Note: Descriptions are shown in the official language in which they were submitted.
1341 p45
O1 LUBRI(:ATING OIL COMPOSITIONS AND
02 FUEh COMPOSITIONS CONTAINING
SUHSTANTI:ALLY STRAIGHT CHAIN PINWHEEL
03 ALKYLPHENYL fOLY(OXYPROPYLENE) AMINOCARBAMATES
04 BACF:GROUND OF THE INVENTION
05
06 field of the Invention
07
08 Numerous deposit-foaming substances are inherent in
9 hydrocarbon fuels. These substances when used in internal
combustion engines tend to form deposits on and around
11 Constricted areas of: the engine contacted by the fuel.
12 Typical areas commonly and sometimes seriously burdened by
13 the formation of deposits include carburetor ports, the
14 throttle body and ve~nturies, engine intake valves, etc.
16 Deposits adversely affect the operation of the vehicle. For
17 example, deposits on. the carburetor throttle body and
18 venturies increase the fuel to air ratio of the gas mixture
19 to the combustion chamber thereby increasing the amount of
unburned hydrocarbon and carbon monoxide discharged from the
21 Chamber. The high fuel-air ratio also reduces the gas
22 mileage obtainable from the vehicle.
23
24 Deposits on the engine intake valves when they get
sufficiently heavy, on the other hand, restrict the gas
26 mixture flow into the combustion chamber. This restriction,
27 starves the en~~ine of air and fuel and results in a loss of
28 power. Deposits on the valves also increase the probability
29 of valve failure due to burning and improper valve seating.
In addition, these deposits may break off and enter the
31 combustion chamber possibly resulting in mechanical damage
32 to the piston, piston rings, engine head, etc.
33
34
1 341 p4 5
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
05 performance and longevity. There are numerous
06 detergent-type gasoline additives currently available which,
p7 to varying degrees, perform these functions.
08
Og Three factors complicate the use of such detergent-type
gasoline additives. First, with regard to automobile
11 engines that require the use of nonleaded gasolines (to
12 prevent disablement of catalytic converters used to reduce
13 emissions), it has been found difficult to provide gasoline
14 of high enough octane to prevent knocking and the
concomitant damage which it causes. The chief problem lies
16 in the area of the degree of octane requirement increase,
1~ herein called "ORI", which is caused by deposits formed by
lg 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 :Eor a prolonged period, will reach an
26 equilibrium. '.Chis is apparently caused by an amount of
2~ deposits in thE~ combustion chamber. Equilibrium is
2g typically rea died after 5,000 to 15,000 miles of automobile
2g operation.
31 The octane requirement increase in particular engines used
32 with commercial gasolines will vary at equilibrium from 5 to
33
34
-2-
1341 045
O1 6 octane units to as high as 12 or 15 units, depending upon
02 the gasoline compositions, engine design and type of op-
03 eration. The seriousness of the.problem is thus apparent.
04 A typical automobile with a research octane requirement of
05 85, when new, may after a few months of operation require 97
06 research octane gasoline for proper operation, and little
07 unleaded gasoline of that octane is available. The ORI
08 problem also exists in some degree with engines operated on
09 leaded fuels. U.S. Patent Nos. 3,144,311; 3,146,203; and
4,247,301 disclose lead-containing fuel compositions having
11 reduced ORI properties.
12
13 The ORI problem is compounded by the fact that the most
14 common method for increasing the octane rating of unleaded
gasoline is to increase its aromatic content. This,
16 however, eventually causes an even greater increase in the
17 octane requirement. Moreover, some of presently used
18 nitrogen-containing compounds used as deposit-control
19 additives and their mineral oil or polymer carriers may also
significantly contribute to ORI in engines using unleaded
21 fuels.
22
23 It is, therefore, particularly desirable to provide deposit
24 control additives which effectively control the deposits in
intake systems of engines, without themselves eventually
26 contributing t~~ the problem.
27
28 In this regard, hydrocarbyl poly(oxyalkylene) amino-
29 carbamates are commercially successful fuel additives which
control combustion chamber deposits thus minimizing ORI.
31
32
33
34
-3-
1341 p45
O1 A second complicating factor relates to the low temperature
02 properties of fuel and lubricating oil additives. Since it
03 is not unusual for :solutions of these additives to be
04 subjected to cold temperature extremes, it is important that
05 solids (such as waxes) are not formed during handling,
06 storage, or in actual field use. When formed, these waxy
07 constituents can totally plug the in-line filtering devices
pg normally in service in additive distribution systems and the
p9 fuel or lube system:. of actual operating engines. Such a
plugging would obviously be catastrophic and must be
11 avoided.
12
13 A third complicating factor relates to the lubricating oil
14 compatibility of t:he~ fuel additive. Fuel additives, due to
their higher boili:ng~ point over gasoline itself, tend to
16 accumulate on surfaces in the combustion chamber of the
17 engine. This accumulation of the additive eventually finds
lg its way into the lubricating oil in the crankcase of the
lg engine via a "blow-b~y" process and/or via cylinder
wall/piston ring "wipe down". In some cases, as much as
21 25%-30% of the non-volatile fuel components, i.e., including
22 fuel additives, will eventually accumulate in the
23 lubricating oil. Insofar as the recommended drain interval
24 for some engines may be as much as 7,500 miles or more, such
fuel additives can accumulate during this interval to
26 substantial quantities in the lubricating oil. In the case
2~ where the fuel additive is not sufficiently lubricating oil
28 compatible, the accumulation of such an oil-incompatible
2g fuel additive :may actually contribute to crankcase deposits
as measured by a Sequence VD test.
31
32
33
34
-4-
1341 p4~
O1 The incompatibility of certain fuel additives in lubricating
02 oils, i.e., oils which contain other additives, arises in
03 spite of the fact that some fuel additives are also known to
04 be lubricating oil dispersants. However, even if employed
05 in a fully formulated lubricating oil as a dispersant rather
06 than as a fuel additive, the incompatibility of these
0'7 dispersants with other additives in the lubricating oil will
08 result in increased crankcase deposits as measured by a
O9 Sequence V-D engine test.
11 Several theories exist as to the cause of the lubricating
12 oil incompatibility of certain fuel/lubricating oil
13 additives. Without being limited to any theory, it is
14 possible that some of these additives when found in the
lubricating oil interfere with other additives contained in
16 the lubricating oil and either counterbalance the
17 effectiveness of these additives or actually cause disso-
18 lution of one or more of these additives. in either case,
1g the incompatibility of the additive with other additives in
the lubricating oil demonstrates itself in less than
21 desirable crankcase deposits as measured by Sequence VD
22 engine tests.
23
24 In another theory, when used as a fuel additive, it is
Possible that the accumulation of the additive into the
26 lubricating oil during the drain interval period surpasses
27 its maximum solubility in the lubricating oil. In this
2g theory, this excess amount of additive is insoluble in the
2g lubricating oi.l and is what causes increased crankcase
deposits.
31
32
33
34
-5-
1 341 04 5
O1 In still another thE~ory, it is possible that the additive
02 will decompose in the lubricating oil during engine
03 operation and the decomposition products are what cause
04 increased crankcase deposits.
05
06 In any case, lubricating oil incompatible additives are less
07 than desirable insofar as their use during engine operation
08 will result in increased deposits in the crankcase. This
09 problem can be cata:ctrophic.
11 It is recognized that hydrocarbyl poly(oxybutylene)
12 aminocarbamates are substantially more expensive than the
13 hydrocarbyl poly(oxypropylene) aminocarbamates. This is
14 because butylene oxide is much more expensive than propylene
oxide. Currently, the price for butylene oxide (BO) is more
16 than four times the price of propylene oxide (PO) on a pound
17 for pound basis. However, because heretofore no known
18 hydrocarbyl poly(oxypropylene) aminocarbamate was found to
19 be sufficiently lubricating oil compatible and non-waxy, it
was necessary to employ the more expensive hydrocarbyl
21 poly(oxybutylene) aminocarbamates which are sufficiently
22 lubricating oil compatible. Accordingly, it would be
23 particularly advantageous to develop hydrocarbyl
24 poly(oxypropylene) aminocarbamates which are compatible in
lubricating oil compositions and are non-waxy at -40°C.
26
27 The instant invention is directed to lubricating oil
28 compositions a:nd fuel compositions containing a novel class
29 of hydrocarbyl poly(axypropylene) aminocarbamates. As a
fuel additive, these novel hydrocarbyl poly(oxyalkylene)
31 aminocarbamates control combustion chamber deposits thus
32 minimizing ORI and in lubricating oil are compatible with
33
34
-6-
1341045
O1 the lubricating oil composition. As a lubricating oil
02 additive, these novel hydrocarbyl poly(oxyalkylene)
03 aminocarbamates provide dispersancy without possessing
04 lubricating oil incompatibility. Significantly, the novel
05 additives of this invention are also liquids which do not
06 form a wax at -40°C in a 50 weight percent solution with
07 toluene.
08
09 Relevant Art
11 Numerous references disclose hydrocarbyl poly(oxyalkylene)
12 aminocarbamates as fuel additives. These include the
13 following U.S. Patent Nos.:
14
4,160,648; 4,243,798; 4,521,610; and
16 4,191,537; 4,270,930; 4,568,358
17 4,197,409; 4,274,837;
18 4,236,020; 4,288,612;
19
Of particular relevance is U.S. Patent No. 4,274,837 which
21 discloses that hydrocarbyl poly(oxyalkylene) aminocarba-
22 mates containing certain poly(oxyalkylene) chains, i.e.,
23 oxypropylene, 'when used in fuels employed in combination
24 with certain lubricating oils, produce crankcase varnish.
This reference further discloses that lubricating oil
26 compatible hydrocarbyl poly(oxypropylene) aminocarbamates
27 are improved b:y employing the poly(oxypropylene) as a
28 copolymer also containing 1 to 5 branched C9 to C30
29 oxyalkylene units.
31 U.S. Patent No. 4,160,648 discloses an intake system
32 deposit control additive for fuels which is a hydrocarbyl
33
34
_7_
1341 045
O1 poly(oxyalkylene) aminocarbamate wherein the hydrocarbyl
02 is from 1 to 30 carbon atoms including alkyl or
03 alkylphenyl groups. Specifically disclosed hydrocarbyl
04 groups include tetrapropenylphenyl, olelyl and a mixture
05 of C16. C18 and C20 alkyl groups. Likewise, U.S. Patent
06 No. 4,288,612 discloses deposit control additives for
07 gasoline engines which are hydrocarbyl poly(oxyalkylene)
08 aminocarbamates wherein the hydrocarbyl group contains
O9 from 1 to about 30 carbon atoms including alkylphenyl
groups wherein the alkyl group is straight or branched
11 chain of from 1 to about 24 carbon atoms. U.S. Patent No.
12 4,568,358 discloses diesel fuel compositions containing an
13 additive such as a hydrocarbyl poly(oxyalkylene)
14 aminocarbamate. This reference discloses hydrocarbyl
groups such as alkyl groups of 1 to 30 carbon atoms; aryl
16 groups of 6 to 30 carbon atoms, alkaryl groups of 7 to 30
1'7 carbon atoms, etc.
18
19 U.S. Patent No. 4,332,595 discloses hydrocarbyl
poly(oxyalkyle:ne) polyamines wherein the hydrocarbyl group
21 is a hydrocarb:yl radical of 8 to 18 carbon atoms derived
22 from linear primary alcohols.
23
24 U.S. Patent Noes. 4,233,168 and 4,329,240 among others
disclose lubri~~ating oil compositions containing a
26 dispersant amount of a hydrocarbyl poly(oxyalkylene)
2~ aminocarbamate.
28
2g While these prior art references disclose fuel
compositions containing C1 to C30 hydrocarbyl poly(oxy-
31 alkylene) aminc~carbamates which include poly(oxypropylene)
32 polymers, none of these references disclose the unique
33
34
_g_
1341045, _ .
hydrocarbyl group of this invention nor do any of these
references suggest that use of this unique hydrocarbyl group
would overcome the art recognized problem of lubricating oil
incompatibility arising from using the prior art hydrocarbyl
poly(oxypropylene) aminocarbamates, and especially the problem
of low temperature wax formation.
SLfMI!~iARY OF THH INVHNTION
The present invention provides a liquid alkylphenyl
poly(oxypropylene) aminocarbamate which does not form a wax when
cooled to -40°C in a 50 weight percent solution with toluene,
said aminocarbamate having at least one basic nitrogen and an
average molecular weight: of about 600 to 6,000 and wherein the
alkyl group of said alkylphenyl poly(oxypropylene)
aminocarbamate is a sub:~tantially straight-chain alkyl group of
from about 30 to 95 carbon atoms derived from a substantially
straight-chain al~~ha olefin oligomer of C8 to C20 alpha olefins,
and further wherein the alkyl group is attached to the phenyl
group at least 6 carbon atoms from the terminus of the longest
chain of the alkyl group.
In a composit:Lon aspect, the instant invention is
directed toward a fuel composition containing a novel class of
hydrocarbyl poly(c~xypropylene) aminocarbamates which as a fuel
additive controls combustion chamber deposits thus minimizing
ORI and in lubrics~ting oal is compatible with the lubricating
oil composition. In particular, the instant invention is
directed toward a fuel <:omposition comprising a hydrocarbon
boiling in the ga~~oline or diesel range and from about 30 to
9
C
1341045
about 5,000 parts per million of the alkylphenyl
poly(oxypropylene) aminocarbamate of the present invention.
9a
1 3 41 04 5
O1 In another composition aspect, the instant invention is
02 directed to a i:uel concentrate comprising an inert stable
03 oleophilic organic solvent boiling in the range of 150° to
04 400°F and from 5 to 50 weight percent of an alkylphenyl
05 poly(oxypropyle~ne) arninocarbamate of this invention.
06
In still another composition aspect, the instant invention
08 is directed to a lubricating oil composition comprising an
O9 oil of lubricating viscosity and a dispersant effective
amount of an alkylphernyl poly(oxypropylene) aminocarbamate
11 of this invention.
12
13 In still another composition aspect, the instant invention
14 is directed to a lubricating oil concentrate comprising
from about 90 to 50 weight percent of an oil of
16 lubricating viscosity and from about 10 to 50 weight
1~ percent of an alkylphenyl poly(oxypropylene)
18 aminocarbamate ~~f this invention.
19
The present invention also relates to the novel alkyl-
21 phenol compound; which are employed to prepare the instant
22 alkylphenyl poly(oxypropylene) aminocarbamates. These
23 novel alkylphenol intermediate compounds are alkylphenols
24 wherein the alk~rl group is a substantially straight-chain
alkyl group of i:rom albout 25 to 50 Carbon atoms and is
26 attached to the pheno:L ring at least 6 carbon atoms from
2~ the terminus of the longest chain of the alkyl group.
28 Preferably, the alkyl group on the alkylphenol will
29 contain from about 28 to 50 carbon atoms, and more
preferably, from about= 30 to 45 carbon atoms. Moreover,
31 the alkyl substituent is preferably derived from a
32 substantially straight. chain alpha olefin oligomer of C8
33 to C20 alpha olefins.
34
-10-
1341 045
O1 Among other factors, the present invention is based on the
02 discovery that t:he "p:inwheel" alklphenyl
03 poly(oxypropylene) am:inocarbamates of the present
04 invention having a substantially straight chain alkyl
05 substituent do not produce wax when cooled to -40°C in a
06 50 wt% solution of toluene. These non-waxy carbamates do
07 not produce any traces of crystalline wax under these
0$ conditions.
09
It is critical that these aminocarbamates are non-waxy at
11 low temperature:. Fuel additives and lubricating oil
12 additives must all be able to be pumped, for example, into
13 fuels, and to operate effectively under cold conditions in
14 such locations as Alaska or Wisconsin in the wintertime.
Even very small amounts of wax, e.g., milligrams, will
16 plug the micron--sized filters that these additives
17 commonly come in contact with. For example, there are
lg micron-sized fiT.ters in the additive distribution and
19 blending system;> whiclh make additive packages and blends
prior to the consumer's purchase. There are also
21 micron-sized fi7Lters in automobiles and diesel engines
22 where the fuel 'Ls filtered prior to combustion.
23
24 DETAI1~ED DESCRIPTION OF TIDE INVENTION
26 The alkylphenyl poly(oxypropylene) aminocarbamates of the
27 present invention consist of an amino moiety and an
28 alkylphenyl pol~t(oxypropylene) polymer bonded through a
29 carbamate linkage, i.e., -OC(O)N<. The specific
alkylphenyl group employed in the instant invention in the
31 alkylphenyl pol~l(oxypropylene) polymer is critical to
32 achieving lubricating oil compatibility for the
33
34
-11-
1341 p45
O1 alkylphenyl pol~~(oxypropylene) aminocarbamates, while
02 providing excellent low temperature properties. In
03 particular, it has been found that employing the
04 "pinwheel" alky:lphenyl group of this invention wherein the
05 alkyl group is o~ubstantially straight-chain of from 25 to
06 50 carbon atoms results in an alkylphenyl
07 poly(oxypropylene) aminocarbamate which is lubricating oil
08 compatible and non-waxy at low temperatures.
09
As used herein, the abbreviation "PO" is meant to
11 designate propylene oxide or propylene oxide-derived
12 polymers. Simi:Larly, the abbreviation "BO" is meant to
13 designate butylene oxide or butylene oxide-derived
14 polymers. Also, the term "EDA" is meant to designate
ethylene diamine or ethylene diamine-derived carbamates.
16 Further, the team "DETA" is meant to designate diethylene
17 triamine or dieithylene triamine-derived carbamates.
18
19 The term "alpha olefin" or "simple alpha olefin" as used
herein refers generally to 1-olefins, wherein the double
21 bond is at the 'terminal position of an alkyl chain. Alpha
22 olefins are almost always mixtures of isomers and often
23 also mixtures o:E compounds with a range of carbon numbers.
24 Low molecular weight alpha olefins, such as the C6, C8,
C10, C12 and C1~~ alpha olefins, are almost exclusively
26 1-olefins. Higher molecular weight olefin cuts such as
27 C16-18' or C20-:Z4 have increasing proportions of the
28 double bond isomerized to an internal or vinylidene
29 position; nonetheless these higher molecular weight cuts
are also called alpha olefins herein.
31
32
33
34
-12-
O1 The term "alpha olefin oligomer(s)" (A00), as used herein
02 means olefin diners, trimers, tetramers and pentamers
03 prepared or derived from C8 to C20 alpha olefins. These
04 A00's have a pinwheel-type structure consisting of
05 primarily internal disubstituted and trisubstituted
06 olefins. The o:Lefin double bond of these A00's is
p7 generally located at least n-2 carbon atoms from the end
pg of the longest continuous carbon chain, where n is the
Og number of carbon atoms in the starting alpha olefin.
11 The Alkyl Substituent
12
13 The alkyl subst:ituent of the alkyphenyl moiety of the
14 present alkylph~~nyl poly(oxpropylene) carbamates is a
substantially sitraight-chain alkyl group having from about
16 25 to 50 carbon atoms. The term "substantially
17 straight-chain" is meant to designate an alkyl group
18 wherein greater than about 80 number percent of the
lg individual carbon atoms in the alkyl substituent are
either primary (CH3-) or secondary (,-CH2-) carbon atoms.
21 Preferably, greeter than 85 number percent of the carbon
22 atoms in the alltyl substituent are primary or secondary
23 carbons.
24
The alkyl substituent in the alkylphenyl poly-
26 (oxypropylene) ;~minocarbamates of the present invention is
2~ arranged in what will herein be designated as a "pinwheel"
28 configuration. This configuration has been found to be
2g critical to providing aminocarbamates having non-waxy low
temperature characteristics.
31
32
33
34
-13-
1341045
O1 By "pinwheel" configuration is meant that the alkyl group
02 is attached, for example to an aromatic ring, at a
03 position significantly removed from the terminus of the
04 longest chain oi: the alkyl group. This results in at
05 least two hydrocarbon tails, or wheels of the pinwheel,
06 emanating from near tlae attachment point. By
07 "significantly removed from the terminus" is meant at
08 least 6 carbon atoms from the terminus of the longest
09 chain of the alb;yl group, preferably at least 8 carbon
atoms toward the' center of the chain. Thus a "pinwheel"
11 alkyl phenol has an alkyl group comprising at least two
12 tails of at least six carbon atoms in length, preferably
13 at least 8 carbon atoms in length.
14
Preferred "pinwheel" compounds useful in this invention
16 are those wherep_n the alkyl substituent has tails which
17 are substantial~Ly straight-chain hydrocarbon radicals.
18
19 As will be discussed in more detail below, the alkylphenyl
substituent of i~he aminocarbamate of this invention is
21 derived from thE~ corresponding alkyl. phenol. A preferred
22 type of alkylphE~nol is that prepared by alkylating phenol
23 with one or mores alpha olefin oligomers. Alkylation with
24 alpha olefin ol'lgomers, such as decene trimer or octene
tetramer, provides alkylphenols having "pinwheel"
26 configurations. Such configurations can be represented by
27 structure A as <~n exa:mple of decene trimer-derived
28 alkylphenol and structure B as an example of octene
29 tetramer-derived alkylphenol, as shawn below. In these
structures, the brackets are intended to denote the
31 various manners of attachment of the alkyl group to the
32 phenol.
33
34
-14-
134~p45
of
02 HO
03
04
05
06
07
08
09 H0
11
12
B
13
14
16 The alpha olefin oligomers used herein are prepared by
17 methods well-kn~~wn in the art. One preferred method of
18 preparing these oligomers is using BF3 as the
19 oligomerization catalyst, as described, for example, in
U~S. Patent Nos. 4,238,343 and 4,045,507, and in
21 Onopchenko, et al., BF3-Catalyzed Oligomerization of
22 Alkenes (Structures, Mechanisms and Properties). 183rd
23 ACS Natl. Meet. (Las Vegas, Mar. 1982). Ind. Eng. Chem.,
24 Prod. Res. Dev., 22(2), 182-91 (June 1983).
26
27
28
29
,
31
32
33
34
-15-
1 34 ~ ~4 5 ~:. .
O1 These alpha olei:in ol:igomers are 75% or more di or
02 trisubstituted zit the olefin site. ~'or example, an alpha
03 olefin trimer hz~s a structure that can be represented by:
04
05
06 R R R
U7
08
09
11 wherein: R = n-2, and n is the carbon number of
12 the starting alpha olefin.
13
14
Alpha olefin ol:igomers are substantially straight-chain with
16 respect to the number of branched (i..e., tertiary or
17 quarternary) carbons as a percent of the total number of
18 carbon atoms. 'that is, greater than 80 percent of the
19 carbon atoms in the molecule are primary or secondary
carbons, prefer~~bly greater than 85 percent.
21
22 Substantially straight-chain alkyl groups are exemplified in
23 Table A below:
24
26
27
28
29
31
32
33
34
-16-
~34~ 045
M
1a
l~ ',?~ (~
'(~," N '~f
N ft5 G ~D O M
U E~ O
1-a ..i V
N ~ V
LL W V1
t~
~J W N O N
O ,~ M M
H ~
N
cp ~ M d'
»
a
0
0
1
w ,-~ E ~
w x -- o r
C~1 a ~' ~ O N N ~Q', O
..Ca 1
H x o
a
.~ U
U ~
x
U ~ U ~r ~t,'
x
a4 _ s~ N .-~ ?~
O rcS P4
a ~ o it
a~ ~ a o
~ +~ G4 _ .~ .~ sa
-.-~ U .-1 pa r--1 rtf fly
'b .t~
(a 1.a U! N 1~"
1.J .IJ L1a _~ ~.~ ~r-1 O rt3
p ~ Ri. U
x rx a~ a
°a O % O ~ Q a ~ ~ts
N ,~ \ O O .~ O
rx w x x 3 x 3
O ~ 11 eW
,,
cu a~ a a~
v .~.~ c~ o w H ao
tr, o a it cu a~ a
.,o~ ~ ~ ~ ~ iu s~ v ~ a n ~C ~s
a u.i p?~., a ~ Ga ~ O ~ FC CO
its v O .1.~ O O -.a N
JJ r-i 1-r ~ CJ M f.-~ M ~ '-1 N M
U1 O C~ E~ v U H U E-~ ~.- _. ...
13~,~Q45_
01 Preferred alpha olefin oligomers (A00's) are derived from Ca
02 to C2~ alpha olefins, more preferably, C1~ to C16 alpha
03 olefins. Preferred AOO's are dimers, trimers, tetramers and
04 pentamers. Prei_erabl:y, the alkyl group of the instant
05 carbamates is derived from alpha olefin oligomers selected
06 from the group consisting of: Ca tetramers, C1~ trimers, C12
0'7 trimers, C14 dirners a:nd trimers, C16 dimers and trimers, Cla
Og dimers and C2~ dimers.
As described above, t:he alkyl substituent of the present
11 alkylphenyl pol~t(oxypropylene) aminocarbamates is arranged
12 in a so-called "pinwheel" configuration. This "pinwheel"
13 configuration is readily distinguishable from alkyl groups
14 wherein the hyd~_ocarbon chains are attached at or near the
terminus of the longest chain of the alkyl group, i.e.,
16 within l to 5 c<~rbon atoms of a terminus. Thus,
1~ aminocarbamates prepared from simple alpha olefins, (as
lg compared to alpha olefin oligomers) as well as their
19 precursors, including the phenols and the alkylphenyl
poly(oxypropylene) alcohols, have alkyl groups in a
21 "terminal" configuration. Compounds having an alkyl group
22 in a terminal configuration are herein designated "terminal
23 compounds", for example, C20-24 terminal alkyl phenols and
24 terminal alkyl ~~arbamates.
26 In terminal compounds such as terminal alkyl phenols, there
2~ is only 1 main chain emanating from near the attachment
2g point of the alkyl group to the phenol. Terminal compounds
2g include those prepared by reacting alpha olefins with phenol
under typical acidic reaction conditions.
31
32
33
34
-la-
1341 045-_
O1 The Preferred Alkyphenyl Group
02
03 The preferred a_~Lkylph~enyl group of the alkylphenyl
04 poly(oxypropylene) aminocarbamate employed in this invention
05 is derived from the corresponding al.kylphenol of Formula I
06 below:
07
08 OH
09 I
11
12 m
13 wherein R is a substantially straight-chain alkyl group of
14 from about 25 to 50 carbon atoms and m is an integer from
1 to 2.
16
17 Preferably, R is a substantially straight-chain alkyl
18 group of from 28 to 50 carbon atoms. More preferably, R
19 is a substantia:Lly straight-chain alkyl group of from 30
to 45 carbon atoms.
21
22 yJhen m is one, i~he alkylphenyl is a monoalkylphenyl;
23 whereas when m :is two, the alkylphenyl is a dialkylphenyl.
24
The alkylphenols of Formula I above are prepared by
26 reacting the appropriate olefin or olefin mixture with
27 phenol in the p~:esence of an alkylating catalyst at a
28 temperature of :From about 60°C to 2U0°C, and preferably
29 125°C to 180°C Either neat or in an essentially inert
solvent at atmospheric pressure. A preferred alkylating
31 catalyst is a sulfonic acid catalyst such as Amberlyst 15R
32 available from l~ohm and Haas, Philadelphia, Pennsylvania.
33
34
-19-
1341 045
O1 Molar ratios of reactants can be employed. When molar
02 ratios are employed, t:he reaction yields a mixture of
03 dialkylphenol, n~onoal~;ylphenol and unreacted phenol. As
04 noted above, dia~lkylphenol and monoalkylphenol can be used
05 to prepare the additives used in the compositions of this
06 invention whereas the unreacted phenol is preferably
removed from then post reaction mixture via conventional
Og techniques. Alt:ernat:ively, molar excess of phenol can be
Og employed, i.e., 2 to 2.5 equivalents of phenol for each
equivalent of olefin with unreacted phenol recycled. The
11 latter process maximi;~es monoalkylphenol. Examples of
12 inert solvents include benzene, toluene, chlorobenzene and
13 250 thinner which is a mixture of aromatics, paraffins and
14 naphthenes.
16 The preferred a7~kylph~enyl group is derived from a pinwheel
1~ phenol. Pinwheel phenols may be prepared from alpha
lg olefin oligomer:~.
19
Useful A00 derived alkylphenols have average molecular
21 weights in the :range of 480 to 790, and average alkyl
22 carbon numbers ranging from 25 to 50, and preferably from
23 28 to 50. More preferred average alkyl carbon numbers are
24 in the range of from 30 to 45.
26 Alternative metlhods of preparing the alkylphenol compounds
2~ used herein are also contemplated. "Pinwheel" alkyl
2g phenols can be synthesized by any number of methods.
2g These methods typically rely upon either preforming the
entire alkyl moiety prior to alkylation of the phenol or
31 subsequently elaborating a preformed alkyphenol wherein
32 the alkyl group has the requisite functionality for
33
34
-20-
1 341 ~4 5
O1 further development to a pinwheel alkyl phenol. Thus, one
02 could alkylate phenol with either a pinwheel olefin or a
03 corresponding a:Lcohol, or alkyl halide, such as a chloride
04 or bromide.
05
06 The exact struci:ure of the final alkyl phenol is difficult
07 to predict with certainty. Alkylations using carbonium
p8 ions result in rearrangements during carbonium ion
O9 formation and reaction. It is also known that the
products of such alkylation schemes can also suffer
11 rearrangements, dealkylations, and realkylations under
12 reaction conditions. Thus, a variety of structures are
13 included in the present invention.
14
Particularly prc~ferre~d monoalkylphenols employed in this
16 invention are either ortho-monoalkyl.phenols of Formula II
17 below:
18
19 ~H
R II
21 0
22
23 or para-monoalkylphenols of Formula III below:
24 OH
I III
26
27
28
R
29
Particularly preferred dialkylphenols employed in this ,
31 invention are generally 2,4-dialkylphenols of Formula IV
32 below:
33
34
-21-
1341045
O1 OH
02 , ~ R
03 O IV
04
05
06 R
07 although there rnay be minor amounts of 2,6-dialkylphenol of
~8 Formula V below.:
09 OH
R. R V
11
12
13 PrefE~rred Poly(oxypropylene) Component
14
The alkylphenyl poly(~oxypropylene) polymers which are
16 utilized in preparing the carbamates of the present
17 invention are monohydroxy compounds, i.e., alcohols, often
18 termed alkylphenyl "capped" poly(oxypropylene) glycols and
19 are to be distinguished from the poly(oxypropylene)
glycols (diols),, which are not alkylphenyl terminated,
21 i.e., not capped. The alkylphenyl poly(oxypropylene)
22 alcohols are produced by the addition of propylene oxide
23 to the alkylphenol of Formula I, i.e.,
24
OH
26
I
27
2g Rm
29 under polymerization conditions, wherein R and m are as
defined above. In general, the poly(oxypropylene) poly-
31 mers will vary :in chain length but their properties
32 closely approximate those of the polymer represented by
33
34
-22-
1341045
the average composition and molecular weight. Each poly-
(oxypropylene) polymer contains at least 1 oxypropylene
unit, preferably from 1 to about.100 oxypropylene units,
more preferably from about 5 to about 50 oxypropylene
units, and most preferably from about 10 to about 25 oxy-
pcopylene units. Method's of production and properties of
these polymers are disclosed in U.S. Patent Nos. 2,841,479
and 2,782,240,
as well as Kirk-Othmer's~ "Encyclopedia of Chemical
Technology", Volume 19, p. 507. An alternative method for
preparing alkylphenyl poly(oxypropylene) polymers having
either 1, 2, or 3 oxypropylene units involves employing a
compound of Formula VI below
CH3
C:l ( CH2CH0 ) qH VI
wherein q is an integer from 1 to 3. When employing the
~'0 compound of Formula VI, the phenoxide of the alkylphenol, I,
is first prepared and then reacted with the compound of
Formula VI to yield the desired alkylphenyl poly(oxypro-
pylene) polymer having from 1 to 3 oxypropylene units.
Compounds of Formula VI are commercially available or can be
prepared by art recognized methods.
Preferred Amine Component
The amine moiety of the alkylphenyl poly(oxypropylene)
v0 aminocarbamate employed, in this invention is preferably
derived from a polyamine having from 2 to about 12 amine
nitrogen atoms and from 2 to about 40 carbon atoms.. The
-23-
,. ,
1341 p45
O1 polyamine is preferably reacted with an alkylphenyl
02 poly(oxypropylene) chloroformate to produce the alkylphenyl
03 poly(oxypropylene) aminocarbamate additives finding use
04 within the scope of the present invention. The
05 chloroformate is itself derived from alkylphenyl
06 poly(oxypropylene) alcohol by reaction with phosgene. The
07 polyamine, encompassing diamines, provides the product
08 alkylphenyl poly(oxypropylene) aminocarbamate with, on
09 average, at least about one basic nitrogen atom per car-
bamate molecule, i.e., a nitrogen atom titratable by a
11 strong acid. The polyamine preferably has a
12 carbon-tonitrogen ratio of from about 1:1 to about 10:1.
13
14 The polyamine ma.y be substituted with substituents selected
from (A) hydrogen, (B:! hydrocarbyl groups of from 1 to about
16 10 carbon atoms, (C) acyl groups of from 2 to about 10
17 carbon atoms, and (D) monoketo, monohydroxy, mononitro,
18 monocyano, lower alkyl and lower alkoxy derivatives of (B)
19 and (C). "Lower", as used in terms like lower alkyl or
lower alkoxy, means a group containing from 1 to about 6
21 carbon atoms. ~~t least one of the substituents on one of
22 the basic nitrogen atoms of the polyamine is hydrogen, e.g.,
23 at least one of.the basic nitrogen atoms of the polyamine is
24 a primary ar sec:ondary amino nitrogen atom.
26 Hydrocarbyl, as used in describing all the components of
27 this invention, denotes an organic radical composed of
28 carbon and hydr~~gen which may be aliphatic, alicyclic,
29 aromatic or combinations thereof, e.g., aralkyl. Prefer-
ably, the hydrocarbyl group will be relatively free of
31 aliphatic unsaturation, i.e., ethylene and acetylenic,
32 particularly acetylenic unsaturation. The substituted
33
34
-24-
1 341 0.4 5 _
Ol polyamines of the present invention are generally, but not
02 necessarily, N-substituted polyamines. Exemplary hydro-
03 carbyl groups anal substituted hydrocarbyl groups include
04 alkyls such as methyl,, ethyl, propyl, butyl, isobutyl,
05 pentyl, hexyl, octyl, etc., alkenyls such as propenyl,
06 isobutenyl, hexe~nyl, octenyl, etc., hydroxyalkyls, such as
07 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl,
08 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl,
09 6-ketooctyl, etc., allcoxy and lower alkenoxy alkyls, such as
ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl,
11 2-(2ethoxyethox~~)ethy:L, 2-(2-(2-ethoxyethoxy)ethoxy)ethyl,
12 3,6,9,12-tetrao}:atetradecyl, 2-(2-ethoxyethoxy)hexyl, etc.
13 The acyl groups of t:he aforementioned (C) substituents are
14 such as propion5il, acetyl, etc. The more preferred
substituents are' hydrogen, Cl-C4 alkyls and Cl-C4
16 hydroxyalkyls.
17
18 In a substituted polyamine the substituents are found at any
19 atom capable of receiving them. The substituted atoms,
e.g., substituted nitrogen atoms, are generally geometric-
21 ally inequivalent, and consequently the substituted amines
22 finding use in 'the present invention can be mixtures of
23 mono- and polysubstituted polyamines with substituent groups
24 situated at equivalent and/or inequivalent atoms.
26 The more preferred polyamine finding use within the scope of
27 the present invention is a polyalkylene polyamine, including
28 alkylene diamine, and including substituted polyamines,
2g e.g., alkyl and hydroxyalkyl-substituted polyalkylene poly-
amine. Preferably, the alkylene group contains from 2 to 6
31 carbon atoms, there being preferably from 2 to 3 carbon
32 atoms between the nitrogen atoms. Such groups are
33
34
-25-
~34~ 045
exemplified by ethylene, 1.,2-propylene
2,2-dimethyl-propylene trimethylene, 1,3,2-hydroxypropylene,
etc. Examples of such polyamines include ethylene diamine,
diethylene triamine, di(trimethylene)triamine, dipropylene
triamine, triethylene tetramine, tripropylene tetramine,
tetraethylene pentamine, pentaethylene hexamine, butylene
diamine and pentylene dis~mine. Such amines encompass isomers
such as branched-chain palyamines and the previously mentioned
substituted polyamines, including hydroxy- and hydrocarbyl-
substituted polyamines. Among the polyalkylene polyamines,
those containing 2-12 amine nitrogen atoms and 2-24 carbon atoms
are especially preferred, and the C2-C3 alkylene polyamines are
most preferred, in particular, the lower polyalkylene
polyamines, e.g., ethylene diamine, diethylene triamine,
propylene diamine, dipropylene triamine, etc.
The amine component of the alkylphenyl
poly(oxypropylene) aminocarbamate also may be derived from
heterocyclic polyamines, heterocyclic substituted amines and
substituted heterocyclic compounds, wherein the heterocycle
comprises one or mare 5-E> membered rings containing oxygen
and/or nitrogen. ~~uch heterocycles may be saturated or
unsaturated and substituted with groups selected from the
aforementioned (A), (B) (C) and (D). The heterocycles are
exemplified by pips~razlnE?s, such as 2-methylpiperazine,
N-(2-hydroxyethyl)yiperazine, l,2bis-(N-piperazinyl)-ethane,
and N,N'bis(N-piperaziny7L)piperazine, 2-methylimadazoline, 3-
aminopiperidine, 2-aminopyridlne,2-(3-aminoethyl)3-pyrroline, 3-
26
1341045
aminopyrrolidine, N-(3-aminopropyl)morpholine, etc. Among the
heterocyclic compounds, the piperazines are preferred.
26a
1341 045
Another class of .suitable polyamines are diaminoethers
represented by Formula VII
H2WX1fOX2~rNH2 VII
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 Formu la VII are disclosed in U.S. Patent
No. 4,521,610.
Typical polyamine:a that can be used to form the compounds
of this invention by reaction with a
poly(oxyalkylene)chloroformate include the following:
ethylene diamine, 1,2-propylene diamine, 1,3-propylene
diamine, diethylen~e triamine, triethylene tetramine,
hexamethylene diamine, tetraethylene pentamine, dimethyl-
aminopropylene di,amine, N-(beta-aminoethyl)-piperazine,
N-(beta-aminoethy.l)piperidine, 3-amino-N-ethylpiperidine,
N-(beta-aminoethyl)morpholine, N,N'-di(beta-aminoethyl)-
piperazine, N,N'-~~i(beta-aminoethylimidazolidone-2;
N-(beta-cyano-eth;yl)ethane-1,2-diamine,
1-amino-3,6,9-triazaoctadecane,
1-amino-3,6-diaza-9-oxadecane, N-(beta-aimonoethyl)di-
ethanol-amine,
N'-acetyl-N-methyl-N-(beta-aminoethyl)ethane-1,2-diamine,
N-acetonyl-1,2-propanediamine, N-(beta-nitro-
ethyl)-1,3-propane diam,ine, 1,3-dimethyl-5(beta-amino-
ethyl)hexahydrotriazine, N-(beta-aminoethyl)hexahydrotri-
azine, 5-lbeta-aminoethyl)-1,3,5-dioxazine,
2-(2-aminoethylamino)-ethanol,
2[2-(2-aminoethylamino)ethylamino)-ethanol.
-27-
tA,
~ ~ 41 04 5
O1 The amine component oi: the alkylphenyl poly(oxypropylene)
02 aminocarbamate may alao be derived from an
03 amine-containing compound which is capable of reacting
04 with an alkylphenyl poly(oxypropylene) alcohol to produce
05 an alkylphenyl ~~oly(oxypropylene) aminocarbamate having at
06 least one basic nitrogen atom. For example, a substituted
07 aminoisocyanate, such as (R)2NCH2CH2NC0, wherein R is, for
08 example, a hydrocarby7l group, reacts with the alcohol to
09 produce the aminocarbamate additive finding use within the
scope of the present :invention. Typical aminoisocyanates
11 that may be used to form the fuel additive compounds of
12 this invention by reaction with a hydrocarbylpoly(oxy-
13 alkylene) alcohol include the following: N,N-(di-
14 methyl)aminoisocyanatoethane, generally, N,N-(dihydrocar-
byl)aminoisocyanatoallcane, more generally, N-(perhydrocar-
16 byl)-isocyanato~>ol-olyalkylene polyamine,
17 N,N-(dimethyl)aminoisocyanatobenzene, etc.
18
19 In many instances the amine used as a reactant in the
production of the carbamate of the present invention is
21 not a single compound but a mixture in which one or
22 several compounds, predominate with the average compo-
23 sition indicated. For example, tetraethylene pentamine
24 prepared by the polymerization of aziridine or the reac-
tion of dichloroethylene and ammonia will have both lower
26 and higher amine members, e.g., triethylene tetramine,
27 substituted pipE~razines and pentaethylene hexamine, but
28 the composition will. Ibe mainly tetraethylene pentamine and
29 the empirical formula of the total amine composition will
closely approxirnate t'.hat of tetraethylene pentamine.
31 Finally, in preparing the compounds of this invention,
32 where the various nitrogen atoms of the polyamine are not
33
34
-28-
1 3 41 04 5
O1 geometrically equivalent, several substitutional isomers
02 are possible and are encompassed within the final product.
03 Methods of preparation of amines, isocyanates and their
04 reactions are detailed in Sidgewick's "The Organic
05 Chemistry of Nitrogen", Clarendon Press, Oxford, 1966;
06 Nollers' "Chemistry of. Organic Compounds", Saunders,
p7 Philadelphia, 2nd Ed. 1957; and Kirk-Othmer's
pg "Encyclopedia of Chemical Technology", 2nd Ed., especially
p9 Volume 2, pp. 99-16.
11 Prei=erred Alkylphenyl
Polyy ox ropylene) Aminocarbamate
12
13 Having described the preferred alkylphenyl
14 poly(oxypropylene) component and the preferred polyamine
component, the preferred alkylphenyl poly(oxypropylene)
16 aminocarbamate additive of the present invention is
17 obtained by linking these components together through a
18 carbamate linkage i.e.,
19
O
II
21 -OCN<
22
23 wherein the ethErr oxygen may be regarded as the terminal
24 hydroxyl oxygen of the alkylphenyl poly(oxypropylene)
alcohol component, and the carbonyl group -C(0)- is pre-
26 ferably provided by tlhe coupling agent, e.g., phosgene.
27
28 The alkylphenyl poly(~oxypropylene) aminocarbamate employed
29 in the present :W vention has at least one basic nitrogen
atom per molecu:Le. A "basic nitrogen atom" is one that is
31 titratable by a strong acid, e.g., a primary, secondary,
32
33
34
-29-
1 341 X14 5
or tertiary amino nitrogen., as distinguished from, for example,
an amido nitrogen, i.e.,
O
-CN< ,
'which is not so titratable. Preferably, the basic nitrogen is
in a primary or secondary amino group.
The preferred alkylphenyl poly(oxypropylene)
aminocarbamate has an average molecular weight of from about 600
to 6,000; preferably an average molecular weight of from 800 to
3,000= and most preferably an average molecular weight of from
1,000 to 2,500.
A preferred class of alkylphenyl poly(oxypropylene)
,3minocarbamate can be described by the following general
Eormula~
CH 0
3
O'~O~CH2CH0 n C'NH-(R1NH) -H
P
R
m
wherein R is a substantially straight-chain alkyl group of from
,about 30 to 45 carbon atoms derived from a substantially
;straight-chain alpha olefin oligomer of C8 to C20 alpha olefins
~3nd R is attached to the phenyl ring at least 6 atoms from the
'terminus of the longest chain of said group R; R1 is alkylene of
2 to 6 carbon atoms; m is an integer from 1 to 2; n is an
integer such that the molecular weight of the compound is from
about 600 to 6,000= and p is an integer from 1 to about 6; and
wherein said compound does not form a wax when cooled to -40oC
in a 50 weight percent solution with toluene.
C
1341045
Ci4 Hydro hilic-Lipophilic Balance
C~ 5
C~6 It is important that the relatively hydrophilic propylene
(~7 oxide polymeric back-bone be balanced by the hydrophobic
(fig alkyl carbons of the alkyl phenol. The aminocarbamates of
(19 this invention must achieve a good hydrophilic-lipophilic
~.p balance (HLB) in order to have sufficient hydrocarbon
~.1 solubility in oil and therefore to not perform
~.2 detrimentally with regard to crankcase varnish.
1. 3
~.4 For good lubricant solubility, It has been found that the
~-5 ratio of the number of carbon atoms in the alkyl group
~_( needs to be about twice the number of propylene oxide
~_7 units. For example, if: the average number of propylene
~~g oxide units is n, then the alkyl chain attached to the
~~g phenoxy radical should have approximately 2n carbon atoms;
;p preferably, between 2n--4 and 2n+4 carbon atoms; most
preferably between 2n and 2n+4 carbon atoms.
:? 2
Preparation of the Alkylphenyl
~~3 Poly(oxypropylene) Aminocarbamate
:? 4
%5 The additives employed in this invention can be most
conveniently prepared by first reacting the appropriate
alkylphenyl poly(oxypropylene) alcohol with phosgene to
a7
produce an alkylphenyl poly(oxypropylene) chloroformate.
a8
The chloroformate~ is then reacted with the polyamine to
:Z 9
.3~ produce the desired allcylphenyl poly(oxypropylene)
aminocarbamate.
:31
:32
:33
:34
-31-
~341p45-
Preparation of aminocarbamates are disclosed in U.S.
Patent Nos. 4,160,648; 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 re~actiorl of the poly(oxypropylene)
compound and phosgene i;s usually carried out on an
essentially equimolar basis, although excess phosgene can
be used to improves the degree of reaction. The reaction
may be carried oui: a temperatures from -10° to 100°C,
1.0 preferably in the range of 0° to 50°C. The reaction will
usually be compleite within 1/4 to 5 hours. Times of reac-
tion will usually be in the range of from 2 to 4 hours.
A solvent may be Bused 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° to 200°C may be utilized, the
a0 desired product may be obtained by water wash and
stripping usually be the aid of vacuum, of any. residual
solvent.
The mole ratio of polyamine to polyether chloroformate
will generally be in tire range from about 2 to 20 moles of
polyamine per mole of c;hloroformate, and more usually 5 to
15 moles of polya.mine per mole of chloroformate. Since
suppression of polysubstitution of the polyamino is
usually desired, large molar excesses of the polyamine
30 will be used. Additionally, the preferred adduct is the ,
monocarbamate compound,, as opposed to the bis(carbamate)
oc disubstituted aminoether.
-32-
C
1341 04 5
O1 The reaction or reactions may be conducted with or without
02 the presence of a reaction solvent. A reaction solvent is
03 generally employed whenever necessary to reduce the
04 viscosity of the reaction product. These solvents should
05 be stable and inert to the reactants and reaction product.
06 Depending on the temperature of the reaction, the
07 particular chloroformate used, the mole ratios, as well as
p8 the reactant concentrations, the reaction time may vary
pg from less than 1. minui~e to 3 hours.
11 After the reaction ha;s been carried out for a sufficient
12 length of time, the reaction mixture may be subjected to
13 extraction with a hydrocarbon-water or
14 hydro-carbon-alcohol-water medium to free the product from
any low-molecular-weight amine salts which have formed and
16 any unreacted d:~amine. The product may then be isolated
1'7 by evaporation of the solvent. Further purification may
lg be effected by column chromatography on silica gel.
19
Depending on the particular application of the composition
21 of this inventi~~n, the reaction may be carried out in the
22 medium in which it will ultimately find use, e.g.,
23 polyether carriers or an oleophilic organic solvent or
24 mixtures thereof and be formed at concentrations which
provide a concentrate of a detergent composition. Thus,
26 the final mixture may be in a form to be used directly for
2~ blending in fuels.
28
2g An alternative proce:;s for preparing the alkylphenyl
poly(oxypropylene) aminocarbamates employed in this
31 invention involves the use of an arylcarbonate
32
33
34
-33-
1341045
intermediate. That is to~ say, the alkylphenyl poly(oxy-
propylene) 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-chlorophenyl chloro-
formate, 2,4-dichlorophesnyl chloroformate, and
p-trifluoromethylphenyl chloroformate. Use of the aryl
carbonate intermedliate allows for conversion to amino-
carbamates containing close to the theoretical basic
nitrogen while em~~loyinc~ less excess of polyamine, i.e.,
molar ratios of ge~neral:ly from 1:1 to about 5:1 of
polyamine to the e~rylcarbonate, and additionally avoids
the generation of hydrogen chloride in the reaction
forming the aminoc:arbamate. Preparation of hydrocarbyl
capped poly(oxyal):ylene) aminocarbamates via an
arylcarbonate intE~rmedi~ate have been previously disclosed.
2, 0
As will be appreciated by those skilled in the art, the
aminocarbamates o:E this invention are mixtures of many
individual compounds.
The alkyl group will typically have a variety of carbon
numbers since the starting olefins are not generally pure
compounds and, for any given carbon number in the alkyl
group, there are many structural isomers. Moreover, mono-
:l0 and dialkyl phenols are generally obtained. Also, the .,
number of propylene oxide units is an average number and
different molecules will have a somewhat different number
of PO units.
-34-
S
1341 045
Also included within the scope of this invention are fully
formulated lubricating oils containing a dispersant
effective amount o,E an alkylphenyl poly(oxyalkylene) amino
carbamate.
Contained in the fully formulated composition is:
1. an alkenyl succinimide,
2. a Group ii metal salt of a dihydrocarbyl
dithiophosphoric acid,
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
alkylated phenate or mixtures thereof.
5. A viscosity index (V'I) improver.
The alkenyl succinimide is present to act as a dispersant and
prevent formation of deposits formed during operation of the
engine. The alkenyl suc:cinimides are well-known in the art.
The alkenyl succinimides~ are the reaction,product of a
2.0 polyolefin polymer-substituted succinic anhydride with an
amine, preferably a polyalkylene polyamine. The polyolefin
polymersubstitutedl succi~nic anhydrides are obtained by
reaction of a polyolefin polymer or a derivative thereof with
maleic anhydride. The succinic anhydride thus obtained is
reacted with the amine compound. The preparation of the
alkenyl succinimides has been described many times in the
art. See, for example, U.S. Patent Nos. 3,390,082;
3,219,666; and 3,1.72,89:2.
Reduction of the alkenyl
';0 substituted succinic anhydride yields the corresponding alkyl
derivative. The <:lkyl succinimides are intended to be
included within the scope of the term "alkenyl succinimide".
_35_
,Au
1341 045
O1 A product comprising predominantly mono or bis-succinimide
02 can be prepared by controlling the molar ratios of the
03 reactants. Thu:;, for example, if one mole of amine is
04 reacted with one mole of the alkenyl or alkyl substituted
05 succinic anhydride, a predominantly mono-succinimide product
06 will be prepared. If two moles of the succinic anhydride are
p7 reacted per mole of polyamine, a bis-succinimide will be
Og prepared.
09
Particularly good results are obtained with the lubricating
11 oil composition:; of this invention when the alkenyl
12 succinimide is a poly:isobutene-substituted succinic anhydride
13 of a polyalkylene polyamine.
14
The polyisobutene from which the polyisobutene-substituted
16 succinic anhydride is obtained by polymerizing isobutene can
17 vary widely in i.ts compositions. The average number of
lg carbon atoms can ran ge from 30 or less to 250 or more, with
19 a resulting number average molecular weight of about 400 or
less to 3,000 or more. Preferably, the average number of
21 carbon atoms per. pol.yisobutene molecule will range from
22 about 50 to about 100 with the polyisobutenes having a
23 number average molecular weight of about 600 to about 1,500.
24 More preferably,, the .average number of carbon atoms per
polyisobutene molecule ranges from about 60 to about 90, and
26 the number average molecular weight ranges from about 800 to
27 1,300. The pol~tisobutene is reacted with malefic anhydride
28 according to well-known procedures to yield the
2g polyisobutene-substituted succinic anhydride.
w
31 In preparing the alkenyl succinimide, the substituted
32 succinic anhydride is reacted with a polyalkylene polyamine
33
34
-36-
1341045
O1 to yield the corresponding succinimide. Each alkylene
02 radical of the ~olyal~;ylene polyamine usually has up to
03 about 8 carbon atoms. The number.of alkylene radicals can
04 range up to about 8. The alkylene radical is exemplified by
05 ethylene, propylene, butylene, trimethylene, tetramethylene,
06 pentamethylene, hexamethylene, octamethylene, etc. The
07 number of amino groups generally, but not necessarily, is
08 one greater than the number of alkylene radicals present in
09 the amine, i.e., if a polyalkylene polyamine contains 3
alkylene radicals, it will usually contain 4 amino radicals.
11 The number of amino r<~dicals can range up to about 9.
12 Preferably, the alkylc~ne radical contains from about 2 to
13 about 4 carbon atoms and all amine groups are primary or
14 secondary. In this c<~se, the number of amine groups exceeds
the number of al.kylene groups by 1. Preferably the
16 polyalkylene pol.yamine contains from 3 to 5 amine groups.
17 Specific examples of 'the polyalkylene polyamines include
18 ethylenediamine, dietlhylenetriamine, triethylenetetramine,
19 propylenediamine~, tri~propylenetetramine,
tetraethylenepentamin~e, trimethylenediamine,
21 pentaethylenehe~~amirie, di-(trimethylene)triamine,
22 tri(hexamethylene)tetramine, etc.
23
24 Other amines su:ltable for preparing the alkenyl succinimide
useful in this :invention include the cyclic amines such as
26 piperazine, morpholine and dipiperazines.
27
28
29
31
32
33
34
-37-
1341045
O1 Preferably the alkenyl. succinimides used in the compositions
02 of this invention have' the following formula:
03
04
05 R CH
~''NfAlkyleneN~ H
06 ~H2--~~ I n
~0 A
07
08
O9 wherein:
11 a. R1 represents an <~lkenyl group, preferably a substan-
12 tially saturated hydrocarbon prepared by polymerizing
13 aliphatic monoolefins. Preferably R1 is prepared from
14 isobutene and has an average number of carbon atoms and a
number average mo:Lecular weight as described above;
16
17 b, the "Alkylene" radical represents a substantially
18 hydrocarbyl group containing up to about 8 carbon atoms
lg and preferably containing from about 2-4 carbon atoms as
described hE~reinabove;
21
22 c. A represent:> a hydrocarbyl group, an amine-substituted
23 hydrocarbyl group, or hydrogen. The hydrocarbyl group
24 and the amine-substituted hydrocarbyl groups are
generally the alkyl and amino-substituted alkyl analogs
26 of the alkyT~.ene radicals described above. Preferably A
27 represents hydrag~en;
28
2g d. n represents an integer of from about 1 to 10, and
preferably i=rom about 3-5.
31
32
33
34
-38-
1341045
Also, included within the term "alkenyl succinimide" are the
modified succinmid~es 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 alkaline earth metal hydrocarbyl sulfonates
may be either petroleum sulfonate, synthetically alkylated
aromatic sulfonate~s, or aliphatic sulfonates such as those
derived from polyi.sobutylene. One of the more important
~;p functions of the .~ulfonates is to act as a detergent and
dispersant. Theses sulfonates are well-known in the art.
The hydrocarbyl group must have a sufficient number of
carbon atoms to reender the sulfonate molecule oil soluble.
Preferably, the h~rdrocarbyl portion has at least 20 carbon
atoms and may be aroma tic or aliphatic, but is usually
alkylaromatic. Most p referred for use are calcium,
magnesium or barium sulfonates which are aromatic in
character.
:30 Certain sulfonate;s are typically prepared by sulfonating a
petroleum fraction having aromatic groups, usually mono- or
dialkylbenzene groups, and then forming the metal salt of
-39-
1341045
O1 the sulfonic acid material. Other feedstocks used for
02 preparing these sulfonates include synthetically alkylated
03 benzenes and aliphatic: hydrocarbons prepared by polymerizing
04 a mono or diolefin, for example, a polyisobutenyl group
05 prepared by polymerizing :isobutene. The metallic salts are
06 formed directly or by metathesis using well-known
07 procedures.
08
09 The sulfonates may be neutral or overbased having base
numbers up to at~out 400 or more. Carbon dioxide and calcium
11 hydroxide or oxide are' the most commonly used material to
12 produce the basic or overbased sulfonates. Mixtures of
13 neutral and overbased sulfonates may be used. The sulfo-
14 nates are ordin~~rily used so as to provide from 0.3% to 10%
by weight of the tot.a:l composition. Preferably, the neutral
16 sulfonates are present from 0.4% to 5% by weight of the
17 total composition and the overbased sulfonates are present
lg from 0.3% to 3% by weight of the total composition.
19
The phenates for' use in this invention are those
21 conventional products which are the alkali or alkaline earth
22 metal salts of alkylated phenols. One of the functions of
23 the phenates is to act as a detergent and dispersant. Among
24 other things, iii prevents the deposition of contaminants
formed during high temperature operation of the engine. The
26 phenols may be mono or polyalkylated.
27
28 The alkyl portion of the alkyl phenate is present to lend
29 oil solubility 'to the phenate. The alkyl portion can be
obtained from n;~turally occurring or synthetic sources.
31 Naturally occurring sources include petroleum hydrocarbons
32 such as white oil and wax. Being derived from petroleum,
33
34
-40-
1 341 p4 5
O1 the hydrocarbon rnoiety is a mixture of different hydrocarbyl
02 groups, the specific composition of which depends upon the
03 particular oil si;.ock which was used as a starting material.
04 Suitable synthetic sources include various commercially
05 available alkene;s and alkane derivatives which, when reacted
06 with the phenol, yield an alkylphenol. Suitable radicals
07 obtained include butyl, hexyl, octyl, decyl, dodecyl,
O8 hexadecyl, eicosyl, tricontyl, and the like. Other suitable
pg synthetic sources of the alkyl radical include olefin
polymers such as polypropylene, polybutylene,
11 polyisobutylene and the like.
12
13 The alkyl group can beg straight-chained or branch-chained,
14 saturated or unsaturated (if unsaturated, preferably
containing not more than 2 and generally not more than 1
16 site of olefinic unsat:uration). The alkyl radicals will
17 generally contain from 4 to 30 carbon atoms. Generally when
lg the phenol is monoalkyl-substituted, the alkyl radical
19 should contain at least 8 carbon atoms. The phenate may be
sulfurized if desired. It may be either neutral or
21 overbased and ii. over!based will have a base number of up to
22 200 to 300 or more. Mixtures of neutral and overbased
23 phenates may be used.
24
The phenates ar~~ ordinarily present in the oil to provide
26 from 0.2% to 27's by weight of the total composition.
27 Preferably, the neutral phenates are present from 0.2% to 9%
2g by weight of the total composition and the overbased
2g phenates are present from 0.2 to 13% by weight of the total
composition. Most preferably, the overbased phenates are
31 present from 0.2% to 5% by weight of the total composition.
32 Preferred metals are calcium, magnesium, strontium or
33 barium.
34
-41-
1341 p45
O1 The sulfurized alkaline earth metal alkyl phenates are
02 preferred. The~;e salts are obtained by a variety of
03 processes such as treating the neutralization product of an
04 alkaline earth metal base and an alkylphenol with sulfur.
05 Conveniently the sulfur, in elemental form, is added to the
06 neutralization product and reacted at elevated temperatures
07 to produce the :~ulfur:ized alkaline earth metal alkyl
p8 phenate.
09
If more alkaline' eartlh metal base were added during the
11 neutralization reaction than was necessary to neutralize the
12 phenol, a basic sulfurized alkaline earth metal alkyl
13 phenate is obtaLned. See, for example, the process of
14 Walker et al, U,.S. Patent No. 2,680,096. Additional
basicity can be obtained by adding carbon dioxide to the
16 basic sulfurized alkaline earth metal alkyl phenate. The
17 excess alkaline earth metal base can be added subsequent to
18 the sulfurization step but is conveniently added at the same
19 time as the alkaline earth metal base is added to neutralize
the phenol.
21
22 Carbon dioxide ~~nd calcium hydroxide or oxide are the most
23 commonly used material to produce the basic or "overbased"
24 phenates. A pr~~cess wherein basic sulfurized alkaline earth
metal alkylphen~ates are produced by adding carbon dioxide is
26 shown in Hannem~an, U.S. Patent No. 3,178,368.
27
28 The Group II metal salts of dihydrocarbyl dithiophosphoric
2g acids exhibit wear, antioxidant and thermal stability
properties. Group II metal salts of phosphorodithioic acids ,
31 have been described previously. See, for example, U.S.
32 Patent No. 3,390,080, columns 6 and 7, wherein these
33
34
-42-
1341045
Ol compounds and their preparation are described generally.
02 Suitably, the Group II metal salts of the dihydrocarbyl
03 dithiophosphoric: acids useful in.the lubricating oil
04 composition of this invention contain from about 4 to about
05 12 carbon atoms in each of the hydrocarbyl radicals and may
06 be the same or c~iffer~ent and may be aromatic, alkyl or
07 cycloalkyl. Preferred hydrocarbyl groups are alkyl groups
OS containing from 4 to ~B carbon atoms and are represented by
Og butyl, isobutyl,, sec.-butyl, hexyl, isohexyl, octyl,
2-ethylhexyl and the like. The metals suitable for forming
11 these salts incT.ude barium, calcium, strontium, zinc and
12 cadmium, of which zinc is preferred.
13
14 Preferably, the Group II metal salt of a dihydrocarbyl
dithiophosphoric: acid has the following formula:
16
17 R2 ~ ~S
18 P
19 /
R30/ ~ M1
2
21
22
23 wherein:
24
e' R2 and R3 each independently represent hydrocarbyl
radicals as described above, and
26
27
28 f. M1 represen~:.s a Group II metal cation as described
above.
2 9w
31 The dithiophosphoric salt is present in the lubricating oil
32 compositions of this invention in an amount effective to
33
34
-43-
1341 045
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
lubricating oil composition will ordinarily contain 0.025 to
0.25% by weight phosphorus and preferably 0.05 to 0.15% by
weight.
~,p Viscosity index (~~I? im;provers are either non-dispersant or
dispersant VI improvers. Non-dispersant VI improvers are
typically hydrocarbyl polymers including copolymers and
terpolymers. Typically hydrocarbyl copolymers are
copolymers of ethylene and propylene. Such non-dispersant
VI improvers are disclosed in 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.
a0 Dispersant VI improvers can be prepared by functionalizing
non-dispersant VI improwers. For example, non-dispersant
hydrocarbyl copolymer and terpolymer VI improvers can be
functionalized to produce aminated oxidized VI improvers
having dispersant properrties and a number average molecular
weight of from 1,500 to 20,000. Such functionalized
dispersant VI improvers are disclosed in U.S. Patents Nos.
3,864,268; 3,769,216; :!,326,804 and 3,316,177.
Other dispersant VI improvers include amine-grafted acrylic
polymers and copolymers wherein one monomer contains at
-44-
1341045
least one amino group. Typical compositions are described
in British Patent No. 1"488,382; and U.S. Patents Nos.
4,89,794 and 4,025,452.
Non-dispersant an<i dispersant VI improvers are generally
employed at from !i to 20 percent by weight in the
lubricating oil composition.
:l 0
Fuel Compositions
The alkylphenyl poly(oxypropylene) aminocarbamates of this
invention will generally be employed in a hydrocarbon
distillate fuel. The proper concentration of this additive
necessary in order to achieve the desired detergency and
dispersancy varies depending upon the type of fuel employed,
the presence of other detergents, dispersants and other
additives, etc. Generally, however, from 30 to 5,000 weight
?.p parts per million (ppm), and preferably 100 to 500 ppm and
more preferably 200 to 300 ppm of alkylphenyl
poly(oxypropylene) aminocarbamate per part of base fuel is
needed to achieves the best results. when other detergents
are present, a less amount of alkylphenyl poly(oxypropylene)
aminocarbamate may be used. For performance as a carburetor
detergent only, lower concentrations, for example 30 to
70 ppm may be prE:ferred. Higher concentrations, f.e., 2,000
to 5,000 ppm may result in a clean-up effect on combustion
chamber deposits..
The deposit control additive may also be formulated as a
concentrate, using an inert stable oleophilic organic
-45-
A
134104
O1 solvent boiling in the range of about 150 to 400°F.
02 Preferably, an aliphatic or an aromatic hydrocarbon solvent
03 is used, such a:~ benzene, toluene, xylene or higher-boiling
04 aromatics or aromatic thinners. Aliphatic alcohols of about
OS 3 to 8 carbon atoms, such as isopropanol, isobutylcarbinol,
06 n-butanol and the like, in combination with hydrocarbon
07 solvents, are also suitable for use with the
08 detergent-dispersant additive. In the concentrate, the
09 amount of the additive will be ordinarily at least 5 percent
by weight and generally not exceed 50 percent by weight,
11 preferably from 10 to 30 weight percent.
12
13 When employing ~~ertain of the alkylphenyl poly(oxypropylene)
14 aminocarbamates of this invention, particularly those having
more than 1 basic nitrogen, it can be desirable to addition-
16 ally add a demulsifier to the gasoline or diesel fuel
17 composition. These demulsifiers are generally added at from
18 1 to 15 ppm in the fuel composition. Suitable demulsifiers
1g include for instance L-15628, a high molecular weight glycol
capped phenol available from Petrolite Corp., Tretolite
21 Division, St. Louis, Missouri, and OLOA 2503ZR, available
22 from Chevron Chemical Company, San Francisco, California.
23
24
26
27
28
29
31
32
33
34
-46-
- 134045
O1 In gasoline fuels, other fuel additives may also be included
02 such as antiknock agents, e.g., methylcyclopentadienyl man-
03 ganese tricarbonyl, tetramethyl or tetraethyl lead, or other
04 dispersants or detergents such as various substituted
05 succinimides, amines, etc. Also included may be lead scav-
06 engers such as aryl halides, e.g., dichlorobenzene or alkyl
07 halides, e.g., erthylene dibromide. Additionally, antioxi-
08 dants, metal deactivai;.ors and demulsifiers may be present.
09
In diesel fuels, other well-known additives can be employed
11 such as pour point depressants, flow improvers, cetane
12 improvers, etc.
13
14 Lubricating Oil Compositions
16 The alkylphenyl poly(oxypropylene) aminocarbamates of this
invention are u:~eful .as dispersant additives when employed
18 in lubricating oils. When employed in this manner, the
lg additive is usually present in from 0.2 to 10 percent by
weight to the total composition, preferably at about 0.5 to
21 8 percent by weight and more preferably at about 1 to 6
22 percent by weight. The lubricating oil used with the addi-
23 five compositions of this invention may be mineral oil or
24 synthetic oils of lubricating viscosity and preferably
suitable for use in the crankcase of an internal combustion
26 engine. Crankcase lubricating oils ordinarily have a
2~ viscosity of ab~~ut 1300 CSt 0°F to 22.7 CSt at 210°F
(99°C).
28 The lubricating oils may be derived from synthetic or
2g natural sources. Mineral oil for use as the base oil in
this invention includes paraffinic, naphthenic and other ,
31 oils that are ordinarily used in lubricating oil composi-
32 Lions. Synthetic oils include both hydrocarbon synthetic
33
34
-47-
1341 n45
O1 oils and synthetic esi~ers. Useful synthetic hydrocarbon
02 oils include liquid polymers of alpha olefins having the
03 proper viscosit~~. Especially useful are the hydrogenated
04 liquid oligomer:~ of Ci~ to C12 alpha olefins such as 1-decene
05 trimer. Likewi:>e, alltyl benzenes of proper viscosity such
06 as didodecyl benzene, can be used. Useful synthetic esters
07 include the esters of both monocarboxylic acid and polycarb-
0g oxylic acids as well ;as monohydroxy alkanols and polyols.
O9 Typical examples are didodecyl adipate, pentaerythritol
tetracaproate, cii-2-ethylhexyl adipate, dilaurylsebacate and
11 the like. Comp:Lex esters prepared from mixtures of mono and
12 dicarboxylic acid and mono and dihydroxy alkanols can also
13 be used.
14
Blends of hydro~~arbon oils with synthetic oils are also
16 useful. For ex~~mple, blends of 10 to 25 weight percent
17 hydrogenated 1-decene trimer with 75 to 90 weight percent
lg 150 SUS (100°F) mineral oil gives an excellent lubricating
1g oil base.
21 Additive concentrates are also included within the scope of
22 this invention. The concentrates of this invention usually
23 include from about 90 to 50 weight percent of an oil of
24 lubricating viscosity and from about 10 to 50 weight percent
of the additive of this invention. Typically, the concen-
26 trates contain sufficient diluent to make them easy to
27 handle during shipping and storage. Suitable diluents for
2g the concentrates include any inert diluent, preferably an
2g oil of lubricating viscosity, so that the concentrate may be
readily mixed with lubricating oils to prepare lubricating
31 oil compositions. Suitable lubricating oils which can be
32 used as diluents typically have viscosities in the range
33
34
-48-
1341045
from about 35 to about 500 Saybolt Universal Seconds (SUS)
at 100°F (38°C), although an oil of lubricating viscosity
may be used.
Other additives which may be present in the formulation
include rust inhibitors, foam inhibitors, corrosion
inhibitors, metal deactivators, pour point depressants,
antioxidants, and a variety of other well-known additives.
;~0 The following examples ace offered to specifically illus-
trate this invention. These examples and illustrations are
not to be construed in any way as limiting the scope of this
invention.
EXAMPLES
Example A
20 Preparation of Alpha-Olefin Oligomers (C14-Derived)
Using a Sulfonic Acid Catalyst
This example shows alpha-olefin oligomers useful in this
invention. Into a dry 500-ml, three-necked round bottom
flask, equipped with a heating mantle, a mechanical stirrer,
and a condenser were charged 200 grams of C14 alpha olefin
(Chevron Chemical. Co., San Francisco) and 10 grams of an
experimental alunnina-supported fluorosulfonic acid catalyst
30 (DOW XUS'~40036.0'1), available from Dow Chemical Company. .
These ingredient~a were heated and stirred under nitrogen for
25 hrs. at 185°C. At this time, the dark reaction mixture
Trade mark -4
fA
f 341 p4 5
O1 was stripped of any residual C14 impurities by heating under
02 vacuum, filtered. The product was analyzed by SFC, thus
03 revealing a 95/5 ratio of olefin dimer to trimer. This
04 product was used for phenol alkylation without further
05 purification. This product could not be induced to
06 crystallize at very low temperatures, and as such was
07 regarded as wax free.
08
p9 Example B
Preparation of Alpha-Olefin Oligomers
11 (~~14-Derived) Using BF3
12
13 This example al:;o shows alpha-olefin oligomers useful in
14 this invention. In this example, the C14 alpha-olefin of
Example A was oligomerized using boron trifluoride gas and
16 an alcohol co-ca,talysi=, as described, for example, in U.S.
1~ Patent Nos. 4,238,343 and 4,045,507. Approximately
18 2_1/2 gallons of a clear light yellow liquid containing
19 approximately 6T% dimE~r, 25% trimer, and 8% tetramer/-
pentamer combined were' prepared. This mixture, having an
21 average molecular weight of 472, was converted to the
22 pinwheel alkyl ~~henol.without further purification. This
23 product was a nonviscous liquid at room temperature and
24 below and was, as such, regarded as wax free.
26
2~ Example C
28 Preparation of Alpha-Olefin Oligomers (C16-Derived)
29 -
31 This example shows oli.gomers useful in this invention. The
32 Procedure of Example A was followed as a C16 as a C16 alpha
33
34
-50-
1341 p45
O1 olefin. The re:~ulting product was an approximately 95/5
02 mixture of dimers to trimers. This product was a nonviscous
03 liquid at room i~emperature and below and was, as such,
04 regarded as wax free.
05
06 Example lA
07 Preparation ~of Pinwheel Alkyl Phenols from
08 (C1~)-Derived) Oligomers of Example B
09
Into a one-liter, three-necked flask, equipped with a
11 heating mantle, mechanical stirrer, and condenser was
12 charged 310 grams (0.66 mole) of the BF3 prepared olefin
13 oligomers of Example 1B. The liquid was heated to 85°C at
14 which time 344 crams (3.83 mole) of liquefied phenol was
added followed by 65 grams of dry Amberlist 15. The
16 reaction mixture' was 'then heated for 24 hours at 150°C at
17 which time the resin was removed by hot suction filtration.
18 Excess phenol was removed by vacuum distillation thus
19 affording 343 gms of <~ non-viscous amber colored pinwheel
alkyl phenol (313 grams; Hydroxyl no. - 105.4). This phenol
21 had an average alkyl carbon content of 36 carbon atoms.
22 This product wa:c converted to polyoxypropylene alcohol
23 without further purification. This phenol was a nonviscous
24 liquid at room temperature and became a thick oil at lower
temperature. No waxing was observed.
26
27
28
29
31
32
33
34
-51-
~341n45
O1 Example is
02 Preparation of Pinwheel Alkyl Phenols
03 from Oligomers of Example C.
04
05
06 The C16-derived olefin. oligomer of Example C was used to
07 alkylate phenol in a manner similar to that described in
08 Example lA. The resulting pinwheel alkyl phenol had an
O9 average alkyl carbon cantent of 34 carbon atoms.
11
12 Comparative Example 1C
13 Preparation of a C20-C24 Terminal Alkylphenol
14
16 To a 5-liter flask, equipped with stirrer, Dean Stark trap;
17 condensor, and nitrogen inlet and outlet was added 500 gm of
18 a substantially straight chain C20 to C24 alpha olefin
19 mixture (approximate olefin content C18 and less-1%;
C20 49%; C22-42%; C24--8%; C26 and greater-0.1%) wherein in
21 the entire olefin fraction at least 15 mole percent of said
22 olefins contain vinyli.dine groups (C20 to C24 alpha olefins
23 are available from Chevron Chemical Company, San Francisco,
24 CA), 656 grams of phenol and 75 grams of a sulfonic acid
cation exchange resin (polystyrene crosslinked with
26 divinylbenzene) catalyst (Amberlyst 15R available from Rohm
27 and Haas, Philadelphia, PA). The reaction mixture was
2g stripped by heating under vacuum and the product was
2g filtered hot over diai~omaceous earth to afford 1050 grams of
a C20 to C24 terminal alkylphenol with a hydroxyl number of
31 120 ( i . a . mg KO~:I/gm s<~mple ) and with approximate 45%
32 para-alkylphenol content. This phenol was a low melting wax
33 at room temperature.
34
-52-
134~~45
O1 Comparative Example 2A
02 Preparat:lon of a C20-C28 Terminal Alkylphenol
03
04
05 To a 2-liter flask, equipped with stirrer, Dean Stark trap,
06 condensor and np_trogen inlet and outlet was added 674 gms of
07 a substantially straight chain C20 to C28 alpha olefin
08 mixture (olefin content: C18-2%; C20-28%; C22-19%; C24-13%;
Og C26-21%; C28-11;x; and greater than C30-6%) wherein in the
entire olefin fraction at least 20 mole percent of said
11 olefins contain vinyl:idine groups (C20-C24 alpha olefins and
12 C24 C28 alpha olefins are available from Chevron Chemical
13 Company, San Francisco, CA and are then physically mixed at
14 an equal mole basis to provide a C20-C28 olefin mixture),
211.5 grams of phenol, 43 grams of a sulfonic acid cation
16 exchange resin (polysityrene crosslinked with divinylbenzene)
17 catalyst (Amberl.yst 15R available from Rohm and Haas,
18 Philadelphia, P~~). The reaction mixture was heated to about
lg 140°C for about 8 hours with stirring under a nitrogen
atmosphere. They reaction mixture was stripped by heating
21 under vacuum and the product was filtered hot over
22 diatomaceous earth to afford 574 grams of a C20-C28
23 alkylphenol with a hydroxyl number of 110 and with 56%
24 Para-alkylphenol contE~nt. This alkylphenol had
approximately 26% dia_lkyl phenol and had an average alkyl
26 carbon number of~ 29. This product was a hard wax at room
2~ temperature.
28
29
31
32
33
34
-53-
1341 p45
O1 Comparative Example 2B
02 Preparation of Low I)ialkyl C20-28 Terminal Alkyl Phenol
03
04
05 The procedure of Example 2A was used except 966 gm C20-C28
06 alpha olefins and 211..5 gm of phenol were used. The
resulting alkyl pheno:L had approximately 6% dialkyl phenol
08 and an average alkyl carbon number of 24. This product was
09 a wax at room te~mperai:ure.
11
12 Comparative Example 2C
Preparation of a C26-Average Terminal Alkyl Phenol
13
14
In a separate procedure, the low dialkyl C20-28 phenol of
16 Example 2B was realky:Lated using an additional 10% C20-C24
1~ alpha Chevron olefin (per conditions described in Example
18 1C). This reaction thus afforded an alkylphenol composed of
19 approximately lE~% dia:Lkyl phenol species. The average alkyl
carbon number ways 26. This product was a wax at room
21 temperature.
22
23 Cornparative Example 3
24 pre~parat_Lon of Tetrapropenylphenol
26
2~ To a 2-liter flask, eduipped with stirrer, Dean Stark trap,
28 condensor, and nitrogen inlet and outlet was added 567 grams
29 of tetrapropylene, 541) grams of phenol, 72 grams of a sul-
Tonic acid cation exchange resin (polystyrene crosslinked w
31 with divinylbenz;ene) catalyst (Amberlyst 15R available from
32 Rohm and Haas, F~hiladelphia, PA). The reaction mixture was
33
34
-54-
1 341 04 5
O1 heated to about 110°C for about 3 hours with stirring under
02 a nitrogen atmosphere.
03
04 The reaction mi:Kture was stripped by heating under vacuum
05 and the resulting product filtered hot over diatomaceous
06 earth to afford 626 grams of tetrapropenylphenol and with a
p7 hydroxyl number of 205 and with 96~ para-alkylphenol
08 content.
09
11 Comparative Example 4
12 Preparation of C20 to C28 Terminal Alkylphenol
13 Poly(oxypropylene) Alcohol
14
To a dried 12-liter 3-necked flask under a nitrogen atmo-
16 sphere was added 3.5 liter of toluene and 2020.5 grams (4.61
1~ moles) of a C20 to C28 terminal alkylphenol prepared in a
lg manner similar i.o Exa:mple 2A. The system was warmed to
19 approximately 60°C and 60 grams (1.54 moles) of metallic
potassium cut into small pieces was slowly added with
21 vigorous stirring. T:he temperature of the reaction system
22 was allowed to increase during this addition and reached
23 approximately 100°C. After 2-1/2 hours, all of the metallic
24 potassium was di.ssolv~ed. The reaction system was then
allowed to cool to 60°C. Afterwards, 4552 grams (78.37
26 moles) of propylene oatide was added to the system by an
2~ addition funnel at an addition rate slow enough to avoid
2s flooding of the vapor condensing system. The system was
29 then gently refl.uxed Eor 72 hours at which point the temper-
ature increased to 110°C and was held there for an addi- '
31 tional 3 hours. The ;system was then cooled to 60°C and the
32 reaction quenched by the addition of 0.54 liter of 3N HC1
33
34
-55-
1 341 d4 5
O1 solution. The system was then dried by azeotropic distill-
02 ation. The system wa:c then diluted with 10 liters of hexane
03 which was afterwards extracted three times with a slightly
04 basic brine solution (pH - 8 to 9). In each extraction, a
05 cuff between the aqueous solution and the hexane solution
06 was formed. The cuff as well as the aqueous solution was
07 discarded after each extraction. The resulting hexane
08 solution was stripped and dried under elevated temperature
O9 and high vacuum to afi:ard 4450 grams of the title compound
as a light weight oil having a molecular weight of approxi-
11 mately 1435 and a hydroxyl number of 39. The product had an
12 average of 17 PCB units. This procedure was repeated to give
13 the product listed as Example 13 below. This product was a
14 waxy paste at room temperature.
16
1~ Cornparative Example 5A
lg Preparaticm of c:20 to C28 Terminal Alkylphenyl
1g Pol~~(oxy~:opylene) Chlorvformate
21 To a 12-liter 3-necked flask under a nitrogen atmosphere was
22 added 3 liters of anhydrous toluene and 3042 grams (2.6
23 moles) of C20 to C28 iterminal alkylphenyl poly(oxypropylene)
24 alcohol prepared as in Example 4 above. The system was
cooled to 5°C with starring. While stirring, 297 grams (3.0
26 moles) of liquid phosgene was added all at once to the
2~ reaction system. The reaction system was allowed to warm to
28 room temperatures and ;stirred gently for 24 hours. In order
2g to remove exces:~ phosgene as well as HC1 formed during the
reaction, the system was vigorously sparged with nitrogen.
31 Infrared analysis of ,gin aliquot revealed a strong chloro-
32 formate absorption at 1785 cm 1 and no detectable alcohol
33
34
-56-
134~~45
O1 absorption at 3150 cm~l. This product was a waxy paste at
02 room temperaturE~.
03
04
05 Example 5B
06 Preparation oi: a Pinwheel Alkylphenyl Poly(oxypropylene)
07 Chloroi:ormat~e from the Poly(oxypropylene)
08 Alcohol of Example 32
09
11 To a cooled (5°(:) mecihanically stirred solution of the
12 pinwheel poly(oxyprop:ylene) alcohol (440 gr, 0.26 moles) of
13 Example 32, derived from C14 oligomer, in 1 liter of dry
14 toluene under a nitrogen atmosphere was added all at once
254 ml of a 20~ solution of phosgene in toluene (242 gr).
16 The reaction mi~cture was allowed to warm to room temperature
17 and stirred geni:ly for 24 hours to remove excess phosgene
lg and the HC1 forrned during the reaction period. Infrared
19 analysis of an aliquot revealed a strong chloroformate
absorption at 1'l85 cm l and no detectable alcohol
21 (3450 cm 1). This product was a liquid at room temperature.
22
23
24 Comparative Example 6
Prep<~ration of C20 to C28 Alkylphenyl
26 Poly(oxypropylene) Ethylene Diamine (EDA) Carbamate
27
28 The entire chlon:oformate/toluene solution of Example 5A
29 was diluted with 4 liters of dry toluene. In a separate
flask, 2565 grams (42.7 moles) ethylene diamine (EDA) was
31 also diluted wii:,h 4 liters of dry toluene. At room
32 temperature, thE~se two solution were rapidly mixed using
33
34
-57-
1 341 04 5
O1 two variable speed tef:lon gear pumps and a 10 inch Kenics
02 static mixer. After fifteen minutes, the crude reaction
03 mixture was stripped, diluted with 12 liters of hexane,
04 washed successively once with water and three times with a
05 slightly basic (pH - 9) brine solution. Phase separation
06 of the aqueous trine solution and the hexane solution was
p7 improved by adding brine as needed. The hexane solution
Og was separated, dried over anhydrous sodium sulfate, fil-
O9 tered and stripped to afford the title product as a light
yellow liquid wr~ich solidified to a loose paste upon
11 cooling and having an alkalinity value of 30 and 0.75
12 weight percent x>asic nitrogen. This preparation was
13 repeated to give the product listed as Example 23 below.
14 This product wa:~ a wa:~cy paste at room temperature and did
not pass the wa}: test as described in Example 45.
16
17
lg Comparative Example 7
lg Preparati.on of C20 to C28 Terminal Alkylphenyl
Poly(oxypropyle:ne) Diethylene Triamine Carbamate
21
22 In the manner dE~scribed in Example 6 above, 2256 grams (1.53
23 moles) of C20 to C28 terminal alkylphenyl poly(oxypropylene)
24 chloroformate prepared similarly to method described in
Example 5A above was treated with 2654 grams (25.8 moles) of
26 diethylene triamine (DETA) to afford the title compound
27 having an alkalinity value of 56 and 1.4 weight percent
2a basic nitrogen. This preparation was repeated to give the
2g product listed ~~s Example 27 below. This product was a waxy
paste at room temperature and failed the wax test of ,
31 Example 45.
32
33
34
-58-
1341045
O1 Comparative Example 8
02 Preparation of _n-Butyl
03 Poly(oxypropylf~ne) Ethylene Diamine Carbamate
04
05 2000 grams (0.91. moles) of n-butyl poly(oxypropylene)
06 alcohol was preFrared :Ln the manner of Example 4 by
07 substituting n-butano:L for the C20 to C28 alkylphenol. The
08 n-butyl poly(ox~~propy:Lene) alcohol was then treated with
09 phosgene in the manner of Example 5A to yield the n-butyl
poly(oxypropylene) ch:loroformate which was reacted with 1093
11 grams (18.2 moles) of ethylene diamine in the manner of
12 Example 6 to yield the title compound as a light yellow
13 liquid having an alkalinity value of 22.5 and 0.56 weight
14 percent basic nitrogen. This product was a liquid at room
temperature and passed the wax test of Example 45.
16
17
18 Comparative Examples 9-17
19
21 Other hydrocarbyl poly(oxyalkylene) alcohols were prepared
22 by employing dii=ferent hydrocarbyl groups including those of
23 Examples 2A and 3; by employing different poly(oxyalkylene)
24 groups of different chain lengths. Examples 9 through 17
found below in '.Cable I summarizes the different hydrocarbyl
26 poly(oxyalkylene) alcohols so prepared.
27
28
29
31
32
33
34
-59-
X341045
O1 TABLE I
02
03 POLY(O:KYALKYLENE) ALCOHO LS OF THE FORMULA
04 R1
05 R3-Of CH2CHO~ nH
06
07 Phenol Avg. No.
08 Source of Alkyl
Ex. R,3 Ex. No. R1 n Carbons
-
09
g n-butyl - -CH3 "37 4
11 10 n-butyl - -CH3 "23 4
12 11 tetrapropenylphenyl 3 -CH3 "20 12
13 12 tetrapropenylphenyl 3 -CH2CH3 "17 12
14 13 X20-28 terminal alkylphenyl 2A -CH3 "17 29
14 X20-28 terminal alkylphenyl 2A -CH3 "14 29
16 15 C20-28 terminal alkylphenyl 2A -CH3 "10 29
17 16 C20-28 terminal alkylphenyl 2A -CH3 "6 29
18 17 X20-28 terminal alkylphenyl 2A -CH2CH3 "17 29
19 29 C20-28 terminal alkylphenyl 2B -CH3 "17 24
30 C20-28 terminal alkylphenyl 2B -CH3 "13 24
21 31 C20-28 terminal alkylphenyl 2C -CH3 "14 26
22 32 a-C14 deri~red pinwheel
23 alkylphenyl lA -CH3 "20 36
24 33 a-C14 oligomer alkylphenyl
alkylphenyl lA -CH3 "16 36
26 34 a-C16 oligomer alkylphenyl
27 alkylphenyl 1B -CH3 "17 34
28
29
31
32
33
34
-60-
1341 04 ~
O1 TABLE II
02
03 Carbamates of the Formula
04
05 R1 0
06 R30f CH2CH0-~nC~N Hf CH2-CH2-NH~
H
p
07
08 Phenol Avg. No.
O9 Source of Alkyl
Ex. R3 Ex. No. R1 n p Carbons
11
12 18 n-butyl - -CH3 "37 1 4
13 19 n-butyl - -CH3 "23 1 4
14 20 tetrapropenylphenyl 3 -CH3 "20 1 12
21 tetrapropenylphenyl 3 -C2H5 "17 1 12
16 22 tetrapropenylphenyl 3 -C2H5 "17 2 12
17 23 C20-28 terminal alkylphenyl 2A -CH3 "17 1 29
18 24 C20-28 terminal alkylphenyl 2A -CH3 "14 1 29
19 25 C20-28 terminal alkylphenyl 2A -CH3 "10 1 29
26 C20-28 terminal alkylphenyl 2A -CH3 "6 1 29
21 27 C20-28 terminal alkylphenyl 2A -CH3 "17 2 29
22 28 C20-28 terminal alkylphenyl 2A -CH3 "17 1 29
23 35 C20-28 terminal alkylphenyl 2B -CH3 "17 1 24
24 36 C20-28 terminal alkylphenyl 2B -CH3 "13 1 24
37 C20-28 terminal alkylphenyl 2B -CH3 "13 2 24
26 38 C20-28 terminal alkylphenyl 2C -CH3 "14 1 26
27 39 a-C14 deri~~ed pinwheel
28 alkylphenyl lA -CH3 "'20 2 36
29 40 a-C14 deri~~ed pinwheel
alkylphenyl lA -CH3 "16 2 36
31 41 a-C16 deri~~ed pinwhee 1
32 alkylphenyl lA -CH3 ~17 2 34
33
34
-61-
1341 045
O1 Comparative Examples 18-28
02
03
04 Other hydrocarb:yl poly(oxyalkylene) aminocarbamates were
05 prepared by employing different hydrocarbyl groups including
06 those of Examples 2 and 3 and by employing poly(oxyalkylene)
p7 groups of different chain lengths. Examples 18 through 28
08 are found in Table II, which summarizes the different
Og hydrocarbyl pol:y(oxyalkylene) aminocarbamates so prepared.
11
12 Comparative Example 29
13 Prepa ration of a C24 Terminal AlkylPhenyl
14 Poly(oxypropylene) Alcohol
16
17 In a manner similar to that described in Example 4, 622 gm
18 (1.45 moles) of the terminal low dialkyl terminal phenol
lg derived from th~~ C20 to C28 alpha olefin (Example 2B) was
converted to 2048 gm of the poly(oxypropylene) alcohol
21 (Hydroxyl #, 40.0; MW, 1402) by reaction with approximately
22 1~ moles of pro~~ylene oxide. This product was a waxy paste
23 at room temperature.
24
26 Comparative Example 30
2~ Preparation of a C24 Average Terminal Alkylphenyl
2g Poly(oxypropylene) Alcohol
29
31 The alkyl phenol of Example 2B was reacted with 13 moles of
32 PO in the manner of Example 4 to give the alkylphenyl
33 poly(oxypropylene) alcohol of the example.
34
-62-
1341 p45
O1 Comparative Example 31
02 Prepar,~tion of a C26 Terminal Alkyl Phenyl
03 Poly(oxypropylene) Alcohol
04
05
06 The alkyl pheno:L of Example 2C was converted to a 14 PO
07 polymer (as determined by Nmr) in a manner similar to that
Og described in Ex~~mple 4, but using 14 moles of PO per mole of
Og phenol. This product was a waxy paste at room temperature.
11
12 Example 32
13 Preparation of Pinwheel Poly(oxypropylene) Alcohols
14 from C14 Oligo:mer Derived Phenol of Example lA
16 This experiment was carried out in dry 2-liter, three-necked
1~ flask, equipped with a heating mantle, mechanical stirrer,
18 and a dry ice condenser fitted to maintain an inert nitrogen
19 atmosphere. To a warm solution of dry toluene (250 ml) and
203 grams (0.36 moles) of the pinwheel alkylphenol of
21 Example lA was slowly added potassium metal (5.4 gr) in
22 small pieces with vigorous mechanical stirring. The pot
23 temperature increased to approximately 100°C during the
24 addition, and ai:ter 2~-1/2 hours, all of the potassium was
dissolved. AftE~r cooling to 60°C, 585 mls of propylene
26 oxide (486 gram:, 8.36 moles) was added in such a way as to
2~ avoid flooding of the vapor condensing system. The reaction
28 Solution was gently refluxed for 72 hours at which point the
29 temperature rose to 1:10°C and was held at temperature for an
additional 3 hours. After cooling to 60°C, the reaction was '
31 quenched with 6C1 ml of 3N HC1 (a slight excess) and dried by
32 azeotropic distillation. The crude product was then diluted
33
34
-63-
1341 045
O1 with hexane (3 Liter),, extracted three times with slightly
02 basic brine. Ire each case, a cuff was formed and discarded.
03 The resulting hexane solution was then stripped and dried
04 under high vacuum to afford 670 gr of a light yellow oil
05 having a molecular weight of approximately 1725 (by hydroxyl
06 number determination). Spectroscopic analysis (1H and 13C
07 Nmr) revealed that this alcohol contained an average of 20
08 propylene oxide monomer units. This product was a non-
p9 viscous liquid apt room temperature and could not be induced
to crystallize apt low temperature.
11
12
13 Example 33
14 Preparation of Pinwheel Alkylphenyl
Poly(oxypropylene) Alcohols
16
17
18 The pinwheel alkyl phenol of example lA (C14-derived) was
19 converted to they poly(oxypropylene) alcohol by reaction with
16 mole equivalents o~E propylene oxide in a manner similar
21 to that described in Example 32.
22
23
24 Example 34
Preparation of Pinwheel Alkylphenyl
26 Poly( c~-xypropylene ) Alcohols
27
28
29 The pinwheel alkyl phenol of example 1B (C16-derived) was
converted to they poly(oxypropylene) alcohol by reaction with ,
31 17 mole equivalents o:E propylene oxide in a manner similar
32 to that described in Example 32.
33
34
-64-
1341 p45
O1 Comparative Example 35
02 Preparation of i:he Terminal Low Dialkyl C20-24 Carbamate EDA
03
04
05 Without further purification, the terminal alkylphenol
06 alcohol of Example 29 was converted to the chloroformate as
07 described in Example 5A, except that a 20 weight percent
08 solution of pho:~gene in toluene was employed rather than
condensed phvsgE~ne li~~uid (for handling convenience and
safety). After reaction, the chloroformate was then
11 rigorously sparcled to remove excess phosgene and the HC1
12 reaction by-product.
13
14 The resulting chloroformate was then converted to the corre-
sponding EDA carbamatcs by reaction with ethylene diamine as
16 described in Example ti. The average alkyl carbon number was
17 24; alkalinity value =- 34; basic nitrogen was 0.85. This
18 product did not pass the wax test of Example 45.
19
Sequence V-D engine tasting as described in Example 43
21 revealed that varnish control was exceedingly poor (4.4,
22 average of three separate tests). In an effort to improve
23 this performances aspect, a similar molecule was synthesized,
24 but with less PCi. This is shown in Example 36.
26
27
28
29
31
32
33
34
-65-
X341045
O1 Cornparative Example 36
02 Preparation of a Terminal C24-Average Alkyl Phenyl
03 Poly(ox~roropylene) EDA Carbamate
04
05
06 In a separate procedure, the terminal "low" dialkylphenol of
Example 2B was c~onveri:ed to a phenol-capped
08 Poly(oxypropylene) alcohol containing 13 PO units using a
Og procedure similar to i:hat described in Example 4. This
alcohol was converted to the corresponding chloroformate, as
11 in Example 5A using a phosgene/toluene solution. The
12 chloroformate was degassed and used without further
13 Purification.
14
One portion of this chloroformate was converted to an EDA
16 carbamate as in Example 6 (alkalinity value = 37, 0.93%
17 basic nitrogen). This product did not pass the wax test of
lg Example 45.
19
21 Cor~aarative Example 37
22 Preparation of a C24 Terminal Alkylphenyl
23 Pol. (y oxypropylene) DETA Carbamate
24
26 The remainder of the chloroformate of Example 36 was
converted to the corresponding DETA carbamate (alkalinity
2g value =67.4, 1.E~9% basic nitrogen) as in Example 7. This
2g product did not pass i~he wax test of Example 45.
31
32
33
34
-66-
1 341 p4 5
O1 Comparative Example 38
02 Preparation of a C24-Average Terminal Alkylphenyl
03 Poly(oxypropylene) EDA Carbamate
04
05
06 The poly(oxypropylene) alcohol of Example 31 was converted
07 to the corresponding chloroformate as in Example 5A and
Og reached with EDA to afford the desired ethylene diamine
p9 carbamate in a manner similar to that of Example 6
(alkalinity value = 39.0, 0.85% basic nitrogen). This
11 product did not pass the wax test of Example 45.
12
13 As demonstrated by Examples 24, 35, 36, 37, and 38, reducing
14 the number of propylene oxide units in the additive backbone
does not improve varnish performance nearly as significantly
16 as does increasing they number of alkyl carbons in the alkyl
17 phenol. As can be seen in Example 35, an average alkyl
lg carbon content of 24 carbon atoms with PO formulations is
1g insufficient to provide the required varnish and sludge
control. Neither by reducing the PO content (Example 36) nor
21 bY switching to DETA c:arbamates (Example 37) can varnish
22 performance be restored to the level exemplified by Example
23 24. However, by increasing the dialkyl content to a higher
24 level (Example 38) performance is restored to base case
values. None of these examples, however, represents a total
26 solution to the overall problem which additionally requires
27 these additives to be nonwaxy at low temperatures, thus
28 passing the test of ESCample 45.
29
31
32
33
34
-67-
1341 p45
O1 Example 39
02 Preparation of Alkylphenyl Poly(oxypropylene)
03 Dieth lenetriamine Carbamate
04
05
06 The chloroformate/tolu.ene solution of Example 5B was diluted
07 to 2 liters with dry t.aluene. In a separate flask,
08 530 grams of diethylene triamine (5.-2 moles) was also
Og diluted to 2 liters with dry toluene. These two solutions
were rapidly mixed using two variable speed teflon gear
11 pumps and a 10-inch Ke~nics static mixer. The crude reaction
12 mixture was then stripped, diluted with 6 liters of hexane,
13 and washed successively with water (4X), basic (pH=9) water
14 (2X), and water (4X). Phase separation was improved by
adding isopropanol as needed. The organic layer was then
16 dried (NaS04), filtered and stripped to afford a light
17 orange product which remained a liquid at -40°C (alkalinity
lg value = 50, 1.25% basic nitrogen). As such, this product
lg was regarded as non-waxy by virtue of passing the wax test
of Example 45. This c:arbamate does not produce detrimental
21 varnish and sludge relLative to the base oil.
22
23
24 Examples 40-41
Preparation of: Aminocarbamates of the Present Invention
26
27
28 The pinwheel alc:ohols 33 and 34 were reacted in a manner
2g similar to Examples 5 and 7 to give a C14-derived DETA
pinwheel carbamate having 16 oxypropylene units and an .
31 average alkyl carbon number of 34 (Example 40) and a
32 C16 derived DETA pinwheel carbamate having 17 oxypropylene
33
34
-68-
~ 341 04 5
O1 units and an average alkyl carbon number of 36 (Example 41).
02 These products pass the wax test at -40°C and do not produce
03 detrimental sludge or varnish relative to base oil.
04
05
06 Example 42
07 Oil solubility Bench Test
08
09
This procedure was designed to determine the oil
11 solubility/compatibili.ty of different additives in a fully
12 formulated lubricating oil. Insofar as as much as 25-30~ of
13 a gasoline additive can enter into the crankcase via blow-by
14 and/or cylinder wall/piston ring "wipe down", this is an
important performance criteria.
16
17 The lubricating oil composition was formulated to contain:
lg 6 percent by weight oi° a monopolyisobutenyl succinimide; 20
19 millimoles per k.ilogr<~m of a highly overbased sulfurized
calcium phenate; 30 m'illimoles per kilogram of a highly
21 overbased sulfurized calcium hydrocarbyl sulfonate; 22.5
22 millimoles per kilogram of a zinc dithiophosphate; 13 weight
23 percent of a commercial non-dispersant viscosity index
24 improver; 5 parts per million of a foam inhibitor in 150N
Exxon base oil t:o give a 10 W 40 formulated oil.
26
2~ The oil solubility of the additive was determined as
2g follows:
29
To a heated solution (50 grams) of the above-described lube
31 oil was added 5C1 gram:a of the neat additive. The mixture
32
33
34
-69-
1341 p45
O1 was then heated with constant stirring to 170°F and main-
02 tained at that temperature for 15 minutes. Dilutions were
03 then prepared according to the desired solubility test range
04 using fresh hot reference oil as the diluent. In each case,
05 the diluted samples were stirred to 170°F for 10 minutes to
06 insure complete mixing. The solutions were then sealed and
p7 left to cool undisturt>ed for from 1-5 days typically at room
OS temperature. Each sample was then rated visually for oil
09 continuity.
11 Additives that were marginally soluble in this blend
12 separated as a denser secondary phase, and were clearly
13 visible as such without the need for centrifugation.
14 Additives which gave rise to oil incompatibility problems
were inherently oil soluble, however, they tended to
16 displace what appears to be the VI (viscosity index)
1'7 improver. This phenonnenon resulted in the separation of the
18 VI improver which is less dense than the bulk oil forming a
1g clear thick upper layer. The solubility/compatibility of a
gasoline additive was thereby defined as the highest con-
21 centration (on a. weight basis) which did not result in the
22 formation of either an insoluble lower additive phase or an
23 insoluble upper VI improver phase.
24
The oil solubility (or insolubility) of the hydrocarbyl
26 poly(oxyalkylene~) aminocarbamates including the alkylphenyl
2~ poly(oxypropylene) am:inocarbamates of this invention is
2g believed to correlate well to the oil solubility of the
2g precursor hydroc:arbyl poly(oxyalkylene) alcohol. Accord-
ingly, Table II7: below contains solubility data for the
31 hydrocarbyl poly(oxya:lkylene) alcohols. Oil solubility is
32 reported in weight percent of additive in the lubricating
33 oil composition..
34
-70-
1 341 p4 5
Ol TA8LE III
02
03 Example No Oil Solubility
04
05
06 9 5
07 10 8
08 1:L 18
09 1 2 27
1:3 40
11 l~l 50
12 15 50
13 lEi 50
14 1'l 50
16 The oil solubil:Lty of the amino carbamates is reported in
17 Table IV.
18
19
Example 43
21 Sequence V-D Test Method
22
23
24 Formulated oils containing alkylphenyl poly(oxypropylene)
aminocarbamate were tested in a Sequence V-D test method as
26 well as formulai:.ed oils containing comparative hydrocarbyl
27 poly(oxyalkylenc~) aminocarbamates. This procedure utilizes
28 a Ford 2.3-liter:, four-cylinder Pinto engine. The test
29 method simulates a type of severe field test service
characterized bbl a combination of low speed, low temperature
31 "stop and go" city driving and moderate turnpike operation.
32 The effectiveness of the additives in the oil is measured in
33
34
-71-
1~~1045
O1 terms of the protection against sludge and varnish deposits
02 on a 0 to 10 scale with 0 being black and 10 indicating no
03 varnish or sludcie deposits. The results of these tests are
04 found in Table 7:V below.
05
06 The reference composition was formulated to contain:
07 6 percent by weight of a mono-polyisobutenyl succinimide; 20
08 millimoles per i;ilogr.am of a highly overbased sulfurized
09 calcium phenate;, 30 millimoles per kilogram of a highly
overbased calcium hydrocarbyl sulfonate; 22.5 millimoles per
11 kilogram of a zinc dithiophosphate; 13 weight percent of a
12 commercial non-dispersant viscosity index improver; 5 parts
13 per million of a foam inhibitor in 150N Exxon base oil to
14 give a 10 W 40 i:ormul,ated oil.
16 Comparisons against tlhis reference were made by employing an
17 oil formulated identically as the reference except for the
18 additional amount of the additive as shown in Table IV
19 below:
21
22
23
24
26
27
28
29
31
32
33
34
-72-
~34~045
O1 TABLE IV
02 Carbamate Performance
and Properties
03
04 Crankcase (3) Crankcase
Oil (1) Wax (2) Av. Varnish Av. Sludge (5)
Av.
05 Ex. Compatibility @ -40C 2.5 (4) 5.5 2.5 5.4 HC #
06
18 0.5 no 4.4 9.2 4
19 1 no 4
08 20 7 no 12
21 15 no 5.7 5.5 9.5 9.55 12
O9 22 15 no 12
11 23 16 yes 29
24 20 yes 6.4 7.5 9.6 9.35 29
12 25 45 yes 29
13 26 50 yes 29
27 16 yes 29
14 28 16 yes 29
35 18 yes 4.4 9.5 24
16 36 20 yes 5.4 9.4 24
37 18 yes 7.4 9.2 24
1~ 38 22 yes 6.2 9.4 26
18
39 18 no (6) (6) 34
19 40 18 no (6) (6) 36
41 18 no (6) (6) 34
21
(1) See Ex. 42
22 (2) See Ex. 45
(3) See Ex. 43 -- ng scale 1-10, with 10 meaning no varn ish
Rati =
23 or sludge.
24 (4) Weight percent ditive.
ad
(5) Average alkyl bon number in alkyl phenyl group
car
(6) These carbamates are not the baseoil
detrimental
relative
to
26 of Example :30.
27
28
29
,
31
32
33
34
-73-
~ 341 p4 5
O1 Examples 18 thro~igh 22 represent prior art hydrocarbyl
02 poly(oxyalkylene) aminocarbamates. This Table establishes
03 that the alkylph~enyl poly(oxypropylene) aminocarbamates of
04 this invention (Examples 39-41) were less detrimental, i.e.
05 gave decreased crankcase deposits, as measured by average
06 varnish in the Sequence V-D results.
07
OS The table also establishes that the additives of this
p9 invention possess lubricating oil compatibility. This is
particularly surprising in view of the fact that prior art
11 hydrocarbyl poly(oxypropylene) aminocarbamates are not
12 lubricating oil compatible, i.e., Examples 18, 19 and 20.
13
14
Example 44
16 TGP. Stability of Amino Carbamates
17
18
19 The thermal oxidative stability of fuel additives can be
measured by thermogravimetric analysis (TGA). The TGA
21 procedure employed Du Pont 951 TGA instrumentation coupled
22 with a microcomputer for data analysis. Samples of the fuel
23 additives, approximately 25 milligrams, were heated isother-
24 mally at 200°C under .air flowing at 100 cubic centimeters
per minute. The weight of the sample was monitored as a
26 function of timE~. Incremental weight loss is considered to
27 be a first order process. Kinetic data, i.e., rate
2g constants and h~~lf-lives, were readily determined from the
29 accumulated TGA data. The half-life measured by this pro-
cedure represents the time it takes for half of the additive
31 to decompose and evaporate. Half-life data for a fuel
32 additive correlates to the likelihood that that additive
33
34
-74-
1341 045
O1 will contribute to ORI. Lower half-lives represent a more
02 easily decomposable product one which will not as likely
03 accumulate and i'orm deposits in the combustion chamber. All
04 of the comparatW a carbamate examples and the carbamate
05 examples of the present invention have good TGA performance,
06 i.e. half lives of less than about 4 hours, and therefore
07 will contribute minimally to ORI.
08
09
Example 45
11 Dei=ermination of Additive Waxiness
12
13
14 Since it is not unusual for solutions of these additives to
be subjected to cold temperature extremes, it is important
16 that solids (typically waxy) are not formed during handling,
17 storage, or in actual field use. When formed, these waxy
18 constituents can totally plug the in-line filtering devices
i9 normally in ser~~ice in additive distribution systems and the
fuel or lube sy;~tems of actual operating engines. Such a
21 plugging would obviously be catastrophic and must be
22 avoided. The following test procedure constitutes a reason-
23 able evaluation of this low temperature tendency and serves
24 as the critical distinguishing feature of this invention
whereby PO oligomers are to be employed as
26 dispersants/detergents.
27
28 The test additive (30 gr) is dissolved in an equivalent
2g weight of reagent grade toluene, cooled to -40°C, and held
at that temperature for four weeks. The sample solution is .
31 then inspected for visual clarity ("brightness"). If any
32 sedimented solids appear or the sample is hazy, the sample
33
34
-75-
1 3 41 04 5
O1 has failed the test. A sample which passes this test is one
02 described as "c7.ear and bright", a well-known
03 industry-designated standard.
04
05
06 Example 46
07 rZeasuring the Epoxide Content
08
09
Nmr spectroscopy provides a method for measuring the
11 backbone "epoxic~e content" of these additives. The ether
12 carbons and thei~.r associated protons are segregated and
13 easily "counted".
14
The "epoxide count", independently determined from carbon
16 and proton Nmr :apectr.a is averaged and gives good repeat-
17 ability and consistent agreement with our experimental
18 charge mole rat:los and reaction mass balance data. Analysis
19 of the polyethers can be done at the alcohol stage or later
on in the products.
21
22 Analyses were performed using a Varian VXR - 300. The
23 polyethers were dissolved "as is" in deuteromethylene
24 chloride (30 mg/ml), and the proton FT Nmr spectra was
determined according to the instrument parameters detailed
26 below.
27
28 For carbon FT Nmr spectra, the polyethers were also
29 dissolved in deuteromethylene chloride (400 mg/ml) which
contained approximately 5 mg of a relaxation agent
31 Cr(III)-tris-acE~tylacetonate, i.e., Cr(III)(AcAc)3.
32 All spectra werE~ determined using high performance 5 mm Nmr
33 tubes.
34
-76-
_ 1341 045
O1 Instrument Conditions
02
03 To Observe Proton To Observe Carbon
04
05 Frequency 299.944MHz 75.429 MHz
06 Spectral Width 5000 Hz 20492 Hz
07 Acq. Time 1.6 Sec 0.4 Sec
08 Relax. Delay 2.0 Sec 2.0 Sec
09 Pulse Width 14° 90°
Temperature Ambient Ambient
11 No. Repetitions 16 2048
12 Spin Rate 20 Hz 24 Hz
13 FT Size 16R 32K
14
Determination oi= Integral Values
16
17 Proton Nmr Specl:ra
18
19 The aromatic protons (6.5 to 7.5 ppm) serve as the internal
standard for this evaluation. When dealing with products
21 derived from "h:igh dialkylation" phenols (20 to 25%), the
22 integral value :Eor this region of the spectra is divided by
23 3.75. This signal value per proton is then used to evaluate
24 ether carbon proton content. Otherwise, this signal is
attributed to four aryl protons (for phenols having <10%
26 dialkylation).
27
28 The ether protons of interest lie in the region between 3.2
29 and 4.0 ppm. Here we see the mass of methylene and methine
protons which include the separated multiplets observed for
31 the first and the last epoxide units assembled in these
32 polyethers. One-half of the total number of PO related
33
34
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1341 045
O1 protons are observed :in this region, whereas only
02 three-eighths of: the BO-related protons are represented
03 here.
04
05 Carbon Nmr Spectra
06
07 The six aromatic; carbons (105 to 160 ppm) serve as the
08 internal standai:d for this evaluation. This is no need to
O9 make any allowances for the presence of dialkyl phenol in
this case.
11
12 The ether carbons of interest lie in the region between 60
13 and 80 ppm. Bearing in mind that only two-thirds of the
14 observable PO-related carbons are counted in this region
(one-half for BO polymers), the calculation to determine
16 epoxide units i;~ straightforward.
17
18
lg Example 47
Determination of the Nature of the Alkylphenyl Group
21
22
23 Analytical methods for determining the general nature of the
24 alkylphenyl substituent of the aminocarbamates can be accom-
plished in the following manner:
26
27 A sample of an alkylphenyl poly(oxyalkylene) aminocarbamate
28 identified by Infrared and Nmr spectroscopy) is hydrolyzed
29 using strong base to afford the corresponding
polyoxyalkylene alcohol. Further nonoxidative thermal ,
31 degradation strips away the polyether portions leaving
32 behind the alkyl phen.al. This residue can then be examined
33
34
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1 3 41 04 5
O1 by Mass Spectroscopy for the appearance of the tropylium ion
02 species. Alkyl phenols tend to fragment in such a way that
03 the larger of the two (or three).benzylic substituents will
04 be eliminated in the formation of the observed phenol ion
05 species. Thus, the tropylium ions generated from simple
06 alpha olefins wall typically contain from 1-3 carbon atoms
07 more than those accounted for by the aromatic ring itself.
0g By comparison, i:he same ionized species generated from the
Og pinwheel alkyl phenols employed in the invention, such as
those derived from an alpha olefin oligomer, will contain
11 many more carbon atoms due to fragmentation at the benzylic
12 positions.
13
14 It is important to recognize that such tropylium ion species
are readily formed from alkyl phenols, and high energy
16 impact ionization may be too severe a technique for all
17 cases. As a result, under forcing conditions, more detailed
lg information concerning the structure of the alkyl portion
19 may be lost. Iz these cases, it is possible to examine "low
energy" impact :ionization which may be useful for observing
21 these tropylium ions. In any event, tropylium ions are
22 noted for their relative stability and more often than not
23 appear as the b,~se ion peak (peak of highest relative
24 intensity). Se~e: Silverstein, Bassler, and Morril,
Spectrometric Identification of Organic Compounds. Wiley
26 and Sons (New Y~crk, 1974) pp. 19-22.
27
2g Another less p referred but supporting analysis can be per-
2g formed by conducting carefully controlled oxidations of the
alkyl phenol si~3e chains. This is typically done via ,
31 aqueous potassium permanganate oxidation under pH conditions
32 designed to control the extent of the oxidative chain
33
34
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1341 045
O1 cleavage reactions desired. If the alkyl phenol has been
02 derived by alky7_ation with, for example, linear alpha ole-
03 fins, then a bimodal distribution of low and high molecular
04 weight alkanoic acids will result. However, if the phenol
05 in question is a pinwheel alkyl phenol and the phenyl ring
06 is attached toward the center of the alkyl chain, then
07 higher molecular weight alkanoic acids will be observed,
Og although they may not comprise the majority of oxidation
Og reaction products. Hence, for a pinwheel alkyl phenol
derived from a C:10 a-olefin oligomer one would expect to
11 observe the corresponding C7-C9 alkanoic acids after
12 degradation. On the other hand, when
13 the phenol derived from simple C20 alpha olefin alkylation
14 is examined, high molecular weight acid fragments will also
be produced and observed which will reflect the existence of
16 these longer chains in the original phenol.
17
lg It should be noted that due to the general severity of these
19 reaction conditions, one may observe only small quantities
of these heavier- acids. However, by derivatization they may
21 be observed chromatographically. In concert with other
22 general data such as phenol MW, dialkylation level, etc.
23 this method can be in:Eormative.
24
26
27
28
29
31
32
33
34
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1341045
Ol Example 48
02 Determination of Average Alkyl Hydrocarbon
03 Content of Alkylphenols
04
05
06 Chemical Method
07
08 After determining the hydroxyl number (mg KOH/gr sample) for
09 a given phenol, the molecular weight is calculated: MW =
56,100/hydroxyl number, wherein 56,100 is the meg. wt. of
11 KOH.
12
13 Since the phenol. portion of these products accounts for 91
14 mass units, the balance (MW - 91) is due to the average
alkyl hydrocarbon content.
16
17 As these alkyl groups are saturated hydrocarbons, dividing
18 the balance portion by 14 (the mass units for a -CH2-
19 moiety) gives the average number of alkyl hydrocarbon atoms
in the phenol.
21
22 Spectroscopic Method
23
24 Alternatively, Dlmr an<~lysis can be used to determine the
average alkyl hydrocarbon content. Nmr analysis of
26 integrated 1H spectra indicate the relative balance of aryl
27 to aliphatic hydrogens which can be used to approximate the
28 average hydrocarbon content of the phenol.
29
This information may <~lso be obtained by using integrated
31 13C Nmr spectra of these products. Thus, the number of
32 aromatic carbonic can be used as an internal standard for
33
34
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1 341 04 5
O1 gauging the average number of saturated carbons in the
02 phenol. TypicaJ.ly, the 1H and 13C Nmr results are averaged
03 and are in good agreement with the chemical determination.
04
05 It is assumed that the average alkyl hydrocarbon content of
06 the phenols doe:c not change during the reaction to make the
07 alcohols, chloroformates and carbamates.
08
09
11
12
13
14
16
17
18
19
21
22
23
24
26
27
28
29
w
31
32
33
34
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