Note: Descriptions are shown in the official language in which they were submitted.
~Z7025S
MODIFIED SUCCINIMIDES (V)
05 BACRGROUND OF ~HE INVEN~ION
1. Field of the Invention
This invention relates to additive~ which are
useful as dispersant and/or detergents in lubricating oils
and fuels. In particular, this invention is directed
10 toward polyamino alkenyl or alkyl succinimides wherein one
or more of the nitrogens of the polyamino moiety is
substituted with
' O O
Il ~
R40R50(C)m~~
wherein R4 is hydrocarbyl of from 1 to 30 carbon atoms; R5
is selected from the group consisting of hydrocarbyl of
from 2 to 30 carbon atoms and -R6-~OR6)p- wherein R6 is
alkylene of 2 to 5 carbon atoms and p is an integer from
1 to 100; and m is an integer of from O to 1.
The modified polyamino alkenyl or alkyl
succinimides of this invention have been found to possess
dispersancy and/or detergency properties when employed in
a lubricating oil. These modified succinimides are also
useful as detergents and/or dispersants in fuels.
2. Prio
Alkenyl or alkyl succinimides have been
previously modified with alkylene oxides to produce
poly(oxyalkylene)hydroxy derivatives thereof. These
alkylene oxide treated succinimides are taught as
additives for lubricating oils (see U.S. 3,373,111 and
3,367,943). U.S. Patent No. 2,991,162 discloses
carburetor detergent additives for gasoline obtained by
reacting an N-alkyl propylene diamine with ethylene
carbonate to produce a two-component detergent additive
consisting of a carbamate and a urea compound. U.S.
Patent No. 3,652,240 discloses carburetor detergent
additives for hydrocarbonaceous fuel which are carbamates
formed by the reaction of an amino-amide with ethylene
V~ii5
01 -2-
carbonate. Karol et al, ~.S. Patent Nos. 4,501,597 and
4,460,381, disclose that the reaction product of oxalic
05 acid with a mono- or bis-succinimide is useful as a fuel
stabilizer and as a carburetor detergent. U.S. Patent
No. 4,482,464 discloses succinimides which have been
modified by treatment with a hydroxyalkylene carboxylic
acid selected from glycolic acid, lactic acid,
2-hydroxymethyl propionic acid and 2,2'-bis-hydroxy-
methylpropionic acid. These modified succinimides of
U.S. 4,432,464 are disclosed as lubricating oil
additives. U.S. 4,490,154 discloses fuels containing an
alkenylsuccinyl polyglycolcarbonate ester as a deposit
control additive. U.SO Patent No. 3,216,936 discloses a
product prepared from an aliphatic amine, a polymer sub-
stituted succinic acid and an aliphatic monocarboxylic
acid. U.S. Patent No. 4,191,537, among others, discloses
hydrocarbyl capped poly(oxyalkylene) polyamino carbamates
useful as dispersants and detergents or fuels and lubri-
cating oils. However, there is no teaching in these
patents, or apparently elsewhere, ~o modify these
polyamino alkenyl or alkyl succinimides in the manner of
this invention.
S~MMARY OF THE INVENTION
It has now been found that polyamino alkenyl or
alkyl succinimides may be modified to yield a polyamino
alkenyl or alkyl succinimide wherein one or more of the
basic nitrogens of the polyamino moiety is substituted
with
O O
P 1~
R40RsO(c)mc
wherein R4 is hydrocarbyl of from 1 to 30 carbon atoms; R5
is selected from the group consisting of hydrocarbyl of
from 2 to 30 carbon atoms or -R6~0R6~p wherein R6 is
alkylene of fro~ 2 to 5 carbon atoms and p is an integer
from 1 to 100; and m is an integer from O to 1. These
modified succinimides are dispersants and/or detergents
lZ70'~55
01 ~3~
for use in fuels or oils. Accordingly, the present
invention also relates to a lubricating oil composition
05 comprising a major amount of an oil of lubricating viscos-
ity and an amount of a modified polyamino alkenyl or alkyl
succinimide sufficient to provide dispersancy and/or
detergency.
Another composition aspect of this invention is
a fuel composition comprising a major portion of a hydro-
carbon boiling in a gasoline or die~el range and an amount
of a modified polyamino alkenyl or alkyl succinimide suf-
ficient to provide dispersancy and/or detergency.
Preferably R4 is hydrocarbyl of from 2 to 20
carbon atoms while R5 is preferably a straight- or
branched-chain alkylene group of from 2 to about 30 carbon
atoms or a straight- or branched-chain alkylene group of
from 2 to about 30 carbon atoms substituted with aryl of
from 6 to lO carbon atoms or alkaryl of from 7 to 12
carbon atoms. Most preferably, R5 is a straight- or
branched-chain alkylene group of from 2 to about 30 carbon
atoms.
Preferably p is an integer from l to 50; more
preferably p is an integer from 2 to 30 and most
preferably p is an integer from 2 to 20 while R6 is
preferably a C2-C4 alkylene group.
In general, the alkenyl or alkyl group of the
succinimide is from lO to 300 carbon atoms. While the
modified succinimides of this invention possess good
detergency properties even for alkenyl or alkyl groups of
less than 20 carbon atoms, dispersancy is enhanced when
the alkenyl or alkyl group is a~ least 20 carbon atoms.
Accordingly, in a preferred embodiment, the alkenyl or
alkyl group of the succinimide is at least 20 carbon atoms
(i.e., the alkenyl or alkyl group is from 20 eo 300 carbon
atoms).
Hydrocarbyl, as used in describing the R4 and R5
groups, denotes an organic radical composed of carbon and
hydrogen which may be aliphatic, aromatic or combinations
thereof, e.g., aralkyl, alkaryl. Suitable hydrocarbyls
1i~70~55
Ol ~4~
are alkyls such as ethyl, propyl, etc.; alkenyls such as
propenyl, isobutenyl, etc.; aralkyl such as benzyl, etc.;
05 alkaryl such as dodecylphenyl (C12H25-C6H4-), etc.; and
aryls such as phenyl, napthyl, etc.
A straight- or branched-chain alkylene group of
from 2 to about 30 carbon atoms refers to straight-chain
alkylene groups such as 1,2-ethylene; 1,3-propylene,
1,5-pentylene, 1,20-eicosylene, 1-30,tricontylene; etc.,
and branched-chain alkylene groups such as 1,2-propylene;
1,3-butylene; 1,2-(2-methyl)pentylene; 1,2-(2-
ethyl)hexylene; l,10-eicosylene; etc.
A straight- or branched-chain alkylene ~roup of
from 2 to about 30 carbon atoms substituted with aryl of
from 6 to 10 carbon atoms or alkaryl of from 7 to 12
carbon atoms refers to the above-described straight- or
branched-chain alkylene groups substituted with an aryl or
an alkaryl group. Suitable aryls include phenyl, napthyl,
etc. Suitable alkaryls include benzyl, etc.
DETAILED DESCRIPTION OF THE INVENTION
The modified polyamino alkenyl or alkyl succini-
mides of this invention are prepared from a polyamino
alkenyl or alkyl succinimide. In turn, these materials
are prepared by reacting an alkenyl or alkyl succinic
anhydride with a polyamine as shown below:
O O
~ O + H2NR~ NRl + H20
O
I
3S wherein R is an alkenyl or alkyl group of from lQ to 300
carbon atoms; and Rl is the remainder of the polyamino
moiety.
These alkenyl or alkyl succinimides that can be
used herein ~re disclosed in numerous references and are
well known in the art. Certain fundamental types of
-5- 6193~-1696
succinimides and related materials encompassed by the term of
art "succinimide" are taught in U.S. Patent Nos. 2,992,708;
3,018,291; 3,024,237; 3,100,673; 3,219,666; 3,172,892; and
3,272,746. The term "succinimide" is understood in the art to
include many of the amide, imide and amidine species which are
also formecl by this reaction. The predominant product however
is succinimide and this term has been generally accepted as
meaning the product of a reaction of an alkenyl substituted
succinic acid or anhydride with a polyamine as shown in
reaction (1) above. As used herein, included within this term
are the alkenyl or alkyl mono-, bis-succinimides and other
higher analo~s.
A(1l_ Succinlc Anhydride
The preparation of the alkenyl-substituted succinic
anhydride by reaction with a polyolefin and maleic anhydride
has been described, e.g. r U.S. Patents Nos. 3,018,250 and
3,024,195. Such methods include the ~hermal reaction of the
polyolefin with maleic anhydride and the reaction of a
halogenated polyolefin, such as a chlorinated polyolefin, with
maleic anhydride. Reduction of the alkenyl-substituted
succinic anhydride yields the corresponding al~yl derivative.
Alternatively, the alkenyl substituted succinic anhydride may
be prepared as described in U.S. Patent Nos. 4,388,471 and
4,450,281.
Polyolefin polymers for reaction with the maleic
anhydride are polymers comprising a major amount of C2 to C5
mono-olefin, e.g., ethylene, propylene, butylene, isobutylene
and pentene. The polymers can be homopolymers such as
polyisobutylene as well as copolymers of 2 or more such olefins
such as copolymers of: ethylene ancl propylene, butylene, and
isobutylene, etc. Other copolymers include those in which a
minor amount of the copolymer monomers, e.g., 1 to 20 mole
f ~
z7al~55
-6- 61g36-1696
percent is a C~ to C~ nonconjuyated diolefin, e.g., a r-opolymer
of isobutylene and butadiene or a copolymer of ethylene,
propylene and 1,4-hexadiene, etc.
The polyolefin polymer, represented in Figure 1 as R,
usually contains from about 10 ~o 300 carbon atoms, although
preferably 20 to 300 carbon atoms. Other preferred embodiments
include 12 to 100 carbon atoms and more preferably 20 to 100
carbon atoms.
A particularly preferred class of olefin polymers
comprises the polybutenes, which are prepared by polymerization
of one or more of 1-butene, 2-butene and isobutene. Especially
desirable are polybutenes containing a substantial proportion
of units derlved from isobutene. The polybutene may contain
; minor amounts of butadiene which may or may not be incorporated
in the polymer. Most often the isobutene units constitute 80%,
preferably at least 90%, of the units in the polymer. These
polybutenes are readily available commercial materials well
known to those skilled in the art. Disclosures thereof will be
found, for example, in U.S. Pa~ent Nos. 3,215,707; 3,231,587;
3,515,669; and 3,579,450, as well as U.S. Patent Mo. 3,912,764.
In addition to the reac-~ion of a polyolefin with
maleic anhydride, many other alkylating hydrocarbons may
likewise be used with maleic anhydride to produce alXenyl
succinic anhydride. Other suitable alkylating hydrocarbons
include cyclic, linear, branched and internal or alpha olefins
with molecular weights in the range 100-~,500 or more with
molecular weights in the range of 200-2,000 being more
preferred. For example, alpha olefins obtained from the
thermal cracking of paraf~in wax. Generally, these olefins
ran~e from 5-20 carbon atoms in length. Another source of
7~5
-6a- 61936-1696
alpha olefins is the ethylene growth process which give3 even
number carbon olefins. Another source of olefins is by the
dimerization of alpha olefins over an appropria~e catalyst such
as the well known Ziegler catalyst. Internal olefins are
easily
~0
7 ~ ~ 5
--7--
01
obtained by the isomerization of alpha olefins over a
suitable catalyst such as silica.
05
The polyamine employed to prepare the polyamino
alkenyl or alkyl succinimides is preferably a polyamine
having from 2 to about 12 amine nitrogen atoms and from 2
to about 40 carbon atoms. The polyamine is reacted with
an alkenyl or alkyl succinic anhydride to produce the
polyamino alkenyl or alkyl succinimide, employed in this
invention. The polyamine is so selected so as to provide
at least one basic amine per ~uccinimide. The polyamine
preferably has a carbon-to-nitrogen ratio of from about
1.1 to about 10:1.
Since the conversion of the basic amine is
believed to efficiently go through a primary or secondary
amine, at least one of the basic amine nitrogens of the
polyamine moiety must be either a primary or secondary
amine.
The polyamino portion of the polyamino alkenyl
or alkyl succinimide may be substituted with substituents
selected from (A) hydrogen, ~B) hydrocarbyl groups of from
1 to about 10 carbon atoms, (C) acyl groups of from 2 to
about 10 carbon atoms, and (D) monoketo, monohydroxy,
mononitro, monocyano, lower alkyl and lower alkoxy deriva-
tives of tB) and (C). ~Lowern, as used in ~erms like
lower alkyl or lower alkoxy, means a group containing from
1 to about 6 carbon atoms.
- 30 Hydrocarbyl, as used in describing the polyamine
components of this invention, denotes an organic radical
composed of carbon and hydrogen which may be aliphatic,
alicyclic, aromatic or combinations thereof, e.g.,
aralkyl. Preferably, the hydrocarbyl group will be rela-
tively free of aliphatic unsaturation, i.e., ethylenic and
acetylenic, particularly acetylenic unsaturation. The
substi~uted polyamines of the present invention are
~enerally, but not necessarily, N-substituted polyamines.
Exemplary hydrocarbyl groups and substituted hydrocarbyl
~40 groups include alkyls such as methyl, ethyl, propyl,
~27~55
~1 -8-
butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such
as propenyl, isobutenyl, hexenyl, octenyl, etc., keto-
05 alkyls, such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy
and lower alkenoxy alkyls, such as ethoxyethyl, ethoxy-
propyl, propoxyethyl, propoxypropyl, 2-(2-
ethoxyethoxy)ethyl, 2-l2-(2-ethoxyethoxy)ethoxy]ethyl,
3,6,9,12-tetraoxatetradecyl, 2-(2-ethoxyethoxy)hexyl,
etc. The acyl groups of the aforementioned (C)
substituents are such as propionyl, acetyl, etc. The more
preferred substituents are hydrogen, Cl-C6 alkyls, and
Cl-C6 hydroxyalkyl.
In a substituted polyamine the substituents are
found at any atom capable of receiving them. The substi-
tuted atoms, e.g., substituted nitrogen atoms, are
generally geometrically inequivalent, and consequently the
substituted amines finding use in the present invention
can be mixtures of mono- and polysubstituted polyamines
with substituent groups situated at equivalent and/or
inequivalent atoms.
The more preferred polyamine finding use within
the scope of the present invention is a polyalkylene poly-
amine, including alkylene diamine, and including substi-
tuted polyamines, e.g., alkyl subs~ituted polyalkylenepolyamine. Preferably, the alkylene group contains from
to 6 carbon atoms, there being preferably from 2 to 3
carbon atoms between the ni~rogen atoms. Such groups are
exemplified by ethylene, 1,2-propylene, 2,2-dimethyl-
propylene, trimethylene, etc. Examples of such polyaminesinclude ethylene diamine, diethylene triamine, di~tri-
methylene)triamine, dipropylene triamine, triethylene
tetramine, tripropylene tetramine, tetraethylene penta-
mine, and pentaethylene hexamine. Such amines encompass
3" isomers such as branched-chain polyamines and the
previously mentioned substituted polyamines, including
hydrocarbyl substituted polyamines. Among the polyalkyl-
ene polyamines, those containing 2-12 amine nitrogen atoms
and 2-24 carbon atoms are especially preferred, and the
~0
~27~
01 -9_
C2-C5 alkylene polyamines are most preferred, in parti-
cular, the lower polyalkylene polyamines, e.g., ethylene
diamine, dipropylene triamine, etc.
The polyamine component also may contain hetero-
cyclic polyamines, heterocyclic substituted amines and
substituted heterocyclic compounds, wherein the hetero-
cycle comprises one or more 5-6 membered rings containing
oxygen and/or nitrogen. Such heterocycles may be
saturated or unsaturated and substituted with groups
selected from the aforementioned (A), (B), (C) and (D).
The heterocycles are exemplified by piperazines, such as
2-methylpiperazine, 1,2-bis-(N-piperazinyl)ethane, and
N,N'-bis(N-piperazinyl)piperazine, 2-methylimidazoline,
3-aminopiperidine, 2-aminopyridine, 2-(3-aminoethyl)-3-
pyrroline, 3-aminopyrrolidine, N-(3-aminopropyl)-
morpholine, etc. Among the heterocyclic compounds, the
piperazines are preferred.
Typical polyamines that can be used to form the
compounds of this invention include the following:
ethylene diamine, 1,2-propylene diamine, 1,3-propylene
diamine, diethylene ~riamine, triethylene tetramins, hexa-
methylene diamine, tetraethylene pentamine, methylamino-
propylene diamine, N-(betaaminoethyl)pipera~ine, N,N'-
di(betaaminoethyl)piperazine~ N,N'-di(beta-aminoethyl)-
imidazolidone-2, N-~beta-cyanoethyl)ethane-1,2-diamine,
1,3,6,9-tetraaminooc~adecane, 1,3,6-triamino-9-oxadecane,
N~methyl-1,2-propanediamine, 2-(2-aminoethylamino)-
ethanolO
Another group of suitable polyamines are thepropyleneamines, tbisaminopropylethylenediamines).
Propyleneamines are prepared by the reaction of acryl-
onitrile with an ethyleneamine, for example, an ethylene-
3~ amine having the formula H2N(CH2CH2NH)zH wherein Z is aninteger from 1 to 5, followed by hydrogenation of the
resultant intermediate. Thus, the product prepared from
ethylene diamine and acryl~nitrile would be
H2~(CH2)3N~(~H2)2NH~CH2)3NH2
-10- 61g36-1696
In many instances the polyamine used as a reactant in
the production of succinimides of the present invention is not
a single compound but a mixture in which one or several
compounds predominate with the average composition indicated.
For example, tetraethylene pentamine prepared by the
polymerization of aziridine or the reaction of dichloroethylene
and ammonia will have both lower and higher amine members,
e.g., triethylene tetramine, substituted piperazines and
pentaethylene hexamine, but the composition will be largely
tetraethylene pentamine and the empirical formula of the total
amine composltion will closely approximate that of
tetraethylene pentamine. Finally, in preparing the succinimide
for use in this invention, where the various nitrogen atoms of
the polyamine are not geometrically equivalent, several
substitutional isomers are possible and are encompassed within
the final product. Methods of preparation of polyamines and
their reactions are detailed in Sidyewich's "The Organic
Chemistry of Nitrogen", Clarendon Press, Oxford, 1966; Noller's
"Chemistry of Organic Compounds", Saunders, Philadelphia, 2nd
Ed., 1957; and Kirk Othmer's "Encyclopedia of Chemical
Technology", 2nd Ed., especially Volumes 2, pp. 99-116.
The reaction of a polyamine with an alkenyl or alkyl
succinic anhydride to produce the polyamine alkenyl or alkyl
succinimides is well known in the art and is disclosed in U.S.
Patents Nos. 2,992,708; 3,018,291; 3,024,237; 3,100,673;
3,219,666; 3,172,892 and 3,272~746.
As noted above, the term "polyamino alkenyl or alkyl
succinimide" refers to both polyamino alkenyl or alkyl mono-
and bis-succinimides and to the higher analogs of polyamino
alkenyl or alkyl poly succinimides. Preparation of the bis-
~f~ 5-
-lOa- 61936-16g6
and higher analogs may be accomplished by controlling the molar
ratio of the reagents. For example, a product comprising
predominantly mono- or
~2~55
01 -1 1-
bis-succinimide can be prepared by controlling th~ molar
ratios of the polyamine and succinic anhydride. Thus, if
05 one mole of polyamine is reacted with one mole of an
alkenyl or alkyl substituted succinic anhydride, a
predominantly mono-succinimide product will be prepared.
If two moles of an alkenyl or alkyl substituted succinic
anhydride are reacted per mole of polyamine, a bis-
succinimide is prepared. Higher analogs may likewise beprepared.
A particularly preferred class of polyamino
alkenyl or alkyl succinimides employed in the instant
invention may be represent~d by Formula Il:
o
R ~ 13
~N~R2-N~a -R2-W
~1 0
II
wherein R is alkenyl or alkyl of from 10 to 300 carbon
atoms; R2 is alkylene of 2 to 10 carbon atoms; R3 is
hydrogen, lower alkyl or lower hydroxy alkyl a is an
integer from O to 10; and W is -NH2 or represents a group
of Formula III:
R ~
~ N-
11
o
III
3~
wherein R is alkenyl or alkyl of from 10 to 300 carbon
atoms; with the proviso that when ~ is the group of
Formula III above, then a is not zero and at least one of
4~ R3 is hydrogen.
~27(~X~S
01 -l2-
As indicated above, the polyamine employed in
preparing the succinimide is often a mixture of dif ferent
05 compounds having an average composition indicated as the
Formula II. Accordingly, in Formula II each value of R2
and R3 may be the same as or different from other R2 and
3'
Preferably ~ is alkenyl or alkyl of from
1~ 20 to 300 carbon atoms. In another preferred embodiment,
R is preferably 12 to 100 carbon atoms and more preferably
20 to lO0 carbon atoms.
Preferably, R2 is alkylene of ~ to 6 carbon
atoms and most preferably is either ethylene or propylene.
Preferably, R3 is hydrogen or lower alkyl.
Preferably, a is an integer from 1 to 6.
In formula II, the polyamino alkenyl or alkyl
succinimides may be conveniently viewed as being composed
of three moieties that is the alkenyl or alkyl moiety R,
the succinimide moiety represented by the formula:
~'
O
and the polyamino moie~y represented by the group
13
~R2-N~aR2-W .
The preferred alkylene polyamines employed in
this reaction are generally represented by the formula:
3~
H2N~R2NH ) a-R2NH2
wherein R2 is an alkylene moiety of 2 to 10 carbon a~oms
and a is an integer from about 0 to 10. However, the
~270255
~1 -l3-
prepara~ion of these alkylene polyamines do not produce a
single compound and cyclic heterocycles, such as
05 piperazine, may be included to some extent in ~he alkylene
diamines.
B. MODIFIED SUCCINIMIDES
The polyamino alkenyl or alkyl succinimides
wherein one or more of the nitrogens of the polyamino
~ ~
moiety is substituted with R40R50( )mC~ wherein R4, R5 and
m are as defined above, are prepared by reacting a
polyamino alkenyl or alkyl Ruccinimide, IV, with a chloro-
formate, V, as shown in reaction (l) belows
O O O O
1~ 11 11 h'
R8R7NH + ClC(C)mR5R4 > R8R7NC(c)mOR5oR4 (1)
IV V VI
wherein R8 and R7 form the remainder of a polyamino
alkenyl or alkyl succinimide and R4, R5 and m are as
defined above.
Reaction (l) is conducted by contacting the
chloroformate, V, with the polyamino alkenyl or alkyl
succinimide, IV. The reaction may be conducted neat or in
a suitable inert diluent. Suitable diluents include ethyl
acetate, toluene, xylene, oil and the like. An organic
base such as pyridine, triethylamine and the like may be
added to the reaction to scavenge the acid generated.
However, the generated acid may also be removed by an
alkaline water wash tPH of from 8-9 or higher) or an
alkaline brine wash (pH of from 8-9 or higher) of the
reaction solution after reaction completion without the
need of added base. The reaction is generally conducted
at from 0C to 50C and is generally complete from within
0.5 to 24 hours. Afterwards, the product may be further
isolated by conventional techniques such as chromatogra-
phy, filtration and the like. If the succinimide contains
hydroxyalkyl, use of lower temperature 1-78C to 0C)
~;~7~
-14-
helps prevent carbonate formation. Carbonates may be
removed via reaction with an amine of the succinimide or
05 an alcohol (i.eO, ethanol) under transesterification
conditions.
Preferably, it is desirable to substitute at
O O
least 20~ of the amines with ~ )mOR5OR4; more preferably
at least 50% of the amines should be converted and most
preferably all of the amines capable of reaction should be
converted.
In general, maximum conversion of the reactive
amines of the polyamino alkenyl or alkyl succinimide can
be obtained by employing a molar charge of chloroformate
to the theoretical basic nitrogen of the alkenyl or alkyl
succinimide of from 0.7:1 to about 1:1. In some cases, a
slight excess of chloroformate may be employed to enhance
reaction rate.
Alternatively, the products of this invention
are also prepared by reacting a polyaminoalkenyl or alkyl
succinimide, IV, with an aryl carbonate as shown in
reaction l(a) below:
O O O O
R8R7NH+arylOC(C)mOR5OR~ RgR7NC(C)mOR5OR4+aryloH (la)
IV VI
wherein R4, R5, R7, R8 and m are as defined above and aryl
is preferably phenyl or substitu~ed phenyl such as
3 p-nitrophenyl, p-chlorophenyl, etc.
Reaction (la) is conducted by contacting the
aryl carbonate with the polyamino alkenyl or alkyl
succinimide, IV. The reaction may be conducted neat or in
a suitable inert diluent. Suitable diluents include
toluene, xylene, thinners, oil, and the like. The
reaction is generally conducted at from 50C to 150C and
is ~enerally complete from within 1 to 4 hours.
Afterwards, the produc~ may be further isolated by
~x~ s
-15-
01
conventional techniques such as 6tripping, chromatography,
filtration, and the like.
05 The aryl carbonate is prepared via conventional
processes from the aryl alcohol and the chloroformate, V,
under conditions known per se.
The chloroformates of formula V are prepared as
shown in reaction (2) below:
O O O O
HOR50R4 ~ Cl(C)mCCl ~ Cl~(C)mOR50R4 (2)
VII VIII V
lS wherein R5 and R4 are as defined above.
This reaction is a conventional process well
known in ~he art and may be conducted by employing phos-
gene (m=O) or oxalyl chloride (m=l) generally in excess.
The reaction is conducted by adding the alcohol, VII, to a
suitable diluent such as toluene, benzene, methylene
chloride, and the like. Phosgene or oxalyl chloride is
then added to the system over a period of time.
Alternatively, the phosgene or oxalyl chloride may be
added to the diluent prior to addition of the alcohol. In
general, approximately 1.1-2.5 equivalents of phosgene or
oxalyl chloride is added per equivalent of alcohol, VII.
The reaction is conducted at from -7~ to 50C, preferably
-10 to lO~C, and is generally complete from within 1/2 to
12 hours. The chloroformate, V, may be isolated by
conventional techniques such as distillation but prefer-
ably the system is stripped of a portion of the inert
diluent which also removes hydrogen chloride gas generated
and excess reagent, VIII. The product, V, contained in
the remaining diluent is then used as is reaction (1)
above.
As used herein, the term ~chloroformate~
includes both the chloroformate tm=O of formula V) and the
chlorodicarbonyloxy analogs (m=l of formula V).
~û
~70~55
-16-
01
As used herein, the term ~molar charge of
chloroformate to the basic nitrogen of a polyamino alkenyl
or alkylsuccinimide" means that the molar charge of
chloroformate employed in the reaction i5 bassd upon the
theoretical number of basic ni~rogens contained in the
succinimide. Thus, when l eguivalent of triethylene
tetraamine tTETA) is reacted with an equivalent of
succinic anhydride, the resulting monosuccinimide will
theoretically contain 3 basic nitrogens. Accordingly, a
molar charge of 1 would require that a mole of chloro-
formate be added for each basic nitrogen or in this case
3 moles of chloroformate for each mole of monosuccinimide
prepared from TETA.
The alcohols, VII, are either commercially
available or may be readily prepared by known processes.
For instance, hydrocarbyl capped poly(oxyalkylene) monools
~i.e., R5 = -R6(OR6)m are described in U.S. Patent
No. 4,l91,537.
2U
These hydrocarbyl-terminated poly(oxyalkylene)
polymers, which are utilized in preparing the chlorofor-
mates used in the present invention are monohydroxy
compounds, i.e., alcohols, often termed monohydroxy
polyethers, or polyalkylene glycol monohydrocarbylethers,
or ~capped" poly(oxyalkylene) glycols and are to be
distinguished from the poly~oxyalkylene) glycols (diols),
or polyols, which are not hydrocarbyl-terminated, i.e.,
not oapped. The hydrocarbyl-terminated poly(oxyalkylene)
alcohols are produced by the addition of lower alkylene
oxides, such as oxirane, e~hylene oxide, propylene oxide,
the butylene oxides, or the pentylene oxides to the
hydroxy compound R~OH under polymerization conditions,
wherein R6 is the hydrocarbyl group which caps the
poly(oxyalkylene) chain. Methods of production and
properties of these polymers are disclosed in U.S. Pat.
Nos. 2,g41,479 and 2,782,240 and the aforementioned Kirk-
Othmer's ~Encyclopedia of Chemical Technology," Volume 19,
p. 507. In the polymerization reaction a single type of
alkylene oxide may be employed, e.g., propylene oxide, in
lV~702~S
0 1 ~
which case the product is a homopolymer, e.g., a poly-
toxYpropylene) propanol. However, copolymers are equally
05 satisfactory and random copolymers are readily prepared by
contacting the hydroxyl-containing compound with a mix~ure
of alkylene oxides, such as a mixture of propylene and
butylene oxides. Block copolymers of oxyalkylene units
also provide satisfactory poly(oxyalkylene) polymers for
1~ the practice of the present invention. Random polymers
are more easily prepared when the reactivities of the
oxides are relatively equal. In certain cases, when
ethylene oxides is copolymerized with other oxides, the
higher reaction rate of ethylene oxide makes the prepara-
tion of random copolymers difficult. In either case,block copolymers can be prepared. Block copolymers are
prepared by contacting the hydroxyl-containing compound
with first one alkylene oxide, then the others in any
order, or repetitively, under polymerization conditions.
A particular block copolymer is represented by a polymer
prepared by polymerizing propylene oxide on a suitable
monohydroxy compound to form a poly(oxypropylene) alcohol
and then polymerizing butylene oxide on the poly(oxy-
propylene) alcohol.
In general, the poly(oxyalkylene) polymers are
mixtures of compounds that differ in polymer chain
length. However, their properties closely approximate
those of the polymer represented by the average composi-
~ion and molecular weigh~.
The hydrocarbylpoly(oxyalkylene) moiety of the
chloroformate is composed of oxyalkylene units containing
from 2 to about 5 carbon atoms. The hydrocarbyl group
contains from 1 to about 30 carbon atoms, preferably from
2 to about 20 carbon atoms. Preferably the oxyalkylene
3S units contain from 3 to 4 carbon atoms and the molecula
weight of the hydrocarbyl poly(oxyalkylene) moiety is from
about 44 to about 10,000, more preferably from about 100
to about 5,000. Each poly(oxyalkylene) polymer contains
from 1 to 100 oxyalkylene units, preferably 2 to about 50
4~ oxyalkylene units, more preferably about 2 to 30 units and
~27~3~5~
01 -18-
most preferably 2 to about 20 such units. In general, theoxyalkylene units may be branched or unbranched. The
05 structures of the C3-C5 oxyalkylene units are any of the
isomeric structures well known to the organic chemist,
e.g., n-propylene, -CH2CH2CH2-; isopropylene, -C~CH3~CH2-;
n-butylene, -CH2CH2CH2CH2-; sec.-butylene, -CH(CH2CH3)CH2-;
tert.-butylene, -C(CH3)2CH2-; disec.-butylene,
-CH(CH3)CH(CH3)-; isobutylene, -CH~CH(CH3)CH2-; etc. The
preferred poly(oxyalkylene) compounds are composed of from
1 to about 50 oxyalkylene units, more preferably about 2
to 30 oxyalkylene units and most preferably 2 to about 20
such units.
The hydrocarbyl moiety (R-~ which terminates the
poly(oxyalkylene) chain contains from 1 to about 30 carbon
atoms, preferably from 2 to about 20 carbon atoms, and is
generally derived from the monohydroxy compound (ROH)
which is the initial site of the alkylene oxide addition
in the polymerization reaction. Such monohydroxy com-
pounds are preferably aliphatic or aromatic alcohols of
from 1 to about 30 carbon atoms, more preferably an
alkanol or an alkylphenol, and most preferably an alkyl-
phenol wherein the alkyl is a straight or branched chain
of from 1 to about 24 carbon atoms. One such preferred
alkyl group is obtained by polymerizing propylene to an
average of 4 units and has the common name of propylene
tetramer. The prcferred material may be termed either an
alkylphenylpoly(oxyalkylene) alcohol or a polyalkoxylated
alkylphenol,
Likewise, hydrocarbyloxyhydrocarbyl alcohols
(i.e., R5 - hydrocarbyl in formula VII above) may be
prepared from the corresponding glycol by art recognized
techniques as shown in reactions (3) - (6) below:
O O
H3R50H -~ CH3COH --~ HOR~j,OCCH3 ~ H20 ( 3 )
IX X XI
~0
~27~S
01 -19-
XI ~ Na ( or K) --> Na+~OR50CCH3 ( 4 )
XI I
o
R4Cl ~ XI I _> R40R50CCH3 ( 5 )
XIII XIV
XIV + base ~ R4oR5oH (~)
VII
wherein R4 and R5 are as defined above and base is an
inorganic base such as potassium bicarbonateO sodium
carbonate, sodium hydroxide and the like. Each of reac-
tions (3)-(6) is a well known and art recognized process.
Reaction (3) is a conventional esterification
reaction and is conducted by combining the diol, IX, with
the acid, X, to yield the monoester XI. Although acetic
acid is employed in reaction (3), any suitable carboxylic
acid such as trichloroacetic acid, propionic acid, benzoic
acid, and the like, may be utilized to form the monoester,
XI. In some instances, an acid catalyst such as sulfuric,
hydrochloric and the like may be employed to enhance ~he
reaction rate. In order to prevent formation of a
diester, an excess of diol, IX, is employed. In general,
from 11l to 4 equivalents of diol, IX, and preferably
2 equivalents per equi~alent of acid, X, are employed in
reaction (3). The reaction may be conducted neat or in a
suitable diluent such as toluene, benzene and the like.
The water generated during ehe reaction may be readily
removed via a Dean-Stark trap. The product ~ster, XI, may
be isolated by conventional techniques such as chromato-
graphy, filtration and the like or used in reaction (4)
without purification.
Reaction ~4) is a conventional reaction of an
alcohol with metallic sodium or potassium to form a sodium
~7~255
~1 -2~-
or potassium salt. Alternatively, potassium t-butoxide
may be employed in place of metallic sodium or
05 potassium. The reaction is generally conducted by adding
an equimolar amount of the metallic sodium or pota~sium to
the alcohol which is generally contained in ~n anhydrous
inert diluent such as tetrahydrofuran, dioxane, toluene
and the like. The reaction is generally conducted at from
0 to 60C and is generally complete from within l to
24 hours. The resulting salt, XII, i5 generally employed
in reaction 15) without isolation and/or purification.
Reaction (5) is a metathesis reaction to form
the ethers, XIV. The reaction is generally conducted by
adding an equimolar amounts of the hydrocarbyl chloride,
XIII to the sodium (or potassium) salt, XII. The réaction
is generally conducted in an inert diluent such as
toluene, dioxane and the like. The reac~ion is generally
conducted at from 0 to ll0~C and is generally complete
from with l to 24 hours. The resulting ether-ester, XIV,
may be isolated by conventional techniques such as
chromatography, filtration and the like or used in
reaction (6) without purification.
Reaction (6) is a conventional hydrolysis reac-
tion to form the alcohol-ether, VII. The reaction is
conducted by adding the ether-ester, XIV, to an aqueous
alcohol solvent such as water/methanol, water/ethanol and
the like. An inorganic base, such as sodium carbonate,
~odium hydroxide, potassium bicarbona~e and the like, is
added to the reaction. The reaction is generally
conducted at from room temperature to about 80C and is
generally complete from within l to 24 hours. The
resulting alcohol-ether, VII may then be isolated by
conventional techniques such as chromatography,
filtration~ distillation and the like.
~ he hydrocarbyl chloride, XIII, may ~e prepared
from the corresponding alcohol via a chlorinating agent
such as thionyl chloride. This reaction is well known and
is described by Buehler and Pearson, Survey of Organic
Synthesis, Vol. l, pp 330-332, Wiley & Sons, N.Y. (1978).
3L;~7~X~
~1 -21-
Accordingly, by employing chloroformate, V, and
a polyamino alkenyl or alkyl succinimide of formula II
05 above in reaction (1) above, compounds of the following
formula are produced:
R ~ l8
1~,;~N~R2_N_taR2_T
o
wherein R is alkenyl or alkyl of from 10 to 300 carbon
atoms; R2 is alkylene of from 2 to 10 carbon atoms; a is
an integer from O to 10; R8 is hydrogen, lower alkyl of
from 1 to 6 carbon atoms, lower hydroxy alkyl of from 1 to
O O
n ~1
6 carbon atoms, and -C(C)mOR50R4 wherein m is an integer
from O to 1, R4 is hydrocarbyl of from 1 to 30 carbon
atoms, R5 is a straight- or branched-chain alkylene group
of from 2 to about 30 carbon atoms, a straight- or
branched-chain alkylene group of from 2 to about 30 carbon
atoms substituted with aryl of from 6 to 10 carbon atoms
or alkaryl of from 7 to 12 carbon atoms, or -R6(0R6)p-
wherein R6 is alkylene of from 2 to 5 carbon atoms and p
is an integer from 1 to 100; T is
O
- 30
~ R
-N ~
or -NHR8 wherein R and R8 are as above defined with ~he
O O
proviso that at least one of R8 is -C(C)mORsOR4-
~0
01 -22
Preferably R is alkenyl or alkyl of from about
20 to 100 carbon atoms. Preferably R2 is alkylene of from
2 to 6 carbon atoms; a is an integer from 1 to 6.
O O
Preferred R8 is CtC)mOR5OR4 while preferred R4 is
hydrocarbyl of from 1 to 20 carbon atoms. Preferably R5
is -R6(O~6)p-; and p is an integer from 2 to 30.
The modified ~uccinimides of this invention can
be reacted at a temperature sufficient to cause reaction
with boric acid or a similar boron compound to form
borated dispersants having utility within the scope of
this invention. In addition to boric acid (boron acid),
examples of suitable boron compounds include boron oxides,
boron halides and esters of boric acid. Generally from
about 0.1 equivalents to 10 eguivalents of boron compound
to the modified succinimide may be employed.
The modified polyamino alkenyl or alkyl
~ succinimides of this invention are useful as detergent and
dispersant additives when employed in lubricating oils.
When employed in this manner, the modified polyamino
alkenyl or alkyl succinimide additive is usually present
in from 0.2 to lQ percent by weight to the to~al composi-
tion and preferably at about 0.5 to 5 percent by weight.The lubricating oil used with the additive compositions of
this invention may ~e mineral oil or synthetic oils of
lubricating viscosity and preferably suitable for use in
the crankcase of an internal combustion engine. Crankcase
lubricating oils ordinarily have a viscosity of about 1300
CSt 0F to 22.7 CSt at ?lO~F (99C). The lubricating oils
may be derived from synthetic or natural sources. Mineral
oil for use as the base oil in this invention includes
paraffinic, naphthenic and other oils that are ordinarily
used in lubricating oil compositions. Syn~hetic oils
include both hydrocarbon synthetic oils and synthetic
esters. Useful synthetic hydrocarbon oils include liquid
polymers of alpha olefins having the proper viscosity.
Especially useful are the hydrogenated liquid oligomers of
~ C6 to C12 alpha olefins such as l-decene trimer.
1~70~55
01 -23-
Likewise, alkyl benzenes of proper viscosity such as
didodecyl benzene, can be used. Useful synthetic esters
include the esters of both monocarboxylic acid and
polycarboxylic acids as well as monohydroxy alkanols and
polyols. Typical examples are didodecyl adipate,
pentaerythrito1 tetracaproate, di-2-ethylhexyl adipate,
dilaurylsebacate and the like. Complex esters prepared
1~ from mixtures of mono and dicarboxylic acid and mono and
dihydroxy alkanols can also be used.
~ lends of hydrocarbon oils with synthetic oils
are also use~ul. For example, blends of 10 to 25 weigh~
percent hydrogenated l-decene trimer with ~5 to 90 weight
percent 150 SUS ~100F) mineral oil gives an excellent
lubricating oil base.
Additive concentrates are also included within
the scope of this invention. The concentrates of this
invention usually include from about 90 to 10 weight per-
cent of an oil of lubricating viscosity and from about 10
to 90 weight percent of the complex additive of this
invention. Typically, the concentrates contain sufficient
diluent to make them easy to handle during shipping and
storageO Suitable diluents for the concentrates include
any inert diluent, preera~1y an oil of lubricating
viscosity, so that the concentrate may be readily mixed
with lubricating oils to prepare lubricating oil compo~
~itions. Suitable lubricating oils which can be used as
- diluents typically have viscosities in the range from
about 35 to about 500 Saybolt Universal Seconds (SUS~ at
100F (38C), 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.
It is also contemplated the modified
succinimides of this invention may be employed as
dispersants and detergents in hydraulic fluids, marine
7{;~
01 -24-
crankcase lubricants and the like. When so employed, themodified succinimide is added at from about 0.1 to lO
05 percent by weight to the oil. Preferably, at from 0.5 to
5 weight percent.
When used in fuels, the proper concentration of
the additive necessary in order to achieve the desired
detergency i5 dependent upon a variety of factors
including the type of fuel used, the presence of other
detergents or dispersants or other additives, etc.
Generally, however, and in th~ preferred embodiment, the
range of concentration of the additive in the base fuel is
10 to 10,000 weight parts per million, preferably from 30
to 2,000 weight part~ per million, and most preferably
from 30 to 700 parts per million of the modified
succinimide per part of base fuel. If other detergents
are pre~ent, a lesser amount of the modified succinimide
may be used.
~U The modified succinimide additives of this
invention may be formulated as a fuel concentrate, using
an inert stable oleophilic or~anic solvent boiling in the
range of about 150 to 400F. Preferably, an aliphatic or
an aromatic hydrocarbon solvent is used, such as benzene,
toluene, xylene or higher-boiling aromatics or aromatic
thinners. Aliphatic alcohols of about 3 to 8 carbon
atoms, such as isopropanol, isobu~ylcarbinol, n-butanol
and the like, in combination with hydrocarbon solvents are
also suitable for use with the fuel additive. In the fuel
concentrate, the amount of the additive will be ordinarily
at least lO percent by weight and generally not exceed
70 percent by weight and preferably from 10 to 25 weight
percent.
The following examples are offered to
specifically illustrate this invention. These examples
and illustrations are not to be construed in any way as
limiting the scope of this invention.
01 -2~-
EXAMPLES
Example I
05 Into a 1 liter three-neck flask equipped with a
mechanical stirrer and nitrogen sweep was placed 200 ml of
methylene chloride containing 18.9 g of oxalylchloride.
To this mixture at room temperature was added dropwise a
solution of methylene chlsride containing 165 9
(O.lO mole) of tetrapropenylphenyl polyoxybutylene alcohol
(C12H25 C6H4-o(c4Hgo)~lgH) ov~r 30 minutes, Upon
completion of addition, the solution was stripped to
remove methylene chloride and excess oxalyl chloride
yielding the chlorodicarbonyloxy
derivative (C12H25-c6H4-O(c4H90)~l8cccl)
chlorodicarbonyloxy derivative was then redissolved in
300 ml methylene chloride.
The methylene chloride solution containing the
chlorodicarbonyloxy derivative was then added to a
composition containing 200 ml methylene chloride, 30 ml
triethylamine and 406 g of a succinimide dispersant com-
position [prepared by reacting 1 mole of polyisobutenyl
succinic anhydride, where the polyisobutenyl group has a
number average molecular weight of about 950, with
0.87 mole of tetraethylene pentaamine; then diluting to
about 35% actives with diluent oil]. The system was
stirred at room temperature for 2 hours afterwards, the
system was partially stripped, diluted with 1 liter
hexane, extracted twice with brine (pH 8-9), dried (MgSO4)
filtered and stripped to afford the amide ester
00
(C12H25-C6H4-O~C4HgOt~l~CCN~) of the monosuccinimide.
3~ Example 2
Into a 1 liter three-neck flask equipped with a
mechanical stirrer and nitrogen sweep was placed 300 ml of
dry toluene~ The system was cooled to 0C and phosgene
gas was bubbled in until 19.9 9 was contained in the
~0
~L~7V~
- 26 -
61936-1696
toluene. At this time, 165 g (0.10 mole) of tetrapropenylphenyl
polyoxybutylene alcohol in toluene was added over 30 minutes.
The system was warmed to room temperature and stirred at room
temperature for 2 hours. At this time, excess phosgene was
removed by vigorous sparging of the reaction system with
nitrogen for 2 hours yielding a toluene solution containing
tetrapropenylphenyl polyoxybutylene chloroformate.
The methylene chloride solution containing the
chloroformate derivative was then added to a composition
containing 200 ml methylene chloride, 30 ml triethylamine and
406 g of a succinimide dispersant composition [prepared by
reacting 1 mole of polyisobutenyl succinic anhydride, where the
polyisobutenyl group has a number average molecular weight of
about 950, with 0.87 mole of tetraethylene pentaamine; then
diluting to about 35~ actives with diluent oil]. The system
was stirred at room temperature for 2 hours afterwards, the
system was partially stripped, diluted with 1 liter hexane,
extracted twice with brine (pH 8-9), dried (MgSO4) filtered and
stripped to afford the carbamate
1
(Cl2H25-c6H4-o~c4H9ot~l8cN~) of the monosuccinimide.
Example 3
Into a 1 liter three~neck flask equipped with a
mechanical stirrer and nitrogen sweep is placed 200 ml of
methylene chloride containing-18.9 g of oxalylchloride. To
this mixture at room temperature is added dropwise a solution
of methylene chloride containing 11.8 g (0.10 mole) of 2-butoxy-
ICH3
ethanol (CH3CH2CH-OCH2CH2OH) over 30 minutes. Upon completion
of addition, the solution is stripped to remove methylene
chloride and excess oxalyl chloride yielding the chlorodi-
1~7~;~55
- 26a -
61936-1696
3 00
11 11
carbonyloxy derivative (CH3CH2CH-OCH2CH20CCCl). The chloro-
dicarbonyloxy derivative is then redissolved in 300 ml
methylene chloride.
~4
~2~
01 -27~-
The methylene chloride solution containing the
chlorodicarbonyloxy derivative is then added to a com-
05 position containing 200 ml methylene chloride, 30 ml
triethylamine and 406 9 of a succinimide dispersant com-
position [prepared by reacting l mole of polyisobutenyl
- succinic anhydride, where the polyisobutenyl group has a
number a~erage molecular weight of about 950, with
0.87 mole of tetraethylene pentaamine; then diluting to
about 35~ actives with diluent oil]. The system is
~tirred at room tempera~ure for 2 hours afterwards, the
system i5 partially stripped, diluted with l liter hexane,
extracted twice with brine (pH 8-9~, dried (MgSO4)
filtered and stripped to afford the amide ester
CH3 OO
11~
(C2H5C-OCH2CH2OCCN-) of the monosuccinimide~
Exam~le 4
Into a 2 liter three-neck flask equipped with a
mechanical stirrer and nitrogen sweep was placed 300 ml of
dry toluene. The system was cooled to 0C and phosgene
gas was bubbled in until 59.7 9 was contained in the
toluene. At this time, 495 9 (0.30 mole) of tetrapro-
penylphenyl polyoxybutylene alcohol in toluene was added
over 30 minutes. The system was warmed to room tempera-
ture and stirred at room temperature for 2 hours. At this
time, excess phosgene was removed by vigorous sparging of
the reaction system with nitrogen for 2 hours yielding a
toluene solution containing tetrapropenylphenyl poly-
oxybutylene chloroformate.
The toluene solution containing the chloro-
formate derivative was then added to a composition
containing 300 ml methylene chloride, 90 ml triethylamine
and 406 9 of a succinimide dispersant composition
Iprepared by reacting l mole of polyisobutenyl su~cinic
anhydride, where the polyisobutenyl group has a number
average molecular weight of about 950, with 0.87 mole of
tetraethylene pentaamine; then diluting to about 35%
actives with diluent oil~. The system was stirred at room
temperature for 2 hours afterwards, the system was
~ s~
01 -28-
partially stripped, diluted with 2 liter hexane, extractedtwice with brine (pH 8-9), dried (MgSO4) filtered and
05 stripped to afford the carbamate
Il
H25-c6H4-otc4H9ot~l8cN-) of the monosuccinimide.
Example_S
Into a 1 liter three-neck flask eguipped with a
mechanical stirrer and nitrogen sweep is placed 200 ml of
methylene chloride containing 18.9 9 of oxalylchloride.
To this mixture at room temperature is added dropwise a
solution of methylene chloride containing 10.4 9
(0.10 mole) of 3-ethoxy-1-propanol (CH3CH20CH2CH2CH2oH)
over 30 minutes. Upon completion of addition, the
solution is stripped to remove methylene chloride and
excess oxalyl chloride yielding the chlorodicarbonyloxy
00
IIN
derivative (CH3CH2OCH2CH2CH2OCCCl). The chlorodicarbonyl-
oxy derivative is then redissolved in 300 ml methylene
chloride.
The r~thylene chloride solution containing the
chlorodicarbonyloxy derivative is then added to a com-
position containing 200 ml methylene chloride, 30 ml
triethylamine and 406 g of a succinimide dispersant com-
position IPrePared by reacting 1.0 mole of polyisobutenyl
succinic anhydride, where the polyisobutenyl group has a
number average molecular weight of about 950, with
0.5 mole of tetraethylene pentaamine; then diluting to
about 35% actives with diluent oil]. The system is
stirred at room temperature for 2 hours afterwards, the
system is partially stripped, diluted with 1 liter hexane,
extracted twice with brine ~pH 8~9~, dried (MgSO4)
filtered and stripped to afford the amide ester
00
(CH3CH2OCH2CH2OCCN=) of the bis-succinimide.
Exarnple 6
(A) In the manner of Example 2, n-butoxyethoxyethanol
(n-C4HgOCH2CH2OCH2CH2OH) was treated with phosgene to form
~;~70~55
01 -29
the corresponding chloroformate (n-C4HgOCH2CH20CH2Cff20CCl).
Into a l-liter 3-neck round bottom fl~sk was
added 94 9 of phenol, 79 9 of pyridine, and 300 ml of
toluene. The system was ~tirred at room temperature and,
over a period of 40 minutes, 1 mole (approximately 224 9)
of the above chlorofonmate was slowly added to the
system. After reaction completion, the product was
extracted with hexane. T~e organic layer was washed three
times with brine and then dried over anhydrous magnesium
sulfate. The solvent was removed by ~tripping to yield
O
the carbonate: In-C4HgOcH2cH2ocH2cH2ococ6Hs).
In a manner similar to ~A) above, ethanol was
used in place of phenol to yield the carbonate:
o
(n-C4H90CH2CH20CH2CH20CoC2H5) -
0
(~) 71.8 g of the carbonate ~n-C4HgOCH2CH2OCH2CH2OC-
OC6H5), prepared ~imilarly ~o (A) ~bove, was added to a
2-liter reaction flask together with 472 g of a ~uccin-
imide dispersant composition iprepared by reacting 1 mole
of polyisobutenyl succinic anhydride, where ~he polyiso-
butenyl group has a number average molecular weight of
about 950, with 0.5 mole of tetraethylene pentaamine; then
3~ diluting to about 50~ actives in diluent oil and having an
alkalinity value = 29.7]. Initially, the combined system
gave an alkalinity value = 25.8. The system was then
heated to 165~C and stirred under a nitrogen atmosphere
for 2 hours at which time ~he alkalinity value of the
system was 140 5. The system was cooled to 80C and an
additional 0.0255 moles ~about 7.2 9) of carbonate was
added. The system was heated to 165C and stirred under
nitrogen for an additional 40 minutes to ~ive a product
having an alkalinity value of
4~
~ ~ 7 ~
01 _30_
Il
13.6 and affording the carbamate (C4HgOCH2CH2OCH2CH2OCM~)
05 of the bissuccinimide.
: Example 7
o
6a 9 g of the carbonate (n-C~HgOcH2cH2ocH~cH
C6H5), prepared similarly to the process described in
Example 6 above, was added to ~ 5-liter reaction flask
together with 1897.2 9 of a succinimide dispersant
composition [prepared by reaction 1 mole of polyisobutenyl
succinic anhydride, where the polyisobutenyl group has a
number average molecular weight of about 950, with
0.87 mole of tetraethylene pentaamine; then diluting to
about 40 active~ with diluent oil and having an alkalinity
value of 48.0]. Initially, the combined system gave an
alkalinity value of 26.3. The ~ystem was then heated to
165C and stirred under a nitrogen atmosphere for 1-1/2
hours. The sy.~tem was then cooled to abou~ 90C while
nitrogen spargingO The system was maineained at this
temperature for 3 hours to give a product having an
alkalinity value of 12.7 and affording the carbamate
o
tc4H9ocH2cH2ocH~cH2ocN~) of the monosuccinimide.
~0
