcase
lubricants, gear lubricants, manual and automatic transmission fluids; oil-
teased
hydraulic fluids, wet brake fluids, and similar lubricants and functional
fluids.
Yet another need is for an automotive or industrial gear oil package which
performs well in synthetic base oils.
In accordance with one embodiment of this invention, there is provided an
additive concentrate which comprises a minor proportion of diluent oil and a
major
Case EI-6214 +
_2_
proportion of additive components, said additive components comprising:
a-1) at least one oil-soluble additive composition formed by heating
concurrently
or in any sequence at least one ashless dispersant which contains basic
nitrogen and/or at least one hydroxyl group with (i) at least one inorganic
S phosphorus acid or anhydride, or at least one partial or total sulfur analog
thereof, or any combination of the foregoing, and (ii) at least one boron
compound; such that a liquid composition is formed; or
a-2) at least one oil-soluble boron-free additive composition formed by
heating
(i) at least one boron-free oil-soluble ashless dispersant containing 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; or
a-3) one or more oil-soluble additive compositions formed by heating
concurrently or in any sequence at .least one ashless dispersant which
contains basic nitrogen and/or at least one hydroxyl group with (i) at least
one water-hydrolyzable organic phosphorus compound and water; and (ii)
at least one baron compound; such that a liquid phosphorus- and boron-
containing composition is formed; or
a-4) one or more oil-soluble boron-free additive compositions formed by
heating
concurrently or in any sequence (i) at least one boron-free oil-soluble
ashless
dispersant which contains basic nitrogen and/or at least one hydroxyl group,
with (ii) -at least one water-hydrolyzable organic phasphorus compound and
water; such that a liquid boron-free phosphorus-containing composition is
fornned; and
b) at least one oil-soluble metal-free sulfur-containing antiwear and/or
extreme
pressure agent having a sulfur content of at least 20% by weight.
The term "component a)" as used hereinafter refers collectively to the above
components a-1), a-2), a-3) and a-4).
The cooperation between components a) and b) of such compositions 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
Case EI-6214 +
_3_
concentrations of component b).
More particularly, the cooperation between components a) and b) can
provide these important performance-improving effects:
1) inhibition of scoring or scuffing such as results from micro-welding of
asperities between relatively moving metallic mechanical energy transferring
surfaces in close proximity to each other, particularly under conditions of
high speed and shock;
2) inhibition of ridging and rippling such as results from metal deformation
or surface flow of relatively moving metallic surfaces in close proximity to
each other, particularly under conditions of low speed and high torque;
3) inhibition of pitting and spilling such as results from metal fatigue in
relatively moving metallic surfaces in close proximity to each other,
particularly under conditions of low speed and high torque; and
4) inhibition of sludge and varnish formation in base oils and/or deposition
of sludge and/or varnish on both stationary and relatively moving parts of
engines, hydraulic systems, gear boxes, power transmissions or like
mechanisms, especially when operated under high temperature conditions.
Thus, the additive combinations of this invention have the capability of
contributing
greatly improved performance properties to base ails of lubricating viscosity,
including animal, vegetable, mineral, and synthetic oils. For example,
significantly
improved properties can be achieved in lubricant compositions of this
invention
when subjected to various API GL-5 test procedures, such as enhanced extreme
pressure properties as seen in the standard L-42 test, improved antirust
performance
as seen in the standard L-33 test, and/or clean gears as seen in the standard
L-60
test. Indeed, particularly preferred compositions of this invention are those
which
sitisfy all of the requirements of the API ~iL-S test procedures. In addition,
particu-
larly preferred compositions of this invention exhibit superior performance in
the
standard planetary spur gear test.
In order to achieve optimum beneficial performance effects such as those
referred to above, components a) and b) should be proportioned such that the
mass
ratio (wt:wt) of sulfur in component b) to phosphorus in component a) is in
the
Case EI-6214+
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- _4-
range of 8:1 to 30:1, more preferably in the range of 10:1 to 20:1, and most
preferably in the range of 14:1 to 20:1. The finished lubricating oils of this
invention
will usually contain at least about 0.5 wt % of sulfur as component b) and
preferably
will contain an amount of component b) to provide a sulfur content in the
finished
lubricant in the range of 1 to 3 wt %, and more preferably in the range of 1.5
to
3 wt %, of the total weight of the composition.
In preferred embodiments, the foregoing additive concentrates further
comprise one or more of the following additive components:
c) at least one oil-soluble amine salt of a mono- or dihydrocarbyl ester of a
monomeric pentavalent acid of phosphorus, preferably wherein the acid is
phosphoric acid or a monothiophosphoric acid; and/or
d) at least one oil-soluble trihydrocarbyl ester of a dithiophosphoric acid;
and/or
e) at least one oil-soluble amine salt of a carboxylic acid; and/or
f) at least one oil-soluble demulsifying agent; and/or
g) at least one oil-soluble copper corrosion inhibitor.
When component a-2) or a-4) is used, the following additive component can also
be used in preferred embodiments:
h) at least one oil-soluble or oil-dispersible boron-containing additve
composition.
Also provided by this invention are lubricant compositions which comprise
a major proportion of at least one oil of lubricating viscosity and a minor
amount
of the various additive combinations referred to hereinabove.
Preferably, the compositions of this invention are ashless compositions (i.e.,
they contain no metal-containing additive components) or are low-ash
compositions
(i.e., base oil containing an additive concentrate or a combination of
additives
pursuant to this invention at a total concentration of 10% by weight will
contain
no more than 100 parts by weight, and more preferably no more than 50 parts by
weight, of added metal per million parts by weight of the total composition.
Component a) -- i.e., a-1), a-2), a-3) or a-4) -- is one indispensable
additive
ingredient of the compositions of this invention.
Case EI-6214 +
Component a-1) -- Phosphorylated & Boronated Ashless Disnersant
These oil-soluble additive compositions are formed by heating concurrently
or any sequence at least one ashless dispersant which contains basic nitrogen
and/or
at least one hydroxyl group with (i) at least one inorganic phosphorus acid or
anhydride or at least one partial or total sulfur analog thereof, or any
combination
of the foregoing, and (ii) at least one boron compound, such that a liquid
compo-
sition is formed. The ashless dispersant which is heated concurrently or in
any
sequence with components (i) and (ii) is preferably a preformed ashless
dispersant
containing basic nitrogen and/or at least one hydroxyl group. Thus, for
example,
any suitable ashless dispersant formed in the customary manner can be heated
with
one or more boron compounds to cause boronation to occur and the resultant
product mixture can then be heated with one or more inorganic phosphorus
compounds such that a liquid phosphorus- and boron-containing composition
[component a-1)] is formed. Conversely, a preformed ashless dispersant can be
heated with one or more inorganic phosphorus compounds and thereafter the
product mixture can be heated with one or mare boron compounds so that a
liquid
phosphorus- and boron-containing composition is formed. The preferred way of
forming component a-1) is to heat a preformed ashless dispersant with a
combina-
tion of one or more inorganic phosphorus compounds and one or more boron com-
pounds to form a liquid phosphorus- and boron-containing composition. In other
words, to form component a-1) in the preferred manner, the preformed ashless
dispersant is concurrently heated with one or more inorganic phosphorus
compounds
and one or more boron compounds. In all cases, the resulting liquid product
com
position when subjected to chemical analysis reveals the presence of both
phosphorus and boron.
Rather than utilizing a preformed ashless dispersant containing basic nitrogen
and/or at least one hydroxyl group, it is possible to produce component a-1)
by:
1) forming the ashless dispersant in the presence of one or more
suitable boron compounds (e.g., boron ester or boron oxide) and then
heating the resultant composition with one or more inorganic
phosphorus compounds; or
2) forming the ashless dispersant in the presence of one or more
base EI-6214+
_6_
suitable inorganic phosphorus compounds (e.g., a phosphorus oxide
or sulfide) and then heating the resultant composition with one or
more boron compounds; or
3) forming the ashless dispersan2 in the presence of one or more
suitable boron compounds (see 1) above) and one or more suitable
inorganic phosphorus compounds (see 2) above); or
4) heating one or more boron compounds with a basic nitrogen-
containing and/or hydroxyl group-containing reactant used in forming
the ashless dispersant, using the resultant boronated reactant to form
the ashless dispersant and then heating the resultant ashless disper-
sans with one or more inorganic phosphorus compounds; or
5) heating one or more inorganic phosphorus compounds with a basic
nitrogen-containing and/or hydroxyl group-containing reactant used
in forming the ashless dispersant, using the resultant phosphorylated
reactant to form the ashless dispersant arid then heating the resultant
ashless dispersant with one or more boron compounds; or
6) heating one or more inorganic phosphorus compounds and one more
boron compounds with a basic nitrogen-containing and/or hydroxyl
group-containing reactant used in forming the ashless dispersant, and
using the resultant phosphorylated and boronated reactant to form
the ashless dispersant.
In all cases, the final product composition [component a-1)] should be a
liquid
composition that on analysis reveals the presence of boron and phosphorus.
~omnonent a-2 - Phosphorvlated AShless Dis~ersant
'These oil-soluble additive compositions are formed by heating (i) at least
one boron-free oil-soluble ashless dispersant containing 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 nitrogen and/or at least one hydroxyl
group.
Thus, for example, any suitable boron-free ashless dispersant formed in the
customary manner can be heated with one or more inorganic phosphorus acids
Case EI-b214 +
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to cause phosphorylation to occur. The resulting liquid product composition
when
subjected to chemical analysis reveals the presence of phosphorus.
Rather than utilizing a preformed ashless dispersant containing basic nitrogen
and/or at least one hydroxyl group, it is possible to produce component a-2)
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
nitrogen-containing and/or hydroxyl group-containing reactant used
in forming the ashless dispersant, and using the resultant
phosphorylated reactant to form the ashless dispersant.
In all such cases, the final product composition [component a-2)] should be a
liquid
that on analysis reveals the presence of phosphonas.
Component a-3) - Phosphorvlated & Boronated Ashless Disp ra n
These oil-soluble additive compositions are formed by heating
concurrently or any sequence at least one ashless dispersant which contains
basic
nitrogen and/or at least one hydroxyl group with (i) at least one water-
hydrolyzable
organic compound of phosphorus -- preferably a water-hydrolyzable ester of an
acid of phosphorus -- and water, and (ii) at least one boron compound, such
that
a liquid phosphorus- and boron-containing composition is formed, and from
which
water has been removed. The ashless dispersant which is heated concurrently or
in any sequence with components (i) and (ii) is preferably a preformed ashless
dispersant contaizaing basic nitrogen and/or at least one hydroxyl group.
Thus,
for example, any suitable ashless dispersant farmed in the customary manner
can
be heated with one or more boron compounds to cause boronation to occur and
the resultant product mixture can then be heated with water and one or more
water-
hydrolyzable organic phosphorus compounds such that a liquid phosphorus- and
boron-containing composition [component a-3)] is formed. Conversely, a
preformed
ashless dispersant can be heated with water and one or more water-hydrolyzable
organic phosphorus compounds and thereafter the product mixture can be heated
with one or more boron compounds so that a liquid phosphorus- and boron-
containing composition is formed. The preferred way of forming component a-3)
is to heat a preformed ashless dispersant with a combination of water, one or
more
Case ~I-6214 +
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water-hydrolyzable organic phasphorus compounds and one or more boron com-
pounds to form a liquid phosphorus- and boron-containing composition. In other
words, to form component a-3) in the preferred manner, the preformed ashless
dispersant is concurrently heated with water, one or mare water-hydrolyzable
S organic phosphorus compounds and one or more boron compounds. In all cases,
the resulting liquid product composition when subjected to chemical analysis
reveals
the presence of both phosphorus and boron.
In the formation of the liquid phosphorus- and boron-containing
composition, water is remaved at least during or after the heating with (i)
and (ii)
(if conducted concurrently) or at least during or after the heating with (i)
(if
conducted sequentially). Such heating is conducted under conditions such that
partial or total hydrolysis of the water-hydrolyzable organic phosphorus
compound
occurs.
Father than utilizing a preformed ashless dispersant containing basic
1S nitrogen and/or at least one hydraxyl group, it is possible to produce
component
a-3) by:
1) forming the ashless dispersant in the presence of one ar more boron
compounds (e.g., boron ester or boron oxide) and then heating the
resultant composition in the presence of water with one or more
water-hydrolyzable organic phosphorus compounds; or
2) forming the ashless dispersant in the presence of one or more
water-hydrolyzable organic phosphorus compounds and then heating
the resultant composition with one or more boron compounds in
the presence of water; or
2S 3) forming the ashless dispersant in the presence of one or more boron
compounds and one or more water-hydrolyzable organic phospharus
compounds and heating the ashless dispersant in the presence of
water either during or after the formation of the ashless dispersant;
or
4) heating ane or more boron campaunds with a basic nitrogen-
containing and/or hydroxyl group-containing reactant used in
forming the ashless dispersant, using the resultant boranated
Case EI-6214+
2 ~'~ ~.~ 4 ~
-9-
reactant to form the ashless dispersant and then heating the
resultant ashless dispersant in the presence of water with one or
more water-hydrolyzable organic phosphorus compounds; or
S) heating one or more water-hydrolyzable organic phosphorus
compounds in the presence of water with a basic nitrogen-containing
and/or hydroxyl group-containing reactant used in forming the
ashless dispersant, using the resultant phosphorylated reactant to
form the ashless dispersant and then heating the resultant ashless
dispersant with one or more baron compounds; or
6) heating in the presence of water one or more water-hydrolyzable
organic phosphorus compounds and one more boron compounds
with a basic nitrogen-containing and/or hydroxyl group-containing
reactant used in forming the ashless dispersant, and using the
resultant phosphorylated and boronated reactant to form the ashless
dispersant.
In all cases, the final product composition [component a-3)] should be a
liquid
composition that on analysis reveals the presence of boron and phosphorus.
component a-4 - Phosphor rLted Ashless Dis~ersant
These oil-soluble boron-free additive compositions are formed by heating
(i) at least one baron-free oil-soluble ashless dispersant which contains
basic
nitrogen and/or at least one hydroxyl group, with (ii) at least one water-
hydrolyzable
organic phosphorus compound and water 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 nitrogen and/or at least one
hydroxyl
group. Thus, for example, any suitable boron-free ashless dispersant fornned
in
the customary manner can be heated with water and one or more water-hydroly
zable organic phosphorus compounds to cause phosphorylation to occur. The
resulting liquid product Composition when subjected to chemical analysis
reveals
the presence of phosphorus.
Rather than utilizing a preforrned ashless dispersant containing basic
nitrogen and/or at least one hydroxyl group, it is possible to produce
component
Case EI-6214+
-10_
a-4) by:
1) forming the ashless dispersant 'in the presence of water and one
or more suitable water-hydrolyzable organic phosphorus compounds
(e.g., a phosphorus oxide or sulfide); or
2) heating water and one or more water-hydrolyzable organic
phosphon~s compounds with a basic nitrogen-containing and/or
hydroxyl group-containing reactant used in forming the ashless
dispersant, and using the resultant phosphnrylated reactant to form
the ashless dispersant.
IO In all such cases, the final product camposition [component a-4)] should be
a liquid
composition that on analysis reveals the presence of phosphorus.
Various methods can be used for removing water from component a-3) or
a-4) during ar after its formation. The preferred method involves applying a
suitable vacuum to the reaction system while heating the water-containing
mixture
to a suitably elevated temperature. In this way the water is readily stripped
off.
When conducting the phasphorylation using a phosphorus ester made from a lower
alcohol such as methanol, ethanol, propanol, 2-propanol, butanol, or isobutyl
alcohol, both lower alcohal liberated in the process and water can be stripped
off
from the product mixture during or on completion of the heating operation.
In any case wherein an ashless dispersant used in forming component a)
is not a liquid but rather is in whole or in part in the solid state of
aggregation
at room temperature (e.g., 25 ° C), it is preferable to dissolve such
dispersant in
a suitable salvent or diluent (polar or non-polar, as may be required to
dissolve
the dispersant) before the dispersant is subjected to phosphorylation and/or
boronation (as the case may be) in forming component a-1) or a-3) or
phosphoryla-
tion in forming component a-2) or a-4). In this connection, the phrase "such
that
a liquid composition is formed" as used herein in connection with such solid
state
dispersants means that component a), including such solvent or diluent, is in
the
liquid state of aggregation at room temperature (e.g., 2S ° C), even
though at a lower
temperature the dispersant may revert in whole or in part to the solid state.
~f
course in any case, component a-1) must be oil-soluble within the meaning of
such
term as set forth hereinafter.
Case EI-b214+
- -11-
Irrespective of the method used in forming component a), 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, or decantation.
The actual chemical structures of all of the final product compositions used
as component a) in the practice of this invention, however prepared, are not
known
with absolute certainty. While it is believed, and in some cases known, that
phosphorus-containing moieties and boron-containing moieties are chemically
bonded to the ashless dispersant, it is possible that in some cases component
a)
is in whole or in part a micellar structure containing phosphorus- and/or
boron-
containing species or moieties. Thus, this invention is not limited to, and
should
not be construed as being limited to, any specific structural configurations
with
respect to component a). As noted above, all that is required is that
component
a) is a liquid that is oil soluble and that if subjected to analysis reveals
the presence
of phosphorus and, in the case of a-1) and 1-3), boron. In addition, component
a) should possess dispersant properties.
Although any of a variety of standard methods can be used to analyze the
dispersant for the presence of phosphorus or baron therein, it is desirable to
use
the analytical procedure set forth in ASTM D-4951. In this procedure it is
convenient to use a Perkin-Elmer Plasma 40 Emission Spectrometer. The
analyzing
wavelengths for acceptable measurements are 213:618 nm and 249.773 nm for
phosphorus and boron, respectively.
Component a) may contain chemical species and/or moieties besides the
phosphorus- and boron-containing species or moieties of a-1) or a-3) or the
phosphorus-containing species and jor moieties of a-2) or a-4), such as, far
example,
nitrogen- and/or oxygen- and/or sulfur-containing species or moieties over and
above the basic nitrogen and/or hydroxyl groups) forming an essential part of
the
initial ashless dispersant itself. It is to be understood that organic
phosphorus-con-
taining compounds may be used along with inorganic phosphorus compounds in
making component a-1) or a-2) and that inorganic phosphorus-containing
compounds may be used along with water and one or more water-hydrolyzable
Case FI-6214 +
_ 12_
organic phosphonas compounds in making component a-3) or a-4). Further, the
inorganic phosphorus compound or compounds can be formed in situ, as, for
example, by heating a mixture of phosphorus and sulfur to form a phosphorus
sulfide, or by treating one or more organic phosphorus compounds to convert
the
same in whole or in part into one or more inorganic phosphorus compounds. The
water-hydrolyzable organic phosphorus compound or compounds can also be formed
in situ, as, for example, by heating a mixture of one or more alcohols or
phenols
with one or more phosphorus halides (e.g., PCl3, POC13, FSCI3, RPC12, ROPCIZ,
RSPCI2, RPOCI.,, ROPOCh, RSPOCh, RPSCh, ROPSC12, RSPSC12, RZPCI,
(RO)ZPCl, (RS)ZPCI, (RO)(RS)PCI, R~POCI, (RO)ZPOCI, (RS)ZPOCI,
(RO)(RS)POCI, RZPSCI, (RO)?PSCI, (RS)ZPSCI, where each R is, independently,
a hydrocarbyl group) and introducing water into the system in order to
hydrolyze
the water-hydrolyzable phosphorus ester so formed.
As used herein, the texm "phosphorylated" means that the ashless dispersant
has been heated with one or more inorganic phosphorus compounds [components
a-1) and a-2)J or with one or more water-hydrolyzable organic phosphorus
compounds and water [components a-3) and a-4)] such that the resultant
product,
on analysis, reveals the presence of phosphorus. Likewise, as used herein, the
term
"boronated" means that the ashless dispersant has been heated with one or more
boron compounds such that the resultant product, on analysis, reveals the
presence
of boron. The terms "phosphorylated" and "boronated" are not to be construed
as requiring that the resultant composition contain chemically bound
phosphorus
or boron.
Any of a variety of ashless dispersants can be utilized in forming component
a) of the compositions of this invention. These include the following types:
Tape A - Carboxylic Ashless Dispersants. These are reaction products of
(i) an acylating agent such as a monocarboxylic acid, or a dicarboxylicMor
other
polycarboxylic acid, or a derivative thereof, with (ii) one or more compounds
which
contain amine groups and/or hydroxyl groups, such that the acylated reaction
product contains basic nitrogen and/or at least one hydroxyl group. These
products,
herein referred to as carboxylic ashless dispersants, are described in many
patents,
including British patent specification No.1,305,529 and the following U. S.
Patents:
Case EI-6214 +
-13-
3,163,603; 3,184,474; 3,215,707; 3,219,666; 3,271,310; 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;
3,697,428;
3,725,441; 3,868,330; 3,948,800; 4,234,435; and Re 26,433.
There are a number of sub-categories of carboxylic ashless dispersants.
One such sub-category which constitutes a preferred type for use in the
formation
of component a) is composed of the polyamine succinamides and more preferably
the polyamine succinimides in which the succinic group contains a hydrocarbyl
substituent containing at least 30 carbon 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.
Representative examples of such dispersants are given in U.S. Pat. lVos.
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 louver alkyl ester with
a
polyamine containing at least one primary amino group. The alkenyl succinic
anhydride may be made readily by heating a mixture of olefin and malefic
anhydride
to 180 ° -220 ° C. The olefin is preferably a polymer or
copolymer of a lower
monoolefin such as ethylene, propylene; 1-butane, and isobutene. The mare pre-
ferred source of alkenyl group is from polyisobutene having a number average
mole-
cular weight of up to 100,000 or higher. In a still more preferred embodiment
the
alkenyl group is a polyisobutenyl group having a number average molecular
weight
(determined using the method described in detail hereinafter) of 500-5,000,
and
preferably 700-2,500, more preferably 700-1,400, and especially 800-1,300. The
isobutene used in making the polyisobutene is usually (but not necessarily) a
mixture
of isobutene and other C4 isomers such as 1-butane. Thus, strictly speaking,
the
acylating agent formed from malefic anhydride and'°polyisobutene" made
from such
mixtures of isobutene and other C4 isomers such as 1-butane, can be termed a
"polybutenyl succinic anhydride" and a succinimide made therewith can be
termed
a "polybutenyl succinimide". However, it is common to refer to such substances
Case EI-6214 +
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as "polyisabutenyl succinic anhydride" and "polyisabutenyl succinimide",
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 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 representative examples include branched-chain alkanes containing
two or mare primary amino groups such as tetraamino-neapentane
polyaminoallcanols such as 2-(2-aminoethylamino)-ethanol and 2-[2-(2-
aminoethylamino)-ethylaminoJ-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-imidazalidone, 2-(2-aminoethylamino)-5-nitropyridine, 3-amino-N-
ethylpiperidine, 2-(2-aminoethyl)-pyridine, S-aminoindole, 3-amino-5-mercapto-
1,2,4-
triazole, and 4-(aminomethyl)-piperidine; and the alkylene polyamines such as
1S propylene diamine, dipropylene triamine, di-(1,2-butylene)triamine, N-(2-
aminoethyl)-1,3-propanediamine, hexamethylenediamine and tetra-(1,2-propylene)-
pentamine.
The most preferred amines are the ethylene polyamines which can be
depicted by the formula
H?N(CH~CH~NI-~)"H
wherein n is an integer from one to ten. These include: ethylene diamine,
diethylene triamine, triethylene tetramine, tetraethylene pentamine,
pentaethylene
hexamin~, including mixtures thereof in which case n is the average value of
the
mixture. The ethylene polyamines which have a primary amine group at each end
can form mono-alkenylsuccinimides and bis-alkenylsuccinimides. Commercially
available ethylene polyamine mixtures usually contain minor amounts of
branched
species and cyclic species such as N-aminaethyl piperazine, N,N'-
bis(aminaethyl)pip-
erazine, N,N'-bis(piperazinyl)ethane, and like compounds. The preferred
commercial mixtures have approximate overall compositions falling in the range
corresponding to diethylene triamine to pentaethylene hexamine, mixtures
generally
corresponding in overall makeup to tetraethylene pentamine being most
preferred.
idlethods for the production of polyalkylene polyamines are known and reported
Case EI-6214+
-15-
in the literature. See for example U.S. Pat. Nos. 4,827,037; and 4,983,736;
and EP
Pub. Nos. 412,611; 412,612; 412,613; 412,614; and 412,615, and references
cited
therein.
Thus especially preferred ashless dispersants for use in the present invention
are the products of reaction of a polyethylene polyamine, e.g., mixture known
in
the trade as "triethylene tetramine" or "tetraethylene pentamine", with a
hydrocarbon-substituted carboxylic acid or anhydride (or other suitable acid
derivative) made by reaction of a polyolefin, preferably polyisobutene, having
a
number average molecular weight of S00 to 5,000, preferably 70U to 2,500, more
preferably 700 to 1,400 and especially 800 to 1,300, with an unsaturated
polycar-
boxylic acid or anhydride, e.g., malefic anhydride, malefic acid, or fumaric
acid,
including mixtures of two or more such substances.
As used herein the term "succinimide" is meant to encompass the completed
reaction ,product from reaction between the amine reactants) and the
hydrocarbon-
substituted carboxylic acid or anhydride (or like acid derivative)
reactant(s), and
is intended to encompass compounds wherein the product rnay 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 moiety.
Residual unsaturation in the alkenyl group of the alkenyl succinimide may
be used as a reaction site, if desired. Far example the alkenyl substituent
may be
hydrogenated to form an alkyl substituent. Similarly the olefinic bonds) in
the
alkenyl substituent may be sulfurized, halogenated, or hydrohalogenated.
Ordinarily,
there is little to be gained by use of such techniques, and thus the use of
alkenyl
succinimides as the precursor of component a) is preferred.
2S Another sub-category of carboxylic ashless dispersants which can be used
in forming component a) includes alkenyl succinic acid esters and diesters of
polyhydric alcohols containing 2-20 carbon atoms and 2-6 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
preferred
and most preferred subgenus, e.g., alkenyl succinic acids and anhydrides,
where
the alkenyl group contains at least 30 carbon atoms and notably,
polyisobutenyl
Case EI-6214+
- -16-
succinic acids and anhydrides wherein the polyisobutenyl group has a number
aver-
age molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably
700
to 1,400, and especially 800 to 1,300. As in the case of the succinimides, the
alkenyl
group can be hydrogenated or subjected to other reactions involving olefinic
double
S bonds.
Alcohols useful in preparing the esters include ethylene glycol, diethylene
glycol, triethylene glycol, tetraethylene glycol, propylene glycol,
tripropylene glycol,
glycerol, sorbitol,1,1,1-trimetlrylol ethane, 1,1,1-trimethylol propane, 1,1,1-
trimethylol
butane, pentaerythritol, and dipentaerythritol.
The succinic esters are readily made by merely heating a mixture of alkenyl
succinic acid, anhydrides or lower alkyl (e.g., C~-C4) 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.
Still another sub-category of carboxylic ashless dispersants useful in forming
component a) comprises an alkenyl succinic ester-amide mixture. These may be
made by heating the above-described alkenyl succinic acids, anhydrides or
lower
alkyl esters with an alcohol and an amine either sequentially or in a mixture.
Alcohols and amines such as those described above are also useful in this
embod-
invent. Additionally, linear and/or branched chain monohydric alcohols such as
1-butanol, 2-butanol, 2-methyl-1-propanol, pentanol, hexanol, octanol,
decanol, lauryl
alcohol, oleyl alcohol, eicosanol, or ethylene glycol monomethyl ether, can be
used
provided they are used with one or more polyamines. 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 2-20 carbon atoms, 1-6 hydroxy groups
and 1-4 amine nitrogen atoms. Examples are ethanolamine, diethanolamine,
N-ethanol-diethylene triarnine, and trimethylol aminomethane.
Here again, the a~kenyl group of the succinic ester-amide can be
hydrogenated or subjected to other reactions involving olefinic double bonds.
Representative examples of suitable ester-amide mixtures are described
in IJ.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.
Case EI-6214 -E
- 17-
Yet another sub-category of carboxylic ashless dispersants useful in forming
component a) comprises the Mannich-based derivatives of hydroxyaryl
succinirnides.
Such campounds can be made by reacting a polyalkenyl succinic anhydride with
an aminophenol to produce an Pd-(hydroxyaryl) hydrocarbyl succinimide which is
then reacted with an alkylene diamine or polyaikylene 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. A,s 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
polyalkearyl
substituent group can be used as a reaction site as for example, by
hydrogenation
or sulfurization.
Type 13 - H~ drocarbyl Polvamine DisRersants. This category of ashless
dispersants which can be used in forming component a) is likewise well known
to
those skilled in the art and fully described in the literature. The
hydrocarbyl
polyamine dispersants are generally produced by reacting an aliphatic or
alicyclic
halide (or mixture thereof) containing an average of at least about 40 carbon
atoms
with one or more amines, preferably polyalkylene polyamines. Examples of such
hydrocarbyl polyamine 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; 3,394,576; and in
European
Patent Publication No> 382,405.
In general, the hydrocarbyl-substituted polyamines are high molecular weight
hydrocarbyl-N-substituted polyamines containing basic nitrogen in the
molecule.
The hydrorarbyl group typically has a number average molecular weight in the
range
of 750-10,000, more usually in the range of 1,000-5,000.
The hydrocarbyl radical may be aliphatic or alicyclic and, except for
adventitious amounts of aromatic components in petroleum mineral oils, will be
free of aromatic unsaturation. 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 hydrocarbyi groups are preferably derived from
petroleum mineral oil, or polyolefins, either homo-polymers or higher-order
Case EI-6214 +
_ 18_
polymers, or 1-olefins of from 2-6 carbon atoms. Ethylene is preferably
copolymerized with a higher olefin to insure oil solubility.
Illustrative polymers include polypropylene, polyisobutyle.ne, or poly-1
butene. The polyolefin group will normally have at least one branch per six
S 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 atones and preferably from
olefins of 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 hydrocarbon 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. Further
more, when speaking of a particular hydrocarbon group, it is intended that the
1S group include the mixture that is normally contained within materials 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 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 (?.) hydrogen; 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) acyi groups of from 2 to 10 carbon atoms,
and (D) monoketo, monohydroxy, mononitro, monocyano, lower alkyl and lower
Case EI-6214 +
_ _ -19- ~D'~~~.~1~
alkoxy derivatives of (B) and (C). "Lower" as used in terms like lower alkyl
or
lower alkoxy, means a group containing 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, denotes an organic radical composed
of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combina-
tions thereof, e.g., aralkyl. Preferably, the hydrocarbyl group will be
relatively
free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly
acetylenic unsaturation. 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, octyl, etc., alkenyls such as
propenyl,
isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-
hydroxypropyl, hydroxyisopropyl, 4-hydroxybutyl, etc., ketoalkyls, such as 2-
ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as
ethoxy-
ethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 2-(2-ethoxycthoxy)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-propyiamine,
di-n-propylamine, etc. Such amines are either commercially available or are
prepared by art recognized procedures.
The polyamine component may also contain heterocyciic 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 unsaturated and
substituted with ga°oups selected from the aforementioned (A), (B),
(C), and (I7).
The heterocyclics are exemplified by piperazines, such as 2-methylpiperazine,
1,2-bis(N-piperazinyl-ethane), and N,N'-bis(N-piperazinyl)piperazine, 2-methyl-
imidazoline, 3-aminopiperidine, 2-aminopyridine, 2-(13-aminoethyl)-3-
pyrroline, 3-
Case EI-6214 +
-20-
aminopyrrolidine, N-(3-aminopropyl)morpholine, etc. Among the heterocyclic
compounds, the piperazines are preferred.
Typical polyamines that can be used to form the hydrocarbyl polyamine
dispersants include the following: ethylene diamine, 1,2-propylene diamine,
1,3
propylene diamine, diethylene triamine, triethylene tetramine, hexamethylene
diamine, tetraethylene pentamine, methylaminopropylene diamine, N-(B-amino-
ethyl)piperazine, N,N'-di(b-aminoethyl)piperazine, N,N'-di(L~-aminoethyl)-
imidazolidone-2, N-(B-cyanoethyl)ethane-1,2-diamine, 1,3,6,9-tetraamino-
octadecane, 1,3,6-triamino-9-oxadecane, N-methyl-1,2-propanediamine, and 2-(2-
aminoethylamino)ethanol.
Another group of suitable polyamines are the polyalkylene amines in
which the alkylene groups differ in carbon content, such as for example
bis(aminopropyl)ethylenediamine. Such compounds are prepared by the
reaction of acrylonitrile with an ethyleneamine, for example, an
ethyleneaanine
having the formula HZH(CH.,CH.,NH)"H wherein n is an integer from 1 to 5,
followed by hydrogenation of the resultant intermediate. Thus, the product
prepared from ethylene diamine and acrylonitrile has the formula H2N-
(CHz)3NI I(CH.,)aNH(CH.,)sNI-L,.
In many instances the polyamine used as a reactant in the production of
the hydrocarbyl-substituted polyamine is not a single compound but a mixture
in
which one or several compounds predominate with the average composition in
dicated. For example, tetraethylene pentamine prepared by the polymerization
of aziridine or the reaction of 1,2-dichloroethane and ammonia will have both
lower and higher amine members, e.g., triethylene tetramine, substituted
piperazines and pentaethylene hexamine, but the composition will be largely
tetraethylene pentamine and the empirical formula of the total amine composi-
tion will closely approximate that of tetraethylene pentamine. Finally, in
preparing the hydrocarbyl-substituted polyamines for use in this invention,
where
the various nitrogen atoms of the polyamine are not geometrically equivalent,
several substitutional isomers are possible and are encompassed with the final
product. Methods of preparation of polyamines and their reactions are detailed
in Sidgewick, The Organic Chemistry of Nitrogen, Clarendon Press, Oxford,
Ca~e E;<-6214 + ~ ~ ,~ ~ ~ 4 ~
- -21-
1966; Nollier, Chemistry of Organic Compounds, Saunders Philadelphia, 2nd
Ed., 1957; and Kirk-Othmer, Encyclopedia of Chemical Technolo~v. 2nd
Edition, especially volume 2, pp. 99-116.
The preferred hydrocarbyl-substituted polyalkylene polyamines for use in
this invention may be represented by the formula
RiNH-(-R~-NH-)Q H
wherein Rl is hydrocarbyl having an average molecular weight of from 750 to
10,000; RZ is alkylene of from 2 to 6 carbon atoms; and a is an integex of
from
0 to 10.
Preferably, Rl is hydrocarbyl having an average molecular weight of from
1,0011 to 10,000. Preferably, R,, is alkylene of from 2 to 3 carbon atoms and
cx is
preferably an integer of from 1 to 6.
T'rpe C - Mannich ~olyamine dispersants. This category of ashless
dispersant which can be utilized in the formation of component a) is comprised
of reaction products of an alkyl phenol, with one or more aliphatic aldehydes
containing from 1 to 7 carbon atoms (especially formaldehyde and derivatives
thereof), and polyamines (especially polyalkylene polyamines of the type
described hereinabove).
Examples of Mannish condensation products, and methods for their
production 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;
3,591,598; 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;904,595; 3,957,746; 3,980,569;
3,985,802; 4,006,089; 4,011,380; 4,025,451; 4,058,468; 4,083,699; 4,090,854;
4,354,950; and 4,485,023.
The polyamine group of the Mannish polyamine dispersants is derived
from polyamine compounds characterized by containing a group of the structure
-NH- wherein the two remaining valances of the nitrogen are satisfied by
hydrogen, amino, or organic radicals banded to said nitrogen atom. These
compounds include aliphatic, aromatic, heterocyclic and carbocyclic
polyamines,
case EI-6214+
-2z-
The source of the oil-soluble hydrocarbyl group in the Mannish polyamine
dispersant is a hydrocarbyl-substituted hydroxy aromatic compound comprising
the reaction product of a hydroxy aromatic compound, according to well known
procedures, with a hydrocarbyl donating agent or hydrocarbon source. The
hydrocarbyl substituent provides substantial oil solubility to the hydroxy
aromatic
compound and, preferably, is substantially aliphatic in character. Commonly,
the
hydrocarbyl substituent is derived from a polyolefin having at least about 40
carbon atoms. The hydrocarbon source should be substantially free from
pendant groups which render the hydrocarbyl group oil insoluble. Examples of
acceptable substituent groups are halide, hydroxy, ether, carboxy, ester,
amide,
vitro and cyano. However, these substituent groups preferably comprise no
more than about 10 weight percent of the hydrocarbon source.
The preferred hydrocarbon sources for preparation of the Mannish
polyamine dispersants are those derived from substantially saturated petroleum
fractions and olefin polymers, 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 copoly-
mers of such olefins with other polymerizable olefinic substances such as
styrene.
z0 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 leapt 50 carbon atoms to provide substantial oil solubility
to
the dispersant. The olefin polymers having a number average molecular weight
between 600 and 5,000 are preferred for reasons of easy reactivity and low
cost.
However, polymers of higher molecular weight can also be used. Especially
suitable hydrocarbon sources are isobutylene polymers.
The Mannish polyamine dispersants are generally prepared by reacting a
hydrocarbyl-substituted hydroxy aromatic compound with an aldehyde and a
polyamine. The aldehyde is typically an aliphatic aldehyde containing 1 to 7
carbon atoms, and in most cases is formaldehyde or a compound such as
formalin or a polyformaldehyde from which formaldehyde is derived during the
Case EI-6214+
' -23-
reaction. 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 reactants are mixed and
heated to a temperature above about 80 ° C. to initiate the reaction.
Preferably,
the reaction is carried out at a temperature from 100 ° to 250 °
C. The resulting
Mamaich 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, benzene, toluene, naphtha, ligroin, or
other
inert solvents to facilitate control of viscosity, temperature, and reaction
rate.
Polyamines are preferred for use in preparing the Mannich polyamine
dispersants, and suitable polyamines include, but are not limited to, alkylene
diamines and polyalkylene polyamines (and mixtures thereof) of the formula:
A-N-(-R-N-)"H
A A
wherein n is an integer from 1 to 10, R is a divalent hydrocarbyl group of
from
1 to 18 carbon atoms, and each A is independently 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 palyamines for use in preparation of the Mannich polyamine
dispersants include, but are not limited ta, methylene polyamines, ethylene
polyamines, butylene polyamines, propylene polyarnines, 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(heptamethylene) triamine, pentaethylene hexamine,
di(trimethylene) triamine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-
Case EI-6214 +
_24_
aminoethyl)imidazoline,1-(2-aminopropyl)piperazine,1,4-bis(2-aminoethyl)piper-
azine and 2-methyl-1-(2-aminobutyl)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 "I~iamines and Higher Amines" in Kirk-Othmer, Enc,~opedia of
Chgmical 'I'~chnoio~v, Second Edition, Vol. 7, pp. 22-39. They are prepared
most conveniently by the reaction of an 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. However,
it
1S 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 dispersants. 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 the hydroxyalkyl groups have IeSS than about 10 carbon
atoms. Examples of suitable hydroxyalkyl-substituted diamines and polyamines
include, but are not limited to, N-(2-hydroxyethyl)ethylenediamine, N,N'-bis(2-
2~ hydroxyethyl)ethylenediamine, mono(hydroxypropyl)diethlenetriamine, (di(hy-
droxypropyl)tetraethylenepentamine and N-(3-hydroxybutyl)tetramethylene-
diamine. 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 useful for the
preparation of the Mannich polyamine dispersants. Examples of such formalde-
hyde yielding reagents are trioxane, paraformaldehyde, trioxymethylene,
aqueous
Case EI-6214+
- -25-
formalin and gaseous formaldehyde. Other aldehydes which can be used include
acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde,
hexanal, heptanal, and mixtures of two or more of these.
The most preferred Mannich base dispersants for use in this invention
are Mannich base ashless dispersants formed by condensing about one molar
proportion of long chain hydrocarbon-substituted phenol with from 1 to 25
moles of formaldehyde and from 0.5 to 2 moles of polyalkylene polyamine.
Ty~pg D - Polymeric polvamine dispersants. Also suitable for preparing
component a) of the compositions of this invention are polymers containing
basic amine groups and oil solubilizing groups (for example, pendant alkyl
groups having at least about 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 aminoalkyl acrylates and amino-
alkyl acrylamides. Examples of polymeric polyamine dispersants are set forth
in
the following patents: U.S. Pat. Nos. 3,329,658; 3,449,250; 3,493,520;
3,519,56;
3,666,730; 3,687,849; 3,702,300.
Type E - Post-treated basic nitrogen-containing and/or hydroxyl
containing ashless disp rg sants. 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 disulfide,
aldehydes, ketones, carboxylic acids, anhydrides of low molecular weight
dibasic
acids, nitrites, and epoxides. Such post-treated ashless dispersants can be
used
in forming component a) of the compositions of this invention provided that
the
post-treated dispersant contains residual basic nitrogen and/or one or more
residual hydroxyl groups. Alternatively, the phosphorylated or the
phosphorylat-
ed and boronated dispersant can be subjected to post-treatment with such
reagents. Likewise, in the case of components a-1) and a-3) the post-treatment
can be conducted in between the phosphorylation and boronation or conversely,
between the boronation and the phosphorylation. Examples of post-treatment
procedures and post-treated ashless dispersants are set forth in the following
U.S. Patents: U.S. Pat. Nos. 3,036,003; 3,087,936; 3,200,107; 3,216,936;
Case EI-6214+
-26-
3,254,025; 3,256,185; 3,278,550; 3,218,428; 3,280,234; 3,281,428; 3,282,955;
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; 3,513,093; 3,533,945; 3,539,633; 3,573,010;
3,579,450; 3,591,598; 3,600,372; 3,639,242; 3,649,229; 3,649,659; 3,658,836;
3,697,574; 3,702,757; 3,703,536; 3,704,308; 3,708,422; 4,025,445; and
4,857,214.
Mannich-based derivatives of hydroxyaryl succinimides that have been
post-treated with CS-C~ lactones such as e-caprolactone and optionally with
other post-treating agents as described for example in U.S. Pat. No. 4,971,711
can also be utilized in forming component a) far use in the practice of this
invention, provided that such post-treated Mannich-based derivatives of
hydroxyaryl succinimides contain basic nitrogen, and/or at least one hydroxyl
group. See also U.S. Pat. Nos. 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 basic nitrogen-containing and/or hydroxyl group-containing ashless
dispersants which may be utilized in forming component a).
One preferred category of post-treated ashless dispersants is comprised of
basic nitrogen-containing and/or hydroxyl group-containing ashless dispersants
which have been heated with (1) a phosphorus compound such that they contain
phosphorus, or (2) a boron compound such that they contain boron, all 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 the patent literature. See
for
example U.S. Pat. Nos. 3,087,936; 3,184,411; 3,185,645; 3,235,497; 3,254,025;
3,265,618; 3,281,428; 3,282,955; 3,284,410; 3,324,032; 3,325,567; 3,338,832;
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; 4,648,980; 4,747,971; 4,857,214;
and
4,873,004. The boron-containing post-treated ashless dispersants of the prior
art
type can be converted into a material suitable for use as component a-1) or a-
3)
simply by conducting a phosphorylation in the manner described herein. tf
desired, additional boron can also be incorporated into a prior art type post-
treated boron-containing ashless dispersant by conducting a boronation in the
Case EI-f214~-
' -27-
manner described herein either before, during or after the phosphorylation. It
is
also possible by using the phosphorylation and/or boronation procedures
described herein to phosphorylate and/or boronate a post-treated ashless
dispersant that already contains phosphorus and/or boron, provided that such
initial post-treated ashless dispersant contains at least some residual basic
nitrogen and/or at least same residual hydroxyl substitution.
The ashless dispersant(s) used in forming component a) can be any
mixture containing any two or more ashless dispersants containing basic
nitrogen
and/or at least one hydroxyl 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
not necessary from a performance standpoint) to select ashless dispersants (as
well as the other components 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 composition in which the total halogen
content, if any, is 100 ppm or less.
Production of Component a-1):
Typical procedures for producing component a-1) phosphorylated and
boronated ashless dispersants involve concurrently or sequentially heating one
or
more ashless dispersants of the types described above with at least one
inorganic
phosphorus compound and at least one boron compound under conditions
yielding a liquid phosphorus- and boron-containing composition. Examples of
inorganic phosphorus compounds which are useful in forming such products
include phosphorous acid (H3P03, sometimes depicted as H,(HP03), and some-
times Balled ortho-phosphorous acid or phosphoric acid), phosphoric acid
(H3P04, sometimes called orthophosphoric acid), hypophosphoric acid (H4P206),
metaphosphoric acid (HPO3), pyrophosphoric acid (H~P,O~), hypophosphorous
acid (H3P0~, sometimes called phosphinic acid), pyrophosphorous acid (H~PzO$,
Case EI-6214+
. ~ _ 2g -
sometimes called pyrophosphonic acid), phosphinous acid (H3P0), tripolyphos-
phoric acid (HSP3Olo), tetrapolyphos,phoric acid (H6P4O13), trimetaphosphoric
acid (H3P309), phosphorus trioxide, phosphorus tetraoxide, and phosphorus
pentoxide. Partial or total sulfur analogs such as phosphorotetrathioic acid
(H3PS4), phosphoromonothioic acid (H3P03S), phosphorodithioic acid
(H3POZS2), phosphorotrithioic acid (H3POS3), phosphorus sesquisulfide,
phosphorus heptasulfide, and phosphorus pentasulfide (PISS, sometimes referred
to as P~SIO) can also be used in forming products suitable for use as
component
a-1) in the practice of this invention. Also usable, though less preferred,
are the
inorganic phosphorus halide compounds such as PC13, PBr3, POCl3, PSC13, etc.
'I'he preferred phosphorus reagent is phosphorous acid, (H3P03).
It will be understood and appreciated by those skilled in the art that the
form or composition of the inorganic compounds) as charged into the mixriare
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. Any such in situ transfor-
mations that may occur are within the purview of this invention provided that
the liquid phosphorylated ashless dispersant reveals on analysis the presence
therein of phosphorus (as well as boron).
Suitable compounds of boron useful in forming the phosphorylated and
boronated ashless dispersants for use as component a-1) include, for example,
boron acids, boron oxides, boron esters, and amine or ammonium salts of boron
acids. Illustrative compounds include boric acid (sometimes referred to as
orthoboric acid), boronic acid, tetraboric acid, metaboric acid, pyroboric
acid,
esters of such acids, such as mono-, di-, and tri-organic esters with alcohols
or
polyols having up to 20 or more carbon atoms (e.g., methanol, ethanol, 2-
propanol, propanol, butanols, pentanols, hexanols, ethylene glycol, propylene
glycol, trimethylol propane, diethanol amine, ete.), boron oxides such as
boric
oxide and boron oxide hydrate, and ammonium salts such as ammonium borate,
ammonium pyroborate, etc. While usable, boron halides such as boron
trifluoride, and boron trich.loride, are undesirable as they tend to introduce
halogen atoms into the boronated dispersant, a feature which is detrimental
Cage EI-6214 +
~~'~~14~
- w -29-
from the environmental, toxicological and conservational standpoints. Amine
borane addition compounds and hydrocarbyl boranes can also be used, although
they tend to be relatively expensive. The preferred boron reagent is boric
acid,
H3B0~.
Optionally, additional sources of basic nitrogen can be included in the
inorganic phosphorus compound-ashless dispersant-boron compound mixture so
as to provide a molar amount (atomic proportion) of basic nitrogen up to that
equal to the molar amount of basic nitrogen contributed by the ashless
dispersant. 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. Examples of suitable
compounds are oleyl amine, N-oleyltrirnethylene diamine, N-tallow diethanol-
amine, 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 copper surfaces.
The concurrent heating step or the combination of sequential heating
steps is conducted at temperatures sufficient to produce a final liquid
composition which contains both phosphorus and boron. The heating can be
carried out in the absence of a solvent by heating a mixture of the ashless
dispersant and one or more suitable inorganic phosphorus compounds, or one or
more suitable boron compounds, or, preferably, a combination of one or snore
suitable inorganic phosphorus compounds and one or more suitable boron
compounds. The temperatures used will vary somewhat depending upon the
nature of the ashless dispersant and the inorganic phosphorus and/or boron
reagent being utilized. Generally speaking however, the temperature will
usually fall within the range of 40 to 200 ° C. The duration of the
heating is
likewise susceptible to variation, but ordinarily will fall in the range of 1
to 3
hours. When conducting the heating in bulk, it is important to thoroughly
agitate the components to insure intimate contact therebetween. When utilizing
Case EI-6214+
- -30_
the preferred phosphorus and boron reagents (phosphorous acid and boric acid),
it is preferable to add water to facilitate initial dissolution of the boric
acid.
Alternatively, the phosphorous acid may be utilised in the form of an aqueous
solution thereby introducing water into the system to facilitate dissolution
of the
S boric acid. Water (and when using boron esters, alcohol) formed in the
process
and any added water is preferably removed from the heated mixture by vacuum
distillation at temperatures of from 100 to 140 ° C. Preferably the
heating step
or steps will be conducted in a diluent oil or other inert liquid medium such
as
light mineral oils, etc.
The amount of phosphorus compound employed in the heating process
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
contributed by an auxiliary nitrogen compound. The amount of boron
compound employed ranges from 0.001 mole to 1 mole per mole of basic
nitrogen and/or hydroxyl in the mixture which is in excess of the molar amount
of inorganic phosphorus compound. When conducting the phosphorylation and
boronation on a sequential basis (or when conducting one of these operations
on
a dispersant which has previously been subjected to the other such operation),
the last-to-be-used reagent(s) -- inorganic phosphorus compounds) or boron
compound(s), as the case may be -- can be used in an amount equivalent to (or
even in excess of) the amount of basic nitrogen and/or hydroxyl groups in the
dispersant being heated with such last-to-be-used reagent(s).
When used, the amount of added water is not particularly critical as it is
removed by distillation during the course of, or at the end of, the heating
step.
Amounts of up to 1% by weight of the mixture being heated are preferred.
When used, the amount of diluent usually ranges from 10 to 50% by weight of
the mixture being subjected to heating.
When conducting the preferred concurrent heating step for production of
component a-1), it is desirable to employ procedures such as described in U.B.
Pat. No. 4,857,214.
For further details concerning procedures for conducting the boronation
operation apart from the phosphorylation operation, reference may be had, for
Case EI-6214 +
- -31-
example, to the disclosures of U.S. Pat. Nos. 3,087,936; 3,254,025; 3,281,428;
3,282,955; 3,284,410; 3,338,832; 3,344,069; 3,533,945; 3,718,663; 4,097,389;
4,554,086; and 4,634,543.
The phosphorylated and buronated dispersants utilized as component a-
1) in the compositions of this invention when in their undiluted state should
have on a weight basis a phosphorus content of at least 100 parts per million
(ppm) (preferably at least 500 ppm and more preferably at least 1,000 ppm) and
a boron content of at least 100 ppm (preferably at least 500 ppm and more
preferably at least 1,000 ppm). 'When forming component a-1) in part by use of
one or more organic phosphorus compounds such as one or more organic
phosphates (e.g., trihydrocarbyl phosphates, dihydrocarbyl monoacid
phosphates,
rnonohydrocarbyl diacid phosphates, or mixtures thereof), phosphates (e.g.,
trihydrocarbyl phosphates, dihydrocarbyl hydrogen phosphates, hydrocarbyl
diacid
phosphates, or mixtures thereof), phosphonates (e.g., hydrocarbyl phosphoric
1S acids, mono- and/or dihydrocarbyl esters of phosphoric acids, or mixtures
thereof), phosphonites (e,g., hydrocarbyl phosphinic acids, mono- and/or
dihydrocarbyl esters of phosphinic acids, or mixtures thereof), etc., or the
partial
or total sulfur analogs thereof, and in part by use of one or more inorganic
phosphorus compounds, the latter should be used in an amount sufficient to
provide at least 10% (preferably at least 50% and more preferably at least
75%)
of the total content of phosphorus in the phosphorylated and boronated
dispersant. For crankcase lubricant usage, component a-1) when in the
undiluted state preferably contains at least 3,000 ppm (more preferably at
least
5,000 ppm and most preferably at least 7,000 ppm) of phosphorus and at least
1,500 ppm (more preferably at least 2,500 ppm and most preferably at least
3,500 ppm) of boron.
The preparation of phosphorylated and boronated ashless dispersants
suitable for use as component a-1) in the compositions of this invention is
illustrated by the following Examples 1-50 in which all parts and percentages
are
by weight unless otherwise clearly specified.
EXAMPLE 1
A mixture is formed from 260 parts of a commercial succinimide ashless
Case EI-6214+ ~ ~ r'
- -32-
dispersant (HiTEC~ 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl
Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada Limited), 100 parts of a
100
Solvent Neutral refined mineral oil diluent, 8 parts of phosphorous acid, 3.5
parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The
mixture is
heated at 100 ° C for two hours until all of the solid materials are
dissolved. A
vacuum of 40 mm Hg is gradually drawn on the product to remove the water
while the temperature is slowly raised to 100 ° C. A clear solution or
composition is obtained which is soluble in oil and suitable for use as
component a-1).
EXAMPLE 2
The procedure of Example 1 is repeated except that the succinimide
ashless dispersant used is derived from polybutene having a number average
molecular weight of 1,100. The average number of succinic groups per alkenyl
group in the succinimide is approximately 1.2.
EXAMPLE 3
'The procedure of Example 1 is repeated except that the succinimide
ashless dispersant used is derived from polybutene having a number average
molecular weight of 2,100.
EXAMPLE 4
The procedure of Example 1 is repeated except that the succinimide
ashless dispersant is replaced by an equal amount of a Mannich polyamine
dispersant (AMOCO~ 9250 dispersant; Amoco Corporation). The Amoco 9250
dispersant as supplied by the manufacturer is believed to be a boronated
dispersant and in such case, another material suitable for use as component a-
1)
can be formed by eliminating the boric acid and water from the procedure used
in this example and thereby conducting phosphorylation on an already
boronated dispersant.
EXAMPLE S
The procedure of Example 1 is repeated except that the succinimide
ashless dispersant is replaced by an equal amount of a commercial ashless
dispersant of the pentaerythritol succinic ester type (Lubrizol~ 936
dispersant;
The Lubrizol Corporation). As in the case of Example 4, the initial dispersant
Case EI-6214 +
-33- ~~~~7~~~
as supplied by the manufacturer is believed to be a boronated dispersant. In
such cases, the dispersant can, if desired, be subjected just to
phosphorylation to
thereby form still another product suitable for use as component a-1).
EXAMPI~
The procedure of Example 1 is repeated except that 11 parts of
phosphorus pentasulfide is used in place of the phosphorous acid, the PISS is
added to the mixture after water distillation, and the mixture is then heated
for
an additional hour at 100 ° C to provide a clear, oil-soluble
composition suitable
far use as component a-1).
lp EXAMPLE 7
The procedure of Example 1 is repeated except that the PISS is replaced
by 7 parts of phosphorus pentoxide (PROS).
EXAMPLE 8
The procedures of Examples 1 through 7 are repeated except that the
tolutriazole is omitted from the initial mixtures subjected to the thermal
processes.
EXAMPLE 9
A mixture of 11,904 parts of a commercial boronated succinimide
(HiTEC~ 648 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum
Additives, Ltd.; Ethyl S.A.; Ethyl Canada Limited) and 96 parts of phosphorous
acid is heated to 100-110 ° C for 2 hours to form a homogeneous liquid
composition suitable for use as component a-1) in the practice of this
invention.
For convenience in handling, 100 Solvent Neutral mineral oil can be added to
form an 80% solution of the additive in the oil.
EXAMPLE 10
A mixture of 260 parts of a commercial succinimide (HiTEC~ 644
dispersant), and 8 parts of phosphorous acid is heated to 100 ° C for 2
hours. To
this product is added 8 parts of orthoboric acid and 4 parts of water, and the
resultant mixture is heated at 100 ° C for another 2 hours. Water
present in the
reaction mixture is removed by applying a vacuum of 40 mm of Hg and
gradually raising the temperature to 110 ° C. The resultant homogeneous
liquid
composition is suitable for use as component a-1).
Case EI-6214+
- -34-
EXAMPLE 11
A mixture of 260 parts of a commercial succinimide (HiTEC~ 644
dispersant), 8 parts of orthoboric acid and 4 parts of water is heated to 100
° C
for 2 hours. Then 8 parts of phosphorous acid is added to the reaction mixture
and the temperature of the mixture is held at 100 ° C for another 2
hours. Water
present in the reaction mixture is removed by applying a vacuum of 40 mm of
Hg and gradually raising the temperature to 110 ° C. The resultant
homogeneous
liquid composition is suitable for use as component a-1).
EXAMPLE 12
A mixture of 260 parts of a commercial succinic pentaerythritol ester
ashless dispersant (Lubrizol~ 936 dispersant), and 8 parts of phosphorous acid
is
heated to 100 ° C for 2 hours. To this product is added 8 parts of
orthoboric
acid and 4 parts of water, and the resultant mixture is heated at 100 °
C for
another 2 hours. Water present in the reaction mixture is removed by applying
a vacuum of 40 mm of Hg and gradually raising the temperature to 110 °
C. The
resultant homogeneous liquid composition is suitable far use as component a-
1).
EXAMPLE 13
A mixture of 260 parts of a commercial succinic pentaerythritol ester
ashless dispersant (Lubrizal~ 936 dispersant), 8 parts of orthoboric acid and
4
parts of water is heated to 100 ° C for 2 hours. Then 8 parts of
phosphorous acid
is added to the reaction mixture and the temperature of the mixture is held at
100 ° C for another 2 hours. Water present in the reaction mixture is
removed
by applying a vacuum of 40 mm of Hg and gradually raising the temperature to
110°C. The resultant homogeneous liquid composition is suitable for use
as
component a-1).
EXAMPLE 14
A mixture of 260 parts of a commercial Mannich polyamine dispersant
(AM(7C0~ 9250 dispersant), and 8 parts of phosphorous acid is heated to
100 ° C for 2 hours. To this product are added 8 parts of arthobaric
acid and 4
parts of water, and the resultant mixture is heated at 100 ° C for
another 2 hours.
Water present in the reaction mixture is removed by applying a vacuum of 40
mm of Hg and gradually raising the temperature to 110 ° C. The
resultant
Case EI-6214+ ~ ~ "~ ~ ~ 4
- -35-
homogeneous liquid composition is suitable for use as component a-1).
EXAMPLE 15
A mixture of 260 parts of a commercial Mannich polyamine dispersant
(AMUCU~ 9250 dispersant), 8 parts of orthoboric acid and 4 parts of water is
heated to 100 ° C for 2 hours. Then 8 parts of phosphorous acid is
added to the
reaction mixture and the temperature of the mixture is held at 100 ° C
for
another 2 hours. Water present in the reaction mixture is removed by applying
a vacuum of 40 mm of Hg and gradually raising the temperature to 110 °
C. The
resultant homogeneous liquid composition is suitable for use as component a-
1).
EXAMPLE 1t
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (I7In = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly polyisobutenyl succinic anhydride acylating agent.
(b) A mixture is prepared by the addition of 57 parts (1.38 equivalents)
of a commercial mixture of ethylene polyamines having the approximate overall
composition of tetraethylene pentamine to 1,067 parts of mineral oil and 893
parts (1.38 equivalents) of substituted succinic acylating agent prepared as
in (a)
while maintaining the temperature at 140-145 ° C. The reaction mixture
is then
heated to 155 ° C over a three hour period and stripped by blowing with
nitrogen. The reaction mixture is filtered to yield the filtrate as an oil
solution
of the desired product composed predominantly of polyisobutenyl succinimides.
(c) A mixture is formed from 250 parts of the polyisobutenyl succinimide
product solution formed as in (b), 8 parts of phosphorous acid, 3.5 parts of
tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The mixture is
heated
at 100 ° C for two hours until all of the solid materials are
dissolved. A vacuum
of 40 mm Hg is gradually drawn on the product to remove the water while the
Case EI-6214+ ~ p'~ ~ 14 ~
- -36-
temperature is slowly raised to 100 ° C. A clear solution or
composition is
obtained which is soluble in oil and suitable for use as component a-1).
EXAMPLE 17
The procedure of Example 16 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXA,~IPLE 18
The procedure of Example 16 is repeated except that 11 parts of
phosphorus pentasulfide is used in place of the phosphorous acid, the PISS is
added to the mixture after water distillation, and the mixture is then heated
for
an additional hour at 100 ° C to provide a clear, oil-soluble
composition suitable
for use as component a-1).
EXAMPLE 19
The procedure of Example 18 is repeated except that the PISS is replaced
by 7 parts of phosphorus pentoxide (Pz05).
EXAMPLE 20
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (ll~In = 2020;
lbw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts (1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added aver 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly 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 ethylene polyamines having the
approximate overall composition of tetraethylene pentamine to 392 parts of
mineral oil and 348 parts (0.52 equivalent) of substituted succinic acylating
agent
prepared as in (a) while maintaining the temperature at 140 ° C. The
reaction:
mixture is then heated to 150 ° C 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 predominantly of polyisobutenyl succinimides.
(c) A mixture is formed from 250 parts of the polyisobutenyl succinimide
Case EI-6214+
-37-
product solution formed as in (b), 8 parts of phospharous acid, 3.5 parts of
tolutriazole, 8 parts of boric acid, and 3.0 parts of water. The mixture is
heated
at 100 ° C for two hours until all of the solid materials are
dissolved. A vacuum
of 40 mm I-Ig is gradually drawn on the product to remove the water while the
temperature is slowly raised to 100 ° C. A clear solution or
composition is
obtained which is soluble in oil and suitable for use as component a-1).
EXAMPLE 21
The procedure of Example 20 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 22 .
The procedure of Example 20 is repeated except that 11 parts of
phosphorus pentasulfide is used in place of the phosphorous acid, the PISS is
added to the mixture after water distillation, and the mixture is then heated
for
an additional hour at 100 ° C to provide a clear, oil-soluble
composition suitable
for use as component a-1).
EXAMPLE 23
The procedure of Example 20 is repeated except that the P,SS is replaced
by 7 parts of phosphorus pentoxide (PZOS).
EXAMPLE 24
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020;
IVIw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts (1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly 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 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of
Polyglycol 112-2 demulsifier (Dow Chemical Company) is heated at 150
° C for
2.5 hours. The reaction mixture is then heated to 210 ° C over a period
of 5
Case EI-6214+ ~ "~ ~ ~ j
-38-
hours and then held at 210 ° C for an additional 3.2 hours. The
reaction mixture
is cooled to 190 ° C and 8.5 parts (0.2 equivalent) of a commercial
mixture of
ethylene polyamines having an overall composition approximating that of
tetraethylene pentamine is added. The reaction mixture is stripped by heating
at 205 ° 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 formed from 300 parts of the ashless dispersant product
solution formed as in (b), 8 parts of phosphorous acid, 3.5 parts of
tolutriazole,
8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100
° C for
two hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg
is gradually drawn on the product to remove the water while the temperature is
slowly raised to 100 ° C. A clear solution or composition is obtained
which is
soluble in oil and suitable for use as component a-1).
EXAMPLE 25
'The procedure of Example 24 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 26
The procedure of Example 24 is repeated except that 11 parts of
phosphorus pentasulfide is used in place of the phosphorous acid, the PISS is
added to the mixture after water distillation, and the mixture is then heated
for
an additional .hour at 100 ° C to provide a clear, oil-soluble
composition suitable
for use as component a-1).
EXAMPLE 27
The procedure of Example 24 is repeated except that the P~S~ is replaced
by 7 parts of phosphorus pentoxide (P,OS):
EXAMPLE 28
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (fin = 2020;
Mw = 6049, both determined using the methodology of LJ.S. Pat. No. 4,234,435)
arid 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
Case EI-6214 +
2~'~614~
-39- -
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly 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 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, 3.S parts of
tolutriazoie,
8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100
° C for
two hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg
is gradually drawn on the product to remove the water while the temperature is
slowly raised to 100 ° C. A clear solution or composition is obtained
which is
soluble in oil and suitable for use as component a-1).
EXAMPLE 29
'The procedure of Example 28 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 30
The procedure of Example 28 is repeated except that 11 parts of
phosphorus pentasulfide is used in place of the phosphorous acid, the PzSS is
added to the mixture after water distillation, and the mixture is then heated
for
an additional hour at 100 ° C to provide a clear, oil-soluble
composition suitable
for use as component a-1).
EXAMPLE 31
2S The procedure of Example 28 is repeated except that the P.,SS is replaced
by 7 parts of phosphorus pentoxide (PZOS).
EXAMPLE 32
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020;
Mw = 6049, both determined using the methodology of I1.S. Pat. No, 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
Case EI-6214+
- - -40-
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly 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 204-227 °
C for 5
hours. The reaction mixture is cooled to 162 ° C and 5.3 parts (0.13
equivalent)
of a commercial ethylene polyamine mixture having an overall composition
approximating that of tetraethylene pentamine is added. The reaction mixture
is
heated at 162-163 ° C for 1 hour, then cooled to 130 ° C and
filtered. The filtrate
is an oil solution of the desired 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, 3.5 parts of
tolutriazole,
8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100
° C fox
two hours until all of the solid materials are dissolved. A vacuum of 40 mm I-
Ig
is gradually drawn on the product to remove the water while the temperature is
slowly raised to 100 ° C. A clear solution or composition is obtained
which is
soluble in oil and suitable for use as component a-1).
EXAMPLE 33
The procedure of Example 32 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAIyIPLE 34
The procedure of Example 32 is repeated except that 11 parts of
phosphorus pentasulfide is used in place of the phosphorous acid, the P.,SS is
added to the mixture after water distillation, and the mixture is then heated
for
an additional hour at 100 ° C to provide a clear, oil-soluble
composition suitable
for use as component a-1 j.
EXAIV1PLE 35
The procedure of Example 32 is repeated except that the PISS is replaced
by 7 parts of phosphorus pentoxide (P,05).
EXAII~IPLE 36
(a) A mixture of 510 parts (0.28 mole) of polysobutene (Mn = 1845;
Case EI-6214+
- -41-
Mw = 5325, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 59 parts (0.59 mole) of malefic anhydride is heated to 110 ° C.
This mixture
is heated to 190 ° C in 7 hours during which 43 parts (0.6 mole) of
gaseous
chlorine is added beneath the surface. At 190-192 ° C, an additional 11
parts
(0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is
stripped by heating at 190-193 ° C with nitrogen blowing for 10 hours.
The
residue is predominantly 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 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of
Polyglycol 112-2 demulsifier is heated at 150 ° C for 2.5 hours. The
reaction
mixture is then heated to 210 ° C over a period of 5 hours and then
held at
210 ° C for an additional 3.2 hours: The reaction mixture is cooled to
190 ° C and
8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines
having
1S an overall composition approximating that of tetraethylene pentamine is
added.
The reaction mixture is stripped by heating at 205 ° 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 formed from 260 parts of the ashless dispersant product
solution formed as in (b), 8 parts of phosphorous acid, 3.5 parts of
tolutriazole,
8 parts of boric acid, and 3.0 parts of water. The mixture is heated at 100
° C for
two houxs until all of the solid materials are dissolved. A vacuum of 40 mm I-
Ig
is gradually drawn on the product to remove the water while the temperature is
slowly raised to 100 ° C: A clear solution or composition is obtained
which is
2S soluble in oil and suitable for use as component a-1).
EXAMPLE 37
The procedure of Example 36 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 38
The procedure of Example 36 is repeated except that lI parts of
phosphorus pentasulfide is used in place of the phosphorous acid, the PASS is
added to the mixture after water distillation, and the mixture is then heated
for
Case EI-6214+
-42-
an additional hour at 100 ° C to provide a clear, oil-soluble
composition suitable
for use as component a-1).
EXAMPLE 39
'The procedure of Example 36 is repeated except that the P,SS is replaced
by 7 parts of phosphonis pentoxide (P205).
EXAMPLE 40
(a) A mixture of 510 parts (0.28 mole) of polyisobutene (11~n = 1845;
Mw = 5325, both determined using the methodology of U.S. Pat. No. 4,234;435)
and 59 parts (0.59 mole) of malefic anhydride is heated to 110 ° C.
This mixture
is heated to 190 ° C in 7 hours during which 43 parts (0.6 mole) of
gaseous
chlorine is added beneath the surface. At 190-192 ° C, an additional 11
parts
(0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is
stripped by heating at 190-193 ° C with nitrogen blowing for 10 hours.
The
residue is predominantly polyisobutenyl succinic anhydride 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 to 113 parts of mineral oil and 161
parts
(0.25 equivalent) of the substituted succinic acylating agent prepared as in
(a)
while maintaining the temperature at 138 ° C. The reaction mixture is
heated to
150 ° C over a 2 hour period and stripped by blowing with nitrogen. The
reaction mixture is filtered to yield the filtrate as an oil solution of the
desired
ashless dispersant product.
EXAMPLE 41
The procedure of Example 40 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 42
The procedure of Example 40 is repeated except that 11 parts of
phosphorus pentasulfide is used in place of the phosphorous acid, the PISS is
added to the mixture after water distillation, and the mixture is then heated
for
an additional hour at 100 ° C to provide a clear, oil-soluble
composition suitable
for use as component a-1).
Case Ef-6214- '~ ~'~ ~ ~ 4
-43-
EXAMPLE 43
The procedure of Example 40 is repeated except that the P,,SS is replaced
by 7 parts of phosphorus pentoxide (P205).
EXAMPLE 44
To a reactor are charged under a nitrogen atmosphere 67.98 parts of a
commercially-available polyisobutenyl succinimide 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 900; the succinimide product having
a ratio of about 1.15 succinic 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 100-105 C, 2.09 parts of boric acid and 2.09 parts of
phosphorous acid are introduced into the reactor, followed by 0.92 part of
tolutriazole (Cobratec TT-100; PMC Specialties Group, Cincinnati, Ohio) and
then 0.78 part of water. The resultant mixture is heated at 100-105 ° C
for two
hours and then the temperature is gradually raised to 115 ° C with the
application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes
and until 120 ° C/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 a-1) in the compositions of this
invention.
EXAMPLE 45
The procedure of Example 44 is repeated except that the tolutriazole is
omitted from the reaction mixture.
EXAMPLE 46
(a) A mixture of 322 parts of the polyisobutene-substituted succinic
acylating agent prepared as in Example 40(a), 68 parts of pentaerythritol and
508 parts of mineral oil is heated at 204-227 ° C for 5 hours. The
reaction
mixture is cooled to 162 ° C 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 162-163
° C
for 1 hour, then cooled to 130 ° C and filtered. The filtrate is an oil
solution of
Case EI-6214 +
w -44-
the desired product.
(b) A mixture is formed from 275 parts of the product solution formed
as in (a), 8 parts of phosphorous acid, 3.5 parts of tolutriazole, 8 parts of
boric
acid, and 3.0 parts of water. The mixture is heated at 100 ° C for two
hours until
all of the solid materials are dissolved. A vacuum of 40 mm Hg is gradually
drawn on the product to remove the water while the temperature is slowly
raised to 100 ° C. A clear solution or composition is obtained which is
soluble in
oil and suitable for use as component a-1).
EXAMPLE 47
The procedures of Examples 1 through 8 are repeated except that in
each case a chemically equivalent amount of trimethyl borate is substituted
for
the boric acid, and the water used with the boric acid is omitted.
EXAMPLE 48
The procedures of Examples 1 through 5, and 10 through 15 are repeated
except that in each case the boronating agent consists of a chemically
equivalent
amount of trimethyl borate in lieu of boric acid, the water used with the
boric
acid is omitted, and the phosphorylating agent consists of a chemically
equivalent amount of a mixture consisting of an equimolar mixture of phospho
rous acid and dibutyl hydrogen phosphate.
EXAMPLE 49
(a) To 120 parts 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 S.6 parts of
sodium
carbonate. The reaction mixture is heated to about 205 ° C and
maintained at
this temperature for about S houxs. A 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 120 ° C 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 reaction product
Case EI-6214 +
-45-
formed as in (a), 20 parts of a 100 Solvent Neutral refined mineral oil
diluent,
2.1 parts of phosphorous acid, 4.6 parts of boric acid, and 1.5 parts of
water.
The resultant mixture is heated at 100-105 ° C for 2 hours and then the
tempera-
ture is gradually raised to 115 ° C with the application of a vacuum to
40 mm Hg.
S Stripping is continued for 90 minutes and until 120 ° C/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 a-1) in the compositions of this invention.
(c) 2 Parts of powdered anhydrous boric acid is added with stirring to 80
parts of a 50 weight percent mineral oil solution of a reaction product formed
as
in (a) heated to 90 ° C. The temperature of the mixture is then
increased to
1S0 ° C and maintained at this temperature for 4 hours while collecting
the water
of reaction overhead. The mixture is then filtered and mixed with 10 parts of
a
100 Solvent Neutral refined mineral oil diluent, and 1.5 parts of phosphorous
1S acid. The resultant mixture is heated at 100-105 ° C for 2 hours and
then the
temperature is gradually raised to 11S ° C with the application of a
vacuum to 40
mm Hg. Stripping is continued for 90 minutes and until 120 ° C/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 a-1).
EXAMPLE 50
(a) Into a reactor are placed 220 parts of p-nonylphenol and 465
parts of diethylenetriamine. The mixture is heated to 80 ° C and 1S2
parts of
37%a formalin is added dropwise over a period of about 30 minutes. The
2S mixture is then heated to 12S ° C 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-malefic anhydride resin
(having a number average molecular weight in the range of 600-700 and a mole
ratio of styrene to malefic anhydride of 1:1), 202.5 parts of octadecyl amine
and
472 parts of a 95 VI lubricating oil having a viscosity at 100 ° F of
150 SUS. The
mixture is heated to 22S ° C for several hours. To this mixture is
added dropwise
Case EI-6214 ~-
- -46-
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 210-230 ° C while
collecting the
water formed during reaction. The polymeric product so formed should have 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.
After raising the temperature of the resulting mixture to 100-105 ° C,
5.7 parts of
boric acid, 4.0 parts of phosphorous acid, and 2.0 parts of water are added.
The
resultant mixture is heated at 100-105 ° C for two hours and then the
tempera-
ture is gradually raised to 115 ° C with the application of a vacuum to
40 mm Hg.
Stripping is continued for 90 minutes and until 120 ° C/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 a-1) in the compositions of this invention.
Production of component a-27:
Typical procedures for producing component a-2) 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 phosphorous
acid (H3P03, sometimes depicted as H,(HP03), and sometimes called ortho-
phosphorous acid), phosphoric acid (H3P04, sometimes called orthophosphoric
acid), hypophosphoric acid (H$P206), metaphosphoric acid (HP03), pyro-
phosphoric acid (H4P207), hypophosphorous acid (H3P02, sometimes called
phosphinic acid), pyrophosphorous acid (H~P205, sometimes called
pyrophosphonic acid), phosphinous acid (H3P0), tripolyphosphoric acid
(HSP3~io), tetrapolyphosphoric acid (H6P4013), trimetaphosphoric acid
(H3P309),
phosphoramidic acid (H~03PNH,), phosphoramidous acid (H4NO,P), and the
like. Partial or total sulfur analogs such as phosphorotetrathioic acid
(H3PS4),
phosphoromonothioic acid (H3PO3S), phosphorodithioic acid (H3POZS2),
phosphorotrithioic acid (H3POS3), can also be used in forming products
suitable
for use as component a-2). The preferred phosphorus reagent is phosphorous
Case EI-6214+
- -47-
acid, (H3PO3).
It will be understood that the form or composition of the inorganic
acids) 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
inorgatuc phosphorus compounds into other inorganic phosphorus compounds or
species. .Any such in situ transformations that may occur are within the
purview
of this invention provided that the liquid phosphorylated ashless dispersant
reveals on analysis the presence therein of phosphorus.
Optionally, additional sources of basic nitrogen can be included in the
inorganic phosphorus compound-ashless dispersant mixture so as to provide a
molar amount (atomic proportion) of basic nitrogen up to that equal to the
molar amount of basic nitrogen contributed by the ashless dispersant.
Preferred
auxiliary nitrogen compounds are long chain primary, secondary and tertiary
alkyl amines containing from 12 to 24 carbon atoms, including their
hydroxyalkyl
and aminoallryl derivatives. The long chain alkyl group may optionally contain
one or more ether groups. Examples of suitable compounds are oleyl amine, N-
oleyltrimethylene diamine, 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 (Ci-C4) alkyl-substituted benzotriazoles, which function to
protect copper surfaces.
The heating step is conducted at temperatures sufficient to produce a
liquid composition which contains phosphorus. The heating can be carried out
in the absence of a solvent by heating a mixture of the ashless dispersant and
one or more suitable inorganic phosphorus compounds. 'The temperatures used
will vary somewhat depending upon the nature of the ashless dispersant and the
inorganic phosphorus reagent being utilized. Generally speaking however, the
temperature will usually fall within the range of 40 to 200 ° C. The
duration of
the heating is likewise susceptible to variation, but ordinarily will fall in
the
range of 1 to 3 hours. When conducting the heating in bulk, it is important to
thoroughly agitate the components to insure intimate contact therebetween.
Case EI-6214+
_48-
When utilizing the preferred phosphorus 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 utilized 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 140 ° C. 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 liquid 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 contributed by an auxiliary nitrogen compound. It is possible however
to use the inorganic phosphorus acids) 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 component a-2) in the
compositions of this invention when in their undiluted state will have on a
weight basis a phosphorus content of at least 5,000 parts per million (ppm)
(preferably at least 6,000 ppm and more preferably at least 7,000 ppm). When
forming component a-2) in part by use of one or more organic phosphorus com
pounds such as one or more organic phosphates (e.g., trihydrocarbyl
phosphates,
2S dihydrocarbyl monoacid phosphates, monohydrocarbyl diacid phosphates, or
mixtures thereof), phosphites (e.g., trihydrocarbyl phosphites, dihydrocarbyl
hydrogen phosphites, hydrocarbyl diacid phosphites, or mixtures thereof),
phosphonates (e.g., hydrocarbyl phosphonic acids, mono- and/or dihydrocarbyl
esters of phosphonic acids, or mixtures thereof), phosphonites (e.g.,
hydrocarbyl
phosphinic acids, mono- and/or dihydrocarbyl esters of phosphinic acids, or
mixtures thereof), etc., or the partial or total sulfur analogs thereof, and
in part
by use of one or more inorganic phosphorus acids, the latter should be used in
Case El-6214 a-
-49-
an amount sufficient to provide at least 25% (preferably at least 50% and more
preferably at least 75%) of the total content of phosphorus in the phos-
phorylated dispersant.
The preparation of phosphorylated ashless dispersants suitable for use as
component a-2) in the compositions of this invention is illustrated by the
following Examples 51-96 in which all parts and percentages are by weight
unless otherwise clearly specified.
EXAMPLE 51
A mixture is formed from 260 parts of a polyisobutenyl succinimide
ashless dispersant (derived from polybutene having a number average molecular
weight of 950 and a mixture of a polyethylene po.lyamines having an average
overall composition approximating that of tetraethylene pentamine), 100 parts
of
a 100 Solvent Neutral refined mineral oil diluent, g parts of solid
phosphorous
acid, and 3.5 parts of tolutriazole. The mixture is heated at 110 ° C
for two
hours. A vacuum of 40 mm 1 ig is gradually drawn on the product to remove
traces of water while the temperature is maintained at 110 ° C. A clear
solution
or compositian is obtained which is soluble in oil and suitable for use as
compo-
nent a-2).
EXAMPLE 52
The procedure of Example 51 is repeated except that the succinimide
ashless dispersant used is derived from polybutene having a number average
molecular weight of 1,150. The average number of succinic groups per alkenyl
group in the succinimide is approximately 1.2.
EXAMPLE 53
The procedure of Example 51 is repeated except that the succinimide
ashless dispersant used is derived from polybutene having a number average
molecular weight of 2,100.
EXAMPLE 54
The procedure of Example 51 is repeated except that the succinimide
ashless dispersant is replaced by an equal amount of a boron-free Mannish
poiyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol
{made from polyisobutene having a number average molecular weight of about
case EI-6zla.+
-so-
1710 and formalin) having a nitrogen content of 1.1%.
EXAMPLE 55
The procedure of Example 51 is repeated except that the succinimide
ashless dispersant is replaced by an equal amount of an ashless dispersant of
the
pentaerythritol succinic ester typEXAMPLE 56
The procedure of Example 51 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 110 ° C to provide a clear, ail-soluble
composition
suitable for use as component a-2).
EXAMPLE 57
The procedure of Example 51 is repeated except that the phosphorous
acid is replaced by 6.4 parts of hypophosphorous acid.
EXAMPLE S8
The procedures of Examples 51 through 57 are repeated except that the
tolutriazole is omitted from the initial mixtures subjected to the thermal
processes.
EXAMPLE 59
To 2,500 parts of a polyisobutenyl succinimide (derived from polyiso-
butene having a number average molecular weight of 950 and a mixture of
polyethylene polyamines having an overall average composition approximating
that of tetraethylene pentamine) warmed to 28 ° C are added 54.31 parts
of
phosphorous acid, 20.27 parts of tolutriazole and 23.91 parts of water. 'This
mix-
ture is heated at 110 ° C for 1.5 hours. Then the reflex condenser is
replaced by
a distillation column and water is removed under vacuum for 2.25 hours at
110 ° C to form a homogeneous liquid composition suitable for use as
component
a-2).
EXAMPLE 60
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 polyamines having an average overall composition
approximating that of tetraethylene pentamine), and 2500 parts of 100 Solvent
hleutral mineral oil is heated to 90-100 ° C. To this mixture is added
200 parts of
Case EI-6214 +
-51-
phosphorous acid and the resultant mixture is heated at 90-100 ° C for
2 hours.
The resultant homogeneous liquid composition is suitable for use as component
a-2).
E~LE 6l.
?~, mixture of 58,415.5 parts of a polyisobutenyl succinimide (derived from
polyisobutene having a number average molecular weight of 1300 and a mixture
of polyethylene polyamines having an overall average composition approximating
that of tetraethylene pentamine), and 12,661.6 parts of 100 Solvent Neutral
mineral oil is heated to 80 ° C. To this mixture is added 1942.28 parts
of
phosphorous acid and the resultant mixture is heated at 110 ° C for 2
hours. The
resultant homogeneous liquid composition is suitable for use as component a-
2).
EXAMPLE 62
The procedure of Example 61 is repeated using 45,600 parts of the
ashless dispersant, 8983.2 parts of the mineral oil diluent, and 2416.8 parts
of
the phosphorous acid.
EXAMPLE 63
A mixture of 14,400 parts of a polyisobutenyl succinimide (derived from
polyisobutene having a number average molecular weight of 950 and a mixture
of polyethylene polyamines having an overall average composition approximating
that of tetraethylene pentamine), an~i 3121.2 parts of 100 Solvent Neutral
mineral oil is heated to 80 ° C. To this mixture is added 478.8 parts
of phos-
phorous acid and the resultant mixture is heated at 110 ° C fox 2
hours. The
resultant homogeneous liquid composition contains about 1.04% of phosphorus
and is suitable for use as component a-2).
EXAMPLE 64
A mixture of 7300 parts of ashless dispersant as used in Example 60,
2500 parts of 100 Solvent Neutral mineral oil, and 200 parts of phosphorous
acid
is formed at room temperature and heated to 110 ° C for two hours. The
resultant homogeneous liquid composition is suitable for use as component a-
2).
EXAMPLE 65
A mixture of 4680 parts of phosphorylated dispersant formed as in
Example 64 and 2340 parts of a commercial boronated succinimide ashless
Case EI-6214+
_52_ ~~7~~.,~~
dispersant (Hi1'EC~' 648 dispersant) 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 110 ° C for two hours, and
this
resultant homogeneous liquid composition is also suitable for use as component
a-2).
EXAMPLE 66
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (IGIn = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C 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)
of a commercial mixture of ethylene polyamines having the approximate overall
composition of tetraethylene pentamine to 1,067 parts of mineral oiI and 893
parts (1.38 equivalents) of substituted succinic acylating agent prepared as
in (a)
while maintaining the temperature at 140-145 ° C. The reaction mixture
is then
heated to 155 ° C over a three hour period 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 farmed from 250 parts of the polyisobutenyl succinimide
product solution formed as in (b), 8 parts of phosphorous acid, and 3.5 parts
of
tolutriazole. The mixture is heated at 100 ° C for two hours. A clear
solution or
composition is obtained which is soluble in oil and suitable for use as com-
ponent a-2).
Case EI-6214 +
-s3- 20"'~~1~~
EXAMPLE 67
The procedure of Example 66 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 68
The procedure of Example 67 is repeated except that the phosphorous
acid is replaced by 11.1 parts of phosphoromonothioic acid (I-~3P03S).
EXAMPLE 69
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (Ivin = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added aver 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C 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 ethylene polyamines having the
approximate overall composition of tetraethylene pentamine to 392 parts of
mineral oil and 348 parts (O.S2 equivalent) of substituted succinic acylating
agent
prepared as in (a) while maintaining the temperature at 140 ° C: The
reaction
mixture is then heated to 1S0 ° C 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 fram 2S0 parts of the polyisobutenyl succinimide
2S product solution formed as in (b), 8 parts of phosphorous acid, and 3.5
parts of
tolutriazole. The mixture is heated at 100 ° C for two hours. A clear
solution or
composition is obtained which is soluble in oil and suitable for use as
component a-2).
EXAMPLE 70
The procedure of Example 69 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
Case EI-6214+
-S4-
EXAMPLE 71
The procedure of Example 70 is repeated except that
the phosphorous acid is replaced by 13.7 parts of phosphoramidic acid,
(HO)ZPONH2.
S EXAMPLE 72
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (IV~n = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts (1.17 moles) of malelc anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts (1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture. is
stripped by heating at 186-190 ° C with nitrogen purged for 26 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 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of
Polyglycol 112-2 demulsifier is heated at 150 ° C for 2.5 hours. The
reaction
mixture is then heated to 210 ° C over a period of 5 hours and then
held at
210 ° C for an additional 3.2 hours. The reaction mixture is cooled to
190 ° C and
8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines
having
an overall composition approximating that of tetraethylene pentamine is added.
The reaction mixture is stripped by heating at 20S ° 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 formed from 300 parts of the ashless dispersant product
solution formed as in (b), 8 parts of phosphorous acid, and 3.S parts of
tolutriazole. The mixture is heated at 100 ° C for two hours. A clear
solution or
composition is obtained which is soluble in oil and suitable for use as
component a-2).
case Ez-6214 +
~Q"~~~4~
- -ss-
EXAMFLE 73
The procedure of Example 72 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
E~
The procedure of Example 73 is repeated except that the phosphorous
acid is replaced by 9.6 parts of orthophosphoric acid.
E%AMPLE 75
(a) A mixrixre of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts (1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At i84-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° G 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 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 mixture is heated at 100 ° C for two hours. A clear
solution or
composition is obtained which is soluble in oil and suitable for use as compo-
vent a-2).
EXAMPLE 76
The procedure of Example 75 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 77
The procedure of Example 76 is repeated except that 11 parts of
phosphoric acid is used in place of the phosphorous acid to provide a clear,
oil-
soluble composition suitable for use as component a-2).
Case E1-6214 -~
' -56-
EXAMPLE 78
The procedure of Example 77 is repeated except that 10 parts of an
equimolar mixture of phosphoric acid and phosphorous acid is used.
EXAMPLE
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene {Mn = 2020;
l~Iw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to I84 ° C in 6 hours during which 85 parts (1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue 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 204-227 °
C for S
hours, The reaction mixture is cooled to 162 ° C and 5.3 parts (0.13
equivalent)
of a commercial ethylene polyamine mixture having an overall composition
approximating that of tetraethylene pentamine is added. The reaction mixture
is
heated at 162-163 ° C for 1 hour, then cooled to 130 ° C and
filtered. The filtrate
is an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 350 parts of the ashless dispersant product
solution formed as in (b), 8 paxts of phosphorous acid, and 3.5 parts of
tolutriazole. The mixture is heated at 100 ° C for two hours. A clear
solution or
composition is obtained which is soluble in oil and suitable for use as com-
ponent a-2).
EXAMPLE 80
The procedure of Example 79 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
Case EI-6214 +
_57_
EXAMPLE 81
The procedure of Example 80 is repeated except that 15.8 parts of
phosphorotetrathioic acid (H3PS4) is used in place of the phosphorous acid.
EXAMPLE 82
(a) A mixture of 510 parts (0.28 mole) of polysobutene (l~n = 1845;
lbw = 5325, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 59 parts (0.59 mole) of malefic anhydride is heated to 110 ° C.
This mixture
is heated to 190 ° C in 7 hours during which 43 parts (0.6 mole) of
gaseous
chlorine is added beneath the surface. At 190-192 ° C, an additional 11
parts
(0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is
stripped by heating at 190-193 ° G with nitrogen blowing for 10 hours.
The resi-
due 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 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of
Polyglycol 112-2 demulsifier is heated at 150 ° C for 2.5 hours. The
reaction
mixture is then heated to 210' C over a period of S hours and then held at
210 ° C for an additional 3.2 hours. The reaction mixture is cooled to
190 ° C and
8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines
having
an overall composition approximating that of tetraethylene pentamine is added.
The reaction mixture is stripped by heating at 205 ° 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 farmed from 260 parts of the ashless dispersant product
solution formed as in (b), 8 parts of phosphorous acid, and 3.5 parts of
tolutriazole. 'The mixture is heated at 100 ° C for two hours. A clear
solution or
composition is obtained which is soluble in oil and suitable for use as compo-
nent a-2).
EXAMPLE 83
The procedure of Example 82 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
Case EI-6214 +
- -58-
EXAMPLE 84
The procedure of Example 83 is repeated except that 6.4 parts of
hypophosphorous acid (H3P0~) is used in place of the phosphorous acid.
EXAMPLES
(a) A mixture of 510 parts (0.28 mole) of polyisobutene (l~n = 1845;
l.~w = 5325, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 59 parts (0.59 mole) of malefic anhydride is heated to 110 ° C.
This mixture
is heated to 190 ° C in 7 hours during which 43 parts (0.6 mole) of
gaseous
chlorine is added beneath the surface. At 190-192 ° C, an additional 11
parts
(0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is
stripped by heating at 190-193 ° C with nitrogen blowing for 10 hours.
The
residue is predominately polyisobutenyl succinic anhydride 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 to 113 parts of mineral oil and 161
paria
(0.25 equivalent) of the substituted succinic acylating agent prepared as in
(a)
while maintaining the temperature at 138 ° C. The reaction mixture is
heated to
150 ° C over a 2 hour period and stripped by blowing with nitrogen. The
reaction mixture is filtered to yield the filtrate as an oil solution of the
desired
ashless dispersant product.
(c) A,mixture is formed from 125 parts of the polyisobutenyl succinimide
product solution formed as in (b), 8 parts of phosphorous acid, and 3.5 parts
of
tolutriazole. The mixture is heated at 100 ° C. to form a composition
which is
soluble in oil and suitable for use as component a-2):
2S EXAMPLE 86
The procedure of Example 85 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
Case EI-6214 +
-59-
EXAMPLE 87
The procedure of Example 86 is repeated except that 9.6 parts of
orthophosphoric acid is used instead of the phosphorous acid.
EXAMPLE 88
To a reactor are charged under a nitrogen atmosphere 67.98 parts of a
cocnznercially-available polyisobutenyl succinimide 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 succinimide product having
a ratio of about 1.15 succinic 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 100-105 ° C, 2.09 parts of phosphorous acid are
introduced
into the reactor, followed by 0.92 part of tolutriazole (Cobratec TT-100). The
resultant mixture is heated at 100-105 ° C for two hours. Then the
temperature
is gradually raised to 115 ° C with the application of a vacuum to 40
mm I~g.
Stripping is continued for 90 minutes and until 120 ° C/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 a-2).
EXAMPLE 89
The procedure of Example 88 is repeated except that the tolutriazole is
omitted from the reaction mixture.
EXAMPLE 90
The procedure of Example 63 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 is about 1.66°/0.
EXAMPLE 91
(a) A mixture of 322 parts of the polyisobutene-substituted succinic
acylating agent prepared as in Example 85(a), 68 parts of pentaerythritol and
508 parts of mineral oil is heated at 204-227 ° C for 5 hours. The
reaction
mixture is cooled to 162 ° C and 5.3 parts of a commercial ethylene
polyamine
mixture having the approximate overall composition corresponding to tetra-
Case EI-6214+
60- 2~~fl~.~~
ethylene pentamine is added. The reaction mixture is heated at I62-163
° C for
1 hour, then cooled to 130 ° C 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 100 ° C for two hours. A clear solution or composition is
obtained
which is soluble in oil and suitable for use as component a-2).
EXAMPLE 92
The procedures of Examples 51 through 55 and 59 through 64 are
repeated except that in each case the phosphorylating agent consists of a
chemi-
cally equivalent amount of a mixture consisting of an equimolar mixture of
phosphorous acid and dibutyl hydrogen phosphite.
EXAMPLE 93
(a) To 120 parts 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 205 ° C and
maintained at
this temperature for about 5 hours. A 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 120 ° C 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 reaction product
formed as in (a), 20 parts of a 100 Solvent Neutral refined mineral oil
diluent,
and 2.1 parts of phosphorous acid. The resultant mixture is heated at 100-
105 ° C for 2 hours and then the temperature is gradually raised to 115
° C with
the application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes
and until 120 ° C/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 a-2).
case EI-6214 +
- -61-
EXAMPLE 94
(a) Into a reactor are placed 220 parts of p-nonylphenol and 465 parts of
diethylenetriamine. The mixture is heated to 80 ° C and 152 parts of
37%
formalin is added dropwise over a period of about 30 minutes. The mixture is
then heated to 125 ° C 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-malefic anhydride resin
(having a number average molecular weight in the range of 600-700 and a mole
ratio of styrene to malefic anhydride of 1:1), 202.5 parts of octadecyl amine
and
472 parts of a 95 VI lubricating oil having a viscosity at 100 ° F of
150 SUS. The
mixture is heated to 225 ° C 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 210-230 ° C while
collecting the
water formed during reaction. The polymeric product so formed should have 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.
After raising the temperature of the resulting mixture to 100-105 ° C,
4.0 parts of
phosphorous acid is added. The resultant mixture is heated at 100-105 °
C for
two hours and then the temperature is gradually raised to 115 ° C with
the
application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes
and until 120 ° C/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 a-2).
EXAMPLE 95
The procedure of Example 63 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 (I-I3PO3). 'This product
contains
approximately 0.40% of phosphorus.
EXAMPLE 96
The procedure of Example 61 is repeated except that the proportions of
the reaction components are 45,600 parts of the succinimide, 10,795.8 parts of
Case EI-6214+
- -62-
0
the process oil, and 604.2 parts of phosphorous acid (H3P03). This product
contains approximately 0.41% of phosphorus.
Productiono fC~mnonent a-3~:
Typical procedures for producing component a-3) phosphorylated and
boronated ashless dispersants involve concurrently or sequentially heating one
or
more ashless dispersants of the types described above with (i) water and at
least
one water-hydrolyzable organic phosphorus compound and (ii) at least one
boron compound under conditions yielding a liquid phosphorus- and boron
containing composition. Examples of organic phosphorus compounds which are
useful in forming such products include mono-, di-, and triesters of
phosphoric
acid (e.g., trihydrocarbyl phosphates, dihydrocarbyl monoacid phosphates,
monohydrocarbyl diacid phosphates, and mixtures thereof), mono-, di-, and
triesters of phosphorous acid (e.g., trihydrocarbyl phosphates, dihydrocarbyl
hydrogen phosphates, hydrocarbyl diacid phosphates, and mixtures thereof),
esters
of phosphonic acids (both "primary", RP(O)(OR)2, and "secondary",
RzP(O)(OR)), esters of phosphinic acids, phosphonyl halides (e.g., RP(O)Cl2
and RZP(O)Cl), halophosphites (e.g., (RO)PCh and (RO)~PCI), halophosphates
(e.g., ROP(O)Ch and (RO)ZP(O)Cl), tertiary pyrophosphate esters (e.g.,
(RO)ZP(O)-O-P(O)(OR),), and the total or partial sulfur analogs of any of the
foregoing organic phosphorus compounds, and the like. Also usable, although
less preferred, are the halophosphine halides (e.g., hydrocarbyl phosphorus
tetra-
halides, dihydrocarbyl phosphorus trihalides, and trihydrocarbyl phosphorus
dihalides), and the halophosphines (monohalophosphines and dahalophosphines).
13y "water-hydrolyzable" is meant that the organic phosphorus compound when
boiled at atmospheric pressure for a period of 5 hours with either (a)
distilled
water, or (a) water adjusted to at least one pH between 1 and 7 by use of
HZSOa, or (c) water adjusted to at least one pH between 7 and 13 with KOH, as
hydrolyzed to the extent of at least 50 mole %. In some cases, hydrolysis of
certain types of organophosphorus compounds results in concomitant oxidation,
and compounds which undergo both hydrolysis and oxidation under the
foregoing conditions are usable in forming the phosphorylated dispersants for
use in this invention. Likewise, certain sulfur-containing organophosphorus
Case EI-6214+
- -63-
compounds undergo loss of sulfur under hydrolysis conditions. Here again,
compounds of this type are suitable for use in forming the phosphorylated
dispersants used in the practice of this invention. Considerable information
exists in the literature concerning hydrolysis of organophosphorus compounds --
S see for example Kosolapoff, Org~noghosphorus Compounds, John Wiley &
Sons, Ine., 1950 (and pertinent references cited therein), Van blazer,
PhosRhorus a,~d i~~Compounds, Interscience Publishers, Inc., Vol. I:
Chemistry,
1958 (and pertinent references cited therein), and Vojvodic, et ai, Arch.
Bele.
Med Soc~~HX~,~ Med. Trav. Med. Leg.. Suppl. (Proc.-World Congr. "New
Compd. Biol. Chem. Warf.: Tox Eval.", 1st, 1984), pp. 49-S2. The preferred
water-hydrolyzable organic phosphorus compounds are the water-hydrolyzable
phosphate esters, and the water-hydrolyzable phosphite esters, especially the
dihydrocarbyl hydrogen phosphites.
Suitable compounds of boron useful in forming the phosphorylated and
1S boronated ashless dispersants for use as component a-3) include, for
example,
boron acids, boron oxides, boron esters, and amine or ammonium salts of boron
acids. Illustrative compounds include boric acid (sometimes referred to as
orthoboric acid), boronic acid, tetraboric acid, metaboric acid, pyroboric
acid,
esters of such acids, such as mono-, di-, and tri-organic esters with alcohols
or
polyols having up to 20 or more carbon atoms (e.g., methanol, ethanol, 2-
propanol, propanol, butanols, pentanols, hexanols, ethylene glycol, propylene
glycol, trimethylol propane, diethanol amine, etc.), boron oxides such as
boric
oxide and boron oxide hydrate, and ammonium salts such as ammonium borate,
ammonium pyroborate, etc. While usable, boron halides such as boron
2S trifiuoride, boron trichloride, and the like, are undesirable as they tend
to
introduce halogen atoms into the boronated dispersant, a feature which is
detrimental from the environmental, toxicological and conservational
standpoints. Amine borane addition compounds and hydrocarbyt boranes can
also be used, although they tend to be relatively expensive. The preferred
boron
ieagent is boric acid, H3BO3.
Optionally, additional sources of basic nitrogen can be included in the
organic phosphorus compound-ashless dispersant-boron compound-water mixture
Case EI-6214+
-64-
so as to provide a molar amount (atomic proportion) of basic nitrogen up to
that equal to the molar amount of basic nitrogen contributed by the ashless
dispersant. 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. Examples of suitable
compounds are oleyl amine, N-oleyltrimethylene diamine, N-tallow diethanol-
amine, 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 (Cl-C4) alkyl-substituted benzotriazoles, which function to
protect copper surfaces.
The concurrent heating step or the combination of sequential heating
steps is conducted at temperatures sufficient to produce a final liquid
composition which contains both phosphorus and boron. The heating can be
carried out in the absence of a solvent by heating a mixture of the ashless
dispersant, water and one or more suitable organic phosphorus compounds, or
one or more suitable boron compounds, or, preferably, a combination of water,
one or more suitable organic phosphorus compounds and one or more suitable
boron compounds. The temperatures used will vary somewhat depending upon
the nature of the ashless dispersant and the organic phosphorus and/or boron
reagent being utilized. Generally speaking however, the temperature will
usually fall within the range of 40 to 200 ° C. The duration of the
heating is
likewise susceptible to variation, but ordinarily will fall in the range of 1
to 3
hours. When conducting the heating in bulk, it is important to thoroughly
agitate the components to insure intimate contact therebetween. When utilizing
the preferred boron reagent (boric acid) in a boronation conducted separately
from the phosphorylation, it is preferable to add water with the boric acid to
facilitate initial dissolution of the boric acid.
Water and relatively volatile alcohols formed in the hydrolysis process
and the added water are preferably removed from the heated mixture by
vacuum distillation at temperatures of from 100 to 140 ° C. Preferably
the
Case EI-6214 +
- -65-
heating step or steps will be conducted in a diluent ail or other inert liquid
medium such as light mineral oils, and the like.
The amount of phosphorus compound employed in the heating process
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
contributed by an auxiliary nitrogen compound. The amount of boron
compound employed ranges from 0.001 mole to 1 male per mole of basic
nitrogen and/or hydroxyl in the mixture which is in excess of the molar amount
of inorganic phosphorus compound. When conducting the phosphorylation and
baronatian on a sequential basis (or when conducting one of these operations
on
a dispersant which has previously been subjected to the other such operation),
the last-to-be-used reagent(s) -- water and organic phosphoms compounds) or
boron compound(s), as the case may be -- can be used in an amount equivalent
to (or even in excess of) the amount of basic nitrogen and/or hydroxyl groups
in
the dispersant being heated with such last-to-be-used reagent(s).
As noted above, insofar as the phosphorylation is concerned, it is
preferable to heat the ashless dispersant with one or more water-hydrolyzable
organic phosphorus compounds in the presence of water. In this case the water
can be added before and/or during the heating step, and before, after, or at
the
same time one or more phosphorus compounds are introduced into the vessel in
which the heating is taking place or is to take place. It is also possible to
heat
the ashless dispersant with the organic phosphorus compound and then
subsequently heat the resultant composition with water, although this
procedure
is less preferred.
The amount of added water is not particularly critical as long as a
sufficient amount is present to effect hydrolysis of the water-hydrolyzable
organic phosphorus compound. Water present in the system can be removed by
distillation (preferably at reduced pressure) during the course of, and
preferably
is removed at the end of, the heating step. Amounts of water up to 15% by
weight of the mixture being heated are preferred, and amounts of water of up
to
5% by weight are particularly preferred. When used, the amount of diluent
usually ranges from 10 to 50% by weight of the mixture being subjected to
Case EI-6214+
- -66-
heating.
The hydrolysis of the water-hydrolyzable organic phosphorus
compounds) employed in the phosphorylation operation can be effected in any
of a variety of ways. For example, the dispersant to be phosphorylated, one or
more water-hydrolyzable organic phosphorus compounds, and water may be
mixed together and heated either in an open system at atmospheric pressure or
in a closed system at superatmospheric pressure. If conducted with an open
system, the temperature may be kept below the boiling point of water and the
mixture subjected to stirring of sufficient intensity to cause and maintain
intimate contact among the components within the hydrolysis reaction mixture.
It is also feasible to raise the temperature of the mixture in an open system
to
the boiling point of water and allow the water vapor either to escape from the
system or to be condensed in a suitable condensing system and returned to the
refluxing hydrolysis reaction mixture. If the water is allowed to escape,
sufficiently large amounts of water should be used to insure that a
substantial
amount of hydrolysis occurs before the supply of water in the hydrolysis
mixture
has been depleted. In all such cases, water can be fed to the system as an
initial
complete charge or it can be fed intermittently or continuously into the
hydrolysis mixture.
When conducting the hydrolysis in a closed system, the system may be
kept at one or more selected autogenous pressures by suitable adjustment and
regulation of the temperature. And, still higher pressures may be imposed upon
the system, as for example by injecting high pressure steam into a sealed
autoclave containing the hydrolysis reaction mixture.
The water itself may be charged to the system in any suitable form, such
as in the form of liquid water, steam, or even ice. Similarly, the water may
be
introduced in the form of hydrated solids so that the water is released by the
application of heat during the course of the hydrolysis operation. Injection
of
wet steam into a well-agitated hydrolysis system is one preferred way of
3~ conducting the operation.
The hydrolysis operation should be conducted under any given set ox
sequence of hydrolysis conditions for a period of time long enough that at
least
Case ~I-6214 +
-67-
10%, preferably at least 50%, and most preferably at least 75%, of the organic
phosphorus compounds) present in the hydrolysis mixture has been hydrolyzed.
The nature of the hydrolysis products can be expected to vary in relation to
the
type of phosphorus compounds) used and the severity of the hydrolysis
conditions imposed upon the hydrolysis system. Thus inorganic and organic
hydrolysis products can be formed in the system, and these in turn can be
expected to be taken up by the ashless dispersant(s) present in the system sub-
stantially as they are formed. Accordingly, although the chemical structures)
of
the phosphorylated dispersant(s) are not known with absolute certainty, it is
reasonable to conclude that at least some interaction occurs between the
dispersant(s) and organic and/or inorganic phosphorus-containing species
formed in the hydrolysis reactions taking place in the system. It is also
conceivable that such interacted components may undergo displacements and/or
other forms of interactions with components present in the hydrolysis system
as
the hydrolysis operation proceeds.
As pointed out above, the phosphorylation may be conducted apart from
the boronation, or it may be conducted concurrently with the boronation. When
performing the phosphorylation and boronation operations concurrently, any of
the foregoing hydrolysis procedures can be utilized, the principal difference
being that one or more boron compounds are used in combination with one or
more water-hydrolyzable organic phosphorus compounds.
If desired, small amounts of one or more acids (e.g., sulfuric acid,
phosphoric acid, phosphorous acid, etc.) or bases (e.g., NaOH, I~OI-I,
ammonium hydroxide, etc.) may be added to the hydrolysis mixture to facilitate
hydrolysis of the organic phosphorus compounds) being used.
For further details concerning procedures for conducting the boronation
operation apart from the phosphorylation operation, reference may be had, for
example, to the disclosures of U.S. Pat. Nos. 3,087,936; 3,254,025; 3,281,428;
3,282,955; 3,284,410; 3,338,832; 3,344,069; 3,533,945; 3,718,663; 4,097,389;
4,554,086; and 4,634,543.
The phosphorylated and boronated dispersants utilized as component a-
3) in the compositions of this invention when in their undiluted state should
Case EI-6214 +
' -68-
have on a weight basis a phosphorus content of at least 100 parts per million
(ppm) (preferably at least 500 ppm and more preferably at least 1000 ppm) and
a baron content of at least 100 ppm (preferably at least S00 ppm and more
preferably at least 1000 ppm). When forming component a-3) in part by use of
S one or more inorganic phosphorus compounds such as phosphorous acid
(H3P03, sometimes depicted as H~(HP03), and sometimes called ortho-
phosphorous acid or phosphoric acid), phosphoric acid (H3PO4, sometimes
called orthophosphoric acid), hypophosphorous acid (H3P0,, sometimes called
phosphinic acid), hypophosphoric acid (HQP.,O6), metaphosphoric acid (HP03),
pyrophosphoric acid (H4P20~), pyrophosphorous acid (H4P,05, sometimes called
pyrophosphonic acid), phosphinous acid (H3P0), tripolyphosphoric acid
(HSP301o), tetrapolyphosphoric acid (H6P4013), trimetaphosphoric acid
(H3P309),
phosphorus trioxide, phosphorus tetraoxide, phosphorus pentoxide, and/or
partial or total sulfur analogs of the foregoing such as phosphorotetrathioic
acid
(H3PS4), phosphoromonothioic acid (I-I3P03S), phosphorodithioic acid
(H3POzS2), phosphorotrithioic acid (H3POS3), phosphorus sesquisulfide,
phosphorus heptasulfide, and phosphorus pentasulfide (PASS, sometimes referred
to as P4Slo), or the like, and in part by use of one or mare water-
hydrolyzable
organic phosphorus compounds, the latter should be used in an amount suffi-
cient to provide at least 10% (preferably at least 50% and more preferably at
least 7S%) of the total phosphorus content of the phosphorylated and boronated
dispersant. For crankcase lubricant usage, component a-3) when in the
undiluted state preferably contains at least 3000 ppm (more preferably at
least
5000 ppm and most preferably at least 7000 ppm) of phosphorus and at least
1500 ppm (more preferably at least 2500 ppm and most preferably at least 3500
ppm) of boron.
The preparation of phosphorylated and boronated ashless dispersants
suitable for use as component a-3) in the compositions of this invention is
illustrated by the following Examples 97-148 in which all parts and
percentages
are by weight unless otherwise clearly specified.
EXAMPLE 97
A mixture is formed from 260 parts of a commercial succinimide ashless
Case EI-6214+
-69-
dispersant (HiTEC~ 644 dispersant), 100 parts of a 100 Solvent Neutral refined
mineral oil diluent, 26 parts of dibutyl hydrogen phosphite, 3.5 parts of
tolutriazole, 10 parts of boric acid, and 8 parts of water. The mixture is
heated
at 100 ° C for two hours u:~til all of the solid materials are
dissolved. A vacuum
of 40 mm Hg is gradually drawn on the product to remove the water and
butanol while the temperature is slowly raised to 100 ° C. A clear
solution or
composition is obtained which is soluble in oil and suitable for use as
component a-3).
EXAMPLE 98
The procedure of Example 97 is repeated except that the succinimide
ashless dispersant used is derived from polybutene having a number average
molecular weight of 1,100. The average number of succinic groups per alkenyl
group in the succinimide is approximately 1.2.
EXAMPLE 99
The procedure of Example 97 is repeated except that the succinimide
ashless dispersant used is derived from polybutene having a number average
molecular weight of 2,100.
EXAMPLE 100
The procedure of Example 97 is repeated except that the succinimide
ashless dispersant is replaced by an equal amount of a Mannich polyamine
dispersant (AMOCO~ 9250 dispersant). The Amoco 9250 dispersant as
supplied by the manufacturer is believed to be a boronated dispersant and in
such case, another material suitable for use as component a-3) can be formed
by
eliminating the boric acid from the procedure used in this example and thereby
conducting phosphorylation on an already boronated dispersant.
EXAMPLE 101
The procedure of Example 97 is repeated except that the succinimide
ashless dispersant is replaced by an equal amount of a commercial ashless
dispersant of the pentaerythritol succinic ester type (Lubrizoh 936
dispersant).
As in the case of Example 100, the initial dispersant as supplied by the
manufacturer is believed to be a boronated dispersant. In such cases, the
dispersant can, if desired, be subjected just to phosphorylation to thereby
form
Case El-6214+
- -70-
still another product suitable for use as component a-3).
EXAMPLE 102
The procedure of Example 97 is repeated except that 16 parts of
trimethyl phosphite is used in place of the dibutyl hydrogen phosphite, to
provide a clear, oil-soluble composition suitable far use as component a-3).
EXyIPLE 10~
The procedure of Example 97 is repeated except that the dibutyl
hydrogen phosphite is replaced by 16.3 parts of O-ethyl-O,O-1,2-ethanediyl
phosphite.
EXAMPLE 104
The procedures of Examples 97 through 103 are repeated except that the
tolutriazole is omitted from the initial mixtures subjected to the thermal
processes.
EXAMPLE 105
A mixture of 12,000 parts of a commercial boronated succinimide
(HiTEC~ 648 dispersant), 90 parts of water, and 584 parts of triphenylmethane
phosphonyl dichloride is heated to 100-110 ° C for 6 hours while
sweeping the
reaction mixture with nitrogen. A vacuum of 40 mm Hg is then gradually
applied to remove water and thereby form a homogeneous liquid composition
suitable for use as component a-3). For convenience in handling, 100 Solvent
Neutral mineral oil can be added to form an 80% solution of the additive in
the
oil.
EXAMPLE 106
A mixture of 260 parts of a commercial succinimide (HiTEC~ 644
dispersant), 3 parts of water, 13 parts of tributyl phosphate, and 4 parts of
phosphorous acid is heated to 100 ° C for 2 hours. To this product is
added 8
parts of orthoboric acid and 4 parts of water, and the resultant mixture is
heated
at 100 ° C for another 2 hours. A vacuum of 40 mm of Hg is applied to
the
system and the temperature is gradually raised to 110 ° C. The
resultant homo-
geneous liquid composition is suitable for use as component a-3).
Case EI-6214 ~-
2~'~~~ ~~
-71-
EXAMPLE 107
A mixture of 260 parts of a commercial succinimide (HiTEC~ 644
dispersant), 8 parts of orthoboric acid and 4 parts of water is heated to
100°C
for 2 hours. Then 16 parts of diethyl hydrogen phosphite and 6 parts of
aqueous
ammonium hydroxide (3N) are added to the reaction mixture and the
temperature of the mixture is held at 100 ° C for another 2 hours. A
vacuum of
40 mm of Hg is applied to the system and the temperature is gradually raised
to
110 ° C. The resultant homogeneous liquid composition is suitable for
use as
component a-3).
EXAMPLE 108
A mixture of 260 parts of a commercial succinic pentaerythritol ester
ashless dispersant (Lubrizoh 936 dispersant), 6 parts of water, and 16 parts
of
methyl dichlorophosphate is heated to 100 ° C for 2 hours. To this
product are
added 8 parts of orthoboric acid and 4 parts of water, and the resultant
mixture
is heated at 100 ° C for another 2 hours. The mixture is then swept
with nitrogen
for one hour at 100 ° C. A vacuum of 40 mm of Hg is applied to the
system and
the temperature is gradually raised to 110 ° C. The resultant
homogeneous liquid
composition is suitable for use as component a-3).
EXAMPLE 109
A mixture of 260 parts of a commercial succinic pentaerythritol ester
ashless dispersant (Lubrizol~ 936 dispersant), 8 parts of orthoboric acid and
6
parts of water is heated to 100 ° C for 2 hours. Then 19 parts of
methyl
bis(phenyl) phosphate, 5 parts of phosphoric acid, and 0.4 part of additional
water are added to the reaction mixture and the temperature of the mixture is
held at 100 ° C for another 2 hours. A vacuum of 40 mm of Hg is applied
to the
system and the temperature is gradually raised to 130 ° C. The
resultant
homogeneous liquid composition is suitable for use as component a-3).
EXAMPLE 110
A mixture of 260 parts of a commercial Mannich polyamine dispersant
(AMOCO~ 9250 dispersant), 8 parts of water, and 35 parts of dibenzyl methyl
phosphate is heated to 100 ° C for 2 hours. To this product is added 8
parts of
orthoboric acid and 4 parts of water, and the resultant mixture is heated at
Case EI-6214+
- -72-
100 ° C for another 2 hours. A vacuum of 40 mm of Hg is applied to the
system
and the temperature is gradually raised to 130 ° C. The resultant
homogeneous
liquid composition is suitable for use as component a-3).
EXAMPLE 111
S A mixture of 260 parts of a commercial Mannich polyamine dispersant
(AMOCO~ 9250 dispersant), 8 parts of orthoboric acid and 4 parts of water is
heated to 100 ° C for 2 hours. Then 9 parts of monophenyl phosphate, 4
parts of
phosphorous acid, and an additional 3 parts of water are added to the reaction
mixture and the temperature of the mixture is held at 100 ° C for
another 2
hours. A vacuum of 40 mm of Hg is applied to the system and the temperature
is gradually raised to 130 ° C. The resultant homogeneous liquid
composition is
suitable for use as component a-3).
EXAMPLE 112
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (11~:n = 2020;
I~w = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts (1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts (1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly polyisobutenyl succinic anhydride acylating agent.
(b) A mixture is prepared by the addition of 57 parts (1.38 equivalents)
of a commercial mixture of ethylene polyamines having the approximate overall
composition of tetraethylene pentamine to 1,067 parts of mineral oil and 893
2S parts (1.38 equivalents) of substituted succinic acylating agent prepared
as in (a)
while maintaining the temperature at 140-145 ° C. The reaction mixture
is then
heated to 155 ° C over a three hour period and stripped by blowing with
nitrogen. The reaction mixture is filtered to yield the filtrate as an oil
solution
of the desired product composed predominantly of polyisobutenyl succinimides.
(c) A mixture is formed from 250 parts of the polyisobutenyl succinimide
product solution formed as in (b), 11 parts of dibutyl chlorophosphate, 5
parts of
phosphoric acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 8 parts
of
Case EI-6214+
_~3_
water. The mixture is heated at 100 ° C for four hours until all of the
solid
materials are dissolved. A vacuum of 40 mm Hg is gradually drawn on the
product to remove the water while the temperature is slowly raised to 100
° C. A
clear solution or composition is obtained which is soluble in oil and suitable
for
S use as component a-3).
EXAMPLE 113
The procedure of Example 112 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 114
The procedure of Example 112 is repeated except that 9 parts of an
equimolar mixture of dibutyl hydrogen phosphate and monobutyl dihydrogen
phosphate is used in place of the dibutyl chlorophosphate to provide a clear,
oii-
soluble homposition suitable for use as component a-3).
EXAMPLE 11S
1S The procedure of Example 112 is repeated except that the dibutyl
chlorophosphate is replaced by 11 parts of mono-2-naphthyl orthophosphate.
EXAMPLE 116
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 11S parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 8S parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional S9
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 2b hours.
The
2S residue is predominantly 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 ethylene polyamines having the
approximate overall composition of tetraethylene pen-tamine to 392 parts of
mineral oil and 348 parts (O.S2 equivalent) of substituted succinic acylating
agent
prepared as in (a) while maintaining the temperature at 140 ° C. The
reaction
mixture is then heated to 150 ° C in 1:8 hours and stripped by blowing
with
nitrogen. The reaction mixture is filtered to yield the filtrate as an oil
solution
Case EI-6214+
-74-
of the desired product composed predominantly of polyisobutenyl succinimides.
(c) A mixture is formed from 250 parts of the polyisobutenyl succinimide
product solution formed as in (b), 18 parts of phenyl dimethyl phosphate, 3.5
parts of tolutriazole, 8 parts of boric acid, and 8 parts of water. The
mixture is
heated at 100 ° C for three hours. A vacuum of 40 mm Hg is gradually
drawn on
the product to remove the water while the temperature is slowly raised to
130 ° C. A clear solution or composition is obtained which is soluble
in oil and
suitable for use as component a-3).
EXAMPLE 117
The procedure of Example 11~ is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 118
The procedure of Example 116 is repeated except that 15 parts of
trimethyl phosphite is used in place of the phenyl dimethyl phosphate to
provide
a clear, oil-soluble composition suitable for use as component a-3).
EXAMPLE 119
The procedure of Example 116 is repeated except that the phenyl
dirnethyl phosphate is replaced by 36 parts of 4-dimethyl-aminophenyl
phosphorus tetrachloride and the heated mixture in (c) is swept with nitrogen
during the three-hour period.
EXAMPLE 120
(a) A mixture of 1,000 parts (0.495 male) of polyisobutene (Mn = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts (1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts (1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly 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 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of
Case EI-6214+
_75-
Polyglycol 112-2 demulsifier is heated at 150 ° C for 2.5 hours. The
reaction
mixture is then heated to 210 ° C over a period of S hours and then
held at
210 ° C for an additional 3.2 hours. The reaction mixture is cooled to
190 ° C and
8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines
having
an overall composition approximating that of tetraethylene pentamine is added.
The reaction mixture is stripped by heating at 205 ° 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 formed from 300 parts of the ashless dispersant product
solution formed as in (b), 37 parts of bis(2-ethylhexyl) hydrogen phosphite,
3.5
parts of tolutriazole, 8 parts of boric acid, and 8 parts of water. 'The
mixture is
heated at 100 ° C for two hours until all of the solid materials are
dissolved. A
vacuum of 40 mm Hg is gradually drawn on the product to remove the water
while the temperature is slowly raised to 130 ° C. A clear solution or
1S composition is obtained which is soluble in oil and suitable for use as
component a-3).
EXAMPLE 121
The procedure of Example 120 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 122
The procedure of Example 120 is repeated except that 26 parts of dibutyl
hydrogen phosphite is used in place of the bis(2-ethylhexyl) hydrogen
phosphite
to provide a clear, oil-soluble composition suitable for use as component a-
3).
EXAMPLE 123
The procedure of Example 120 is repeated except that the bis(2-
ethylhexyl) hydrogen phosphite is replaced by 15 parts of trimethyl phosphite.
EXAMPLE 124
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (Ivln = 2020;
Mw = 6049, both determined using the methodology of LJ.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts (1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
Cage El-6214+
-76-
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly 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 S.S hours. 'The reaction mixture is filtered at 130
° C to yield 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), 27 parts of dibutyl chlorophosphate, 3.5 parts of
tolutriazole, 8 parts of boric acid, and 8 parts of water. The mixture is
heated at
100 ° C for two hours until all of the solid materials are dissolved. A
vacuum of
40 mm Hg is gradually drawn on the product to remove the water while the
temperature is slowly raised to 100 ° C. A clear solution or com-
position is
1S obtained which is soluble in oil and suitable for use as component a-3).
EXAMPLE 125
The procedure of Example 124 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 126
The procedure of Example 124 is repeated except that 8 parts of ethyl
dichlorophosphate and 4 parts of phosphorous acid are used in place of the
dibutyl chlorophosphate to provide a clear, oil-soluble composition suitable
for
use as component a-3).
EXAMPLE 127
2S The procedure of Example 124 is repeated except that the dibutyl
chlorophosphate is replaced by 10 parts of dibutyl hydrogen phosphite and S
parts of phosphoric acid.
EXAMPLE 128
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (lV~n = 2020;
Mw = 6049, bath determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts (1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
Case EI-6214 +
-77-
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominantly 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 pentaeiythritol and 508 parts of mineral oil is heated at 204-227 °
C for 5
hours. The reaction mixture is cooled to 162 ° C and 5.3 parts (0.13
equivalent)
of a commercial ethylene polyamine mixture having an overall composition
approximating that of tetraethylene pentamine is added. The reaction mixture
is
heated at 162-163 ° C for 1 hour, then cooled to 130 ° C and
filtered. The filtrate
is an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 350 parts of the ashless dispersant product
solution formed as in (b), 16 parts of diethyl hydrogen phosphate, 3.5 parts
of
tolutriazole, 8 parts of boric acid, and 6 parts of water. The mixture is
heated at
100 ° C for two hours until all of the solid materials are dissolved. A
vacuum of
40 mm Hg is gradually drawn on the product to remove the water while the
temperature is slowly raised to 100 ° C. A clear solution or
composition is
obtained which is soluble in oil and suitable for use as component a-3).
EXAMPLE 129
The procedure of Example 128 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 130
The procedure of Example 128 is repeated except that 20 parts of diethyl
chlorophosphate is used in place of the diethyl hydrogen phosphate to provide
a
clear, oil-soluble composition suitable for use as component a-3).
EXAMPLE 131
The procedure of Example 128 is repeated except that the diethyl
hydragen phosphate is replaced by 12 parts of ethyl dibutyl phosphate and 4
parts of phasphorous acid.
Case EI-6214+
_78_
E%AMPLE 132
(a) A mixture of 510 parts (0.28 mole) of polyisobutene
(Mn = 1845; Mw = 5325, both determined using the methodology of U.S. Pat.
No. 4,234,435) and 59 parts (0.59 mole) of malefic anhydride is heated to
110°C.
This mixture is heated to 190 ° C in 7 hours during which 43 parts (0.6
mole) of
gaseous chlorine is added beneath the surface. At 190-192 ° C, an
additional 11
parts (0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is
stripped by heating at 190-193 ° C with nitrogen blowing for 10 hours.
The resi-
due is predominantly 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 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of
Polyglycol 112-2 demulsifier is heated at 150 ° C for 2.5 hours. The
reaction
mixture is then heated to 210 ° C over a period of 5 hours and then
held at
210 ° C for an additional 3.2 hours. The reaction mixture is cooled to
190 ° C and
8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines
having
an overall composition approximating that of tetraethylene pentamine is added.
The reaction mixture is stripped by heating at 205 ° 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 formed from 260 parts of the ashless dispersant product
solution formed as in (b), 20 parts of ethyl dichloro phosphate, 3.5 parts of
tolutriazole, 8 parts of boric acid, and 8 parts of water. The mixture is
heated at
100 ° C for two hours until all of the solid materials are dissolved. A
vacuum of
40 mm I-Ig is gradually drawn on the product to remove the water while the
temperature is slowly raised to 100 ° C. A clear solution or
composition is
obtained which is soluble in oil and suitable for use as component a-3).
EXAMPLE 133
The procedure of Example 132 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
E;YAMPLE 134
The procedure of Example 132 is repeated except that 23 parts of butyl
Case EI-6214+
- -79-
dichloro phosphate is used in place of the ethyl dichloro phosphate to provide
a
clear, oil-soluble composition suitable for use as component a-3).
EXAMPLE 135
The procedure of Example 132 is repeated except that the ethyl dichloro
phosphate is replaced by 30 parts of monobutyl-mono-2-ethylhexyl hydrogen
phosphite.
EXAMPLE 13,~
(a) A mixture of 510 parts (0.28 mole) of polyisobutene
(Mn = 1845; Mw = 5325, both determined using the methodology of U.S. Pat.
No. 4,234,435) and 59 parts (0.59 mole) of malefic anhydride is heated to 110
° C.
This mixture is heated to 190 ° C in 7 hours during which 43 parts (0.6
mole) of
gaseous chlorine is added beneath the surface. At 190-192 ° C, an
additional 11
parts (0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is
stripped by heating at 190-193 ° C with nitrogen blowing for 10 hours.
The resi
due is predominantly polyisobutenyl succinic anhydride 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 to 113 parts of mineral oil and 161
parts
(0.25 equivalent) of the substituted succinic acylating agent prepared as in
(a)
while maintaining the temperature at 138 ° C. The reaction mixture is
heated to
150°C over a 2 hour period and stripped by blowing with nitrogen. The
reaction mixture is filtered to yield the filtrate as an oil solution of the
desired
ashless dispersant product.
(c) A mixture is formed from 125 parts of the polyisobutenyl succiniznide
product solution formed as in (b), 9 parts of monobenzyl phosphate and 4 parts
of phosphorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 6
parts
of water. The mixture is heated at 100 ° C for two hours until all of
the solid
materials are dissolved. A vacuum of 40 mm Hg is gradually drawn on the pro-
duct to remove the water while the temperature is slowly raised to 100
° C. A
clear solution or composition is obtained which is soluble in oil and suitable
for
use as component a-3).
Case EI-6214 +
80 -
EXAMPLE 137
The procedure of Example 136 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
E~CAMPLE 138
S The procedure of Example 136 is repeated except that 14 parts of
dibenayl phosphate is used in place of the monobenzyl phosphate to provide a
clear, oil-soluble composition suitable for use as component a-3).
EXAMPLE 139
The procedure of Example 136 is repeated except that the monobenzyl
phosphate is replaced by 17 parts of rnonophenyl dibenzyl phosphate.
EXAMPLE 140
To a reactor are charged under a nitrogen atmosphere 67.98 parts of a
commercially-available polyisobutenyl succinimide 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 900; the succinimide product having
a ratio of about 1.15 succinic 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 100-10S ° C, 2.09 parts of boric acid and 4.6
parts of dibutyl
hydrogen phosphite are introduced into the reactor, followed by 0.92 part of
tolutriazole (Cobratec TT-100) and then 3 parts of water. The resultant
mixture
is heated at 100-lOS ° C far two hours and then the temperature is
gradually
raised to 11S ° C with the application of a vacuum to 40 mm Hg.
Stripping is
continued for 90 minutes and until 120 ° C/40 mm Hg has been reached. A
flow
2S 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 a-3).
EXAMPLE 141
The procedure of Example 140 is repeated except that the tolutriazole is
omitted from the reaction mixture.
EXAMPLE 142
(a) A mixture of 322 parts of the polyisobutene-substituted succinic
acylating agent prepared as in Example 136(a), 68 parts of pentaerythritol and
Case EI-6214+
- -81-
508 parts of mineral oil is heated at 204-227 ° C for 5 hours. The
reaction
mixture is cooled to 162 ° C 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 162-163
° C
for 1 hour, then cooled to 130 ° C and filtered. The filtrate is an oil
solution of
the desired product.
(b) A mixture is formed from 27S parts of the product solution formed
ro
as in (a), 20 parts of diisopropyl hydrogen phosphate, 3.5 parts of
tolutriazole, 8
parts of boric acid, and 8 parts of water. The mixture is heated at
100°C for
two hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg
is gradually drawn on the product to remove the water while the temperature is
slowly raised to 100 ° C. A clear solution or composition is obtained
which is
soluble in oil and suitable for use as component a-3).
EXAMFLE 143
The procedures of Examples 97 through 104 are repeated except that in
each case a chemically equivalent amount of trimethyl borate is substituted
for
the boric acid.
EXAMPLE 144
The procedures of Examples 97 through 101, and 106 through 111 are
repeated except that in each case the boronating agent consists of a
chemically
equivalent amount of trimethyl borate in lieu of boric acid, and the
phosphorylating agent consists of a chemically equivalent amount of a mixture
consisting of an equimolar mixture of phosphorous acid and dibutyl hydrogen
phosphate.
EXAMPLE 145
(a) To 120 parts 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 205 ° C and
maintained at
this temperature for about 5 hours. A 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
Case EI-6214+
_ g2 -
methanol to remove excess pentaethylene hexamine. The hexane is stripped
from the product by heating the mixture to 120 ° C 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 reaction product
formed as in (a), 20 parts of a 100 Solvent Neutral refined mineral oil
diluent,
5.0 parts of dibutyl hydrogen phosphite, 4.6 parts of boric acid, and 3.0
parts of
water. The resultant mixture is heated at 100-10S ° C for 2 hours and
then the
temperature is gradually raised to 115 ° C with the application of a
vacuum to 40
mm Hg. Stripping is continued for 90 minutes and until 120 ° C/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 a-3) in the compositions of this invention.
(c) 2 Parts of powdered anhydrous boric acid is added with stirring to 80
parts of a 50 weight percent mineral oil solution of a reaction product formed
as
in (a) heated to 90 ° C. The temperature of the mixture is then
increased to
150 ° C and maintained at this temperature for 4 hours while collecting
the water
of reaction overhead. The mixture is then filtered and mixed with 10 parts of
a
100 Solvent Neutral refined mineral oil diluent, ~.6 parts of dibutyl hydrogen
phosphite and 3.0 parts of water. The resultant mixture is heated at 100-105
° C
for 2 hours and then the temperature is gradually raised to 115 ° C
with the
application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes
and until 120 ° C/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 a-3).
EXAMPLE 146
(a) Into a reactor are placed 220 parts of p-nonylphenol and 465 parts of
diethylenetriamine. The mixture is heated to 80 ° C and 152 parts of
37%
formalin is added dropwise over a period of about 30 minutes. The mixture is
then heated to 125 ° C 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-maleie anhydride resin
Case EI-6214 +
. . _g3_
(having a number average molecular weight in the range of b00-700 and a mole
ratio of styrene to malefic anhydride of 1:1), 202.5 parts of octadecyl amine
and
472 parts of a 95 VI lubricating oil having a viscosity at 100 ° F of
150 SUS. The
mixture is heated to 225 ° C 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 210-230 ° C while
collecting the
water formed during reaction. The polymeric product so formed should have a
nitrogen content of about 2.1 weight percent.
(c) To a reactor are charged 250 parts of the basic nitrogen polymer
produced as in (b) and 50 parts of a 100 Solvent Neutral refined mineral oil.
After raising the temperature of the resulting mixture to 100-105 ° C,
5.7 parts of
boric acid, 35 parts of dibutyl hydrogen phosphite, and 8 parts of water are
added. The resultant mixture is heated at 100-105 ° C for two hours and
then
the temperature is gradually raised to 115 ° C with the application of
a vacuum
to 40 mm Hg. Stripping is continued for 90 minutes and until 120 ° C/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 a-3).
EXAMPLE 147
The procedure of Example 128 is repeated except that the diethyl
hydrogen phosphite is replaced by 10 parts of dimethyl hydrogen phosphite.
EXAMPLE 148
The procedure of Example 128 is repeated except that the diethyl
hydrogen phosphite is replaced by 5 parts of dimethyl hydrogen phosphite and 4
parts of phosphorous acid.
Production of Component a-4):
Typical procedures for producing component a-4) phosphorylated ashless
dispersants involve heating one or more ashless dispersants of the types
described above with at least one water-hydroiyzable organic phosphorus
compound and water under conditions yielding a liquid phosphorus-containing
composition.
The water-hydrolyzable organic phosphorus compounds used and the conditions
Case E1-6214+
- -84- ~~~~~.~1~
under which they are used are the same as described above in connection with
production of component a-3), except of course no boron compound is employed
in the process.
Usually the phosphorylated dispersants utilized as component a-4) in the
compositions of this invention when in their undiluted state will have on a
weight basis a phosphorus content of at least 5,000 parts per million (ppm)
(preferably at least 6,000 ppm and more preferably at least 7,000 ppm).
The preparation of phosphorylated ashless dispersants suitable for use as
component a-4) in the compositions of this invention is illustrated by the
Examples 149-198 in which all parts and percentages are by weight unless
otherwise clearly specified.
EXAMPLE 149
A mixture is formed from 260 parts of a polyisobutenyl succinimide
ashless dispersa.nt (derived from polybutene having a number average molecular
weight of about 950 and a mixture of a polyethylene polyamines having an
average overall composition approximating that of tetraethylene pentamine),
100
parts of a 100 Solvent Neutral refined mineral oil diluent, 26 parts of
dibutyl
hydrogen phosphite, 3.5 parts of tolutriazole and 8 parts of water. The
mixture
is heated at 110 ° C for two hours. A vacuum of 40 mm Hg is gradually
drawn
on the product to remove water and butanol while the temperature is
maintained at 110 ° C. A clear solution or composition is obtained
which is
soluble in oil and suitable for use as component a-4).
EXAMPLE 150
The procedure of Example 149 is repeated except that the succinimide
ashless dispersant used is derived from polybutene having a number average
molecular weight of 1,100. The average number of succinic groups per alkenyl
group in the succinimide is approximately 1:2.
EXAMPLE 151
The procedure of Example 149 is repeated except that the succinimide
ashless dispersant used is derived from polybutene having a number average
molecular weight of 2,100.
Case EI-6214 +
-85- ~1~~~~~~
EXAMPLE 152
The procedure of Example 149 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
S (made from polyisobutene having a number average molecular weight of about
1710 and formalin) having a nitrogen content of 1.1 %.
EXAMPLE 153
The procedure of Example 149 is repeated except that the succinimide
ashless dispersant is replaced by an equal amount of an ashless dispersant of
the
pentaerythritol succinic ester ty~XAMPLE 154
The procedure of Example 149 is repeated except that 16 parts of
trimethyl phosphate is used in place of the dibutyl hydrogen phosphate to
provide
a clear, oil-soluble composition suitable for use as component a-4).
EXAMPLE 155
The procedure of Example 149 is repeated except that the dibutyl
hydrogen phosphate is replaced by 16.3 parts of O-ethyl-O,O-1,2-ethanediyl
phosphate.
EXAMPLE 156
The procedures of Examples 149 through 155 are repeated except that
the tolutriazole is omitted from the initial mixtures subjected to the thermal
processes.
EXAMPLE 157
A mixture of 12,000 parts of a commercial boron-free succinimide
(HiTEC~ 644 dispersant), 90 parts of water, and 584 parts of triphenylmethane
phosphonyl dichloride is heated to 100-110 ° C for 6 hours while
sweeping the
reaction mixture with nitrogen. A vacuum of 40 rnm Hg is then gradually ap-
plied to remove water and thereby form a homogeneous liquid composition
suitable for use as component a-4). For convenience in handling, 100 Solvent
Neutral mineral oil can be added to form an 80% solution of the additive in
the
oil.
Case EI-6214 +
-86-
EXAMPLE 158
A mixture of 260 parts of a commercial succinimide (HiTEC~ 644
dispersant), 3 parts of water, 13 parts of tributyl phosphate, and 4 parts of
phosphoraus acid is heated to 100 ° C for 2 hours. Then a vacuum of 40
mm of
Hg is applied to the system and the temperature is gradually raised to 110
° C.
The resultant homogeneous liquid composition is suitable for use as component
a-4).
EXAMPLE 159
A mixture of 260 parts of polyisobutenyl succinimide (derived from
polybutene having a number average molecular weight of about 1,100 and a
mixture of polyethylene polyamines having an average overall composition
approximating that of tetraethylene pentamine), 4 parts of water, 16 parts of
diethyl hydrogen phosphite and 6 parts of aqueous ammonium hydroxide (3Nj is
heated at 100 ° C for 2 hours. A vacuum of 40 mm of Hg is applied to
the sys-
tem and the temperature is gradually raised to 110 ° C. The resultant
homogeneous liquid composition is suitable for use as component a-4).
EXAMPLE 160
A mixture of 260 parts of a polyisobutenylsuccinic pentaerythritol ester
ashless dispersant, 6 parts of water, and 16 parts of methyl dichlorophosphate
is
heated to 100 ° C for 2 hours. The mixture is then swept with nitrogen
for one
hour at 100 ° C. A vacuum of 40 mm of Hg is applied to the system and
the
temperature is gradually raised to 110 ° C. The resultant homogeneous
liquid
composition is suitable for use as component a-4).
EXAMPLE 161
A mixture of 260 parts of a succinic pentaerythritol ester ashless
dispersant, 6.5 parts of water, 19 parts of methyl bis(phenyl) phosphate, and
5
parts of phosphoric acid is heated at a temperature 100 ° C for 2
hours. A
vacuum of 40 mm of Hg is applied to the system and the temperature is
gradually raised to 130 ° C. The resultant homogeneous liquid
composition is
suitable for use as component a-4).
Case EI-6214 +
- -87-
EXAMPLE 162
A mixture of 260 parts of a Mannich polyamine dispersant, 8 parts of
water, and 35 parts of dibenzyl methyl phosphate is heated to 100 ° C
for 2
hours. A vacuum of 40 mm of Hg is applied to the system and the temperature
S is gradually raised to 130 ° C. The resultant homogeneous liquid
composition is
suitable for use as component a-4).
SAMPLE 1_C~3_
A mixture of 260 parts of a Mannich polyamine dispersant, 9 parts of
monophenyl phosphate, 4 parts of phosphorous acid, and 7 parts of water is
heated to 100 ° C for 2 hours. A vacuum of 40 mm of Hg is applied to
the
system and the temperature is gradually raised to 130 ° C. 'fhe
resultant
homogeneous liquid composition is suitable for use as component a-4).
EXAMPLE 164
A mixture of 46.8 parts of phosphorylated dispersant formed as in
1S Example 158 and 23.4 parts of a commercial boronated succinimide ashless
dispersant (HiTEC~ 648 dispersant) 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 110 ° C for two hours, and
this
resultant homogeneous liquid composition is also suitable fox use as component
a-4) in the practice of this invention.
EXAMPLE 165
(a) A mixture of 1,000 parts (0.495 male) of polyisobutene (IVIn = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 11S parts (1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts (1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue is predominately polyisobutenyl succinic anhydride asylating agent.
(b) A mixture is prepared by the addition of 57 parts ( 1.38 equivalents)
of a commercial mixture of ethylene polyamines having the approximate overall
composition of tetraethylene pentamine to 1,067 parts of mineral ail and 893
Case EI-6214+ ~ ~'~
_ 88 -
parts (1.38 equivalents) of substituted succinic acylating agent prepared as
in (a)
while maintaining the temperature at 140-145 ° C. The reaction mixture
is then
heated to 1SS ° C over a three hour period 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 polyisobutenyl succiniznide
product solution formed as in (b), 11 parts of dibutyl chlorophosphate, 5
parts of
phosphoric acid, 3.5 parts of tolutriazole, and 8 parts of water. The mixture
is
heated at 100 ° C for four hours until all of the solid materials are
dissolved. A
vacuum of 40 mm Hg is gradually drawn on the product to remove the water
while the temperature is slowly raised to 100 ° C. A clear solution or
composition is obtained which is soluble in oil aad suitable for use as
component a-4).
EXAMPLE 166
The procedure of Example 165 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 167
The procedure of Example 165 is repeated except that 9 parts of an
equimolar mixture of dibutyl hydrogen phosphate and monobutyl dihydrogen
phosphate is used in place of the dibutyl chlorophosphate to provide a clear,
oil-
soluble composition suitable for use as component a-4).
EXAMPLE 168
The procedure of Example 165 is repeated except that the dibutyl
chlorophosphate is replaced by 11 parts of mono-2-naphthyl orthophosphate.
2S EXAMPLE 169
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020;
I~Iw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts (1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts (1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
Case EI-6214 +
_89_
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 ethylene polyamines having the
approximate overall composition of tetraethylene pentamine to 392 parts of
mineral oil and 348 parts (0.52 equivalent) of substituted succinic acylating
agent
prepared as in (a) while maintaining the temperature at 140 ° C. The
reaction
mixture is then heated to 150 ° C 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 succiniznides.
(c) A mixture is formed from 250 parts of the polyisobutenyl succinimide
product solution formed as in (b), 18 parts of phenyl dimethyl phosphate, 3.5
parts of tolutriazole, and 8 parts of water. The mixture is heated at l0U
° C for
three hours. A vacuum of 40 mm Hg is gradually drawn on the product to
remove the water while the temperature is slowly raised to 130° C. A
clear
solution or composition is obtained which is soluble in oil and suitable for
use as
component a-4).
E%AMPLE 17U
The procedure of Example 169 is repeated except that 15 parts of
trimethyl phosphite is used in place of the phenyl dimethyl phosphate to
provide
a clear, oil-soluble composition suitable for use as component a-4).
EXAMPLE 171
The procedure of Example 169 is repeated except that the phenyl
dimethyl phosphate is replaced by 36 parts of 4-dimethyl-aminophenyl
phosphorus tetrachloride and the heated mixture in (c) is swept with nitrogen
during the three-hour period.
EXAMPLE 172
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
Case EI-6214 -E
- 90 -
stripped by heating at 186-190 ° C with nitrogen purged for 26 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 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of
Polyglycol 112-2 demulsifier is heated at 150 ° C for 2.5 hours. The
reaction
mixture is then heated to 210 ° C over a period of 5 hours and then
held at
210 ° C for an additional 3.2 hours. The reaction mixture is cooled to
190 ° C and
8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines
having
an overall composition approximating that of tetraethylene pentamine is added.
The reaction mixture is stripped by heating at 205 ° 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 formed from 300 parts of the ashless dispersant product
solution formed as in (b), 37 parts of bis(2-ethylhexyl) hydrogen phosphite,
3.5
parts of tolutriazole, and 8 parts of water. The mixture is heated at 100
° C for
two hours until all of the solid materials are dissolved. A vacuum of 40 mm Hg
is gradually drawn on the product to remove the water while the temperature is
slowly raised to 130 ° C. A clear solution or composition is obtained
which is
soluble in oil and suitable for use as component a-4).
EXAMPLE 173
The procedure of Example 172 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAIvIPLE 174
The procedure of Example 172 is repeated except that 26 parts of dibutyl
hydrogen phosphite is used in place of the bis(2-ethylhexyl) hydrogen
phosphite
to provide a clear, oil-soluble composition suitable for use as component a-
4).
EXAMPLE 175
The procedure of Example 172 is repeated except that the bis(2-ethyl-
hexyl) hydrogen phosphite is replaced by 15 parts of trimethyl phosphite.
Case EI-6214 +
_91_
EXAMPLE 176
(a) A mixture of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020;
Ii~w = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 8S parts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 hours. The reaction mixture is
stripped by heating at 186-190 ° C 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 dispersant product.
(c) A mixture is formed from 300 parts of the ashless dispersant product
solution formed as in (b), 27 parts of dibutyl chlorophosphate, 3.5 parts of
tolutriazole, and 8 parts of water. The mixture is heated at 100 ° C
for two hours
until all of the solid materials are dissolved. A vacuum of 40 mm Hg is
gradually drawn on the product to remove the water while the temperature is
slowly raised to 100 ° C. A clear solution or composition is obtained
which is
soluble in oil and suitable for use as component a-4).
EXAMPLE 177
The procedure of Example 176 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 178
The procedure of Example 176 is repeated except that 8 parts of ethyl
dichlorophosphate and 4 parts of phosphorous acid are used in place of the
dibutyl chlorophosphate to provide a clear, oil-soluble composition suitable
for
use as component a-4).
EXAMPLE 179
The procedure of Example 176 is repeated except that the dibutyl chloro-
phosphate is replaced by 10 parts of dibutyl hydrogen phosphite and S parts of
Case EI-6214 +
-92-
phosphoric acid.
EXAMPLE 180
(a) A mixttue of 1,000 parts (0.495 mole) of polyisobutene (Mn = 2020;
Mw = 6049, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 115 parts ( 1.17 moles) of malefic anhydride .is heated to 110 ° C.
This
mixture is heated to 184 ° C in 6 hours during which 85 pasts ( 1.2
moles) of
gaseous chlorine is added beneath the surface. At 184-189 ° C, an
additional 59
parts (0.83 mole) of chlorine is added over 4 houxs. The reaction mixture is
stripped by heating at 186-190 ° C with nitrogen purged for 26 hours.
The
residue 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 204-227 °
C for 5
hours. The reaction mixture is cooled to 162 ° C and 5.3 parts (0.13
equivalent)
of a commercial ethylene polyamine mixture having an overall composition
approximating that of tetraethylene pentamine is added. The reaction mixture
is
heated at 162-163 ° C for 1 hour, then cooled to 13U ° C and
filtered. The filtrate
is an oil solution of the desired ashless dispersant product.
(c) A mixture is formed from 350 parts of the ashless dispersant product
solution formed as in (b), 16 parts of diethyl hydrogen phosphite, 3.5 parts
of
tolutriazole, and 6 parts of water. The mixture is heated at 100 ° C
for two hours
until all of the solid materials are dissolved. A vacuum of 40 mm Hg is gradu
ally drawn on the product to remove the water while the temperature is slowly
raised to 100 ° C. A clear solution or composition is obtained which is
soluble in
oil and suitable for use as component a-4).
EXAMPLE 181
The procedure of Example 180 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 182
The procedure of Example 180 is repeated except that 20 parts of diethyl
chlorophosphate is used in place of the diethyl hydrogen phosphite to provide
a
clear, oil-soluble composition suitable for use as component a-4).
Case EI-6214+
- -93-
EXAMPLE 183
The procedure of Example 180 is repeated except that the diethyl
hydrogen phosphate is replaced by 12 parts of ethyl dibutyl phosphate and 4
parts of phosphorous acid.
$ EXAMPLE 184
(a) A mixture of 510 parts (0.28 mole) of polysobutene (Iv~n = 1845;
Mw = 5325, both determined using the methodology of U.S. Pat. No. 4,234,435)
and 59 parts (0.59 mole) of malefic anhydride is heated to 110 ° C.
This mixture
is heated to 190 ° C in 7 hours during which 43 parts (0.6 mole) of
gaseous
chlorine is added beneath the surface. At 190-192 ° C, an additional 11
parts
(0.16 mole) of chlorine is added over 3.5 hours. The reaction mixture is
stripped by heating at 190-193 ° C with nitrogen blowing 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 equivalent) of pentaerythritol and 8.6 parts (0.0057
equivalent) of
Polyglycol 112-2 demulsifier is heated at 150 ° C for 2.5 hours. The
reaction
mixture is then heated to 210 ° C over a period of 5 hours and then
held at
210 ° C for an additional 3.2 hours. The reaction mixture is cooled to
190 ° C and
8.5 parts (0.2 equivalent) of a commercial mixture of ethylene polyamines
having
an overall composition approximating that of tetraethylene pentamine is added.
The reaction mixture is stripped by heating at 205 ° 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 formed from 260 parts of the ashless dispersant product
solution formed as in (b), 20 parts of ethyl dichloro phosphate, 3.5 parts of
tolutriazole, and 8 parts of water. The mixture is heated at 100 ° C
for two hours
until all of the solid materials are dissolved. A vacuum of 40 mm 1-ig is
gradu-
ally drawn on the product to remove the water while the temperature is slowly
raised to 100 ° C. A clear salutaon or composition is obtained which as
soluble in
oil and suitable for use as component a-4).
Case EI-6214 +
-94-
EXAMPLE 185
The procedure of Example 184 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
E~PLE 186
The procedure of Example 184 is repeated except that 23 parts of butyl
dichloro phosphate is used in place of the ethyl dichloro phosphate to provide
a
clear, oil-soluble composition suitable for use as component a-4).
EXAMPLE 187
The procedure of Example 184 is repeated except that the ethyl dichloro
phosphate is replaced by 30 parts of monobutyl-mono-2-ethylhexyl hydrogen
phosphite.
EXAMPLE 188
(a) A mixture of 510 parts (0.28 mole) of polyisobutene (Mn = 1845;
Ie~fw = 5325, both determined using the methodology of U.S. Pat. No.
4,234,435)
and 59 parts (0.59 mole) of malefic anhydride is heated to 110 ° C.
This mixture
is heated to 190 ° C in 7 hours during which 43 parts (O.b mole) of
gaseous
chlorine is added beneath the surface. At 190-192 ° C, an additional 11
parts
(0.16 mole) of chlorine is added over 3.S hours: The reaction mixture is
stripped by heating at 190-193 ° C with nitrogen blowing for 10 hours.
The
2U residue is predominately polyisobutenyl succinic anhydride 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 to 113 parts of mineral oil and lbl
parts
{0.25 equivalent) of the substituted succinic acylating agent prepared as in
{a)
while maintaining the temperature at 138 ° C. The reaction mixture is
heated to
150 ° C over a 2 hour period and stripped by blowing with nitrogen. The
reaction mixture is filtered to yield the filtrate as an oil solution of the
desired
ashless dispersant product.
{c) A mixture is formed from 125 parts of the polyisobutenyl succinimide
product solution formed as in (b), 9 parts of monobenzyl phosphate and 4 parts
of phosphorous acid, 3.5 parts of tolutriazole, and 6 parts of water. 'The
mixture
is heated at 100°C for two hours until all of the solid materials are
dissolved. A
Case EI-6214+
- -y5-
vacuum of 40 mm Hg is gradually drawn on the product to remove the water
while the temperature is slowly raised to 100 ° C. A clear solution or
composition is obtained which is soluble in oil and suitable for use as
component a-4).
EXAMPLE 189
The procedure of Example 188 is repeated except that the tolutriazole is
eliminated from the reaction mixture of (c).
EXAMPLE 190
The procedure of Example 188 is repeated except that 14 parts of
dibenzyl phosphate is used in place of the monobenzyl phosphate to provide a
clear, oil-soluble composition suitable for use as component a-4).
EXAMPLE 191
The procedure of Example 188 is repeated except that the monoben~yl
phosphate is replaced by 17 parts of monophenyl dibenzyl phosphate.
EXAMPLE 192
To a reactor are charged under a nitrogen atmosphere 67.98 parts of a
commercially-available polyisobutenyl succinimide 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 900; the succinimide product having
a ratio of about 1.15 succinic 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 100-105 ° C, 4.6 parts of dibutyl hydrogen
phosphite is
introduced into the reactor, followed by 0.92 part of tolutriazole (Cobratec
TT-
100), and then 3 parts of water. The resultant mixture is heated at 100-105
° C
for two hours and then the temperature is gradually raised to 115 ° C
with the
application of a vacuum to 40 mm Hg. Stripping is continued for 90 minutes
and until 120 ° C/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 a-4).
Case EI-6214 ~-
° -96-
EXAMPLE 193
The procedure of Example 192 is repeated except that the tolutriazole is
omitted from the reaction mixture.
EXAMPLE 194
(a) A mixture of 322 parts of the polyisobutene-substituted succinic
acylating agent prepared as in Example 188(a), 68 parts of pentaerythritol and
508 parts of mineral oil is heated at 204-227 ° C for 5 hours. The
reaction
mixture is cooled to 162 ° C and 5.3 parts of a commercial ethylene
polyamine
mixture having the approximate overall composition corresponding to tetra-
ethylene pentamine is added. The reaction mixture is heated at 162-163
° C for
1 hour, then cooled to 130 ° C 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), 20 parts of diisopropyl hydrogen phosphite, 3.5 parts of
tolutriazole,
and 8 parts of water. The mixture is heated at 100 ° C for two hours
until all of
the solid materials are dissolved. A vacuum of 40 mm Hg is gradually drawn on
the product to remove the water while the temperature is slowly raised to
100 ° C. A clear solution or composition is obtained which is soluble
in oil and
suitable for use as component a-4).
EXAMPLE 195
(a) To 120 parts 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 205 ° C and
maintained at
this temperature for about 5 hours. A 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 120 ° C 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 reaction product
Case EI-6214+
- -97-
formed as in (a), 20 parts of a 100 Solvent Neutral refined mineral oil
diluent,
5.0 parts of dibutyl hydrogen phosphite, and 3.0 parts of water. The resultant
mixture is heated at 100-105 ° C for 2 hours and then the temperature
is
gradually raised to 115 ° C with the application of a vacuum to 40 mm
Hg.
Stripping is continued for 90 minutes and until 120 ° C/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 a-4).
EXAMPLE 196
(a) Into a reactar are placed 220 parts of p-nonylphenol and 465
parts of diethylenetriamine. The mixture is heated to 80 ° C and 152
parts of
37% formalin is added dropwise over a period of about 30 minutes. The
mixture is then heated to 125 ° C for several hours until the evolution
of water
has ceased. The resultant product should contain approximately 16-20% nitro-
gen.
(b) Into a reactor are placed 202 parts of styrene-malefic anhydride resin
(having a number average molecular weight in the range of 600-700 and a mole
ratio of styrene to malefic anhydride of 1:1), 202.5 parts of octadecyl amine
and
472 parts of a 95 VI lubricating oil having a viscosity at 100 ° F of
150 SUS. The
mixture is heated to 225 ° C 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 210-230 ° C while
collecting the
water formed during reaction. The polymeric product so formed should have a
nitrogen content of about 2.1 weight percent.
(c) To a reactor are charged 250 parts of the basic nitrogen polymer
produced as in (b) and 50 parts of a 100 Solvent Neutral refined mineral oil.
After raising the temperature of the resulting mixture to 100-105 ° C,
35 parts of
dibutyl hydrogen phosphite and 8 parts of water are added. The resultant
mixture is heated at 100-105 ° C for two hours and then the temperature
is gra-
dually raised to 115 ° C with the application of a vacuum to 40 mm Hg.
Stripping is continued for 90 minutes and until 120 ° C/40 mm Hg has
been
reached. A flow of dry nitrogen is then applied to the system and the product
Case EI-6214 +
-98-
mixture is allowed to cool. The product mixture is suitable for use as
component a-4) in the compositions of this invention.
EXAMPL>;~ 197
The procedure of Example 196 is repeated except that the dibutyl
hydrogen phosphate is replaced by 10 parts of dimethyl hydrogen phosphate.
EXAIV~,PLE 198
The procedure of Example 196 is repeated except that the dibutyl
hydrogen phosphate is replaced by S parts of dimethyl hydrogen phosphate and 4
parts of phosphorous acid.
A particularly preferred embodiment of this invention involves using as
component a-1) and a-3) a phosphorylated and boronated 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
succination 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 1.3, the alkenyl group being derived
from a
polyolefin (most preferably a polyisobutene) having a number average molecular
weight in the range of 600 to 1,300 (more preferably in the range of 700 to
1,250
and most preferably in the range of 800 to 1,200).
Another particularly preferred embodiment of this invention involves
using as component a-2) and a-4) 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
succination 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 1.3, the alkenyl group being derived
from a
polyolefin (most preferably a polyisobutene) having a number average molecular
weight in the range of 600 to 1,300 (more preferably in the range of 700 to
1,250
and most preferably in the range of 800 to 1,200).
To determine the succination ratio of the alkenyl succinic acylating
agents utilized in forming such particularly preferred ashless dispersants;
A. The number average molecular weight (Mn) of the polyalkene from
Case EI-6214 -~
- -99-
which the substituent is derived is determined by use of either of two
methods,
namely, vapor pressure osmometry (VPO) or gel permeation chromatography
(GPC). The VPO determination should be conducted in accordance with
ASTM D-2503-82 using high purity toluene as the measuring solvent.
S Alternatively, a GFC 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
benzene copolymer of controlled particle and pore sizes. When the polyalkene
molecules from which the substituent 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 slighly or are totally
excluded
from the pores. As a consequence, these larger polyalkene molecules are re-
tarded in their progress through the columns to a lesser extent. Thus a
velocity
separation occurs 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 polyalkene standards and an internal standard method. Details concern-
ing such GPC procedures and methods for column calibration are extensively
reported in the literature. See far example, W. W. Yau, J. J. ICirkland, and
D.
D. Bly, Modern Size-Exclusion Liquid Chromatography, John Wiley & Sons,
1979, Chapter 9 (pages 28S-341), and references cited therein.
B. The total weight of the substituent groups present in the substituted
succinic acylating agent is determined by conventional methods ror
determination of the number of carbonyl functions. The preferred procedure for
use involves nonaqueous titration of the substituted acylating agent with
standardized sodium isopropoxide. In this procedure the titration is conducted
in a 1:1 mineral spirits:l-butanol solvent system. An alternative, albeit less
preferred, procedure is the ASTM D-94 procedure.
The results from procedures A and 8 above are used in calculating the
weight of substituent groups per unit weight of total sample.
Case EI-6214+
- - 100 -
C. In determining the succination ratio of the alkenyl succinic acylating
agents, the determination is to be based on the active portion of the sample.
That is to say, alkenyl succinic acylating agents are often produced as a
mixture
with an inactive diluent. 'i'hus for the purpose of succination ratio
determination, such diluent should not be considered a part of the succinic
acylating agent, and accordingly a separation as between the diluent and the
alkenyl succinic acylating agent should be accomplished. Such separation can
be
effected before determination of total weight of the subtituent groups present
in
the substituted succinic acylating agent. However, it is preferable to effect
such
separation after such determination using a mathematical correction of the
result. The separation itself can be achieved using a silica gel column
separation technique. A low molecular weight non-polar hydrocarbon solvent,
such as hexane and more preferably pentane, is used as the solvent whereby the
unreactive diluent is readily eluted from the column. The substituted succinic
acylating agent entrained in the column can then be recovered by use of a more
polar elution solvent, preferably methanol/methylene dichloride.
omnonent ~ - Mewl-Free Sulfur-Containing Antiwear and/or Extreme
Pressure Agent
A variety of oil-soluble metal-free sulfur-containing antiwear and/or
extreme pressure additives can be used as the other indispensable component in
the practice of this invention, provided they have the requisite minimum
sulfur
content of at least 20 wt %. Examples are included within the categories of
dihydrocarbyl polysulfides; sulfurized olefins; trithiones; sulfurized thienyl
deriva
tives; sulfurized terpenes; sulfurized oligomers of CZ-C$ monoolefins;
xanthates;
hydrocarbyl trithiocarbonates; and sulfurized Diels-Alder adducts such as
those
disclosed in U.S, reissue patent Re 27,331. Specific examples include
sulfurized
polyisobutene of Mn 1,100, sulfurized isobutylene, sulfurized diisobutylene,
sulfurized triisobutylene, dicyclohexyl polysulfide, diphenyl polysulfide,
dibenzyl
polysulfide, dinonyl polysulfide, and mixtures of di-tert-butyl polysulfide
such as
mixtures of di-tert-butyl trisulfide, di-tert-butyl tetrasulfide and di-tert-
butyl pen-
tasulfide, among others. Combinations of such categories of sulfur-containing
antiwear and/or extreme pressure agents can also be used, such as a
Case EI-6214+
- - 101 -
combination of sulfurized isobutylene and di-tert-butyl trisulfide, a
combination
of sulfurized isobutylene and dinonyl trisulfide, a combination of sulfurized
triisobutylene and dibenzyl polysulfide.
The preferred sulfur-containing antiwear and/or extreme pressure agents
are the oil-soluble active sulfur-containing antiwear and/or extreme pressure
agents. Generally speaking, these are substances which possess a linkage of
two
or more sulfur atoms (e.g., -S-S-, -S-S-S-, -S-S-S-S-, -S-S-S-S-S-, etc.).
To determine for the purpose of this invention whether a sulfur
containing material is an active sulfur-containing material, use can be made
of a
i0 copper coupon corrosion test conducted as follows: A copper coupon
approximately 70 x 15 mm and about 1.25 mm in thickness is cleaned by use of
steel wool (0000 grade), washed with heptane, and then with acetone, dried,
and
weighed to the nearest 0.1 mg. The cleaned coupon is placed in a test tube and
covered completely with the composition to be tested, and the system is heated
to 125 ° C by means of an oil bath. After holding the system at 125
° C for three
hours, the copper coupon is removed from the test tube, rinsed with heptane,
and then with acetone. The dried coupon is then rubbed with a paper towel
moistened with acetone to remove any surface flakes formed by copper
corrosion. The coupon is then air-dried and weighed to the nearest 0.1 mg.
The difference in weight between the initial copper coupon and the coupon
after
the test represents the extent to which the copper was corroded under the test
conditions. Therefore the larger the weight difference, the greater the copper
corrosion; and thus the more active the sulfur compound. For the purposes of
this invention, if the coupon weight loss is 30 milligrams or more, the sulfur-
containing agent is considered "active". Oil-soluble sulfur-containing
antiwear
and/or extreme pressure agents yielding a weight loss of above SO mg in the
above test are more preferred.
Another test which can be used for determining the activity of a sulfur
containing additive for use as component b) is the 4-Ball EP test, listed as
ASTM D 2783-88, (Measurement of Extreme Pressure Properties of Lubricating
Fluids). In general, the higher the weld point in the test, the more active is
the
sulfur-containing additive. Thus a sulfur additive at 1% (wt) concentration
Case EI-6214 t
. - 102 -
achieving or exceeding 250 kilograms weld point is deemed active for the
purposes of this invention.
Because of the toxicity of hydrogen sulfide, it is important to utilize in
the practice of this invention oil-soluble sulfur-containing antiwear and/or
extreme pressure agents, and more preferably oil-soluble active sulfur-
containing
antiwear and/or extreme pressure agents, that yield less than 25 ppm, and more
preferably less than 10 ppm, and most preferably no detectable amounts, of
vapor space Ii2S when heated in the concentrated state for one week at 65
° C.
HiTEC~ 309 and 312 sulfurized isobutylene additives (Ethyl Petroleum
Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada
Ltd.)
are especially desirable in this respect.
The most preferred oil-soluble metal-free sulfur-containing antiwear
and/or extreme pressure agents from the cost-effectiveness standpoint are the
sulfurized olefins containing at least 30% by weight of sulfur, the
dihydrocarbyl
polysulfides containing at least 25% by weight of sulfur, and mixtures of such
sulfurized olefins and polysulfides. Of these materials, di-tert-alkyl
polysulfides
having a sulfur content of at least 35% by weight are particularly desirable.
Sulfurized isobutylene having a sulfur content of at least 40% and as much as
50% by weight or more and a chlorine content of less than 1% by weight is the
most especially preferred material.
Methods of preparing sulfurized olefins are described in U.S. Pat. lVos.
2,995,569; 3,673,090; 3,703,504; 3,703,505; 3,796,661; 3,8?3,454; 4,795,576;
4,954,274; and 4,966,720. Also useful are the sulfurized olefin derivatives
described in U.S. Pat. No. 4,654,156.
~omponent c) - Amine Salt of Mono- and or Dihvdrocarbvl Ester of a
Monomeric Pentavalent Acid of Phosphorus
This optional but preferred component is composed of one or more
oil-soluble amine salts of one or more partial esters of one or mare
phosphoric
acids and/or thiophosphoric acids. Such compounds may be collectively
represented by the formulas
Case EI-6214 +
- - 103 -
X 4 t-~
Xz
(R~X~) _ P I+'NH~RZ C
(X3H)
(-) (-)
X$
Xs
/ r+~
(R3X5) - P' 2 NH3R4 (II)
~X~
1 2 c_.
R5X
t+t
P - X11 NH3R7 (111)
~R6X10)
or mixtures thereof. In Formulas I, II and III; each of R1, RZ, R3, R4, R5,
Rb,and
R' is, independently, a hydrocarbyl group and each of Xl, X2, X~, X4, X5; X6,
X',
Xg, X'', X'°, X11, and X12 is, independently, an oxygen atom or a
sulfur atom.
In one preferred sub-category the amine salts are formed with one or
more partially esterified monothiophosphoric acids. These are compounds of
Formulas (I), (II), and (III) above wherein. only one of Xl, Xz, X~, and X4,
only
one of X5, X6, X', and X$, and only one of X9, Xl°, X11, and Xlz is a
sulfur atom.
In another preferred sub-category the amine salts are formed with one or
more partially esterified phosphoric acids. These are compounds of Formulas
(I), (II), and (III) above wherein all of Xl, X2, X3, X4, X5, X6, X', X8, X9,
X'°,
X'1, and X12 are oxygen atoms.
Case EI-6214+ i
~~ li~~~~
- 10~.
Another preferred sub-category of amine salts are those formed with one
or more partially esterified dithiophosphoric acids. 'These are compounds of
Formulas (I), (II), and (III) above wherein two of X', Xz, X3, and X4, two of
X5,
X6, X', and X8, and two of X9, X'°, X", and X'z are sulfur atoms.
Also useful are amine salts of Formulas (I), (II), and (III) above wherein
three or four of X', Xz, X3, and X4, three or four of X5, X6, X', and X8, and
three or four of X'', X'°, X", and X'z are sulfur atoms.
V~Ihile all of the above oil-soluble amine salts are useful as components
in the compositions of this invention, it is most preferred to include at
least one
oil-soluble amine salt of a dihydrocarbyl monothiophosphoric acid (one sulfur
atom per molecule), either alone or in combination with at least one oil-
soluble
amine salt of a dihydrocarbyl phosphoric acid (no sulfur atom in the
molecule).
Use can be made of the octylamine, nonylamine, decylamine,
undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine,
hexadecylamine, heptadecylamine, octadecylamine, cyclohexylamine, phenyl
amine, mesitylamine, oleylamine, cocoamine, soyamine, Clz-as tertiary alkyl
primary amine, C2z_za tertiary alkyl primary amine, and phenethylamine salts
or
adducts of the above and similar partially esterified acids of
monothiophosphoric
acid, including mixtures of any such compounds. Generally speaking, the
preferred amine salts are salts of aliphatic amines, especially the saturated
or
olefinically unsaturated aliphatic primary amines, such as n-octylamine, 2-
ethylhexylamine, tert-octylamine, n-decylamine, the Clo, Clz, Cia and C16
tertiary
alkyl primary amines (either singly or in any combinations thereof, such as a
mixture of the Clz and C14 tertiary alkyl primary amines), n-undecylamine,
lauryl
amine, hexadecylamine, heptadecylamine, octadecylamine, the Czz and Cz4
tertiary alkyl primary amines (either singly or in combination), decenylamine,
dodecenylamine, palmitoleylamine, oleylamine, linoleylamine, eicosenylamine,
ete. Secondary hydrocarbyl amines and tertiary hydrocarbyl amines can also be
used either alone or in combination with each other or in combination with pri-
mary amines. 'Thus any combination of primary, secondary and/or tertiary
amines, whether monoamine or polyamine, can be used in forming the salts or
adducts. Use of primary amines is preferred. Especially preferred amines are
Case EI-6214+
. - 105 -
alkyl monoamines and alkenyl monoamines having from 8 to 24 carbon atoms in
the molecule.
Methods for the preparation of such amine salts are well known and
reported in the literature. See for example, U.S. Pat. Nos. 2,063,629;
2,224,695;
2,447,288; 2,616,905; 3,984,448; 4,431,552; Pesin et al, Zhurnal Obshchei
IChimii
Vol. 31, No. 8, pp. 2508-2515 (1961); and International Application
Publication
No. WO 87/07638.
Amine salts of partially esterified monothiophosphoric acids are usually
made by reacting a mono- and/or dihydrocarbyl phosphite with sulfur or an
active sulfur-containing compound such as are referred to above under the cap-
tion "Sulfur-Containing Antiwear and/or Extreme Pressure Agents" and one or
more primary or secondary amines. Such reactions tend to be highly exothermic
reactions which can become uncontrollable, if riot conducted properly. One
preferred method of forming these amine salts involves a process which
comprises (i) introducing, at a rate such that the temperature does not exceed
about 60 ° C, one or more dihydrocarbyl hydrogen phosphites, such as a
diaikyl
hydrogen phosphite, into an excess quantity of one or more active sulfur-
contain-
ing materials, such as sulfurized branched-chain olefin (e.g., isobutylene,
diisobutylene, triisobutylene, etc.), while agitating the mixture so formed,
(ii)
introducing into this mixture, at a rate such that the temperature does not
exceed about 60 ° C, one or more aliphatic primary or secondary amines,
prefer-
ably one or more aliphatic primary monoamines having in the range of 8 to 24
carbon atoms per molecule while agitating the mixture so formed; and (iii)
maintaining the temperature of the resultant agitated reaction mixture at
between 55 and 60 ° C until reaction is substantially complete. Another
suitable
way of producing these amine salts is to concurrently introduce all three of
the
reactants into the reaction zone at suitable rates and under temperature
control
such that the temperature does not exceed about 60 ° C.
Component d) - Trihydrocarbyl Ester of a Dithiophosphoric Acid
This group of optional but preferred compounds is composed of
O,O-dihydrocarbyl-S-hydrocarbyl thiothionophosphates (also known as O,O-
dihydrocarbyl-S-hydrocarbyl phosphorothiothionates) which can be represented
Ca;:e EI-6214 ~-
. ~ - 106- ~~ ~~3~~~
by the general formula:
S
Rl-O-P-O-Rz
S
R3
wherein each of R1, Rz, and R3 is independently a hydrocarbyl group,
especially
where R3 is an alicyclic hydrocarbyl group. Particularly preferred are the
O,O-dialkyl-S-hydrocarbyl phosphorothiothionates wherein R3 is an alicyclic
group an Rl and Rz are alkyl groups each having up to 18 carbon atoms and
most preferably up to 12 carbon atoms.
These compounds can be made by various known methods. Probably the
most efficacious method involves reacting phosphorus pentasulfide (PISS, often
regarded as P4Sio) with the appropriate alcohols or mixture of alcohols.
Compounds in which one of the hydrocarbyl groups differs from the other two
are preferably made by first reacting the phosphorus pentasulfide with an
appropriate alcohol to form an intermediate product, viz. (RO)zPSSi~, which in
turn is reacted with a compound containing at least one reactive olefinic
double
bond. See in this connection U.S. Pat. Nos. 2,528,732, 2,561,773, 2,665,295,
2,767,206, 2,802,856, 3,023,209, and J. Org. Chem., 19 3, 28, 1262-8.
Exemplary compounds suitable for use in the compositions of this
invention include such compounds as trioctylphosphorothiothionate,
tridecylphosphorothiothionate, trilaurylphosphorothiothionate, O,O-diethyl
bicyclo(2.2.1)-hepten-2-yl phosphorothiothionate, O,O-diethyl 7,7-dimethyl-
bicyclo(2.2.1)-5-hepten-2-yl phosphorothiothionate, the product formed by
reaction of dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-
tetrahydrophthalic acid dimethyl ester, the product formed by reaction of
dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-tetrahydro-
phthalic acid dibutyl ester, the product formed by reaction of
dithiophosphoric
acid-O,O-dibutyl ester with cis-endomethylene-tetrahydrophthalic acid dilauryl
ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl
ester with 2,5-endomethylene-1-methyl-tetrahydrobenzoic acid butyl ester, the
Case EI-6214 +
- 107 -
product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with
2,5-endomethylene-1-methyl-tetrahydrobenzoic acid decyl ester, the product
formed by reaction of dithiophosphoric acid-O,O- dimethyl ester with
2,S-endomethylene-6-methyl-tetrahydrobenzoin acid ethyl ester, the product
formed by reaction of dithiophosphoric acid-O,O-diethyl ester with
2,5-endomethylene-tetrahydrobenzyl alcohol, the product formed by reaction of
dithiophosphoric acid- O,O-dimethyl ester with the Diels-Alder adduct of
cyclopentadiene and allyl alcohol (2 mots : 1 mol), the product formed by
reaction of dithiophosphoric acid-O,O-dimethyl ester with 2,5-endomethylene-
tetrahydrophenyl acetate, the product formed by reaction of dithiophosphoric
acid-O,O-dibutyl ester with the Diels-Alder adduct of cyclopentadiene and
vinyl
acetate (2 mots : 1 mal), the product formed by reaction of dithiophosphoric
acid-O,O-dimethyl ester with the bis-cyclopentadiene adduct of p-benzoquinone,
the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester
with
the azodicarboxylic acid diethyl ester, the product formed by reaction of
dithiophosphoric acid-O,O- dimethyl ester with dicyclopentadiene, the product
formed by reaction of dithiophosphoric acid- O,O-dibutyl ester with dicyclo-
pentadiene, the product formed by reaction of dithiophosphoric acid-O,O-
dioctyl
ester with dicyclopentadiene, the product formed by reaction of
dithiophosphoric
acid- O,O-dilauryl ester with dicyclopentadiene, the product formed by
reaction
of dithiophosphoric acid-O,O-di-2-ethylhexyl ester with wax olefin, the
product
formed by reaction of dithiophosphoric acid-O,O-di-2-ethylhexyl ester with
oleyl
alcohol, the product formed by reaction of dithiophosphoric acid-O,O-di-2-
ethylhexyl ester with linseed oil, the product formed by reaction of dithio-
phosphoric acid-O,O-diamyl ester with alpha pinene, the product formed by
reaction of dithiophosphoric acid-O,O-diphenyl ester with alpha pinene, the
product formed by reaction of dithiophosphoric acid-O,O-diamyl ester with
allo-ocimene, and the product formed by reaction of dithiophosphoric acid-O,O-
dioctyl ester with dipentene.
Co ~onent e~- Amine Salt of a Carboxylic Acid
Another component which can be and preferably is used in the composi-
tions of this invention is one or more amine salts of one or more long chain
Case Ei-6214 a-
~~°~~~4~
- l08
carboxylic acids. The acids can be monocarboxylic acids or polycarboxylic
acids.
Generally speaking, these acids contain from 8 to SO carbon atoms in the mole-
cule and thus the salts are oil-soluble. A variety of amines can be used in
forming such salts, including primary, secondary and tertiary amines, and the
S amines can be monoamines, or polyamines. Further, the amines may be cyclic
or acyclic aliphatic amines, aromatic amines, heterocyclic amines, or amines
containing various mixtures of acyclic and cyclic groups.
Preferred amine salts include the alkyl amine salts of alkanoic acid and
the alkyl amines salts of alkanedioic acids.
The amine salts are formed by classical chemical reactions, namely, the
reaction of an amine or mixture of amines, with the appropriate acid or
mixture
of acids. Accordingly, further discussion concerning methods for the
preparation
of such materials would be redundant.
Among the amine salts of long-chain acids that may be used are the
following: lauryl ammonium laurate (i.e., the lauryl amine salt of lauric
acid),
stearyl ammonium laurate, cyclohexyl ammonium laurate, octyl ammonium
laurate, pyridine laurate, aniline laurate, lauryl ammonium stearate, stearyl
ammonium stearate, cyclohexyl ammonium stearate, octylammonium stearate,
pyridine stearate, aniline stearate, lauryl ammonium octanoate, stearyl
ammonium octanoate, cyclohexyl ammonium octanoate, octyl ammonium
octanoate, pyridine octanoate, aniline octanoate, nonyl ammonium laurate,
nonyl
ammonium stearate, nonyl ammonium octanoate, lauryl ammonium nonanoate,
stearyl ammonium nonanoate, cyclohexyi ammonium nonanoate, ociyl
ammonium nonanoate, pyridine nonanoate, aniline nonanoate, nonyl ammonium
nonanoate, lauryl ammonium decanoate, stearyl ammonium decanoate,
cyclohexyl ammonium decanoate, octyl ammonium decanoate, pyridine
decanoate, aniline decanoate, decyl ammonium laurate, decyl ammonium
stearate, decyl ammonium octanoate, decyl ammonium nonanoate, decyl
ammonium decanoate, bis ociyl amine salt of suberic acid, bis cyclohexyl amine
salt of suberic acid, bis lauryl amine salt of suberic acid, bis stearyl amine
salt of
suberic acid, bis octyl amine salt of sebacic acid, bis cyclohexyl amine salt
of
sebacic acid, bis lauryl amine salt of sebacic acid, bis stearyl amine salt of
Cafe EI-6214 +
- - 109 -
sebacic acid, the tert-dodecyl and tert-tetradecyl primary amine salts of
octanoic
acid, the tert-decyl and tert-dodecyl primary amine salts of octanoic acid,
the
tert-dodecyl and tert-tetradecyl primary amine salts of lauric acid, the tert-
decyl
and tent-dodecyl primary amine salts of lauric acid, the tert-dodecyl and
tent-tetradecyl primary amine salts of stearic acid, the tert-decyl and tert-
dodecyl
primary amine salts of stearic acid, the hexyl amine salt of C.,4-dicarboxylic
acid,
the octyl amine salt of C,g-dicarboxylic acid, the octyl amine salt of
C~-dicarboxylic acid, the decyl amine salt of C3p-dicarboxylic acid, the octyl
amine salt of C3i dicarboxylic acid, the bis lauryldimethyl amine salt of
traumatic
acid, diethyl ammonium laurate, dioctyl ammonium laurate, dicyclohexyl
ammonium laurate, diethyl ammonium octanoate, dioctyl ammonium octanoate,
dicyclohexyl ammonium octanoate, diethyl ammonium stearate, dioctyl
ammonium stearate, diethyl ammonium stearate, dibutyl ammonium stearate,
dicyclopentyl ammonium stearate, dipropyl ammonium benzoate, didecyl
ammonium benzoate, dimethylcyclohexyl ammonium benzoate, triethyl
ammonium laurate, triethyl ammonium octanoate, triethyl ammonium stearate,
triethyl ammonium benzoate, trioctyl ammonium laurate, trioctyl ammonium
octanoate, trioctyl ammonium stearate, and trioctyl ammonium benzoate. It will
be understood of course that the amine salt of the monocarboxylic and/or
polycarboxylic acid used should be sufficiently soluble in the base ail used
as to
provide homogeneous solution at the concentration employed.
Among the preferred amine salts are the primary amine salts of long
chain monocarboxylic acids in which the amine thereof is a monoalkyl
monoamine, RNI-I2; the secondary amine salts of long chain monocarboxylic
acids in which the amine thereof is a dialkyl monoamine, R~NH; the tertiary
amine salts of long chain monocarboxylic acids in which the amine thereof is a
trialkyl monoamine, R3N; the bis primary amine salts of long chain
dicarboxylic
acids in which the amine thereof is a monoalkyl monoamine, RNHL,; the bis
secondary amine salts of long chain dicarboxylic acids in which the amine
thereof is a dialkyl monoamine, R~NH; the bis tertiary amine salts of long
chain
dicarboxylic acids in which the amine thereof is a trialkyl monoamine, R3N;
and
mixtures thereof. In the foregoing formulae, R is an alkyl group which
contains
Case EI-6214+
- 110 -
up to 30 or more carbon atoms, and preferably from 6 to 24 carbon atoms.
Com~o_~tent f~ - Demulsifier
Typical additives which rnay be employed as demulsifiers include alkyl
benzene sulfonates, polyethylene oxides, polypropylene oxides, block
copolymers
of ethylene oxide and propylene oxide, and salts and esters or oil soluble
acids.
Com o~ne~~) - ~ppgr Corrasi~n_ Inhibitor
One type of copper corrosion inhibitor additives is comprised of
thiazoles, triazoles and thiadiazoles. Examples of such compounds include ben-
zotriazole, tolyltriazole, octyltriazole, decyltriazole, dodecyltriazole,
2-mercaptobenzothiazole, 2,S-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-
hydrocarbyithio-1,3,4-thiadiazoles, 2-mercapto-S-hydrocarbyldithio-1,3,4- thia-
diazoles, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and 2,S-
(bis)hydrocarbyldi-
thio)-1,3,4-thiadiazoles. The preferred compounds are the 1,3,4-thiadiazoles,
especially the 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles and the
2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, a number of which are available
as
articles of commerce. Such compounds are generally synthesized from hydrazine
and carbon disulfide by known procedures. See for example 'U.S. Pat. Nos.
2,749,311; 2,760,933; 2,765,289; 2,850,453; 2,910,439; 3,663,561; 3,862,798;
3,840,549; and 4,097,387.
Other suitable inhibitors of copper corrosion include ether amines; poly-
ethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and
ethoxylated alcohols; and imidazolines. 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.
Case EI-6214+
- - 111 -
Component h~ - Boron-Containing Additive
The boron-containing 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 the disclosures of 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;
3,009,799; 3,014,061; and 3,092,586.
Other ~~tional Additive Components
The oleaginous fluids and additive concentrates of this invention 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 oleaginous composition (lubricant
or
functional fluid) is to be subjected. Some of these other additives are
referred
to below.
A Supplemental phosphorus-containing antiwear and~or extreme
pressure agents. Supplemental metal-free phosphorus-containing antawear
and/or extreme pressure agents can be used in the compositions of this
invention. Such compounds are for the most part partially or fully esterified
acids of phosphorus, and include for example phosphates, phosphites,
phosphonates, phosphonites, and their various sulfur analogs. Examples include
Case EI-6214 +
. ~ - 112
monohydrocarbyl phosphites; rnonohydrocarbyl phosphates; monohydrocarbyl
mono-, di-, tri-, and tetrathiophosphites; monohydrocarbyl mono-, di-, tri-,
and
tetrathiophosphates; dihydrocarbyl phosphites; dihydrocarbyl phosphates;
dihydrocarbyl mono-, di-, tri-, and tetrathiophosphites; dihydrocarbyl mono-,
di-,
tz~i-, and tetrathiophosphates; trihydrocarbyl phosphites; trihydrocarbyl-
phosphates; trihydrocarbyl mono-, di-, tri-, and tetrathiophosphites;
trihydrocarbyl mono-, di-, tri-, and tetrathiop.hosphates; the various
hydrocarbyl
phosphonates and thiophosphonates; the various hydrocarbyl phosphonites and
thiophosphonites, and analogous oil-soluble derivatives of polyphosphoric and
polythiophosphoric acids; and many others. A few specific specific examples of
such compounds are tricresyl phosphate, tributyl phosphite, triphenyl
phosphite,
tz~i-(2-ethylhexyl) phosphate, dihexyl thiophosphite, diisooctyl
butylphosphonate,
tricyclohexyl phosphate, cresyl diphenyl phosphate, tris(2-butoxyethyl)
phosphite,
diisopropyl dithiophosphate, tris(tridecyl)tetrathiophosphate, tris(2-
chloroethyl)
phosphate, and like compounds.
B~Suppleznental ashless dispersants. Airy of a variety of additional ash
less dispersants can be utilized in the compositions of this invention. These
include carboxylic ashless dispersants, polymeric polyamine dispersants, and
post-treated dispersants of these types. All such materials which have been
described hereina.bove.
C) Antioxidants: Most oleaginous compositions will contain 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, and phosphorus-containing
antioxidants.
Illustrative sterically hindered phenolic antioxidants include ortho-
alkylated phenolic compounds such as 2,6-di-tart-butylphenol, 4-methyl-2,6-di-
tart-butylphenol, 2,4,6-tri-tart-butylphenol, 2- tart-butylphenol, 2,6-di-
isopropylphenol, 2-methyl-6- tart-butylphenol, 2,4-dimethyl-6-tent-
butylphenol,
4-(N,N-diznethylaminomethyl)- 2,6-di-tart-butylphenol, 4-ethyl-2,6-di-tert-
Case EI-6214+
- - 113 -
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.
Also useful are methylene-bridged alkylphenols, and these can be used
singly or in combinations with each other, or in combinations with
sterically-hindered unbridged phenolic compounds. Illustrative methylene
bridged compounds include 4,4'-methylenebis(6-tert-butyl-o-cresol),
4,4'-methylenebis(2-tert-amyl-o-cresol), 2,2'-methylene-bis(4-methyl-6-tent-bu-
tylphenol), 4,4'-methylene-bis(2,6-di-tert-butylphenal), and similar
compounds.
Preferred are mixtures of methylene-bridged alkylphenols such as are described
in U.S. Pat. No. 3,211,652.
Amine antioxidants, especially oil-soluble aromatic secondary amines can
also be used. Although aromatic secondary monoamines are preferred, aromatic
secondary polyamines are also suitable. Illustrative aromatic secondary
monoamines include diphenylamine, alkyl diphenylamines containing 1 or 2 alkyl
substituents each having up to about 16 carbon atoms, phenyl-a-naphthylamine,
phenyl-Q-naphthylamine, alkyl- or aralkyl-substituted phenyl-a-naphthylamine
containing one or two alkyl or aralkyl groups each having up to about 16
carbon
atoms, alkyl- or aralkyl-substituted phenyl-pnaphthylamine containing one or
two
alkyl or aralkyl groups each having up to about 16 carbon atoms, and similar
compounds.
A preferred type of aromatic amine antioxidant is an alkylated
diphenylamine of the general formula
R~ ~ NH ~ RZ
wherein Rl is an alkyl group (preferably a branched alkyl group) having 8 to
12
carbon atoms, (more preferably 8 or 9 carbon atoms) and R, is a hydrogen atom
or an alkyl group (preferably a branched al),yl group) having 8 to 12 carbon
atoms, (more preferably 8 or 9 carbon atoms). Most preferably, Rl and R,, are
the same. Qne such preferred compound is available commercially as
Case EI-6214 +
- - - 114 -
Naugalube 438L, a material which is understood to be predominately a 4,4'-di-
nonyldiphenylamine (i.e., bis(4-nonylphenyl)amine) wherein the nonyl groups
are
branched.
Another useful type of antioxidant for inclusion in the 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 about 50 weight percent of which mixture of
phenols is camposed 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 so as to produce a liquid product. Typical phenol
mixtures useful in making such liquid product compositions 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 preferably kept within the
range of 15 ° C to 70 ° C, most preferably between 40 ° C
to 60 ° C.
Mixtures of different antioxidants can also be used. One suitable mixture
is comprised of a combination of (i) an oil-soluble mixture of at least three
different sterically-hindered tertiary butylated monohydric phenols which is
in
the liquid state at 25 ° C, (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 alkyl
group having 8 to 12 carbon atoms, the proportions of (i), (ii) 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).
T~~Rust inhibitors. The compositions of this invention may also contain
a suitable quantity of a rust inhibitor. This may be a single compound or a
mixture of compounds having the property of inhibiting corrosion of ferrous
metal surfaces. Such materials include include oil-soluble monocarboxylic
acids
such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic
acid,
linoleic acid, linolenic acid, behenic acid, cerotic acid, etc., and oil-
soluble
polycarboxylic acids including dimer and trimer acids, such as are produced
from
tall oil fatty acids, oleic acid, or linoleic acid. Other suitable corrosion
inhibitors
Case EI-6214+
- ~ - 115 -
include alkenylsuccinic acids in which the alkenyl group contains 10 or more
carbon atoms such as, for example, tetrapropenylsuccinic acid, tetrade-
cenylsuccinic acid, and hexadecenylsuccinic acid; long-chain a,w-diearboxylic
acids in the molecular weight range of 600 to 3000; and other similar
materials.
Products of this type are currently available from various commercial sources,
such as, for example, the dimer and trimer acids sold under the HY~TRENE
trademark by the Humco Chemical Division of Witco Chemical Corporation and
under the EMPOL trademark by Emery Chemicals. Another useful type of
acidic corrosion inhibitors are the half esters of aikenyl succinic acids
having 8
to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols.
The corresponding half amides of such alkenyl succinic acids are also useful.
Although added in acidic form, some or all of the carboxylic groups of these
carboxylic acid type corrosion inhibitors may be neutralized by excess amine
present in the compositions. Other suitable corrosion inhibitors include ether
amines; acid phosphates; amines; polyethoxylated compounds such as
ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; and
imidazolines. 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 0
R~- C - C - OR5
Ra ~
R3~N - G -- C ORS
RZ 0
wherein each of R1, Rz, R5, R6 and R' is, independently, a hydrogen atom or a
hydrocarbyl group containing 1 to 30 carbon atoms, and wherein each of R3 and
R4 is, independently, a hydrogen atom, a hydrocarbyl group containing 1 to 30
carbon atoms, or an acyl group containing from 1 to 30 carbon atoms. The
case EI-6214-+.
- - 116 -
groups Rl, R2, R3, R4, R5, R6 and R', when in the form of hydrocarbyl groups,
can be, for example, alkyl, cycloalkyl or aromatic containing groups.
Preferably
Ri and R$ are the same or different straight-chain or branched-chain
hydrocarbon radicals containing 1-20 carbon atoms. Most preferably, Rl and RS
are saturated hydrocarbon radicals containing 3-6 carbon atoms. RZ, either R3
or R°, R6 and R', when in the form of hydrocarbyl groups, are
preferably the
same or different straight-chain or branched-chain saturated hydrocarbon
radicals. Preferably a dialkyl ester of an aminosuccinic acid is used in which
Rl
and RS are the same or different alkyl groups containing 3-6 carbon atoms, RZ
is
a hydrogen atom, and either R3 or R'~ is an alkyl group containing 15-20
carbon
atoms or an aryl 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 RS are isobutyl, RZ
is a hydrogen atom, R3 is octadecyl and/or octadecenyl and R4 is
3-carboxy-1-oxo-2-propenyl. In such ester R6 and R' are most preferably
hydrogen atoms.
E) Antifoam agents. Suitable antifoam agents include silicones and
organic polymers such as acrylate polymers. Various antifoam agents are
described in Foam Control Agents 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
2S carboxylates.
F) Friction modifiers. These materials include such substances as the
alkyl phosphonates as disclosed in U.S. Pat. No. 4,356,097, aliphatic
hydrocarbyl-
substituted succinimides derived from ammonia or alkyl monoamines as
disclosed in European Patent Publication No. 20037, dimer acid esters as
disclosed in U.S. Pat. 4,105,571, and oleamide. Such additives, when used are
generally present in amounts of 0.1 to 3 weight percent. Glycerol oleates are
another example of fuel economy additives and these are usually present in
very
Case EI-b214 a-
- ~ - 117 -
small amounts, such as 0.05 to 1 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 esters, aliphatic carboxylic ester-amides, aliphatic phosphates,
aliphat-
ic thiophosphonates, aliphatic thiophosphates, etc., wherein the aliphatic
group
usually contains above about eight carbon atoms so as to render the compound
suitably 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 derivative
and a long chain amide.
Gl Seal swell aeents. Additives may be introduced into the compositions
of this invention in order to improve the seal performance (elastomer
compatibility) of the compositions. 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 Corp. and
Hatcol 2352, 2962, 2925, 2938, 2939, 2970, 3178, and 4322 polyol esters from
Hatco Corp. 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,
ete.) can
also be used. Examples of such materials include the n-octyl, 2-ethylhexyl,
isodecyl, and tridecyl diesters of adipic acid, azelaic acid, and sebacic
acid, and
the n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl,
and tridecyl diesters of phthalic acid.
Hl Viscosity index improvers. Depending upon the viscosity grade
required, the lubricant compositions can contain one or mare viscosity index
improvers (polymeric materials which are often supplied in the form of a
solution in a solvent or carrier fluid). Among the numerous types of materials
known for such use are hydrocarbon polymers grafted with, for example,
Case EI-6214+
- - 118 -
nitrogen-containing polymers, olefin polymers such as polybutene, ethylene-pro-
pylene copolymers, hydrogenated polymers and copolymers and terpolymers of
styrene with isoprene and/or butadiene, polymers of alkyl acrylates or alkyl
methacryiates, copolymers of alkyl methacrylates with N-vinyl pyrrolidone or
dimethylaminoalkyl methacrylate; post-grafted polymers of ethylene-propylene
with an active monomer such as malefic anhydride which may be further reacted
with an alcohol or an alkylene polyamine; and styrene/maleic anhydride
polymers post-treated with alcohols and/or amines.
Dispersant viscosity index improvers, which combine the activity of
14 dispersants and viscosity index improvers, suitable for use in the
compositions of
this invention are described, 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; 4,149,984; 4,160,739; and
4,519,929.
I~Pour point depressants. Another useful type of additive which can be
included in compositions of this invention is one or more pour point
depressants. The use of pour point depressants in oil-base compositions to
improve the low temperature properties of the compositions is well known to
the art. See, for example, the books Lubricant Additives by C. V. Smalheer and
R. Kennedy Smith (Lezius-Hiles Co. Publishers, Cleveland, Ohio, 1967); ear
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). Among the types of compounds which function
satisfactorily as pour point depressants in the compositions of this invention
are
polymethacrylates, polyacrylates, condensation products of haloparaffin waxes
and aromatic compounds, and vinyl carboxylate polymers. Also useful as pour
point depressants are terpolymers made by polymerizing a dialkyl fumarate, vi-
nyl 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.
J) Other metal corrosion inhibitors. In order to protect such metals as
lead, cadmium, aluminum, magnesium, silver, zinc and alloys thereof etc.,
special
corrosion inhibitors can be used. These include such substances as gallic acid
esters, and phthalic acid esters.
The above description of other additives which can be used in the
Case EI-6214+
- - 119 -
compositions of this invention is not to be construed as limitive, as many
other
types of additives can be used in such compositions. The only requirements are
that such other additives not excessively interfere with the performance of
the
compositions of this invention and that they exhibit suitable compatibility
with
the additives otherwise being employed therein.
K Free Amine. The free amines which can be employed in the
compositions of this invention can be any of the amines referred to above in
connection with the amine salts of partial esters of phosphoric acid or
thiophosphoric acids or in connection with the amine salts of carboxylic
acids,
provided that the amines are oil-soluble. Of the various amines, the preferred
type is composed of alkyl primary monoamines, and alkenyl primary
monoamines, especially those containing from 6 to 24 carbon atoms. Examples
of such amines include hexylamine, octylamine, nonylamine, decylamine,
undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine,
hexadecylamine, heptadecylamine, octadecylamine, eicosylamine, docosylamine,
tetracosylarnine, oleylamine, cocoarnine, soyamine, C12_14 tertiary alkyl
primary
amine, and C"_24 tertiary alkyl primary amine.
Generally speaking, the free amine used in the compositions will
correspond to the amine used in forming either the amine salt of the
phosphorus
acid or the amine salt of the carboxylic acid, or both.
The term "free amine" refers to the form of the amine as it is charged
into the blender or mixing vessel in which the additive concentrate or the
lubricating oil or functional fluid composition is being formed. Some or all
~f
the free amine may complex with or react with other components being used in
the product being formed, such as acidic additive components. Thus the term
"free amine" does not signify or imply that the amine must remain free -- all
or
part of it may remain uncomplexed and unreacted, but this is not a
requirement.
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 ingredient concentrations. The base oils not only can be
hydrocarbon oils of lubricating viscosity derived from petroleum (or tar
sands,
Case EI-6214+
- w - 120 -
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-a-olefins (e.g., hydrogenated or unhydrogenated a-olefin oligomers such
as
hydrogenated poly-1-decene); alkyl esters of dicarboxylic acids; complex
esters of
dicarboxylic acid, polyglycol and alcohol; alkyl esters of carbonic or
phosphoric
acids; polysilicones; fluorohydrocarbon oils; and mixtures of mineral, natural
and/or synthetic oils in any proportion, etc. The term "base oil" for this
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 viscosity refined from
crude oil of any source including Gulf Coast, Midcontinent, Pennsylvania,
California, Alaska, Middle East, North Sea, etc. Standard refinery operations
may be used in processing the mineral oil. Among the general types of
petroleum oils useful in the compositions of this invention are solvent
neutrals,
bright stocks, cylinder stocks, residual oils, hydrocracked base stocks,
paraffin
oils including pale oils, and solvent extracted 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 C,-Ch olefins, carboxylic acid esters of both
monoalcohols and polyols, polyethers, silicones, polyglycols, silicates,
alkylated
aromatics, carbonates, thiocarbonates, orthoformates, phosphates and phos-
phites, borates and halogenated hydrocarbons. Representative of such oils are
hamo- and interpolyrners of CZ-C12 monoolefinic hydrocarbons, alkylated
benzenes (e.g., dodecyl benzenes, didodecyl benzenes, tetradecyl benzenes,
dinonyl benzenes, di-(2-ethylhexyl)benzenes, wax-alkylated naphthalenes); and
Case EI-6214+
- - 121 -
polyphenyls (e.g., biphenyls, terphenyls).
Alkylene oxide polymers and interpolymers and derivatives 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 1000, Biphenyl ether of polyethylene glycol having a molecular weight of
500-
1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-
1500) oz mono- and poly-carboxylic esters thereof, for example, the acetic
acid
ester, mixed C~-C6 fatty acid esters, or the C13 Oxo acid diester of
tetraethylene
glycol.
Another suitable class of synthetic oils comprises the esters of
dicarboxylic acids (e.g., phthalic acid, succinic acid, malefic acid, azelaic
acid,
suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer)
wifh a
variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-
ethylhexyl alcohol, ethylene glycol). Specific examples of these esters
include
dibutyl adipate, di(2-ethylhexyl) adipate, didodecyl adipate, di(tridecyl)
adipate,
di(2-ethylhexyl) sebacate, dilauryl sebacate, di-n-hexyl fumarate, dioctyl
sebacate,
diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate,
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 twa moles of 2-ethylhexanoic acid.
Other esters which may be used include those made from C3-C1$
monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol,
trimethylolpropane, pentaerythritol and dipentaerythritol. Trimethylol propane
tripelargonate, pentaerythritol tetracaproate, the ester formed from
trimethylolpropane, caprylic acid and sebacic acid, and the polyesters derived
from a C4 C14 dicarboxylic acid and one or more aliphatic dihydric C3-C12
alto'
hols 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-, polyaryi-, polyalkoxy-, or
Case EI-6214+
- 122- ~~~~~ ~a
polyazyloxy-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(meth-
ylphenyl)siloxanes. Other synthetic lubricating 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-Clb a-olefins, such as hydrogenated
or
unhydrogenated oligomers formed from 1-decease. 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 1-alkene
oligomers of this type are available as articles of commerce, e.g., under the
trade
designations ETHYLFLO 162, ETHYLFLO 164, ETHYLFLO 166,
ETHYLFLO 168, ETHYLFLO 170, E'THYLFLO 174, and ETI-iYLFLO 180
poly-a-olefin oils (Ethyl Corporation; Ethyl Canada Limited; Ethyl S.A.).
Blends of such materials can also be used in order to adjust the viscometrics
of
the given base oil. Suitable 1-alkene oligomers are also available from other
suppliers. As is well known, hydrogenated oligomers of this type contain
little, if
any, residual ethylenic unsaturation.
Preferred oligamers are formed by use of a Friedel-Crafts catalyst (espe
cially boron trifluoride promoted with water or a Cl_~o alkanol) followed by
catalytic hydrogenation of the oligomer so formed using procedures such as are
described in the foregoing U.S. patents.
Other catalyst systems which can be used to form oligomers of 1-alkene
hydrocarbons, which, on hydrogenation, provide suitable oleaginous liquids
include Ziegler catalysts such as ethyl aluminum sesquichloride with titanium
tetrachloride, aluminum alkyl catalysts, chromium oxide catalysts on silica or
alumina supports and a system in which a boron trifluoride catalyst
oligomerization is followed by treatment with an organic peroxide.
It is also possible in accordance with this invention to utilize blends of
Case EI-b214 +
- ~ -123-
one or more liquid hydrogenated 1-alkene oligomers in combination with other
oleaginous materials having suitable viscosities, provided that the resultant
blend
has suitable compatibility and possesses the physical 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, cottonseed oil, soybean oil, sunflower oil, safflower oil, hemp
oil,
linseed oil, tung oil, oiticica oil, jojoba oil, and meadowfoam oil. Such oils
may
be partially or fully hydrogenated, i~ 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 (iii),
or (ii)
and (iii), or (i), (ii) and (iii) does not mean that these various types of
oils are
necessarily equivalents 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 availability or low cost. Thus, the skilled
artisan
will recognize that while the various types of base oils discussed above 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 characteristics
and properties of the base oil or fluid. When employing free amine, the amount
employed is most preferably the amount sufficient to render the pH (determined
as described hereinafter) of the finished additive concentrate as formed
within
the range of 4 to 9. The amounts of the other components will vary in
accordance with such factors as the viscosity characteristics of the base oil
or
fluid employed, the viscosity characteristics desired in the finished product,
the
service conditions for which the finished product is intended, and the perfor-
mance characteristics desired in the finished product. However, generally
Case Ei-6214 +
- - 124 -
speaking, when using component a-1) or a-3), the following concentrations
(weight percent) of the components (active ingredients) in the base oils or
fluids
are illustrative:
Typical Preferred
Ranae Ranae
P- & B-contg dispersant 1 - 2 -
7 5
S-contg antiwaar/E.P. agent 2 - 3 -
6 4
Amine salt of P-contg acid-ester0 - 0 -
3 2
Trihydrocarbyl dithiophosphate0 - 0 -
3 2
1~ Amine salt of carboxylic acid 0 - 0.01 -
1 2
Demulsifier 0 - 0 -
1 0.2
Cu corrosion inhibitor 0 - 0.01 -
0.5 0.2
Supplemental P-antiwear/E.P. 0 - 0.05 -
agent 0.7 0.4
Supplemental ashless dispersant0 - 0 -
3 2
Antioxidant 0 - 0 -
2 1
Rust inhibitor 0 - 0.02 -
2 1
1$ Antifoam agent 0 - 0.0002-
0.3 0.1
Friction modifier 0 - 0 -
3 1
Seal swell agent 0 - 0 -l0
20
Viscosity index improver 0 - 0 -
20 15
Pour point depressant 0 - 0 -
2 1
Other metal corrosian inhibitors0 - 0 -
1 0.5
Free amine 0 2 0.3 -
- 1
2p
Likewise, generally speaking, when using component a-2) or a-4), the following
concentrations (weight percent) of the components (active ingredients) in the
base oils
25 or fluids are illustrative:
cave Er-szm+
- 125 -
Typical Preferred
Ranae Ranae
P-contg dispersant 1 - 2 -
7 5
S S-contg antiwear/E.P. agent 2 - 3 -
6 4
Amine salt of P-contg acid-ester0 - 0 -
3 2
Trihydrocarbyl dithiophasphate 0 - 0 -
3 2
Amine salt of carboxylic acid 0 - 0.01 -
1 2
Demulsifier 0 - 0 -
1 0.2
Cu corrosion inhibitor 0 0.5 0.01 -
- 0.2
B-contg additive 0 5 0 -
- 2
Supplemental P-antiwear/E.P. 0 0.7 0.05 -
agent - 0.4
Supplemental ashless dispersant0 3 o -
- 2
Antioxidant 0 2 0 - 1
-
Rust inhibitor 0 2 0.02 1
- -
Antifoam agent 0 0.3 0.0002 0.1
- -
Friction modifier 0 3
_
0 _ 1
Seal swell agent 0 20 0 - l0
-
1$ viscosity index improver o 20 0 - 15
-
Pour point depressant 0 2 0 - 1
-
Other metal corrosion inhibitors0 1 0 - 0.5
-
Free amine 0 2 0.3 1
- -
The individual components can be separately blended into the base oil or fluid
or can be blended therein in various subcombinations, if desired. Moreover,
such
components can be blended in the form of separate solutions in a diluent.
Except for
viscosity index improvers and/or pour point depressants (which in many
instances are
blended apart from other components); it is preferable to blend the other
selected
components into the base ail by use of an additive concentrate of this
invention, as this
simplifies the blending operations, reduces the likelihood of blending errors,
and takes
advantage of the compatibility and solubility characteristics afforded by the
overall con-
centrate.
The additive concentrates of this invention will contain the individual
components in amounts proportioned to yield finished oil or fluid blends
consistent
Case EI-b214 +
~~~~3.4~
- - 126 -
with the concentrations tabulated above. In most cases, the additive
concentrate will
contain one or more diluents such as light mineral oils, to facilitate
handling and
blending of the concentrate. 'Thus concentrates 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, and transformer oils. The compositions are particularly suitable for use
as
20 automotive and industrial gear oils.
Blendine
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 ingredients. Those
skilled in the
art are cognizant of and familiar with the procedures suitable for formulating
and
blending additive concentrates and lubricant compositions. Usually the order
of
addition of components to the blending tank or vessel is not critical provided
of course,
that the components being blended at any given time are not incompatible or
excessively reactive 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 ingre-
dients thereto, so as to maintain the temperature at, say, 40-60 ° C,
and preferably no
higher than about 60 ° C. 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
be
controlled so as not to cause any significant amount of thermal degradation or
unwanted chemical interactions.
When forming the lubricant compositions of this invention, 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
Case EI-6214+
- 127 -
oil and achievement of product uniformity.
The following examples illustrate preferred additive concentrates and
oleaginous
compositions containing such concentrates. These examples are not intended to
limit,
and should not be construed as limiting, this invention.
EXAMPLE I
To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0
parts
of a product formed by reaction of dicyclopentadiene with dithiophosphoric
acid-0,0-
dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl,
40% are
isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite,
and 1.75
parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components
of the
reaction vessel are agitated and maintained at 30 ° C for 10 minutes.
To this mixture is
added 6.0 parts of a product composed of Ch and C,4 tertiary alkyl monoamines
(Primene~ 81R amine; Rohm & Haas), and the mixture is stirred for 20 minutes
without application of heat. Then another 4.9 parts of this tertiary alkyl
monoamine
product is added and the contents of the reaction vessel are maintained at 50
° C for 1
hour with continuous stirring. While cooling the vessel contents to 40
° C, 4.31 parts of
oleic acid and 0.58 part of antifoam agent (M530; Monsanto Company) are added.
Then, without application of heat, 1.8 parts of 2-tert-dodecyldithio-5-
mercapto-1,3,4-
thiadiazole, 12.3 parts of a phosphorylated and boronated composition formed
as in
Example 44 hereinabove, 0.77 parts of an ethylene oxide-propylene oxide block
copolymer (Pluronic L-121 demulsifier; BASF Corporation) and 11.53 parts of
process
oil are added to the contents of the reaction vessel. The resulting additive
concentrate
of this invention is stirred for 60 minutes to insure homogeneity.
EXAMPLE iI
To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3
parts
of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1
part of
tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition,
the com-
ponents of the reaction vessel are agitated and maintained at 30 ° C
for 10 minutes. To
this mixture are added 3.7 parts of Cl., and Cl4 tertiary alkyl monoamines
(Primene~
81R amine), 3.7 parts of Clb and C1A primary amines, 1.0 part of octyl amine,
and 3
parts of process oil, and the mixture is stirred for 20 minutes while
maintaining the
contents of the reaction vessel at 50 ° C for 1 hour with continuous
stirring. Then, while
case EI-6214 +
- - 128 -
cooling the contents to 40 ° C, 0.6 part of C~ dimer acid, 0.6 part of
caprylic acid, 1.0
part of antifoam agent (M530), and 3.2 parts of process oil are added.
Thereafter,
without application of heat, 2.7 parts of 2-tert-dodecyldithio-5-mercapto-
1,3,4-thia-
diazole, 12.2 parts of a phosphorylated and boronated ashless dispersant
formed as in
Example 44 hereinabove, 0.5 part of ethylene oxide-propylene oxide block
copolymer
(Pluronic L-101 demulsifier; BAS1F Corporation), 2.9 parts of phenolic
antioxidant
(ETTI-TIYL~ antioxidant 733) and 3.4 parts of process oil are added to tha
contents of
the reaction vessel. The resulting additive concentrate of this invention is
stirred for 60
minutes.
EXAMPLE III
To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6
parts of
dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicy-
clopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar
basis
40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-
ethylhexyl, and
1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the
components of
the reaction vessel are agitated and maintained at 30 ° C for 10
minutes. To this mix-
ture are added 3.9 parts of C~~ and Cl$ primary amines, 0.7 part of octyl
amine, and 9.1
parts of process oil, and the mixture is stirred for 20 minutes while
maintaining the
contents of the reaction vessel at 50 ° C for 1 hour with continuous
stirring. Then, while
cooling the contents to 40 ° C, 0.7 part of caprylic acid, 0.7 part of
acrylate copolymer
(M544 defaamer), and 5.8 parts of process oil are added. Thereafter, without
applica-
tion of heat, 12.0 parts of a phosphorylated and boronated ashless dispersant
formed as
in Example 44 hereinabove, 1.5 parts of 2-tert-dodecyldithio-5-mercapto-1,3,4-
thiadiazole, 0.8 part of hydrogenated castor oil ethoxylate (Chemax HC~-5;
Chernax,
Inc.), and 4.8 parts of process oil are added to the contents of the reaction
vessel. The
resulting additive concentrate of this invention is stirred for 60 minutes.
EXAMPLE IV
To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8
parts of
dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicy-
clepentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar
basis
40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-
ethylhexyl, and
1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the
components of
Case EI-6214+
- - 129 -
the reaction vessel are agitated and maintained at 30 ° C for 10
minutes. To this
mixture are added 3.3 parts of Clb and Cl$ primary amines, and 8.3 parts of
process oil,
and the mixture is stirred for 20 minutes while maintaining the contents of
the reaction
vessel at 50 ° C for 1 hour with continuous stirring. Then, while
cooling the contents to
40 ° C, 0.6 part of caprylic acid, 0.6 part of acrylate copolymer (M544
defoamer), and
8.3 parts of process oil are added. Thereafter, without application of heat,
12.8 parts of
a phosphorylated and boronated ashless dispPrsant formed as in Example 44
hereinabove, 1.3 parts of 2-tert-dodecyldithio-5-mercapto-1,3,4-thiadiazole,
and 8.3 parts
of process oil are added to the contents of the reaction vessel. The resulting
additive
concentrate of this invention is stirred for 60 minutes.
EXAMPLE V
To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0
parts
of a product farmed by reaction of dicyclopentadiene with dithiophosphoric
acid-0,0-
dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl,
40% are
isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite,
and 1.75
parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components
of the
reaction vessel are agitated and maintained at 30 ° C for 10 minutes.
To this mixture is
added 6.0 parts of a product composed of Cl~ and Cl~ tertiary alkyl monoamines
(Primene~ 81R amine), and the mixture is stirred for 20 minutes without
application of
heat. Then another 4.9 parts of this tertiary alkyl monoamine product is added
and the
contents of the reaction vessel are maintained at 50 ° C for 1 hour
with continuous
stirring. While cooling the vessel contents to 40 ° C, 4.31 parts of
oleic acid and 0.58
part of antifoam agent (M530) are added. Then, without application of heat,
1.8 parts
of 2-tert-dodecyldithio-5-mercapto-1,3;4-thiadiazole, 12.3 parts of a
phosphorylated
composition formed as in Example 51 hereinabove, 0.77 parts of an ethylene
oxide-
propylene oxide block copolymer (Pluronic L-121 demulsifier) and 11.53 parts
of
process oil are added to the contents of the reaction vessel. The resulting
additive
concentrate of this inventian is stirred for 60 minutes to insure homogeneity.
EXAMPLE VI
To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3
parts
of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1
part of
tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition,
the com-
Case EI-6214-s~
- - 130 -
ponents of the reaction vessel are agitated and maintained at 30 ° C
for 10 minutes. To
this mixture are added 3.7 parts of Cl, and C14 tertiary alkyl monoamines
(Primene~
81R amine), 3.7 parts of C16 and Ct8 primary amines, 1.0 part of octyl amine,
and 3.2
parts of process oil, and the mixture is stirred for 20 minutes while
maintaining the
contents of the reaction vessel at 50 ° C for 1 hour with continuous
stirring. Then, while
cooling the contents to 40 ° C, 0.6 part of C~ dimer acid, 0.6 part of
caprylic acid, 1.0
part of antifoam agent (M530), and 3.2 parts of process oil are added.
Thereafter,
without application of heat, 2.7 parts of 2-tert-dodecyldithio-5-mercapto-
1,3,4-thia-
diazole, 12.2 parts of a phosphorylated ashless dispersant formed as in
Example 51
hereinabove, 0.5 part of ethylene oxide-propylene oxide block copolymer
(Pluronic L-
101 demulsifier), 2.9 parts of phenolic antioxidant (ETHYL~ antioxidant 733)
and 3.4
parts of process oil are added to the contents of the reaction vessel. The
resulting
additive concentrate of this invention is stirred for 60 minutes.
EXAMPLE VII
Ta a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6
parts of
dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicy-
clopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar
basis
40% of the alkyl groups are isopropyl, 40% are isobutyl and 2U% are 2-
ethylhexyl, and
1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the
components of
the reaction vessel are agitated and maintained at 30 ° C for 10
minutes. To this mix-
ture are added 3.9 parts of Clb arid Cis primary amines, 0.7 part of octyl
amine, and 9.1
parts of process oil, and the mixture is stirred for 20 minutes while
maintaining the
contents of the reaction vessel at 50 ° C for 1 hour with continuous
stirnng. Then, while
cooling the contents to 40 ° C, 0.7 part of caprylic acid, 0.7 part of
acrylate copolymer
(M544 defoamer), and 5.8 parts of process oil are added. Thereafter, without
applica-
tion of heat, 22.0 parts of a phosphorylated ashless dispersant formed as in
Example 51
hereinabove, 1.5 parts of 2-tert-dodecyldithio-5-mercapto-1,3,4-thiadiazole,
0.8 part of
hydrogenated castor oil ethoxylate (Chemax HCO-5), and 4.8 parts of process
oil are
added to the contents of the reaction vessel. The resulting additive
concentrate of this
invention is stirred for 60 minutes.
EXAMPLE VIII
To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8
parts of
Case EI-6214+ ~ ~ "~
- - 131 -
dibutyl hydrogen phosphate, 16.6 parts of a product formed by reaction of dicy-
clopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar
basis
40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-
ethylhexyl, and
1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the
components of
the reaction vessel are agitated and maintained at 30 ° C for 10
minutes. To this
mixture are added 3.3 parts of Clb and Ct8 primary amines, and 8.3 parts of
process oil,
and the mixture is stirred for 20 minutes while maintaining the contents of
the reaction
vessel at 50 ° C for 1 hour with continuous stirring. Then, while
cooling the contents to
40°C, 0.6 part of caprylic acid, 0.6 part of acrylate copolymer (M544
defoamer), and
8.3 parts of process oil are added. Thereafter, without application of heat,
12.8 parts of
a phosphorylated ashless dispersant formed as in Example S 1 hereinabove, 1.3
parts of
2-tert-dodecyldithio-5-mercapto-1,3,4-thiadiazole, and 8.3 parts of process
oil are added
to the contents of the reaction vessel. The resulting additive concentrate of
this
invention is stirred for 60 minutes.
EXAMPLE IX
To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0
parts
of a product formed by reaction of dicyclopentadiene with dithiop.hosphoric
acid-0,0-
dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl,
40% are
isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphate,
and 1.75
parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components
of the
reaction vessel are agitated and maintained at 30 ° C for 10 minutes.
To this mixture is -
added 6.0 parts of a product composed of C~2 and C14 tertiary alkyl monaamines
(Primene~ 81R amine), and the mixture is stirred for 20 minutes without
application of
heat. Then another 4.9 parts of this tertiary alkyl monoamine product is added
and the
contents of the reaction vessel are maintained at 50 ° C for 1 hour
with continuous
stirring. While cooling the vessel contents to 40 ° C, 4.31 parts of
oleic acid and 0.58
part of antifoam agent (M530) are added. Then, without application of heat,
1.8 parts
of 2-tert-dodecyldithio-S-mercapto-1,3,4-thiadiazole, 12.3 parts of a
phosphorylated and
boronated composition formed as in Example 140 hereinabove, 0.77 parts of an
ethylene oxide-propylene oxide block copolymer (Pluronic L-121 demulsifier)
and 11.53
parts of process oil are added to the contents of the reaction vessel. The
resulting add-
itive concentrate of this invention is stirred for 60 minutes to insure
homogeneity.
Case EI-6214+
- - 132 -
EXAMPLE X
To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3
parts
of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphate, 0.1
part of
tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition,
the com-
ponents of the reaction vessel are agitated and maintained at 30 ° C
for 10 minutes. To
this mixture are added 3.7 parts of Ch and C14 tertiary alkyl monoamines
(Primene~
8llt amine), 3.7 parts of Clb and Cl8 primary amines, 1.0 part of octyl amine,
and 3.2
parts of process oil, and the mixture is stirred for 20 minutes while
maintaining the
contents of the reaction vessel at SO ° C for 1 hour with continuous
stirring. Then, while
cooling the contents to 40 ° C, 0.6 part of C~ dimer acid, 0.6 part of
caprylic acid, 1.0
part of antifoam agent (M530), and 3.2 parts of process oil are added.
Thereafter,
without application of heat, 2.7 parts of 2-tert-dodecyldithio-5-mercapto-
1,3,4-
thiadiazole, 12.2 parts of a phosphorylated and boronated ashless dispersant
formed as
in Example 140 hereinabove, 0.5 part of ethylene oxide-propylene oxide block
copolymer (Pluronic L-101 demulsifier), 2.9 parts of phenolic antioxidant
(ETHYL~
antioxidant 733) and 3.4 parts of process oil are added to the contents of the
reaction
vessel. The resulting additive concentrate of this invention is stirred for 60
minutes.
EXAMPLE XI
To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6
parts of
dibutyl hydrogen phosphate, 18.9 parts of a product formed by reaction of dicy
clopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar
basis
40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-
ethylhexyl, and
1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the
components of
the reaction vessel are agitated and maintained at 30 ° C for 10
minutes. To this mix
ture are added 3.9 parts of Clb and Cl8 primary amines, 0.7 part of octyl
amine, and 9.1
parts of process oil, and the mixture is stirred for 20 minutes while
maintaining the
contents of the reaction vessel at 50 ° C for 1 hour with continuous
stirring. Then, while
cooling the contents to 40 ° C, 0.7 part of caprylic acid, 0.7 part of
acrylate copolymer
(M544 defoamer), and S.8 parts of process oil are added. Thereafter, without
applica-
tion of heat, 12.0 parts of a phosphorylated and boronated ashless dispersant
formed as
in Example 140 hereinabove, 1.5 parts of 2-tert-dodecyldithio-5-mercapto-1,3,4-
thiadiazole, 0.8 part of hydrogenated castor oil ethoxylate (Chemax HCO-5),
and 4.8
Cause EI-6214 +
- 133 l-
parts of process oil are added to the contents of the reaction vessel. The
resulting
additive concentrate of this invention is stirred for 60 minutes.
EXAMPLE XII
To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8
parts of
dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicy-
clopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which ~on a
molar basis
40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-
ethylhexyl, and
1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the
components of
the reaction vessel are agitated and maintained at 30 ° C for 10
minutes. To this
mixture are added 3.3 parts of Clb and Cl$ primary amines, and 8.3 parts of
process oil,
and the mixture is stirred for 20 minutes while maintaining the contents of
the reaction
vessel at 50 ° C for 1 hour with continuous stirring. Then, while
cooling the contents to
40 ° C, 0.6 part of caprylic acid, 0.6 part of acrylate copolymer (M544
defoamer), and
8.3 parts of process oil are added. Thereafter, without application of heat,
12.8 parts of
a phosphorylated and boronated ashless dispersant formed as in Example 140
herein-
above, 1.3 parts of 2-tert-dodecyldithio-5-mercapto-1,3,4-thiadiazole, and 8.3
parts of
process oil are added to the contents of the reaction vessel. The resulting
additive
concentrate of this invention is stirred for 60 minutes.
EXAMPLE XIII
To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0
parts
of a product formed by reaction of dicyclopentadiene with dithiophosphoric
acid-0,0-
dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl,
40% are
isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite,
and 1.75
parts of 2-ethylhexyl acid phosphate: Throughout this addition, the components
of the
reaction vessel are agitated and maintained at 30 ° C for 10 minutes.
To this mixture is
added 6.0 parts of a product composed of C1., and C14 tertiary alkyl
monoamines
(Primene'~ 81R amine), and the mixture is stirred for 20 minutes without
application of
heat. Then another 4.9 parts of this tertiary alkyl monoamine product is added
and the
contents of the reaction vessel are maintained at 50 ° C for 1 hour
with continuous
stirring. While cooling the vessel contents to 40 ° C, 4.31 parts of
oleic acid and 0.58
part of antifoam agent (M530) are added. Then, without application of heat,
1.8 parts
of 2-tert-dodecyldithio-5-mercapto-1,3,4-thiadiazole, 12.3 parts of a
phosphorylated and
Case EI-6214+
- - 134 -
boronated composition formed as in Example 192 hereinabove, 0.77 parts of an
ethylene oxide-propylene oxide block copolymer (Pluronic L-121 demulsifier)
and 11.53
parts of process oil are added to the contents of the reaction vessel. The
resulting add-
itive concentrate of this invention is stirred for 60 minutes to insure
homogeneity.
EXAMPLE XIV
To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3
parts
of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1
part of
tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition,
the com-
ponents of the reaction vessel are agitated and maintained at 30 ° C
for 10 minutes. To
this mixture are added 3.7 parts of Cl., and C14 tertiary alkyl monoamines
{Primene~
81R amine), 3.7 parts of Clb and Clg primary amines, 1.0 part of octyl amine,
and 3.2
parts of process oil, and the mixture is stirred for 20 minutes while
maintaining the
contents of the reaction vessel at 50 ° C for 1 hour with continuous
stirring. Then, while
cooling the contents to 40 ° C, 0.6 part of C~ dimer acid, 0.6 part of
caprylic acid, 1.0
part of antifoam agent (M530), and 3.2 parts of process oil are added.
Thereafter,
without application of heat, 2.7 parts of 2-tert-dodecyldithio-5-mercapto-
1,3,4-
thiadiazole, 12.2 parts of a phosphorylated and boronated ashless dispersant
formed as
in Example 192 hereinabove, 0.5 part of ethylene oxide-propylene oxide block
copolymer (Pluronic L-101 demulsifier), 2.9 parts of phenolic antioxidant
(ETH~CL~
antioxidant 733) and 3.4 parts of process oil are added to the contents of the
reaction
vessel. The resulting additive concentrate of this invention is stirred for 60
minutes.
EXAMPLE XV
To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6
parts of
dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicy
clopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar
basis
40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-
ethylhexyl, and
1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the
components of
the reaction vessel are agitated and maintained at 30 ° C for 10
minutes. To this mix-
ture are added 3.9 parts of C16 and C1g primary amines, 0.7 part of octyl
amine, and 9.1
parts of process oil, and the mixture is stirred for 20 minutes while
maintaining the
contents of the reaction vessel at 50 ° C for 1 hour with continuous
stirring. Then, while
cooling the contents to 40 ° C, 0.7 part of caprylic acid, 0.7 part of
acrylate copolymer
Case EI-6214 +
-135-
(M544 defoamer), and 5.8 parts of process oil are added. Thereafter, without
applica-
tion of heat, 12.0 parts of a phosphorylated and boronated ashless dispersant
fornied as
in Example 192 hereinabove, 1.5 parts of 2-tert-dodecyldithio-5-mercapto-1,3,4-
thiadiazole, 0.8 part of hydrogenated castor oil ethoxylate (Chemax HCO-5),
and 4.8
S parts of process oil are added to the contents of the reaction vessel. The
resulting
additive concentrate of this invention is stirred for 60 minutes.
EXAMPLE XVI
To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8
parts of
dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicy-
clopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar
basis
40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-
ethylhexyl, and
1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the
components of
the reaction vessel are agitated and maintained at 30 ° C for 10
minutes. To this
mixture are added 3.3 parts of Clb and Cl8 primary amines, and 8.3 parts of
process oil,
and the mixture is stirred for 20 minutes while maintaining the contents of
the reaction
vessel at 50 ° C for 1 hour with continuous stirring. Then, while
cooling the contents to
40 ° C, 0.6 part of caprylic acid, 0.6 part of acrylate copolymer (M544
defoamer), and
8.3 parts of process oil are added. Thereafter, without application of heat,
12.8 parts of
a phosphorylated and boronated ashless dispersant formed as in Example 192
herein-
above, 1.3 parts of 2-tert-dodecyldithio-5-mercapto-1,3,4-thiadiazole, and 8.3
parts of
process oil are added to the contents of the reaction vessel. The resulting
additive
concentrate of this invention is stirred for 60 minutes.
EXAMPLE XVII
The effectiveness of the compositions of this invention was illustrated in
several
2S standard L-37 and L-42 tests. In one set of L-37 and L-42 tests, the
composition was
prepared by blending together the following components in which the
proportions are
by weight:
Phosphorylated ashless dispersant 4.00%
Sulfurized isobutylene 3.50%
Exxon 1365 mineral oil 28.68%
Eaacon 2507 mineral oil (Bright Stock) 63.82%
The phosphorylated ashless dispersant was formed from a polyisobutenyl
succinimide,
Case EI-6214+
- - - 136 -
viz., HiTEC~ 646 additive (Ethyl Petroleum Additives, Inc.; Ethyl Petroleum
Additives,
Ltd.; Ethyl S.A.; Ethyl Canada Ltd.). Phosphorylation was accomplished in the
manner
of Example 51 using 2.7 parts by weight of 1-IiTEC~ 646 additive, 0.3 parts by
weight of
solid phosphorous acid (H3P03), and 1 part by weight of process oil diluent.
The
sulfurized isobutylene was HiTEC~ 309 sulfurized isobutylene additive; (Ethyl
Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl
Canada
Ltd.). This oil blend had kinematic viscosity at of 153.98 cSt at 40 °
C, and 16.63 cSt at
100 ° C.
The results in terms of numerical ratings of the L-37 test were as follows:
10Description Rin Pinion
Ridging 0.00 0.00
Rippling 0.00 0.01
Spalling 0.00 0.00
Wear 0.01 U.O1
15Pitting 0.01 0.01
Scoring 0.00 0.00
The above numerical scale
is as follows:
None - 0.00
Trace - 0.01
20Light - 0.50
Medium - 5.00
Heavy - 10.00
The Ring-Gear Drive Side
Inspection after completion
of a High-Speed, Low Torque
100-minute run, was rated The Pinion-Drive Side and Ring-Gear
Satisfactory. Drive
25Side Inspection after the resulted in the following Gear-tooth
complete test surface
condition ratings:
Description Pinion Ring; Gear
Burnish Heavy Light
Wear Trace Trace
30Surface fatigue
a) Rippling Trace None
b) Ridging None None
Case ~I-6214 a-
- - 137 -
c) Pitting Trace Trace
d) Spalling None None
Scoring None None
Discoloration Light Light
Corrosion Trace Trace
Deposits None None
Inspection before and after the complete test resulted in the following
l3acklash
measurements:
initial 0.004 cm
After test 0.005 cm
After the test the axle shafts, axle housing, carrier housing, pinion
assembly, ring-gear
assembly and differential assembly were rated in Good condition, the bearings
(races)
and differential pins showed Light discoloration and the bearings (rollers)
showed Light
discoloration with a Trace of corrosion.
In the L-42 test, the Sequence 3 inspection showed no scoring on either the
drive side or the coast side of the ring gear. The end of test inpection gave
the
following results:
Ring Gear, Drive Side 4% scored
Ring Gear; Coast Side 6% scored
Pinion Gear, Drive Side 5% scored
Pinion Gear, Coast Side 8% scored
Another L-42 test was conducted using the same oil compasition as above except
that
the sulfurized isobutylene was replaced by an equal amount of a di-tart-butyl
polysufide
composed mainly of the trisulfide. In this L-42 test, the Sequence 3
inspection showed
no scoring on either the drive side or the coast side of the ring gear, and
the end of
test inpection showed the following:
Ring Gear, Drive Side No Scoring
Ring Gear, Coast Side _. 10% scored
Pinion Gear, Drive Side No Scoring
Pinion Gear, Coast Side 13% scored
These results are considered a pass, and actually are better than the results
achieved
with a passing reference oil.
Case El-6214 +
- 138 -
The procedure used in determining pH of preferred additive concentrates of
this invention involves diluting the sample of the composition in a mixture of
methanol and toluene and then assaying "non-aqueous" pH with a conventional pH
probe as used in aqueous systems.
Copper corrosion ratings for the purposes of this invention are conducted
using the standard ASTM D-130 procedure modified to the extent that the
additive
concentrate to be tested is first stored in an oven for 120 hours at 65
° C. Then the
concentrate is blended into the test oil to the selected test concentration
and the test
is conducted at 121 ° C.
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 to dissolve therein at ordinary temperatures to a concentration at least
equivalent to the minimum concentration specified 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 completely 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 invention, provided they do
not
significantly interfere with the performance or usefulness of the composition
in which
they are employed.
