Note: Descriptions are shown in the official language in which they were submitted.
1341005
O1 FUEL COMPO:~ITION:i AND LUBRICATING OIL COMPOSITIONS
02 CONTAINING VERY LONG CHAIN ALKYLPHENYL
03 PC1LY ( OX'.~tALKYLENE ) AMINOCARBAMATES
04
05 BACKGROUND OF THE INVENTION
06 1. Field of then Invention
07
08 Numerous deposit;-form:ing substances are inherent in hydro-
09 carbon fuels. ~'hese :substances when used in internal
combustion engines tend to form deposits on and around
11 constricted areas of ithe engine contacted by the fuel.
12 Typical areas commonly and sometimes seriously burdened by
13 the formation of: depo:aits include carburetor ports, the
14 throttle body and venituries, engine intake valves, etc.
16 Deposits adversely af:Eect the operation of the vehicle. For
17 example, deposits on ithe carburetor throttle body and ven-
18 turies increase the fuel to air ratio of the gas mixture to
19 the combustion c;hambe:r thereby increasing the amount of
unburned hydrocarbon and carbon monoxide discharged from the
21 chamber. The high final-air ratio also reduces the gas
22 mileage obtainable from the vehicle.
23
24 Deposits on the engine intake valves when they get suffi-
ciently heavy, on the other hand, restrict the gas mixture
26 flow into the combustion chamber. This restriction, starves
27 the engine of ai.r and fuel and results in a loss of power.
28 Deposits on the valves also increase the probability of
29 valve failure due to lburning and improper valve seating. In
addition, these deposits may break off and enter the com-
31 bustion chamber possilbly resulting in mechanical damage to
32 the piston, pisi:on rings, engine head, etc.
33
34
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1 341 005
O1 The formation of these' deposits can be inhibited as well as
02 removed by incorporating an active detergent into the fuel.
03 These detergents. function to cleanse these deposit-prone
04 areas of the harmful deposits, thereby enhancing engine per-
05 formance and longevity. There are numerous detergent-type
06 gasoline additives cui:rently available which, to varying
07 degrees, perform theses functions.
08
09 Two factors comp~licatEa the use of such detergent-type
gasoline additives. First, with regard to automobile
11 engines that reqyire t:he use of nonleaded gasolines (to
12 prevent disablement of: catalytic converters used to reduce
13 emissions), it h.as been found difficult to provide gasoline
14 of high enough octane to prevent knocking and the con-
comitant damage which it causes. The chief problem lies in
16 the area of the degree of octane requirement increase,
17 herein called "O~RI", which is caused by deposits formed by
18 the commercial gasoline.
19
The basis of the ORI problem is as follows: each engine,
21 when new, requires a certain minimum octane fuel in order to
22 operate satisfactorily without pinging and/or knocking. As
23 the engine is operated on any gasoline, this minimum octane
24 increases and, in most: cases, if the engine is operated on
the same fuel far a prolonged period, will reach an
26 equilibrium. This is apparently caused by an amount of
27 deposits in the combu:ction chamber. Equilibrium is typi-
28 cally reached after 5,000 to 15,000 miles of automobile
29 operation.
31 The octane requirement: increase in particular engines used
32 with commercial gasoli.nes will vary at equilibrium from 5 to
33 6 octane units to as high as 12 or 15 units, depending upon
34
_2_
1 341 005
I)1 the gasoline compositions, engine design and type of opera-
I)2 tion. The seriousness of the problem is thus apparent. A
I)3 typical autamobi:Le witlh a research octane requirement of 85,
I)4 when new, may afl:er a few months of operation require 97
I)5 research octane c)asoline for proper operation, and little
I)6 unleaded gasoline' of t'.hat octane is available. The ORI
I)7 problem also exists in some degree with engines operated on
I)8 leaded fuels. U.S. Patent Nos. 3,144,311; 3,146,203; and
I)9 4,247,301 disclose lead-containing fuel compositions having
:LO reduced ORI properties.
:l 1
:L2 The ORI problem :is compounded by the fact that the most
:l3 common method fo;r increasing the octane rating of unleaded
:l4 gasoline is to increase its aromatic content. This, how-
:l5 ever, eventually causes an even greater increase in the
:L6 octane requirement. Moreover, some of presently used
:l7 nitrogen-containing compounds used as depositcontrol addi-
:l8 tives and their mineral oil or polymer carriers may also
:l9 significantly contribute to ORI in engines using unleaded
:20 fuels.
:21
:22 it is, therefore, particularly desirable to provide deposit
:23 control additives which effectively control the deposits in
:24 intake systems of engines, without themselves eventually
:25 contributing to the problem.
.26
:27 In this regard, hydrocarbyl poly(oxyalkylene) aminocarba-
:28 mates are commercially successful fuel additives which
:29 control combustion chamber deposits thus minimizing ORI.
31 The second complicating factor relates to the lubricating
32 oil compatibility of the fuel additive. Fuel additives, due
33 to their higher boiling point over gasoline itself, tend to
34 accumulate on surfaces. in the combustion chamber of the
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1 341 005
O1 engine. This accumulation of the additive eventually finds
02 its way into the lubricating oil in the crankcase of the
03 engine via a "blow-by''' process and/or via cylinder
04 wall/piston ring "wipes down". In some cases, as much as
05 25~-30~ of the nonvolatile fuel components, i.e., including
06 fuel additives, will eventually accumulate in the lubri-
07 eating oil. Insofar as the recommended drain interval for
08 some engines may be asp much as 7,500 miles or more, such
09 fuel additives can accumulate during this interval to sub-
stantial quantities in the lubricating oil. In the case
11 where the fuel additive is not sufficiently lubricating oil
12 compatible, the accumulation of such an oil-incompatible
13 fuel additive many actually contribute to crankcase deposits,
14 i.e., varnish and sludge, as measured by a Sequence V-D
test.
16
17 The incompatibility of certain fuel additives in lubricating
18 oils, i.e., oil:; which contain other additives, arises in
19 spite of the fact thai:. some fuel additives are also known to
be lubricating c>il dispersants.
21
22 Several theorie:c exist as to the cause of the lubricating
23 oil incompatibility o:E certain fuel additives. Without
24 being limited to any theory, it is possible that some of
these fuel additives when found in the lubricating oil
26 interfere with other additives contained in the lubricating
27 oil and either counterbalance the effectiveness of these
28 additives or actually cause dissolution of one or more of
29 these additives including possibly the fuel additive itself.
In either case, the incompatibility of the fuel additive
31 with other addii:ives in the lubricating oil demonstrates
32 itself in less i~han desirable crankcase deposits as measured
33 by Sequence V-D engine tests.
34
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1341 005
O1 In another theory, it is possible that the accumulation of
02 the fuel additive into the lubricating oil during the drain
03 interval period surpasses its maximum solubility in the
04 lubricating oil. In this theory, this excess amount of fuel
05 additive is insoluble in the lubricating oil and is what
06 causes increased. cranl~:case deposits.
07
08 In still another theory, it is possible that the fuel addi-
09 tive will decom~~ose in the lubricating oil during engine
operation and th.e decomposition products are what cause
11 increased crankcase dEaposits.
12
13 In any case, lut~ricati.ng oil incompatible fuel additives are
14 less than desirable insofar as their use during engine
operation will result in increased deposits in the crank-
16 case. This prot~lem can be severe. Accordingly, it would be
17 particularly adv~antage~ous to develop a good deposit control
18 fuel additive which does not contribute to ORI and which
19 additionally possesse:> lubricating oil compatibility.
21 The instant invention is directed to fuel compositions con-
22 taining a novel class of alkylphenyl poly(oxyalkylene)
23 aminocarbamates which as a fuel additive controls combustion
24 chamber deposit:, thus minimizing ORI and in lubricating oil
have improved compatibility in the lubricating oil composi-
26 tion. The novel. addii:ives of this invention are very long
27 chain alkylphen~~l poly(oxyalkylene) aminocarbamates having a
28 molecular weight: of about 800 to 6,000 wherein the alkyl
29 group of said al.kylphf~nyl group contains at least 40 carbon
atoms.
31
32 This invention i.s also directed toward dispersants compat-
33 ible in lubricating o:il. In particular, this invention is
34 directed toward dispe:rsant additives possessing improved
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1341005
O1 compatibility in lubricating oil which are alkylphenyl
02 poly(oxyalkylene) aminocarbamates having at least one basic
03 nitrogen and wherein the alkyl group of said alkylphenyl
04 poly(oxyalkylene) aminocarbamate contains at least 40 carbon
05 atoms.
06
07 The incompatibility of certain dispersant additives in
08 lubricating oil, i.e., oils which contain other additives,
09 is recognized in the art and arises in spite of the fact
that certain of these additives are known lubricating oil
11 dispersants.
12
13 Several theories exist as to the cause of the lubricating
14 oil incompatibility of certain additives. Without being
limited to any theory, it is possible that some of these
16 additives interfere with other additives contained in the
17 lubricating oil and either counterbalance the effectiveness
18 of these additives or actually cause dissolution of one or
19 more of these additives, including possibly the dispersant
additive itself.
21
22 In another theory, it is possible that the additive will
23 decompose in the lubricating during engine operation and the
24 decomposition products are what cause increased crankcase
deposits.
26
27 In still another theory, it is also possible that the
28 incompatibility of the additive is related to its oil
29 solubility.
31 Lubricating oil incompatibla additives are less than desir-
32 able insofar as their use during engine operation will
33 result in increased crankcase deposits, i.e., varnish and
34
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1341005
O1 sludge, in the crankcase as measured by Sequence V-D engine
02 tests. This problem can be severe.
03
04 The instant invention is directed to a novel class of very
05 long chain alkylphenyl poly(oxyalkylene) aminocarbamates
06 which provide improved. compatibility in lubricating oil
07 compositions. The novel additives of this invention are
08 alkylphenyl poly(oxyalkylene) aminocarbamates having a
09 molecular weight of about 800 to 6,000 wherein the alkyl
group of said alkylphe~nyl poly(oxyalkylene) aminocarbamate
11 contains at least 40 carbon atoms.
12
13 2. Prior Art
14
Numerous references disclose C1 to C30 hydrocarbyl poly(oxy-
16 alkylene) aminocarbamates as fuel additives. These include
17 the following U.S. Patients Nos.:
18
19 4,160,648; 4,243,798; 4,521,610; and
4,191,537; X1,270,930; 4,568,358.
21 4,197,409; 4,274,837;
22 4,236,020; 4,288,612;
23
24 Of particular rerlevanc:e is U.S. Patent No. 4,274,837 which
discloses that hydrocarbyl poly(oxyalkylene) aminocarbamates
26 containing certain po:ly(oxyalkylene) chains, i.e., oxypro-
27 pylene, when used in :Fuels employed in combination with
28 certain lubricating oils, produce crankcase varnish. This
29 reference further discloses that lubricating oil compatible
hydrocarbyl pol5~(oxypropylene) aminocarbamates are improved
31 by employing the poly(oxypropylene) as a copolymer having 1
32 to 5 C9 to C30 oxyalk;ylene units.
33
34
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1341 005
O1 U.S. Patent No. 4,160,648 discloses an intake system deposit
02 control additive for fuels which is a hydrocarbyl poly(oxy-
03 alkylene) aminocarbama.te wherein the hydrocarbyl group is
04 from 1 to 30 carbon atoms including alkyl or alkylphenyl
05 groups. Specifically disclosed hydrocarbyl groups include
06 tetrapropenylphenyl, olelyl and a mixture of C16, C18 and
07 C20 alkyl groups. Lil~:ewise, U.S. Patent No. 4,288,612
08 discloses deposit control additives for gasoline engines
09 which are hydrocarbyl poly(oxyalkylene) aminocarbamates
wherein the hydrocarbyl group contains from 1 to about 30
11 carbon atoms including alkylphenyl groups wherein the alkyl
I2 group is straight or branched chain of from 1 to about 24
13 carbon atoms. tt.S. Patent No. 4,568,358 discloses diesel
14 fuel compositions containing an additive such as a hydro-
carbyl poly(oxy~~lkylene) aminocarbamate. This reference
16 discloses hydro<:arbyl groups such as alkyl groups of 1 to 30
17 carbon atoms; aryl groups of 6 to 30 carbon atoms, alkaryl
18 groups of 7 to :30 carbon atoms, etc.
19
U.S. Patent No. 4,332,595 discloses hydrocarbyl poly(oxy-
21 alkylene) polyamines wherein the hydrocarbyl group is a
22 hydrocarbyl radical of 8 to 18 carbon atoms derived from
23 linear primary alcohols.
24
U.S. Patent Nos. 4,233,168 and 4,329,240 among others
26 disclose lubricating oil compositions containing a
27 dispersant amount of a hydrocarbyl poly(oxyalkylene)
28 aminocarbamate.
29
While these prior art: references disclose fuel compositions
31 containing C1 to C30 hydrocarbyl poly(oxyalkylene) amino-
32 carbamates, nor..e of i:hese references disclose the unique
33 alkylphenyl group of this invention nor do any of these
34 references suggest that use of this unique alkylphenyl group
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1 341 005
(!1 would provide improved compatibility in lubricating oil
(12 compositions.
03
04 SUMMARY OF THE INVENTION
OS
06 The instant invention is directed toward a novel class of
07 alkylphenyl poly(oxyalkylene) aminocarbamates which possess
!)8 improved compatibility with lubricating oil compositions.
09 In particular, the instant invention is directed toward an
:LO alkylphenyl poly(oxyalkylene) aminocarbamate having at least
:Ll one basic nitrogen and an average molecular weight of about
:l2 800 to 6.000 and wherein the alkyl group of said alkylphenyl
:L3 poly(oxyalkylene) aminocarbamate contains at least 40 carbon
:L4 atoms and the pol.y(oxy<~lkylene) polymer is derived from C2
:LS to C5 oxyalkylene~ units with the proviso that if the
:L6 poly(oxyalkylene;~ polymer is a homopolymer of oxyethylene
:L7 then the poly(ox~rethyl~ene) polymer does not contain more
:18 than 25 oxyethyle~ne units. The instant invention is based
;19 on the discovery that ruse of the unique alkylphenyl group,
.20 i.e., an alkylphe~nyl group wherein the alkyl group contains
:21 at least 40 carbon atoms, imparts to the alkylphenyl poly-
22 (oxyalkylene) am:lnocar'.bamate improved lubricating oil
23 compatibility.
24
25 The compounds of this invention are useful dispersants in
26 lubricating oil. Thus, in its composition aspect, the
27 instant invention is directed toward a lubricating oil
28 composition comprising an oil of lubricating viscosity and a
29 dispersant effective amount of an alkylphenyl poly(oxy-
30 alkylene) aminoc.~rbamate of this invention.
31
32 The instant invention is also directed toward a fuel compo-
33 sition containing a novel class of alkylphenyl poly-
3q (oxyalkylene) aminocarbamates which as a fuel additive
_g_
1341005
controls combustion c;hamber deposits thus minimizing ORI
and in lubricating oi.I provide improved compatibility
with the lubricating oil composition. In particular, the
instant invention is directed toward a fuel composition
comprising a hydrocarbon boiling in the gasoline or
diesel range and from about 30 to about 5,000 parts per
million of a fuel soluble alkylphenyl poly(oxyalkylene)
aminocarbamate having at least one basic nitrogen and an
average molecular weight of about 800 to 6,000 and
wherein the alkyl group of said alkylphenyl
poly(oxyalkylene) ami.nocarbamate contains at least 40
carbon atoms and the poly(oxyalkylene) polymer is derived
from CZ to C5 ox:yalky7_ene units with the proviso that if
the poly(oxyalkylene) polymer is a homopolymer of
oxyethylene then the poly(oxyethylene) polymer does not
contain more than 25 oxyethylene units. The instant
invention is based on the discovery that use of the
unique alkylphenyl group, i.e., an alkylphenyl group
wherein the alkyl group contains at least 40 carbon
atoms, imparts to the: alkylphenyl poly(oxyalkylene)
aminocarbamate improved lubricating oil compatibility
without contributing to ORI.
According to an aspeca of the present invention, an
alkylphenyl poly(oxya.lkylene) aminocarbamate having at
least one basic nitrogen and an average molecular weight
of about 800 to 6,000 and wherein the alkyl group of said
alkylphenyl poly(oxya.lkylene) aminocarbamate contains
from 40 to 200 carbon. atoms and the poly(oxyalkylene)
polymer is derived from C2 to C5 oxyalkylene units with
the proviso that if the poly(oxyalkylene) polymer is a
homopolymer of oxyeth.ylene then the poly(oxyethylene)
polymer does not contain more than 25 oxyethylene units.
~B
1341005
According to a furthear aspect of the present invention, a
compound of Formula V
R1 0
CH2CH;nOC-NHER2NH~QH
R,~
V
wherein R is am alkyl. group having from 40 to 200 carbon
atoms; R~ is hydrogen or alkyl of from 1 to 3 carbon
atoms; R2 is al:kylene of from 2 to 6 carbon atoms; m is an
integer from 1 to 2; n is an integer such that the
molecular weight of t:he compound is from about 800 to
6,000; and p is an integer from 1 to 6 and with the
proviso that if R~ is hydrogen then n is an integer from 1
to 25.
According to another aspect of the present invention, a
lubricating oil composition comprising an oil of
lubricating viscosity and a dispersant effective amount
of an alkylphenyl pol.y(oxyalkylene) amino carbamate
having at least one basic nitrogen and an average
molecular weight of about 800 to 6,000 and wherein the
alkyl group of said alkylphenyl poly(oxyalkylene)
aminocarbamate contains from 40 to 200 carbon atoms and
the poly(oxyalkylene) polymer is derived from C2 to C5
(oxyalkylene) units with the proviso that if the
poly(oxyalkylene) polymer is a homopolymer of
(oxyethylene) then tree poly(oxyethylene) polymer does not
containing more than 25 (oxyethylene) units.
According to another aspect of the present invention, a
fuel composition comprising a hydrocarbon boiling in the
gasoline or diesel range and from about 30 to about 5,000
parts per million of a fuel soluble alkylphenyl
poly(oxyalkylene) ami.nocarbamate having at least one
basic nitrogen and an average molecular weight of about
loa
fB
1341 005
800 to 6,000 and wherein the alkyl group of said
alkyphenyl poly(oxyalkylene) aminocarbamate contains from
40 to 200 carbon atoms and the poly(oxyalkylene) polymer
is derived from C2 to C5 oxyalkylene units with the
proviso that if the p~oly(oxyalkylene) polymer is a
homopolymer of oxyeth.ylene then the poly(oxyethylene)
polymer does not contain more than 25 oxyethylene units.
DETAILED DESCRIPTION OF THE INVENTION
The alkylphenyl poly(oxyalkylene) aminocarbamates of the
present invention consist of an amino moiety and an
alkylphenyl pol;y(oxyalkylene) polymer bonded through a
carbamate linkage, i.e., -OC(O)N<. The specific
alkylphenyl group employed in the instant invention in
the alkylphenyl poly(oxyalkylene) polymer is critical to
achieving improved lubricating oil compatibility for the
alkylphenyl pol:y(oxyalkylene) aminocarbamates. In
particular, it lhas been found that employing the
alkylphenyl group of this invention wherein the alkyl
group contains .at least 40 carbon atoms
10b
1341 005
O1 results in an alkylphenyl poly(oxyalkylene) aminocarbamate
02 which has improved lubricating oil compatibility.
03
04 The Preferred Alkylphenyl Group
05
06 The preferred alkylphenyl group of the alkylphenyl
07 poly(oxyalkylene) aminocarbamate employed in this invention
08 is derived from the corresponding alkylphenol of Formula I
09 below:
11 OH
12
13
14 R
m
16 wherein R is an alkyl group of at least 40 carbon atoms and
17 m is an integer from 1 to 2.
18
19 Preferably, m i;~ one.
21 Preferably R is an alkyl group of from 50 to 200 carbon
22 atoms. More preferably, R is an alkyl group of from 60 to
23 100 carbon atom: .
24
When m is one, l:he alkylphenyl is a monoalkylphenyl; whereas
26 when m is two, i:he alkylphenyl is a dialkylphenyl.
27
2g The alkylphenol:a of Formula I above are prepared by reacting
2g the appropriate olefin or olefin mixture with phenol in the
presence of an ~~lkylating catalyst at a temperature of from
31 about 60°C to 2i)0°C, and preferably 125°C to
180°C either
32 neat or in an e~;sentially inert solvent at atmospheric
33 pressure: Preferred alkylating catalysts are a sulfonic
34 acid catalyst such as Amberlyst 1~ available from Rohm and
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1 X41 005
O1 Haas, Philadelphia, Pennsylvania, or boron trifluoride (or
02 an etherate of boron t:rifluoride). Molar ratios of reac-
03 tarts can be employed. when molar ratios are employed, the
'04 reaction yields a mixture of dialkylphenol, monoalkylphenol
'05 and unreacted phenol. As noted above, dialkylphenol and
'06 monoalkylphenol can be used to prepare the additives used in
the compositions of this invention whereas the unreacted
'08 phenol is preferably removed from the post reaction mixture
X09 via conventional techniques. Alternatively, molar excess of
:10 phenol can be employed, i.e., 2 to 2.5 equivalents of phenol
:11 for each equivalent of: olefin with unreacted phenol
:12 recycled. The latter process maximizes monoalkylphenol.
:13 Examples of inert solvents include benzene, toluene, chloro-
:14 benzene and 250 thinner which is a mixture of aromatics,
:15 paraffins and na.phthenes.
:l6
:17 Particularly preferred alkylphenols employed in this
:18 invention are monoalkylphenols represented by Formula II
:19 below:
a1 OH
:Z 2
a3 II
a4
a5
:Z 6 R
wherein R is as defined above.
a8
'Z9 A particularly preferred class of olefins for use in
preparing alkyli~henols useful in this invention are
31 polyolefin polymers. Polyolefin polymers are polymers
32 comprising a major amount of C3 to C5 monoolefin, e.g.,
:33 ethylene, propy:Lene, butylene, isobutylene and pentene.
.34 The polymers can be homopolymers such as polyisobutylene
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1341005
as well as copolymers of two or more such olefins such as
copolymers of: ethylene and propylene, butylene, and
isobutylene, etc. Other copolymers include those in which
a minor amount of the copolymer monomers, e.g., 1 to 20
mole percent is a C4 to C8 nonconjugated diolefin, e.g., a
copolymer of isobutylene and butadiene or a copolymer of
ethylene, propylene and 1,4-hexadiene, etc.
The polyolefin polymer usually contains at least 40 carbon
atoms, although preferably 50 to 200 carbon atoms and more
preferably 60 to 100 carbon atoms.
A particularly preferred class of olefin polymers com-
prises the polybutenes, which are prepared by polymer-
ization of one or more of 1-butene, 2-butene and
isobutene. Especially desirable are polybutenes con-
taining a substantial proportion of units derived from
isobutene. The polybutene may contain minor amounts of
butadiene which may or may not be incorporated in the
polymer. Most often the isobutene units constitute 80%,
preferably at least 90%, of the units in the polymer.
These polybutenes are readily available commercial mate-
rials well known to those skilled in the art. Disclosures
thereof will be found, for example, in U.S. Patents
Nos. 3,215,707; 3,231,587; 3,515,669; and 3,579,450, as
well as U.S. Patent No. 3,912,764.
In addition to the reaction of a polyolefin with phenol,
many other alkylating hydrocarbons may likewise be used
with phenol to produce alkylphenol. Other suitable alkyl-
ating hydrocarbons include cyclic, linear, branched and
internal or alpha olefins having molecular weights of at
13
1341005
O1 least about 560. For example, alpha olefins obtained from
02 the ethylene growth process gives even number carbon ole-
03 fins. Another source of olefins is by the dimerization of
04 alpha olefins over an appropriate catalyst such as the
05 well-known Ziegler catalyst. Internal olefins are easily
06 obtained by the isomerization of alpha olefins over a
07 suitable catalyst such as silica.
08
09 Preferred Poly(oxyalkylene) Component
11 The alkylphenyl poly(oxyalkylene) polymers which are
12 utilized in preparing the carbamates of the present inven-
13 tion are monohyd~roxy compounds, i.e., alcohols, often
14 termed alkylpher,~yl "capped" poly(oxyalkylene) glycols and
are to be distir.~guishe~d from the poly(oxyalkylene) glycols
16 (diols), which acre noi: alkylphenyl terminated, i.e., not
17 capped. The alk.ylphenyl poly(oxyalkylene) alcohols are
18 produced by the addition of lower alkylene oxides, such as
19 ethylene oxide, propylene oxide, the butylene oxides,
or the pentylene~ oxidE~s to the alkylphenol of Formula I,
21 i.e.,
22
23
24 OH
I ,
26
27
m
28
29 under polymerization conditions, wherein R and m are as
defined above. Preferred poly(oxyalkylene) polymers are
31 those derived from C3 to C4 oxyalkylene units; more prefer-
32 ably C3 oxyprop;~lene 'units. Methods of production and
33 properties of these polymers are disclosed in U.S. Patent
34 Nos. 2,841,479 and 2,782,240 and Kirk-Othmer's "Encyclopedia
-14-
1341 005
O1 of Chemical Technology", Volume 19, p. 507. In the polymer-
02 ization reaction, a single type of alkylene oxide may be
03 employed, e.g., propylene oxide, in which case the product
04 is a homopolymer, e.g., a poly(oxypropylene) propanol.
05 However, copolymers are equally satisfactory and random
06 copolymers are readily prepared by contacting the hydroxyl-
07 -containing compound with a mixture of alkylene oxides, such
OS as a mixture of propylene and butylene oxides. Block
09 copolymers of oxyalkyl.ene units also provide satisfactory
poly(oxyalkylene) polymers for the practice of the present
11 invention.
12
13 Homopolymers of poly(oxyethylene) polymers are much more
14 hydrophilic than homopolymers of C3-C5 poly(oxyalkylene)
polymers. Accordingly, when homopolymers of poly(oxy-
16 ethylene) polymers area employed, the amount of poly(oxy-
17 ethylene) must be limited so as to ensure fuel
18 dispersency/detergency and lubricating oil compatibility of
19 the final carbam.ate. In general, this is accomplished by
limiting the poly(oxyethylene) polymer to about 25 oxy-
21 ethylene units or les:~; although preferably about 10 oxy-
22 ethylene units or les:>~ and most preferably about 5
23 oxyethylene units or less.
24
Likewise, copolymers containing a mixture of oxyethylene
26 units and C3-C5 oxyal~:ylene units are formulated to ensure
27 that the copolymer possesses fuel solubility and lubricating
28 oil compatibility.
29
In general, the poly(oxyalkylene) polymers are mixtures of
31 compounds that differ in polymer chain length. However,
32 their properties; closely approximate those of the polymer
33 represented by t:he average composition and molecular weight.
34
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1341005
O1 In general, the very long chain alkylphenyl terminating
02 group on the alkylphe;nyl poly(oxyalkylene) aminocarbamates
03 of this invention allow for use of less oxyalkylene units in
04 the poly(oxyalkylene) polymer to ensure fuel dispersancy/-
05 detergency solubility and lubricating oil compatibility than
06 are necessary in prior art carbamate fuel additives. Accor-
07 dingly, while longer poly(oxyalkylene) polymers are func-
08 tional in this i.nvent:ion, such longer polymers are not
09 necessary. Therefore, each poly(oxyalkylene) polymer
utilized in thi:~ invention contains at least 1 oxyalkylene
11 unit, preferably from 1 to about 100 oxyalkylene units, more
12 preferably from about 1 to about 25 oxyalkylene units, even
13 more preferably from about 1 to about 10 oxyalkylene units,
14 and most preferably about 5 oxyalkylene units or less. It
is understood that if the poly(oxyalkylene) polymer is a
16 homopolymer of poly(oxyethylene), the polymer length is
17 governed by the constraints discussed above.
18
19 An alternative method for preparing alkylphenyl poly(oxy-
alkylene) polymers ha~~ing 1, 2 or 3 oxyalkylene units
21 involves employing a compound of Formula III below:
22
23 R1
24 C;1(CH2CH0)qH III
26 wherein q is an integer from 1 to 3 and R1 is hydrogen or
27 a C1 to C3 alkyl group. When employing the compound of
28 Formula III, the phenoxide of the alkylphenol, I, is first
29 prepared and then reacted with the compound of Formula III
to yield the desired a~lkylphenol poly(oxyalkylene) polymer
31 having from 1 to 3 oxyalkylene units. Compounds of
32 Formula III are either' commercially available or can be
33 prepared by art recognized methods.
34
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1341005
O1 Preferred Amine Component
02
03 The amine moiety of th,e alkylphenyl poly(oxyalkylene)
04 aminocarbamate employed in this invention is preferably
05 derived from a polyamine having from 2 to about 12 amine
06 nitrogen atoms and from 2 to about 40 carbon atoms. The
07 polyamine is preferably reacted with an alkylphenyl poly-
08 (oxyalkylene) chlorofcrrmate to produce the alkylphenyl
09 poly(oxyalkylene) aminocarbamate additives finding use
within the scope of the present invention. The chloro-
11 formate is itself derived from alkylphenyl poly(oxy-
12 alkylene) alcohol by reaction with phosgene. The
13 polyamine, encom~.passing diamines, provides the product
14 alkylphenyl poly(oxya7.kylene) aminocarbamate with, on
average, at least about one basic nitrogen atom per
16 carbamate molecuale, i,.e., a nitrogen atom titratable by a
1~ strong acid. The polyamine preferably has a carbon-to-
18 nitrogen ratio of frorn about 1:1 to about 10:1.
19
The polyamine may be substituted with substituents
21 selected from (A) hydrogen, (B) hydrocarbyl groups of from
22 1 to about 10 ce~rbon atoms, (C) acyl groups of from 2 to
23 about 10 carbon atoms, and (D) monoketo, monohydroxy,
24 mononitro, monoc:yano, lower alkyl and lower alkoxy
derivatives of I:B) and (C). "Lower", as used in terms
26 like lower alky7~ or lower alkoxy, means a group containing
27 from 1 to about 6 carbon atoms. At least one of the
28 substituents on one of the basic nitrogen atoms of the
29 polyamine is hydrogen, e.g., at least one of the basic
nitrogen atoms of the polyamine is a primary or secondary
31 amino nitrogen ~~tom.
32
33 Hydrocarbyl, as used in describing all the components of
34 this invention, denotes an organic radical composed of
-17-
'341005
O1 carbon and hydrogen which may be aliphatic, alicyclic,
02 aromatic or combinations thereof, e.g., aralkyl. Prefer-
03 ably, the hydrocarbyl group will be relatively free of
04 aliphatic unsaturation, i.e., ethylene and acetylenic,
05 particularly acetylenic unsaturation. The substituted
06 polyamines of the present invention are generally, but not
07 necessarily, N-substituted polyamines. Exemplary hydro-
08 carbyl groups and substituted hydrocarbyl groups include
09 alkyls such as methyl, ethyl, propyl, butyl, isobutyl,
pentyl, hexyl, octyl, etc., alkenyls such as propenyl,
11 isobutenyl, hexe:nyl, octenyl, etc., hydroxyalkyls, such as
12 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl,
13 4-hydroxybutyl, ~etc., ketoalkyls, such as 2-ketopropyl,
14 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such
as ethoxyethyl, ~ethoxypropyl, propoxyethyl, propoxypropyl,
16 2-(2-ethoxyethox:~)ethyl, 2-(2-(2-ethoxyethoxy)ethoxy)-
17 ethyl, 3,6,9,12-tetraoxatetradecyl, 2-(2-ethoxyethoxy)
18 hexyl, etc. The acyl groups of the aforementioned (C)
19 substituents are such as propionyl, acetyl, etc. The more
preferred substi~tuents are hydrogen, Cl-C4 alkyls and
21 Cl-C4 hydroxyalk~~ls.
22
23 In a substituted polya:mine the substituents are found at
24 any atom capable of receiving them. The substituted
atoms, e.g., substituted nitrogen atoms, are generally
26 geometrically inE~quivalent, and consequently the sub-
27 stituted amines ~:inding use in the present invention can
28 be mixtures of mono- a:nd poly-substituted polyamines
29 with substituent groups situated at equivalent and/or
inequivalent atoms.
31
32 The more preferred pol~yamine finding use within the scope
33 of the present invention is a polyalkylene polyamine,
34 including alkylene diamine, and including substituted
-18-
~ 34~ 005
O1 polyamines, e.g., alkyl and hydroxyalkylsubstituted poly-
02 alkylene polyamine. Preferably, the alkylene group con-
03 tains from 2 to 6 carbon atoms, there being preferably
04 from 2 to 3 carbon atoms between the nitrogen atoms. Such
05 groups are exemplified by ethylene, 1,2-propylene, 2,2-di-
06 methylpropylene trimethylene, 1,3,2-hydroxypropylene, etc.
07 Examples of such polya.mines include ethylene diamine,
08 diethylene triamine, dli(trimethylene)triamine, dipropylene
09 triamine, triethylene tetramine, tripropylene tetramine,
tetraethylene pentamir~e, and pentaethylene hexamine. Such
11 amines encompass isomers such as branchedchain polyamines
12 and the previously mentioned substituted polyamines,
13 including hydroxy- and hydrocarbylsubstituted polyamines.
14 Among the polyalkylene~ polyamines, those containing 2-12
amine nitrogen atoms and 2-24 carbon atoms are especially
16 preferred, e.g., ethy7Lene diamine, propylene diamine,
17 butylene diaminE~, pentylene diamine, hexylene diamine,
18 diethylene triamine, dipropylene triamine, and the C2-C3
19 alkylene polyami.nes are most preferred, in particular, the
lower polyalkylene po:lyamines, e.g., ethylene diamine,
21 diethylene triamine, propylene diamine, dipropylene
22 triamine, etc.
23
24 The amine component of the alkylphenyl poly(oxyalkylene)
aminocarbamate also may be derived from heterocyclic
26 polyamines, hetE~rocyclic substituted amines and substi-
27 tuted heterocyc:lic compounds, wherein the heterocycle
28 comprises one or more 5-6 membered rings containing oxygen
29 and/or nitrogen. Such heterocycles may be saturated or
unsaturated and substituted with groups selected from the
31 aforementioned (A), (B), (C) and (D). The heterocycles
32 are exemplified by piperazines, such as 2-methylpiper-
33 azine, N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-pipera-
34 zinyl)ethane, and N,N~bis(N-piperazinyl)piperazine,
-19-
34? 005
2-methylimidazoline, 3-aminopiperidine, 2-aminopyridine,
2-(3-aminoethyl)3-~pyrro:line, 3-aminopyrrolidine,
N-(3-aminopropyl)morpho:Line, etc. Among the heterocyclic
compounds, the piperazines are preferred.
Another class of :~uitab:le polyamines are diaminoethers
represented by Formula :IV
H2N-X.1 f 0X2 ~ rNH2 I V
wherein X1 and X2 are independently alkylene from 2 to
about 5 carbon atoms and r is an integer from 1 to about
10. Diamines of Formula IV are disclosed in U.S. Patent
No. 4,521,610.
Typical polyamine:; that can be used to form the compounds
of this invention by reaction with a poly(oxyalkylene)-
chloroformate incJ.ude the following: ethylene diamine,
1,2-propylene diamine, :1,3-propylene diamine, diethylene
triamine, triethyl.ene tetramine, hexamethylene diamine,
tetraethylene pent:amine, dimethylaminopropylene diamine,
N-(beta-aminoethyl.)piperazine, N-(beta-aminoethyl)piper-
idine, 3-amino-N-eathylpiperidine, N-(beta-aminoethyl)-
morpholine, N,N'-di(bet;a-aminoethyl)piperazine,
N,N'-di(beta-aminoethylimidazolidone-2; N-(beta-cyano-
ethyl)ethane-1,2-diamin~e, 1-amino-3,6,9-triazaoctadecane,
1-amino-3,6-diaza--9-oxadecane, N-(beta-aminoethyl)-di-
ethanolamine, N'-acetyl-N'-methyl-N-(beta-aminoethyl)-
ethane-1,2-diaminE~, N-acetonyl-1,2-propanediamine,
N-(beta-nitroethy:L)-1,3-propane diamine, 1,3-dimethyl-5-
(beta-aminoethyl)hexahydrotriazine, N-(beta-amino-
ethyl)hexahydrotr:iazine, 5-(beta-aminoethyl)-1,3,5-
d
'' ,
~ 3'~~ 005
O1 dioxazine, 2-(2-aminoe~thylamino)-ethanol, 2[2-(2-amino-
02 ethylamino)ethylamino]-ethanol.
03
04 The amine component of: the alkylphenyl poly(oxyalkylene)
05 aminocarbamate may al:~o be derived from an amine-contain-
06 ing compound which is capable of reacting with an alkyl-
07 phenyl poly(oxyalkylene) alcohol to produce an alkylphenyl
08 poly(oxyalkylene) aminocarbamate having at least one basic
09 nitrogen atom. For ea:ample, a substituted aminoiso-
cyanate, such as (R3)~,NCH2CH2NC0, wherein R3 is, for
11 example, a hydrocarby7L group, reacts with the alcohol to
12 produce the amir.~ocarbamate additive finding use within the
13 scope of the prersent :invention. Typical aminoisocyanates
14 that may be used to form the fuel additive compounds of
this invention t>y reaction with a hydrocarbylpoly(oxy-
16 alkylene) alcohol inc:Lude the following: N,N-(dimethyl)-
17 aminoisocyanatoe~thane, generally, N,N-(dihydrocarbyl)-
18 aminoisocyanatoalkane, more generally, N-(perhydrocarbyl)-
19 isocyanatopolyal_kylen~e polyamine, N,N-(dimethyl)aminoiso-
cyanatobenzene, etc.
21
22 In many instancE~s the amine used as a reactant in the
23 production of the carbamate of the present invention is
24 not a single compound but a mixture in which one or
several compounds, predominate with the average composi-
26 tion indicated. For example, tetraethylene pentamine
27 prepared by the polymerization of aziridine or the
28 reaction of dichloroethylene and ammonia will have both
29 lower and higher amine members, e.g., triethylene
tetramine, substituted piperazines and pentaethylene
31 hexamine, but the composition will be mainly tetraethylene
32 pentamine and the empirical formula of the total amine
33 composition will closely approximate that of tetraethylene
34 pentamine. Finally, in preparing the compounds of this
-21-
1341 00~
Ol invention, where the various nitrogen atoms of the poly-
02 amine are not geometrically equivalent, several substitu-
03 tional isomers are possible and are encompassed within the
04 final product. Methods of preparation of amines, iso-
05 cyanates and their reactions are detailed in Sidgewick's
06 "The Organic Chemistry of Nitrogen", Clarendon Press,
07 Oxford, 1966; Hollers' "Chemistry of Organic Compounds",
08 Saunders, Philadelphia, 2nd Ed. 1957; and Kirk-Othmer's
09 "Encyclopedia of Chemical Technology", 2nd Ed., especially
Volume 2, pp. 99-116.
11
12 Preferred Alkylphenyl
13 Pol (y oxyalkylene) Aminocarbamate
14
Having described the preferred alkylphenyl poly(oxy-
16 alkylene) component and the preferred polyamine component,
17 the preferred alkylphenyl poly(oxyalkylene) aminocarbamate
18 additive of the present invention is obtained by linking
19 these components together through a carbamate linkage
i.e.,
21
22
23 0
24 -0-C-N<
26 wherein the ether oxygen may be regarded as the terminal
27 hydroxyl oxygen of the alkylphenyl poly(oxyalkylene)
28 alcohol component, and the carbonyl group -C(0)- is
29 preferably provided by the coupling agent, e.g., phosgene.
31 The alkylphenyl poly(oxyalkylene) aminocarbamate employed
32 in the present invention has at least one basic nitrogen
33 atom per molecule. A "basic nitrogen atom" is one that is
34 titratable by a strong acid, e.g., a primary, secondary,
-22-
1341 005
O1 or tertiary amino nitrogen, as distinguished from, for
02 example, an amido nitragen, i.e.,
03
04
05 0
06 II
-CN< ,
07
08
09 which is not so titratable. Preferably, the basic
nitrogen is in a primary or secondary amino group.
11
12 The preferred al:kylphenyl poly(oxyalkylene) aminocarbamate
13 has an average m~~lecular weight of from about 800 to
14 6,000; preferably an average molecular weight of from 800
to 3,000; and most preferably an average molecular weight
16 of from 1,000 to 2,500.
17
18 A preferred clas;~ of alkylphenyl poly(oxyalkylene) amino-
19 carbamate can be described by the following Formula V
21
22 R1 0
23 I II
~<~fOCH2CH~nOCNH~R2NH~pH V
24
Rm
26 wherein R is an <~lkyl group containing at least 40 carbon
27 atoms; R1 is hyd~:ogen or alkyl of 1 to 3 carbon atoms; R2
28 is alkylene of f~:om 2 to about 6 carbon atoms; m is an
29 integer from 1 to 2; n is an integer such that the
molecular weight of the compound is from about 800 to
31 6,000; and p is an integer from 1 to about 6 and with the
32 proviso that if Rl is 'hydrogen then n is an integer from 1
33 to 25.
34
-23-
1341 005
Preparation of the Alkylphenyl
PoT. ox alkylene) Aminocarbamate
The additives employed in this invention can be most
conveniently prepared by first reacting the appropriate
alkylphenyl poly(oxyalkylene) alcohol with phosgene to
produce an alky:lphenyl poly(oxyalkylene) chloroformate.
The chloroformaite is then reacted with the polyamine to
produce the desired alkylphenyl poly(oxyalkylene)
aminocarbamate.
Preparation of ~~minocarbamates are disclosed in U.S.
Patent Nos. 4,150,648; 4,191,537; 4,197,409; 4,236,020:
4,243,798 4,270,930; 4,274,837; 4,288,612: 4,512,610;
and 4,568,358. In general, the reaction of the
poly(oxyalkylen~~) compound and phosgene is usually
carried out on ;gin essentially equimolar basis, although
excess phosgene can be used to improve the degree of
reaction. The :reaction may be carried out at
temperatures from -10°C to 100°C., preferably in the
range of 0°C to 50°C. The reaction will usually be
complete within 1/4 to 5 hours. Times of reaction will
usually be in t:he range of from 2 to 4 hours.
A solvent may b~e used in the chloroformylation reaction.
Suitable solvents include benzene, toluene, etc.
The reaction of the resultant chloroformate with the
amine may be carried out neat or preferably in solution.
Temperatures of from -10°C to 200°C may be utilized, the
desired product may b~e obtained by water and stripping
usually be the aid of vacuum, of any residual solvent.
The mol ratio of polyamine to polyether chloroformate
will generally be in the range from about 2 to 20 mols of
24
N
;~::a~ a. ,.,'~~'.~'
1341005
O1 polyamine per mol of c:hloroformate, and more usually 5 to 15
02 mols of polyamin.e per mole of chloroformate. Since suppres-
03 lion of polysubstituti.on of the polyamino is usually
04 desired, large molar excesses of the polyamine will be used.
05 Additionally, th.e preferred adduct is the monocarbamate
06 compound, as opposed t:o the bis(carbamate) or disubstituted
07 aminoether.
08
09 The reaction or reactions may be conducted with or without
the presence of a reac:tion solvent. A reaction solvent is
11 generally employed whenever necessary to reduce the vis-
12 cosity of the reaction product. These solvents should be
13 stable and inert. to the reactants and reaction product.
14 Depending on the temperature of the reaction, the particular
chloroformate used, the mol ratios, as well as the reactant
16 concentrations, the reaction time may vary from less than 1
17 minute to 3 hours.
18
19 After the reaction has been carried out for a sufficient
length of time, the reaction mixture may be subjected to
21 extraction with a hydrocarbonwater or hydrocarbonalcohol-
22 water medium to free t:he product from any lowmolecularweight
23 amine salts which havE~ formed and any unreacted diamine.
24 The product may then be isolated by evaporation of the
solvent. Further purification may be effected by column
26 chromatography on silica gel.
27
28 Depending on they particular application of the composition
29 of this invention, the reaction may be carried out in the
medium in which it will ultimately find use, e.g., polyether
31 carriers or an oleoph:ilic organic solvent or mixtures
32 thereof and be formed at concentrations which provide a
33 concentrate of a detergent composition. Thus, the final
34
-25-
1341005
mixture may be in a form to be used directly for blending in
fuels.
An alternative process for preparing the alkylphenyl poly-
(oxyalkylene) aminocarbamates employed in this invention
involves the use of an arylcarbonate intermediate. That is
to say, the alkylphenyl poly(oxyalkylene) alcohol is reacted
with an aryl chloroformate to form an arylcarbonate which is
then reacted with the polyamine to form the aminocarbamate
employed in this invention. Particularly useful aryl
chloroformates include phenyl chloroformate, p-nitrophenyl
chloroformate, 2,4-dinitrophenyl chloroformate, p-chloro-
phenyl chloroformate, 2,4-dichlorophenyl chloroformate, and
p-trifluoromethylphenyl chloroformate. Use of the aryl
carbonate intermediate allows for conversion to amino-
carbamates containing close to the theoretical basic
nitrogen while employing less excess of polyamine, i.e.,
molar ratios of generally from 1:1 to about 5:1 of polyamine
to the arylcarbonate, and additionally avoids the generation
of hydrogen chloride in the reaction forming the aminocarba-
mate.
Also included within the scope of this invention are fully
formulated lubricating ails containing a dispersant effec-
tive amount of an alkylp~henyl poly(oxyalkylene) aminocar-
bamate. Contained in th,e fully formulated composition is:
1. an alkenyl succinimide,
2. a Group II metal salt of a dihydrocarbyl
dithiophosphoric acid,
26
x,
1341005 '
3. a neutral or overbased alkali or alkaline earth
metal hydrocarbyl sulfonate or mixtures thereof, and
4. a neutral or overbased alkali or alkaline earth
metal alky:lated phenate or mixtures thereof.
5. A viscosity index (VI) improver.
The alkenyl succinimide is present to act as a dispersant
and prevent formation of deposits formed during operation
of the engine. The alkenyl succinimides are wellknown in
the art. The a:Lkenyl succinimides are the reaction
product of a po:Lyolefin polymersubstituted succinic
anhydride with ~~n amine, preferably a polyalkylene
polyamine. The polyolefin polymersubstituted succinic
anhydrides are obtained by reaction of a polyolefin
polymer or a derivative thereof with malefic anhydride.
The succinic anlZydride thus obtained is reacted with the
amine compound. The preparation of the alkenyl
succinimides ha;s been described many times in the art.
See, for example, U.S. Patents Nos. 3,390,082; 3,219,666;
and 3,172,892. Reduction of the alkenyl substituted
succinic anhydride yields the corresponding alkyl
derivative. The alkyl succinimides are intended to be
included within the scope of the term "alkenyl
succinimide". .~ product comprising predominantly mono or
bissuccinimide can be prepared by controlling the molar
ratios of the reactants. Thus, for example, if one mole
of amine is reacted with one mole of the alkenyl or alkyl
substituted succinic anhydride, a predominantly
monosuccinimide product will be prepared. If two moles
of the succinic anhydride are reacted per mole of
polyamine, a bissuccinimide will be prepared.
27
x
T,
1341005
O1 Particularly good results are obtained with the lubricating
02 oil compositions of this invention when the alkenyl succi-
03 nimide is a polyisobutenesubstituted succinic anhydride of a
04 polyalkylene polyamine.
05
06 The polyisobutene from which the polyisobutenesubstituted
07 succinic anhydride is obtained by polymerizing isobutene can
08 vary widely in its compositions. The average number of
09 carbon atoms can range from 30 or less to 250 or more, with
a resulting number average molecular weight of about 400 or
11 less to 3,000 or more. Preferably, the average number of
12 carbon atoms per polyisobutene molecule will range from
13 about 50 to about 100 with the polyisobutenes having a num-
14 ber average molecular weight of about 600 to about 1,500.
More preferably, the average number of carbon atoms per
16 polyisobutene molecule ranges from about 60 to about 90, and
17 the number average molecular weight ranges from about 800 to
18 1,300. The polyisobutene is reacted with malefic anhydride
19 according to wellknown procedures to yield the polyiso-
butene-substituted succinic anhydride.
21
22 In preparing the alkenyl succinimide, the substituted
23 succinic anhydride is reacted with a polyalkylene polyamine
24 to yield the corresponding succinimide. Each alkylene
radical of the polyalkylene polyamine usually has from 2 up
26 to about 8 carbon atoms. The number of alkylene radicals
27 can range up to about 8. The alkylene radical is exem-
28 plified by ethylene, propylene, butylene, trimethylene,
29 tetramethylene, pentamethylene, hexamethylene, octa-
methylene, etc. The number of amino groups generally, but
31 not necessarily, is one greater than the number of alkylene
32 radicals present in the amine, i.e., if a polyalkylene
33 polyamine contains 3 alkylene radicals, it will usually
34 contain 4 amino radicals. The number of amino radicals can
-28-
1341005
O1 range up to about 9. Preferably, the alkylene radical
02 contains from about 2 to about 4 carbon atoms and all amine
03 groups are primary or secondary. in this case, the number
04 of amine groups exceeds the number of alkylene groups by 1.
05 Preferably the holyal)cylene polyamine contains from 3 to 5
06 amine groups. ~~pecif:ic examples of the polyalkylene poly-
07 amines include e~thylenediamine, diethylenetriamine, tri-
08 ethylenetetramine, propylenediamine, tripropylenetetramine,
09 tetraethylenepentamincs, trimethylenediamine, pentaethylene-
hexamine, di(tri.methy:lene)triamine, tri(hexamethylene)tetra-
11 mine, etc.
12
13 Other amines suitable for preparing the alkenyl succinimide
14 useful in this i.nvent:ion include the cyclic amines such as
piperazine, morpholine and dipiperazines.
16
17 Preferably the alkeny:l succinimides used in the compositions
18 of this invention have the following formula
19
21 /O
22 Rl-C;H-C
~~N~-Alkylene-N~ H
23 C:H2-C~ ~ n
24 0 A
wherein:
26
27 a. R1 represents an alkenyl group, preferably a substan-
28 tially saturated hydrocarbon prepared by polymerizing
29 aliphatic mono-olefins. Preferably R1 is prepared from
isobutene ~~nd has an average number of carbon atoms and
31 a number average molecular weight as described above;
32
33 b, the "alkyl~~ne" radical represents a substantially
34 hydrocarbyl group containing from 2 up to about 8
-29-
X341005
carbon atoms and preferably containing from about 29
carbon atoms as described hereinabove;
c. A represents a hydrocarbyl group, an amine-substituted
hydrocarbyl group, or hydrogen. The hydrocarbyl group
and the amine-substituted hydrocarbyl groups are gener-
ally the alkyl and amino-substituted alkyl analogs of
the alkylene radicals described above. Preferably A
represents hydrogen;
d. n represents an integer of from 1 to about 8, and
preferably from about 3-5.
Also included within the term alkenyl succinimide are the
modified succinimides which are disclosed in U.S. Patent
No. 4,612,132.
The alkenyl succinimide is present in the lubricating oil
compositions of the invention in an amount effective to act
as a dispersant and prevent the deposit of contaminants
formed in the oil during operation of the engine. The
amount of alkenyl succinimide can range from about 1 percent
to about 20 percent weight of the total lubricating oil
composition. Preferably the amount of alkenyl succinimide
present in the lubricating oil composition of the invention
ranges from about :1 to about 10 percent by weight of the
total composition.
The alkali or alka:Line earth metal hydrocarbyl sulfonates
may be either petroleum sulfonate, synthetically alkylated
aromatic sulfonate;a, or aliphatic sulfonates such as those
derived from polyi;sobutylene. One of the more important
functions of the s,~lfonates is to act as a detergent and
dispersant. These sulfonates are wellknown in the art. The
;° ;
.._ 1341 005
O1 hydrocarbyl group must: have a sufficient number of carbon
02 atoms to render the sulfonate molecule oil soluble. Prefer-
03 ably, the hydrocarbyl portion has at least 20 carbon atoms
04 and may be aromatic or aliphatic, but is usually alkylaroma-
05 tic. Most preferred i:or use are calcium, magnesium or
06 barium sulfonate~s which are aromatic in character.
07
08 Certain sulfonat:es area typically prepared by sulfonating a
09 petroleum fraction haring aromatic groups, usually mono- or
dialkylbenzene groups,, and then forming the metal salt of
11 the sulfonic acid material. Other feedstocks used for
12 preparing these sulfomates include synthetically alkylated
13 benzenes and aliphatic hydrocarbons prepared by polymerizing
14 a mono- or diolefin, Eor example, a polyisobutenyl group
prepared by pol5rmerizing isobutene. The metallic salts are
16 formed directly or by metathesis using well-known
17 procedures.
18
19 The sulfonates may be neutral or overbased having base num-
bers up to abouit 400 or more. Carbon dioxide and calcium
21 hydroxide or oxide are the most commonly used material to
22 produce the ba sic or overbased sulfonates. Mixtures of
23 neutral and overbased sulfonates may be used. The sulfo-
24 nates are ordinarily used so as to provide from 0.3% to 10%
by weight of the total composition. Preferably, the neutral
26 sulfonates are present from 0.4% to 5% by weight of the.
27 total composition and the overbased sulfonates are present
28 from 0.3% to 3% by weight of the total composition.
29
The phenates for use in this invention are those conven-
31 tional products which are the alkali or alkaline earth metal
32 salts of alkylated phenols. One of the functions of the
33 phenates is to act as. a detergent and dispersant. Among
34 other things, it prevents the deposition of contaminants
-31-
1341 005
~Dl formed during hi~3h temperature operation of the engine. The
~D2 phenols may be mono- or polyalkylated.
~D 3
~D4 The alkyl portion of the alkyl phenate is present to lend
~D5 oil solubility t~~ the phenate. The alkyl portion can be
~D6 obtained from naturally occurring or synthetic sources.
~D7 Naturally occurring sources include petroleum hydrocarbons
~D8 such as white oil and wax. Being derived from petroleum,
~D9 the hydrocarbon moiety is a mixture of different hydrocarbyl
:10 groups, the specific composition of which depends upon the
:ll particular oil stock which was used as a starting material.
:L2 Suitable synthetic sources include various commercially
:L3 available alkenes and alkane derivatives which, when reacted
:l4 with the phenol, yield an alkylphenol. Suitable radicals
:L5 obtained include butyl, hexyl, octyl, decyl, dodecyl, hexa-
:L6 decyl,.eicosyl, tricontyl, and the like. Other suitable
:l7 synthetic sources of the alkyl radical include olefin poly-
:l8 mers such as polypropylene, polybutylene, polyisobutylene
:L9 and the like.
:20
:21 The alkyl group can be straight-chained or branch-chained,
:22 saturated or unsaturated (if unsaturated, preferably
:23 containing not more than 2 and generally not more than 1
:24 site of olefinic unsat.uration). The alkyl radicals will
:25 generally contain from 4 to 30 carbon atoms. Generally when
:26 the phenol is monoalkylsubstituted, the alkyl radical should
:27 contain at least 8 carbon atoms. The phenate may be sul-
:28 furized if desired. I:t may be either neutral or overbased
:29 and if overbased will have a base number of up to 200 to 300
:30 or more. Mixtures of neutral and overbased phenates may be
31 used.
32
33 The phenates are ordinarily present in the oil to provide
34 from 0.2% to 27% by weight of the total composition.
-32-
- 1 341 005
O1 Preferably, the neutral phenates are present from 0.2% to 9%
02 by weight of the total composition and the overbased
03 phenates are present from 0.2 to 13% by weight of the total
04 composition. Mast preferably, the overbased phenates are
05 present from 0.2% to 5% by weight of the total composition.
06 Preferred metals are calcium, magnesium, strontium or
07 barium.
08
09 The sulfurized alkaline earth metal alkyl phenates are pre-
ferred. These salts acre obtained by a variety of processes
11 such as treating the neutralization product of an alkaline
12 earth metal base and an alkylphenol with sulfur. Conven-
13 iently the sulfur, in elemental form, is added to the
14 neutralization product: and reacted at elevated temperatures
to produce the sulfuri.zed alkaline earth metal alkyl
16 phenate.
17
18 If more alkaline earth metal base were added during the
19 neutralization reaction than was necessary to neutralize the
phenol, a basic sulfurized alkaline earth metal alkyl
21 phenate is obtained. See, for example, the process of
22 Walker et al, U.S. Pai:ent No. 2,680,096. Additional
23 basicity can be obtained by adding carbon dioxide to the
24 basic sulfurizecl alkaline earth metal alkyl phenate. The
excess alkaline earth metal base can be added subsequent to
26 the sulfurization step but is conveniently added at the same
27 time as the alkaline earth metal base is added to neutralize
28 the phenol.
29
Carbon dioxide and calcium hydroxide or oxide are the most
31 commonly used material to produce the basic or "overbased"
32 phenates. A process wherein basic sulfurized alkaline earth
33 metal alkylphenates are produced by adding carbon dioxide is
34 shown in Hanneman, U.S. Patent No. 3,178,368.
-33-
134100
O1 The Group II metal sa7.ts of dihydrocarbyl dithiophosphoric
02 acids exhibit wear, antioxidant and thermal stability
03 properties. Group II metal salts of phosphorodithioic acids
04 have been described previously. See, for example, U.S.
05 Patent No. 3,390,080, columns 6 and 7, wherein these com-
06 pounds and their preparation are described generally. Suit-
07 ably, the Group II metal salts of the dihydrocarbyl
08 dithiophosphoric acid:> useful in the lubricating oil compo-
09 sition of this invention contain from about 4 to about 12
carbon atoms in each of the hydrocarbyl radicals and may be
11 the same or different and may be aromatic, alkyl or cyclo-
12 alkyl. Preferred hydrocarbyl groups are alkyl groups con-
13 taining from 4 to 8 carbon atoms and are represented by
14 butyl, isobutyl, sec.butyl, hexyl, isohexyl, octyl,
2-ethylhexyl and the like. The metals suitable for forming
16 these salts include barium, calcium, strontium, zinc and
17 cadmium, of which zinc: is preferred.
18
19 Preferably, the Group II metal salt of a dihydrocarbyl
dithiophosphoric acid has the following formula:
21
22 R2G~
P
23 R3~./ \S M1
24 2
26
27 wherein:
28 e. R2 and R3 each independently represent hydrocarbyl
29 radicals as described above, and
31 f' M1 represents a Group II metal cation as described
32 above.
33
34 The dithiophosphoric :.alt is present in the lubricating oil
compositions of this invention in an amount effective to
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1341 005
inhibit wear and oxidation of the lubricating oil. The
amount ranges from about 0.1 to about 4 percent by weight of
the total composition, preferably the salt is present in an
amount ranging from about: 0.2 to about 2.5 percent by weight
of the total lubricating oil composition. The final lubri-
cating oil composition will ordinarily contain 0.025 to
0.25% by weight phosphorus and preferably 0.05 to 0.15% by
weight.
Viscosity index (VI) improvers are either non-dispersant or
dispersant VI impravers. Nondispersant VI improvers are
typically hydrocart~yl po7.ymers including copolymers and
terpolymers. Typically hydrocarbyl copolymers are
copolymers of ethylene and propylene. Such nondispersant VI
improvers are disclosed i.n U.S. Patents Nos. 2,700,633;
2,726,231; 2,792,288; 2,933,480; 3,000,866; 3,063,973; and
3,093,621.
Dispersant VI impro~vers c;an be prepared by functionalizing
nondispersant VI im~provens. For example, nondispersant
hydrocarbyl copolymer anal terpolymer VI improvers can be
functionalized to ~~roduce~ aminated oxidized VI improvers
having dispersant ~~ropert:ies and a number average molecular
weight of from 1,500 to 20,000. Such functionalized
dispersant VI impro~vers are disclosed in U.S. Patents
Nos. 3,864,268; 3,769,21E>; 3,326,804 and 3,316,177.
Other dispersant VI improvers include amine-grafted acrylic
polymers and copolymers wherein one monomer contains at
least one amino group. 7eypical compositions are described
in British Patent rlo. 1,488,382; and U.S. Patents
AI
1341005
Nos. 4,089,794 and 4,025,452.
Nondispersant and dispersant VI improvers are generally
employed at from ~~ to 20 percent by weight in the
lubricating oil composil~ion.
Lubricai:ing Oil Compositions
The alkylphenyl poly(oxyalkylene) aminocarbamates of this
invention are useful as dispersant additives when employed
in lubricating oils. When employed in this manner, the
additive is usually present in from 0.2 to 10 percent by
weight to the total composition, preferably at about 0.5 to
8 percent by weight and more preferably at about 1 to 6
percent by weight. The lubricating oil used with the
additive compositions oil this invention may be mineral oil
or synthetic oils of lubricating viscosity and preferably
suitable for use in the crankcase of an internal combustion
engine. Crankcases lubricating oils ordinarily have a
viscosity of about. 1300 CSt 0°F to 22.7 CSt at 210°F
(99°C).
The lubricating oils may be derived from synthetic or
natural sources. Mineral oil for use as the base oil in
this invention includes paraffinic, naphthenic and other
oils that are ordinaril~t used in lubricating oil composi-
tions. Synthetic oils :include both hydrocarbon synthetic
oils and synthetic: esters. Useful synthetic hydrocarbon
oils include liquid pol~tmers of alpha olefins having the
proper viscosity. Especially useful are the hydrogenated
liquid oligomers of C6 ito C12 alpha olefins such as 1-decene
trimer. Likewise, alkyl benzenes of proper viscosity such
as didodecyl benzene, can be used. Useful synthetic esters
include the estera of both monocarboxylic acid and
36
xi
~a ;~
1341005
O1 polycarboxylic acids as well as monohydroxy alkanols and
02 polyols. Typical examples are didodecyl adipate,
03 pentaerythritol tetracaproate, di-2-ethylhexyl adipate,
04 dilaurylsebacate and the like. Complex esters prepared from
05 mixtures of mono and dicarboxylic acid and mono and
06 dihydroxy alkanols can also be used.
07
08 Blends of hydrocarbon oils with synthetic oils are also
09 useful. For example, blends of 10 to 25 weight percent
hydrogenated 1-decene trimer with 75 to 90 weight percent
11 150 SUS (100°F) mineral oil gives an excellent lubricating
12 oil base.
13
14 Additive concentrates are also included within the scope of
this invention. The concentrates of this invention usually
16 include from about 90 to 50 weight percent of an oil of
17 lubricating visc~~sity and from about 10 to 50 weight percent
18 of the additive of this invention. Typically, the concen-
19 trates contain s~.~fficient diluent to make them easy to
:20 handle during shipping and storage. Suitable diluents for
21 the concentrates include any inert diluent, preferably an
:22 oil of lubricating viscosity, so that the concentrate may be
23 readily mixed with lubricating oils to prepare lubricating
:24 oil compositions. Suitable lubricating oils which can be
:25 used as diluents typically have viscosities in the range
:26 from about 35 to about 500 Saybolt Universal Seconds (SUS)
:27 at 100°F (38°C), although an oil of lubricating viscosity
:28 may be used.
:29
30 Other additives iahich may be present in the formulation
31 include rust inhibitors, foam inhibitors, corrosion
32 inhibitors, metal deactivators, pour point depressants,
33 antioxidants, and a variety of other well-known additives.
34
-37-
1 341 00~
O1 Fuel Compositions
02
'03 The alkylphenyl poly(oxyalkylene) aminocarbamates of this
invention will g~anerally be employed in a hydrocarbon
~D5 distillate fuel. The proper concentration of this additive
'06 necessary in ord~sr to achieve the desired detergency and
dispersancy varies depending upon the type of fuel employed,
the presence of ether detergents, dispersants and other
additives, etc. Generally, however, from 30 to 5,000 weight
:LO parts per million (ppm), and preferably 100 to 500 ppm and
:~1 more preferably 200 to 300 ppm of alkylphenyl poly(oxy-
:~2 alkylene) aminoc.arbamate per part of base fuel is needed to
:L3 achieve the best results. When other detergents are
present, a less amount of alkylphenyl poly(oxypropylene)
~~5 aminocarbamate may be used. For performance as a carburetor
:l6 detergent only, lower concentrations, for example 30 to 100
:L7 ppm may be preferred. Higher concentrations, i.e., 2,000 to
:l8 5,000 ppm may result in a clean-up effect on combustion
:l9 chamber deposits as well as the entire intake system.
a0
al The deposit control additive may also be formulated as a
22 concentrate, using an inert stable oleophilic organic
23 solvent boiling in the range of about 150 to 400°F. Prefer-
24 ably, an aliphatic or an aromatic hydrocarbon solvent is
25 used, such as benzene, toluene, xylene or higherboiling
:~6 aromatics or aromatic thinners. Aliphatic alcohols of about
:~7 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol,
28 n-butanol and the like, in combination with hydrocarbon
29 solvents are also suitable for use with the detergent-dis-
:30 persant additive. In the concentrate, the amount of the
:31 additive will be ordinarily at least 5 percent by weight and
:32 generally not e~s:ceed 50 percent by weight, preferably from
:33 10 to 30 weight percent.
:34
_3$_
1341005
O1 When employing certain of the alkylphenyl poly(oxyalkylene)
02 aminocarbamates of this invention, particularly those having
03 more than 1 basic nitrogen, it can be desirable to addi-
04 tionally add a demulsifier to the gasoline or diesel fuel
05 composition. These demulsifiers are generally added at from
06 1 to 15 ppm in the fuel composition. Suitable demulsifiers
07 include for instance L-1562?, a high molecular weight glycol
08 capped phenol available from Petrolite Corp., Tretolite
09 Division, St. Louis, Missouri, and OLOA 2503 available
from Chevron Chemical Company, San Francisco, California.
11
12 In gasoline fuels, other fuel additives may also be included
13 such as anti-knock agents, e.g., methylcyclopentadienyl
14 manganese tricar:bonyl, tetramethyl or tetraethyl lead,
tertbutyl methyl peroxide or other dispersants or detergents
16 such as various substituted succinimides, amines, etc. Also
17 included may be .Lead scavengers such as aryl halides, e.g.,
18 dichlorobenzene ~~r alkyl halides, e.g., ethylene dibromide.
19 Additionally, antioxidants, metal deactivators and
demulsifiers may be present.
21
22 In diesel fuels, other well-known additives can be employed
23 such as pour point depressants, flow improvers, cetane
24 improvers, etc.
26 The following ex<~mples are offered to specifically illus-
27 trate this inven~~ion. These examples and illustrations are
28 not to be construed in any way as limiting the scope of this
29 invention.
31
32
33
34
-39-
~ 34~ 005
O1 EXAMPLES
02 Example 1
03
04 Preparation of C65 to C70 Alkylphenyl
05 Poly(oxypropylene) Alcohol
06
07 To a dried 5-liter, 3-neck flask under a nitrogen atmo-
08 sphere was added 1.5 liters of dry toluene and 1125 grams
09 H-1008 (an alkyl;phenol, prepared from polybutene-24,
having a hydroxyl number of approximately 34, and a number
11 average of approximately 65-70 carbon atoms in the alkyl
12 portion of the alkylphenol. H-100? also contains approxi-
13 mately onethird (1/3) inactive compounds. H-1008 is
14 available from Amoco Petroleum Additives Company, Clayton,
Missouri). The system was warmed to approximately 60°C
16 and 5.5 grams (0.14 moles) of metallic potassium cut into
17 small pieces was slowly added with vigorous stirring. The
18 temperature of the reaction system was allowed to increase
19 during this addition and reached approximately 105°C.
After 2-1/2 hours, a:ll of the metallic potassium was
21 dissolved. The reaction system was then allowed to cool
22 to 40°C. Afterwards, 131.5 grams (about 5 equivalents per
23 equivalent of alkylphenol) of propylene oxide was added to
24 the system by an addition funnel at an addition rate slow
enough to avoid flooding of the vapor condensing system.
26 The system was then gently refluxed for 13 hours at which
27 point the temperature increased to 113°C and was held
2g there for an addition 3.5 hours. The system was then
2g cooled to 60°C and the reaction quenched by the addition
of 0.075 liter of 2N HC1 solution. The system was then
31 dried by azeotropic distillation to yield a toluene
32 solution of the crude product. The system was then
33 diluted with 1 liter of toluene.
34
-40-
1 341 005
iExample 2
Preparation of C65 to C70 Alkylphenyl
Poly( os;yprop:Ylene ) Chloroformate
The toluene solution containing the product of Example 1
above in a 5-liter, 3-neck flask under a nitrogen atmo-
sphere was cooled t:o about 5°C with stirring. While
stirring, 301 grams of a 20~ solution of phosgene in
toluene was added all at once to the reaction system. The
reaction system was allowed to warm to room temperature
and stirred gently for 2~4 hours. In order to remove
excess phosgene as well as HC1 formed during the reaction,
the system was vigorously sparged with nitrogen. After
completion of the reaction, an infrared analysis of an
aliquot revealed a stron<3 chloroformate absorption at 1785
cm 1 and no detectable alcohol absorption at 3450 cm 1.
Example 3
Preparation of C65 to C70 Alkylphenyl
Poly(oxypropylene) Ethylene Diamine Carbamate
The entire chloroformate,itoluene solution of Example 2 was
diluted with 4 liters of dry toluene. In a separate
flask, 487 grams of: ethylene diamine (8.1 moles) approxi-
mately 20 equivalents pe:r equivalent of chloroformate, Was
also diluted with ~! lite:rs of dry toluene. At room tem-
perature, these two solutions were rapidly mixed using two
variable speed Teflon gear pumps and a 10-inch KenicvNi
static mixer. After fifteen minutes, the crude reaction
mixture was strippead, diluted with 10 liters of hexane,
and washed successively once with water and three times
with a slightly ba:>ic (p1H =9) brine solution. Phase
41
i.
,.y,,~y
1341 005
O1 separation of the aqueous brine solution and the hexane
02 solution was improved by adding isopropanol as needed.
03 The hexane solution was separated, dried over anhydrous
04 sodium sulfate, filtered and stripped to afford the title
05 product as a thick orange liquid having an alkalinity
06 value of 17.7 and 0.44 weight percent basis nitrogen.
07
OS Example 4
09
Preparation of C65 to C70 Alkylphenol
11 Poly(oxypropylene) Diethylene Triamine Carbamate
12
13 In the manner described in Example 3 above, a C65 to C70
14 alkylphenyl poly(oxypropylene) chloroformate (prepared
from 1168 grams of H-1.00? alkylphenol, 0.73 moles) pre-
16 pared similarly to the' methods described in Examples 1 and
17 2 above was treated with 814 grams (7.89 moles), approxi-
18 mately 20 equivalents per equivalent of chloroformate, of
19 diethylene triamine to afford the title compound having~an
alkalinity values of 2!i.7 and 0.64 weight percent basic
21 nitrogen.
22
23 Re:Eerence Example A
24
Preparation of Tetrapropenylphenol
26
27 To a 2-liter flask, equipped with stirrer, Dean Stark
28 trap, condensor,, and :nitrogen inlet and outlet was added
29 567 grams of te~:.rapropylene, 540 grams of phenol, 72 grams
of a sulfonic a~:id ration exchange resin (polystyrene
31 crosslinked with divinylbenzene) catalyst (Amberlyst 15R
32 available from Rohm and Haas, Philadelphia, Pennsylvania).
33 The reaction mixture was heated to about 110°C for about 3
34 hours with stirring under a nitrogen atmosphere. The
-42-
1 X41 005
O1 reaction mixture was :.tripped by heating under vacuum and
02 the resulting product filtered hot over diatomaceous earth
03 to afford 626 grams of: tetrapropenylphenol and with a
04 hydroxyl number of 205 and with 96~ paraalkylphenol
05 content.
06
07 Reference alkylphenyl poly(oxyalkylene) aminocarbamates
08 were prepared from the' tetrapropenyl alkylphenol of
09 Reference Example A in a manner similar to Examples 1-4
above. Reference Examples B through D found in Table I
11 below summarizes the different tetrapropenylphenyl
12 poly(oxyalkylene) aminocarbamates so prepared.
13
14 TABLE I
16 COMPOUNDS OF THE FORMULA
:17
:18 R1 0
~19 R3 f OCH2CH~nOCINH~-R2NH~pH
;2 0
21 Example R3 R1 R2 n p
22
23 B tetrapropeny:lphenyl -C2H5 -CH2CH2- 17 1
24 C tetrapropeny:lphenyl -CH3 -CH2CH2- 20 1
D tetrapropeny:lphenyl -CH3 -CH2CH2- 5 1
26 3 C65 to C70 a:lkylphenyl -CH3 -CH2CH2- 5 1
a7 4 C65 to C70 a:lkylphenyl -CH3 -CH2CH2- 5 2
;Z 8
,Z9 Example 5
31 Oil Solubility Bench Test
:32
This procedure was designed to determine the oil solubil-
33
.34 ity/compatibili~~y of different additives in a fully
formulated lubricating oil. Insofar as up to 25-30$ of a
-43-
1341 005
gasoline additive can enter into the crankcase via
"blow-by" and/or cylinder wall/piston ring "wipe down",
this is an import~~nt performance criteria.
The lubricating oi.l composition was formulated to contain:
6 percent by weight of a mono-polyisobutenyl succinimide;
20 millimoles per kilogram of a highly overbased sul-
furized calcium phenate;; 30 millimoles per kilogram of a
highly overbased :;ulfurized calcium hydrocarbyl sulfonate;
22.5 millimoles peer kilogram of a zinc dithiophosphate; 13
weight percent of a commercial nondispersant C2-C3
copolymer viscosity index improver; 5 parts per million of
a foam inhibitor in 150tJ ExxoriN'base oil to give a 10 W 40
formulated oil.
The oil solubility of the additive was determined as
follows:
To a heated solution (50 grams) of the above-described
fully formulated lubricating oil was added 50 grams of the
neat additive. The mixi:ure was then heated with constant
stirring to 170°F and maintained at that temperature for
15 minutes. Dilut.ions were then prepared according to the
desired solubility test range using fresh hot reference
oil as the diluent.. In each case, the diluted samples
were stirred to 1T0°F for 10 minutes to insure complete
mixing. The solutions were then sealed and left to cool
undisturbed for from 1-5 days typically at room tempera-
ture. Each sample was i:hen rated visually for oil
continuity.
Additives that were marginally soluble in this blend
separated as a denser secondary phase, and were clearly
visible as such without the need for centrifugation.
44
Additives which gave rise to oil incompatibility probe ~ 1
were inherently oil soluble, however, they tended to
displace what appears to be the VI improver. This
phenomenon resulted in the separation of the VI improver
which is less dense than the bulk oil forming a clear
thick upper layer. The solubility/compatibility of a
gasoline additive was thereby defined as the highest con-
centration (on a, weight basis) which did not result in the
formation of either an insoluble lower additive phase or
an insoluble upper VI improver phase.
Table II below contains compatibility data for the
hydrocarbyl poly(oxyaT_kylene) aminocarbamate. Oil
compatibility is repoi:ted as weight percent of additive in
the lubricating oil composition.
manr.~ r r
Example Oil Compatibility (Wt %)
3 50
4 50
B 15
C 7
D 11
The above data demonstrates that the additives of the
instant invention pos:~ess improved oil compatibility over
prior art compounds.
-45-
