CA1270255A

CA1270255A - Modified succinimides (v)

Info

Publication number: CA1270255A
Application number: CA000504571A
Authority: CA
Inventors: Robert H. Wollenberg; Thomas F. Buckley
Original assignee: Chevron Research and Technology Co
Current assignee: Chevron USA Inc
Priority date: 1985-04-12
Filing date: 1986-03-20
Publication date: 1990-06-12
Anticipated expiration: 2007-06-12
Also published as: EP0198690A3; EP0198690A2; BR8601619A

Abstract

ABSTRACT OF THE DISCLOSURE
Disclosed herein are additives which are useful as dispersants and detergents in lubricating oils and fuels, In particular, this invention is directed toward polyamino alkenyl or alkyl succinimides wherein one or more of the amino nitrogens of the succinimide is substi-tuted with

Description

~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 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 obtained by the isomerization of alpha olefins over a suitable catalyst such as silica.

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 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-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 ~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~

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 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 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.

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~

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

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

~ 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 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 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{;~

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 (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~

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 (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-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 -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 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~

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 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 (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 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) -(~) 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

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A polyamino alkenyl or alkyl succinimide wherein one or more of the nitrogens of the polyamino moiety is substituted with 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 from 2 to 5 carbon atoms and p is an integer from 1 to 100; and m is an integer of from 0 to 1.

2. A polyamino alkenyl or alkyl lsuccinimide as defined in Claim 1 wherein R4 is hydrocarbyl of from 2 to 20 carbon atoms.

3. A polyamino alkenyl or alkyl succinimide as defined an Claim 2 wherein the alkenyl or alkyl moiety is from about 20 to 300 carbon atoms.

4. A polyamino alkenyl or alkyl succinimide as defined in Claim 3 wherein R5 is a straight- or branched-chain alkylene group of from 2 to about 30 carbon atoms o.
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 7 to 12 carbon atoms.

5. A polyamino alkenyl or alkyl succinimide as defined in Claim 4 wherein R5 is a straight- or branched-chain alkylene group of from 2 to about 30 carbon atoms.

6. A polyamino alkenyl or alkyl succinimide as defined in Claim 5 wherein m is 0.

7. A polyamino alkenyl or alkyl succinimide as defined in Claim 5 wherein m is 1.

8. A polyamino alkenyl or alkyl succinimide as defined in Claim 3 wherein R5 is -R6?OR6?p wherein R6 is alkylene of from 2 to 5 carbon toms and p is an integer from 1 to 100.

9. A polyamino alkenyl or alkyl succinimide as defined in Claim 8 wherein R6 is alkylene of from 3 to 4 carbon atoms.

10. A polyamino alkenyl or alkyl succinimide as defined in Claim 9 wherein p is an integer from 1 to 50.

11. A polyamino alkenyl or alkyl succinimide as defined in Claim 10 wherein p is an integer from 2 to 20.

12. A polyamino alkenyl or alkyl succinimide as defined in Claim 11 wherein m is 0,

13. A polyamino alkenyl or alkyl succinimide as defined in Claim 11 wherein m is 1.

14. A polyamino alkenyl or alkyl succinimide as defined in Claim 1 wherein is

15. A compound of the formula wherein R is alkenyl or alkyl of from 10 to 300 carbon; R2 is alkylene of from 2 to 10 carbon atoms; a is an integer from 0 to 10; R8 is hydrogen, lower alkyl of from 1 to 6 carbon atoms and wherein m is an integer from 0 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 or 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?OR6?p wherein R6 is alkylene of from 2 to 5 carbon atoms and p is an integer from 1 to 100; T is or -NHR8 wherein R and R8 are as defined above with the proviso that at least one of R8 is .

16. A compound of the formula defined in Claim 15 wherein R is alkenyl or alkyl of from 20 to 300 carbon atoms.

17. A compound of the formula defined in Claim 16 wherein R is alkenyl or alkyl of from 20 to 100 carbon toms.

18. A compound of the formula defined in Claim 17 wherein a is an integer of from 1 to 6.

19. A compound of the formula defined in Claim 18 wherein R2 is alkylene of from 2 to 6 carbon atoms.

20. A compound of the formula defined in Claim 19 wherein R4 is hydrocarbyl of from 2 to 20 carbon atoms.

21. A compound of the formula defined in Claim 20 wherein R5 is a straight- or branched-chain alkylene group of from 2 to about 30 carbon atoms.

22. A compound of the formula defined in Claim 20 wherein R5 is -R6?OR6?p wherein R6 is alkylene of from 2 to 5 carbon atoms and p is an integer from 1 to 100.

23. A compound of the formula defined in Claim 22 wherein R6 is alkylene of from 3 to 4 carbon atoms and p is an integer from 2 to 20.

24. A compound of the formula defined in Claim 19 wherein is .

25. A compound of the formula defined in Claim 19 wherein is .

26. A lubricating oil composition containing an oil of lubricating viscosity and a dispersant effective amount of a polyamino alkenyl or alkyl succinimide wherein one or more of the nitrogens of the polyamino moiety is substi-tuted with 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 from 2 to 5 carbon atoms and p is an integer from 1 to 100; and m is an integer of from 0 to 1.

27. The lubricating oil composition as defined in Claim 26 wherein R4 is hydrocarbyl of from 2 to 20 carbon atoms.

28. The lubricating oil composition as defined in Claim 27 wherein the alkenyl or alkyl moiety is from about 20 to 300 carbon atoms.

29. The lubricating oil composition as defined in Claim 28 wherein R5 is 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 10 carbon atoms or alkaryl of 7 to 12 carbon atoms.

30. The lubricating oil composition as defined in Claim 29 wherein R5 is a straight- or branched-chain alkylene group of from 2 to about 30 carbon atoms.

31. The lubricating oil composition as defined in Claim 30 wherein m is 0.

32. The lubricating oil composition as defined in Claim 30 wherein m is 1.

33. The lubricating oil composition as defined in Claim 28 wherein R5 is -R6?OR6?p wherein R6 is alkylene of from 2 to 5 carbon toms and p is an integer from 1 to 100.

34. The lubricating oil composition as defined in Claim 33 wherein R6 is alkylene of from 3 to 4 carbon atoms.

35. The lubricating oil composition as defined in Claim 34 wherein p is an integer from 1 to 50.

36. The lubricating oil composition as defined in Claim 35 wherein p is an integer from 2 to 20.

37. The lubricating oil composition as defined in Claim 36 wherein m is 0.

38. The lubricating oil composition as defined in Claim 36 wherein m is 1.

39. The lubricating oil composition as defined in Claim 26 wherein is .

40. A lubricating oil composition containing an oil of lubricating viscosity and a dispersant effective amount of a compound of the formula wherein R is alkenyl or alkyl of from 10 to 300 carbon; R2 is alkylene of from 2 to 10 carbon atoms; a is an integer from 0 to 10; R8 is hydrogen, lower alkyl of from 1 to 6 carbon atoms and wherein m is an integer from 0 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 or 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?OR6?p wherein R6 is alkylene of from 2 to 5 carbon atoms and p is an integer from 1 to 100; T is or -NHR8 wherein R and R8 are as defined above with the proviso that at least one of R8 is .

41. The lubricating oil composition as defined in Claim 40 wherein R is alkenyl or alkyl of from 20 to 300 carbon atoms.

42. The lubricating oil composition as defined in Claim 41 wherein R is alkenyl or alkyl of from 20 to 100 carbon toms.

43. The lubricating oil composition as defined in Claim 42 wherein a is an integer of from 1 to 6.

44. The lubricating oil composition as defined in Claim 43 wherein R2 is alkylene of from 2 to 6 carbon atoms.

45. The lubricating oil composition as defined in Claim 44 wherein R4 is hydrocarbyl of from 2 to 20 carbon atoms.

46. The lubricating oil composition as defined in Claim 45 wherein R5 is a straight- or branched-chain alkylene group of from 2 to about 30 carbon atoms.

47. The lubricating oil composition as defined in Claim 45 wherein R5 is -R6?OR6?p wherein R6 is alkylene of from 2 to 5 carbon atoms and p is an integer from 1 to 100.

48. The lubricating oil composition as defined in Claim 47 wherein R6 is alkylene of from 3 to 4 carbon atoms and p is an integer from 2 to 20.

49. The lubricating oil composition as defined in Claim 44 wherein is .

50. The lubricating oil composition as defined in Claim 44 wherein is .

51. A lubricating oil concentrate comprising from about 10 to 90 weight percent of an oil of lubricating viscosity and from about 90 to about 10 weight percent of a compound as defined in Claim 1.

52. A lubricating oil concentrate comprising from about 10 to about 90 weight percent of an oil of lubricat-ing viscosity and from about 90 to about 10 weight percent of a compound of the formula defined in Claim 15.

53. A fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from 10 to 10,000 parts per million of a compound as defined in Claim 1.

54. A fuel composition comprising a hydrocarbon boiling in the gasoline or diesel range and from 10 to 10,000 parts per million of a compound as defined in Claim 15.

55. A fuel concentrate comprising from about 30 to go weight percent of an inert oleophilic organic solvent and from about 10 to about 70 weight percent of a compound as defined in Claim 1.

56. A fuel concentrate comprising from about 30 to about 90 weight percent of an inert oleophilic organic solvent and from about 10 to about 70 weight percent of a compound of the formula defined in Claim 15.