USOO6358892B1

(12) United States Patent (10) Patent No.: US 6,358,892 B1

Harrison et al. (45) Date of Patent: Mar. 19, 2002

(54) POLYALKYLENE SUCCINIMIDES AND 5,716,912 A 2/1998 Harrison et al. ............ 508/192
POST TREATED DERVATIVES THEREOF 5,821,205. A * 10/1998 Harrison et al. ............ 508/291
5,849,676 A * 12/1998 Harrison et al. ............ 508/291
(75) Inventors: James J. Harrison, Novato; William 5,851,965 A * 12/1998 Harrison et al. ............ 508/291
R. Ruhe, Jr., Benecia, both of CA (US) 5,853,434 A 12/1998 Harrison et al. .............. 44/331
5,872,083 A * 2/1999 Harrison et al. ............ 508/287
(73) Assignee: Chevron Chemical Company, San FOREIGN PATENT DOCUMENTS
Ramon, CA (US)
EP O682102 A2 * 11/1965
Notice: Subject to any disclaimer, the term of this EP OO72645 * 2/1983
patent is extended or adjusted under 35 EP O146.162 * 6/1985
EP O65 7475 * 6/1995
U.S.C. 154(b) by 0 days. GB 1488486 * 10/1977
This patent is Subject to a terminal dis OTHER PUBLICATIONS
claimer.
E.S. Forbes and E.I. Neustadter “The Mechanism of Action
(21) Appl. No.: 09/176,278 of Polyisobutenyl Succinmide Lubricating Oil Additives.”
(Tribology, vol. 5, No. 2, pp. 72-77; Apr. 1972).*
(22) Filed: Jan. 27, 1998 S.T. Roby, R.E. Kornbrekke and J.A. Supp, “Deposit For
mulation in Gasoline Engines, Part 2, Dispersant Effects on
Related U.S. Application Data Sequence VE Deposits.” (Journal of the Society of Tribolo
gists and Lubrication Engineers, vol. 50, 12,989-995; Dec.
(60) Division of application No. 08/631,648, filed on Apr. 9, 1994).*
1996, now Pat. No. 5,716,912, which is a continuation-in
part of application No. 08/566,231, filed on Dec. 1, 1995, * cited by examiner
now Pat. No. 5,821.205.
(51) Int. Cl." .................... C10M 133/44; C10M 149/10 Primary Examiner Margaret Medley
(52) U.S. Cl. ....................... 508/192; 508/222; 508/291; (74) Attorney, Agent, or Firm Walter L. Stumpf, Richard
526/262 J. Sheridan
(58) Field of Search .......................... 44/330, 331, 346, (57) ABSTRACT
44/317; 508/192, 222; 526/262; 558/286,
295, 297 A Succinimide composition is prepared by reacting a mixture
of an alkenyl or alkylsuccinic acid derivative, an unsaturated
(56) References Cited acidic reagent copolymer, and a polyamine under reactive
U.S. PATENT DOCUMENTS conditions, then treating the reaction product with either a
cyclic carbonate or a linear mono- or polycarbonate or boron
3,172,892 A * 3/1965 Le Suer et al. .......... 260/326.5 compound under reactive conditions. The alkenyl or alkyl
3,219,666 A 11/1965 Norman et al. ............. 260/268 Substituent of the alkenyl or alkylsuccinic acid derivative
3,361,673 A * 1/1968 Stuart et al. has a Mn of from 1800 to 3000. The unsaturated acidic
3,381,022 A 4/1968 Le Suer ................... 260/404.8 reagent copolymer has a Mn of from 2000 to 4800, and is a
3,455.827 A * 7/1969 Mehmedbasich copolymer of an unsaturated acidic reagent and an olefin
3,912,764 A * 10/1975 Palmer, Jr. ............... 260/346.8
4,234,435 A * 11/1980 Meinhardt et al. having an average of from 14 to 30 carbon atoms. The
4,612,132 A * 9/1986 Wollenberg et al. polyamine has at least three nitrogen atoms and 4 to 20
4,747,965 A * 5/1988 Wollenberg et al. carbon atoms. The mixture contains from 1.5 to 10 equiva
5,112,507 A * 5/1992 Harrison lents of the alkenyl or alkylsuccinic acid derivative per
5,241,003 A * 8/1993 Degonia et al. ............ 525/123 equivalent of unsaturated acidic reagent copolymer and from
5,266,186 A * 11/1993 Kaplan .................. 208/48 AA 0.4 to 1.0 moles of polyamine per equivalent of alkenyl or
5,286.799 A * 2/1994 Harrison et al. ..... ... 525/285 alkylsuccinic acid derivative plus unsaturated acidic reagent
5,319,030 A * 6/1994 Harrison et al. ............ 525/285 copolymer.
5,334.321 A * 8/1994 Harrison et al.
5,356,522 A * 10/1994 Lal et al. ............... 204/192.15
5,356,552 A * 10/1994 Harrison et al. 5 Claims, No Drawings
 US 6,358,892 B1
1 2
POLYALKYLENE SUCCINIMIDES AND known processes. For example, there is a well-known ther
POST TREATED DERVATIVES THEREOF mal process (see, e.g., U.S. Pat. No. 3,361,673), an equally
well-known chlorination process (see, e.g., U.S. Pat. No.
This application is a division of application U.S. Ser. No. 3,172,892), a combination of the thermal and chlorination
08/631,648, filed Apr. 9, 1996 and now U.S. Pat. No. processes (see, e.g., U.S. Pat. No. 3,912,764), and free
5,716,912, which is a continuation-in-part of application radical processes (see, e.g., U.S. Pat. Nos. 5.286,799 and
U.S. Ser. No. 08/566,231, filed Dec. 1, 1995 and now U.S. 5,319,030). Such compositions include one-to-one mono
Pat. No. 5,821,205, both of which are incorporated by meric adducts (see, e.g., U.S. Pat. Nos. 3,219,666 and
reference herein in their entirety. 3,381,022), as well as “multiply adducted” products, adducts
The present invention relates to novel compositions having alkenyl-derived Substituents adducted with at least
comprising polyalkylene Succinimides and post-treated 1.3 Succinic groups per alkenyl-derived Substituent (see,
derivatives of polyalkylene Succinimides. In a further aspect, e.g., U.S. Pat. No. 4,234,435).
the invention relates to methods of preparing these compo U.S. Pat. Nos. 3,361,673 and 3,018,250 describe the
Sitions and their uses as dispersants in lubricating oils and reaction of an alkenyl- or alkyl-Substituted Succinic anhy
deposit inhibitors in hydrocarbon fuels. In another aspect, 15 dride with a polyamine to form alkenyl or alkyl Succinim
the invention relates to concentrates, lubricating oil ides lubricating oil dispersants and/or detergent additives.
compositions, and hydrocarbon fuel compositions contain U.S. Pat. No. 4,612,132 teaches that alkenyl or alkyl
ing Such novel compositions. Succinimides may be modified by reaction with a cyclic or
BACKGROUND OF THE INVENTION linear carbonate or chloroformate Such that one or more of
the nitrogens of the polyamine moiety is Substituted with a
Lubricating oil compositions for internal combustion hydrocarbyl oxycarbonyl, a hydroxyhydrocarbyl
engines generally contain a variety of additives to reduce or oxycarbonyl, or a hydroxy poly(oxyalkylene) oxycarbonyl.
control deposits, wear, corrosion, etc. Similarly, liquid These modified Succinimides are described as exhibiting
hydrocarbon fuels for internal composition engines, at a improved disperSancy and/or detergency in lubricating oils.
25
minimum, contain additives which control or reduce the U.S. Pat. No. 4,747,965 discloses modified Succinimides
formation of deposits. The present invention is concerned similar to those disclosed in U.S. Pat. No. 4,612,132, except
with compositions useful as dispersants or deposit inhibi that the modified Succinimides is described as being derived
torS. from Succinimides having an average of greater than 1.0
In lubricating oils, dispersants function to control Sludge, Succinic groups per long chain alkenyl Substituent.
carbon, and Varnish produced primarily by the incomplete The effect of the alkenyl-derived substituent’s molecular
oxidation of the fuel, or impurities in the fuel, or impurities weight on the performance of Succinimides as lubricating oil
in the base oil used in the lubricating oil composition. additives is described in “The Mechanism of Action of
Dispersants also control Viscosity increase due to the pres Polyisobutenyl Succinimide Lubricating Oil Additives,” by
ence of Soot in diesel engine lubricating oils. 35 E. S. Forbes and E. L. Neustadter (Tribology, Vol. 5, No. 2,
Deposit inhibitors in fuel control or reduce engine depos pp. 72-77 (April, 1972)). This article discusses, in part, the
its also caused by incomplete combustion of the fuel. Such effect of polyisobutenyl Min on the detergency properties of
deposits can form on the carburetor parts, throttle bodies, a polyisobutenyl succinimide. However, as shown in FIG. 1
fuel injectors, intake parts, and valves. Those deposits can on page 76 of their article, the results of the tests Forbes and
present Significant problems, including poor acceleration 40 NeuStadter conducted indicate that Succinimides having a
and Stalling, and increased fuel consumption and exhaust 1300 Mn polyisobutenyl substituent are more effective as
pollutants. detergents than those having a polyisobutenyl Substituent
One of the most effective class of lubricating oil dispers with a Mn of 2000 or greater. In showing the effect of
ants and fuel deposit inhibitors are polyalkylene Succinim polyisobute nyl molecular weight on Succinimide
ides. In Some cases, the Succinimides have also been found 45 detergency, this article teaches that maximum detergency
to provide fluid-modifying properties, or a So-called ViscoS performance is obtained when the polyisobutenyl group has
ity indeX credit, in lubricating oil compositions. That results a Mn of about 1300.
in a reduction in the amount of Viscosity indeX improver A recent article by S. T. Roby, R. E. Kornbrekke, and J.
which would be otherwise have to be used. A drawback of A. Supp “Deposit Formulation in Gasoline Engines, Part 2,
Succinimide dispersants is that they have generally been 50 Dispersant Effects on Sequence VE Deposits' JOURNAL OF
found to reduce the life of fluorocarbon elastomers. In THE SOCIETY OF TRIBOLOGISTS AND LUBRICATION
general, for a given Succinimide dispersant, a higher nitro ENGINEERS, Vol. 50, 12,989–995 (December 1994) teaches
gen content gives better disperSancy but poorer fluorocarbon that the length of the dispersant alkyl side chain influences
elastomer compatibility. deposit control performance, and that, at the same nitrogen
Therefore, as well as improving the disperSancy and VI 55 level, the low molecular weight (side chain 1000 daltons)
credit properties of polyalkylene Succinimides, it would be dispersants that were tested were poorer than the tested high
desirable to improve the fluorocarbon elastomer compatibil molecular weight (side chain 2000 daltons) succinimide
ity of such dispersants. It would further be desirable to dispersants. This teaching is also consistent with our prior
improve the Stability of polyalkylene Succinimides, particu observation comparing 950 Mnside chain succinimides with
larly hydrolytic stability and shear stress stability. It would 60 2200 Mn side chain Succinimides.
also be desirable to improve Soot disperSancy, especially U.S. Pat. No. 4,234,435 teaches a preferred polyalkene
where the lubricating oil is intended for use in diesel engine derived Substituent group with a Mn in the range of
crankcases. 1500–3200. For polybutenes, an especially preferred Mn
Polyalkylene Succinimides are generally prepared by the range is 1700–2400. This patent also teaches that the Suc
reaction of the corresponding polyalkylene Succinic anhy 65 cinimides must have a Succinic ratio of at least 1.3. That is,
dride with a polyalkyl polyamine. Polyalkylene Succinic there should be at least 1.3 Succinic groups per equivalent
anhydrides are generally prepared by a number of well weight of polyalkene-derived Substituent group. Most
 US 6,358,892 B1
3 4
preferably, the succinic ratio should be from 1.5 to 2.5. This acidic reagent (for example copolymers of unsaturated
patent further teaches that its dispersants also provide an acidic reagents and C-olefins) and a polyamine having at
improvement in Viscosity index. That is, these additives least three nitrogens per molecule. The C-olefin moiety of
impart fluidity modifying properties to lubricant composi the copolymer may also be Substituted with various
tions containing them. This is considered desirable for use in Substituents, So long as the Substituent does not interfere
multigrade lubricating oils but undesirable for Single-grade with the reaction or adversely affect performance of the
lubricating oils. product. Because of competing and Sequential reactions, the
Polyamino alkenyl or alkyl Succinimides and other addi reaction product will be a mixture of compounds, which
tives useful as dispersants and/or detergents, Such as Man function as dispersants. Thus, by varying the mole ratio of
nich bases, contain basic nitrogen. While basicity is an reactants, variations in the products, and correspondingly
important property to have in the dispersant/detergent variations in the properties of product, can be obtained. The
additive, it is believed that the initial attack on fluorocarbon reaction product will be a mixture because all of the reac
elastomer Seals used in Some engines involves attack by the tants are generally furnished commercially as mixtures.
basic nitrogen. This attack leads to the loSS of fluoride ions, It is believed that the improvement in properties is pri
and eventually results in cracks in the Seals and loSS of other 15
marily due to the production of a new polyalkylene Succin
desirable physical properties in the elastomer. imide that can be represented by the following formula:
A variety of post-treatments for improving various prop
erties of alkenyl Succinimides are known to the art, a number (I)
of which are described in U.S. Pat. No. 5,241,003.
Example 2 of U.S. Pat. No. 5,266,186 discloses the
preparation of dispersants by reacting certain
polyisobutenyl-Succinic anhydride adducts (see footnote 2
of Table 2) with ethylenediamine, followed by reaction with
a maleic anhydride/O-olefin copolymer. The patent teaches 25
that, by functioning as an iron Sulfide dispersant, the product
is useful to inhibit sludge deposits in refinery processing
equipment caused by the heat treatment of hydrocarbon feed Int.
StockS.
U.S. Pat. No. 5,112,507 discloses a polymeric ladder type
polymeric Succinimide dispersant in which each side of the wherein:
ladder is a long chain alkyl or alkenyl, generally having at
least about 30 carbon atoms, preferably at least about 50 W is a nitrogen-containing group Selected from the group
carbon atoms. The dispersant is described as having consisting
improved hydrolytic Stability and shear StreSS Stability, pro 35 R
duced by the reaction of certain maleic anhydride-olefin
copolymers with certain polyamines. The patent further
teaches that the polymer may be post-treated with a variety of O O
of post-treatments, and describes procedures for post
treating the polymer with cyclic carbonates, linear mono- or 40
polycarbonates; boron compounds (e.g., boric acid), and
fluorophosphoric acid and ammonia Salts thereof. R2
U.S. Pat. Nos. 5,334,321 and 5,356,552 disclose certain /
and -N
cyclic carbonate post-treated alkenyl or alkylsuccinimides
having improved fluorocarbon elastomer compatibility, 45
Ye
which are preferably prepared by the reaction of the corre
sponding Substituted Succinic anhydride with a polyamine R is a polyalkyl or polyalkylene having a number average
having at least four nitrogen atoms per mole.
European Application, EP 0 682 102 A2 discloses a molecular weight of at least 1000 preferably from 1800
proceSS which comprises reacting: a copolymer of an olefin 50
to 3000,
and maleic anhydride, an acyclic hydrocarbyl-Substituted R" is an alkyl having an average of from 12 to 28 carbon
Succinic acylating agent, and an alkylene polyamine. These atoms,
products are useful in lubricating oil compositions as addi Z is a polyalkylene polyamine linking radical;
tives for use as dispersants having Viscosity indeX improver m is a whole integer of from 1 to 3
properties. 55 n is a whole integer of from 1 to 3;
SUMMARY OF THE INVENTION X is a whole integer of from 2 to 20;
The present invention provides novel polymers compris Int. is an initiating radical;
ing polyalkylene Succinimides and post-treated derivatives Ter. is a terminating group; and
thereof. These polymers, and in particular the post-treated 60 wherein Rand R are independently hydrogen, alkyl,
derivatives, have excellent dispersant properties, improved phenyl, or taken together are alkylene to give a ring
hydrolytic and Shear StreSS Stability, and improved fluoro grOup.
carbon elastomer compatibility. In a preferred embodiment The (Int.) and (Ter.) Substituent are carried over into the
the polymers are essentially chlorine-free. present composition from the maleic anhydride reactant and
The polyalkylene Succinimides of the present invention 65 are present in the copolymer reactants as a result of the free
can be prepared by the reaction of alkyl or alkenyl Succinic radical initiator used to prepare the copolymer. Typical (Int.)
acid derivatives with certain copolymers of an unsaturated and (Ter.) group include
 US 6,358,892 B1
S 6
alkylsuccinic acid derivative plus unsaturated acidic reagent
O O copolymer. Preferably, the acid derivative is an anhydride,
R5-; R5-O-R-C -/.: R-O-C
--/ s
and the unsaturated acidic reagent copolymer is a copolymer
MO of maleic anhydride and an olefin, and the polyamine has at
least Six nitrogen atoms per mole.
R6 O Additional aspects of the invention will be apparent from
R5-O-C-O- R-4/M the following detailed description.
R7 O DETAILED DESCRIPTION OF THE
INVENTION
wherein R is hydrogen, alkyl, aryl, alkaryl, cycloalkyl, In its broadest aspect, the present invention involves a
alkoxy, cycloalkoxy, acyl, alkenyl, cycloalkenyl, alkynyl; or polymer having the general formula:
alkyl, aryl or alkaryl optionally substituted with 1 to 4
Substituents independently Selected from nitrile, keto, 15 (I)
halogen, nitro, alkyl, aryl, and the like; and R and R are
independently hydrogen, alkyl, aryl, alkaryl, and the like.
Typically the (Int.) group and (Ter) group will be the
Same but may also be different because of Secondary or
competing reactions in the initial copolymerization or the
Subsequent reaction used to prepare the composition of the
present invention; including, in Some reaction with organic
Solvents Such as toluene, resulting in a benzyl radical
initiator or terminating group. Int.
The corresponding post-treated derivative can be obtained 25
by treating the reaction product with the desired post wherein:
treatment. For example, the reaction product is preferably
treated with a cyclic carbonate, preferably ethylene W is a nitrogen-containing group Selected from the group
carbonate, preferably by the procedure described in U.S. Pat. consisting
Nos. 4,612,132 and 5,334.321 hereby incorporated by ref
CCCC. R
The present invention further provides lubricating oil
compositions comprising a major amount of a base oil of
lubricating Viscosity and a minor amount of the compounds of O O
of the invention (“active ingredients”). The active ingredi 35
ents can be applied at effective amounts, which are highly
effective to control engine Sludge and varnish and yet be
compatible with fluorocarbon elastomer engine Seals. The
invention also provides a concentrate comprising about 20 to
60 wt.% of the compounds or compound mixtures and about 40
40 to 80 wt.% of a compatible liquid diluent designed to be
added directly to a base oil. Both the lubricating oil com
position and concentrate may also contain other additives R is a polyalkyl or polyalkylene having a number average
designed to improve the properties of the base oil, including molecular weight of from 1800 to 3000,
other detergent-dispersants. 45 R" is an alkyl having an average of from 12 to 28 carbon
The present invention further provides a fuel composition atoms,
comprising a major amount of hydrocarbons boiling in the Z is a polyalkylene polyamine linking radical;
gasoline or diesel range and from 10 to 10,000 parts per m is a whole integer of from 1 to 3
million parts of the hydrocarbon of a compound or mixture
of compounds of the present invention. 50
n is a whole integer of from 1 to 3;
The composition of the present invention can be prepared X is a whole integer of from 2 to 20;
reacting a mixture under reactive conditions, wherein the Int. is an initiating radical;
mixture comprises: Ter. is a terminating group; and
(a) an alkenyl or alkylsuccinic acid derivative, wherein wherein R and R are independently hydrogen, alkyl,
the alkenyl or alkyl substituent has a Mn of from 1800 55 phenyl, or taken together are alkylene to give a ring group.
to 3000; In simplified terms, the compound of formula (I), shown
(b) an unsaturated acidic reagent copolymer of above, can be considered a polyalkylene Succinimide pro
(1) an unsaturated acidic reagent and duced by the reaction of a copolymer (the unsaturated acidic
(2) an olefin having an average of from 14 to 30 carbon reagent copolymer) with a monomer (the alkene or alkyl
atoms, wherein the copolymer has a Mn of from 60 Succinic acid derivative) in which the monomer is linked to
2000 to 4800; and the polymer units by a polyamine linking group. Because the
(c) a polyamine having at least three nitrogen atoms and polyalkylene Succinimide mixture contains about from 1.5
4 to 20 carbon atoms. to 10 equivalents of alkenyl or alkylsuccinic acid derivative
The mixture contains about from 1.5 to 10 equivalents of per equivalent of unsaturated acidic reagent copolymer, and
the alkenyl or alkylsuccinic acid derivative per equivalent of 65 about from 0.4 to 1.0 equivalents of polyamine per equiva
the unsaturated acidic reagent copolymer and about from 0.4 lent of alklenyl or alkylsuccinic acid derivative plus unsat
to 1.0 moles of the polyamine per equivalent of alkenyl or urated acidic reagent copolymer, other Structures, Such as
 US 6,358,892 B1
7 8
(II) and (III), shown below, can also be present, depending anhydride with a polyamine. Alkenyl or alkyl Succinimides
on the ratios of alkenyl or alkylsuccinic acid derivative, are disclosed in numerous references and are well known in
unsaturated acidic reagent copolymer, and polyamine. the art. Certain fundamental types of Succinimides and
related materials encompassed by the term of art “Succin
(II) 5 imide" are taught in U.S. Pat. Nos. 2,992,708; 3,018,291;
W 3,024,237; 3,100,673; 3,219,666; 3,172,892; and 3,272,746,
Z.
the disclosures of which are hereby incorporated by refer
CCC.
N The term “Total Base Number or “TBN refers to the
amount of base equivalent to milligrams of KOH in 1 gram
of sample. Thus, higher TBN numbers reflect more alkaline
products and therefore a greater alkalinity reserve. The TBN
of a sample can be determined by ASTM Test No. D2896 or
(III) any other equivalent procedure.
15
Int The term “SAP" refers to Saponification Number and can
be determined by the procedure described in ASTM D94 or
any other equivalent procedure.
The term “TAN’ refers to Total Acid Number and can be
determined by the procedure described in ASTM D 664 or
any other equivalent procedure.
The “Succinic ratio” or “Succination ratio” refers to the
ratio calculated in accordance with the procedure and math
ematical equation set forth in columns 5 and 6 of U.S. Pat.
25 No. 5,334.321, hereby incorporated by reference. The cal
culation is asserted to represent the average number of
Succinic groups in an alkenyl or alkylsuccinic anhydride per
Int
alkenyl or alkyl chain.
The term “PIBSA” means polyisobutenyl succinic anhy
dride.
wherein W, R, R', R, and R, Z, m, n, X, Int., Ter are the The term “hydrocarbon soluble compatible salt” refers to
Same as described above. a Salt which is Soluble in an oil of lubricating Viscosity or a
In addition to the predominant polymer of formula (I), hydrocarbon fuel Suitable for use in Spark-ignition or diesel
(II), or (III), the reaction will typically contain more com engines and which is compatible with Such composition.
plex reaction products and polymers because of competing 35 The term “alkenyl or alkylsuccinic acid derivative” refers
and Sequential reactions, and because the alkenyl or alkyl to a structure having the formula
Succinic acid derivative might contain more than one Suc
cinic anhydride moiety per long chain alkyl or alkenyl group
or contain unsaturated acidic reagent oligomers. R-CH-C
A”
Referring to formulas (I), (II), and (III), the preferred 40 V
L
compounds or compound mixtures are those wherein Z is a M
polyamino radical having about from 3 to 7, more CH -
preferably, about 4 to 5 nitrogen atoms and 8 to 20 carbon
atOmS.
The initiating group and terminating group will be a 45
function of the initiator used to initiate the free radical
reaction used to prepare the copolymer and may vary with wherein Land M are independently Selected from the group
the particular copolymer and Secondary reactions. Discount consisting of -OH, -Cl, -O-, lower alkyl or taken
ing Secondary reactions, the preferred Int. and Ter. groups together are -O- to form an alkenyl or alkylsuccinic
are where R' is a preferred alkyl group are 50
anhydride group.
The term "unsaturated acidic reagent” refers to maleic or
fumaric reactants of the general formula:
CH --U-;
O 4. ; CH
UHis 4. O O

CH
VO- VO 55
VC-CHECHHCA.
X X

Definitions
wherein X and X’ are the same or different, provided that at
As used herein the following terms have the following 60 least one of X and X is a group that is capable of reacting
meanings, unless expressly Stated to the contrary. to esterify alcohols, form amides, or amine Salts with
The term “Succinimide' is understood in the art to include ammonia or amines, form metal Salts with reactive metals or
many of the amide, imide, etc. Species which are also formed basically reacting metal compounds and otherwise function
by the reaction of a Succinic anhydride with an amine. The as acylating agents. Typically, X and/or X" is -OH,
predominant product, however, is Succinimide and this term 65 -O-hydrocarbyl, -OM' where M represents one equiva
has been generally accepted as meaning the product of a lent of a metal, ammonium or amine cation, -NH2, -Cl,
reaction of an alkenyl- or alkyl-Substituted Succinic acid or -Br, and taken together X and X can be -O- so as to
 US 6,358,892 B1
9 10
form an anhydride. Preferably, X and X’ are such that both product. However, commercially, the expense of this would
carboxylic functions can enter into acylation reactions. rarely be justified and accordingly the commercial product
Maleic anhydride is a preferred unsaturated acidic reactant. will generally be a mixture in which formulas (I), (II), and
Other Suitable unsaturated acidic reactants include electron (III) will be the predominant compounds.
deficient olefins Such as monophenyl maleic anhydride; Water, present in the System or generated by the reaction
monomethyl, dimethyl, monochloro, monobromo, of the amine with the Succinic or maleic anhydride moieties
monofluoro, dichloro and difluoro maleic anhydride, of (A) and (B) alkyl succinimide, is preferably removed
N-phenyl maleimide and other Substituted maleimides, iso from the reaction System during the course of the reaction
maleimides, fumaric acid, maleic acid, alkyl hydrogen male via azeotroping or distillation. After reaction completion, the
ates and fumarates, dialkyl fumarates and maleates, fuma System can be stripped at elevated temperatures (typically
ronilic acids and maleanic acids, and maleonitrile, and 100°OC. to 250'OC.) and reduced pressures to remove any
fumaronitrile. Volatile components which may be present in the product.
Synthesis The Alkenyl or AlkylSuccinic Acid Derivatives
The compounds of the present invention can be prepared 15 Reactant (A)
by contacting the desired alkyl or alkenyl Succinic acid Alkyl and alkenylsuccinic acid derivatives having a cal
derivative with an unsaturated acidic reagent copolymer and culated Succinic ratio of about from 1:1 to 2.5:1, and
polyamine under reactive conditions: preferably about from 1:1 to 1.5:1, may be used in the
present process. More preferably, the alkyl or alkenyl Suc
R cinic acid derivatives have a Succination ratio of about from
V 1:1 to 1.2:1. Most preferably, alkyl or alkenylsuccinic anhy
CH-CH M
drides are used. Accordingly we prefer to use alkenyl
OFC
o Y=o EU - V Succinic anhydride prepared by the thermal process, both
/ because the calculated Succination ratio of material prepared
L. M. CH-CH
25
by this proceSS is typically 1.0 to 1.2, and because the
Int: produce is essentially chlorine-free because chlorine is not
used in the Synthesis.
(B)
NH Z NH2 - - (I)
The thermal reaction of a polyolefin with maleic anhy
dride is well known and is described, for example, in U.S.
(C) Pat. No. 3,361,673. The less desirable is the chlorination
process characterized by the reaction of a chlorinated
wherein R, R', Z, L, M, n, (Int) and (Ter) are as defined polyolefin, with maleic anhydride, which is also well known
above. and is described, for example, in U.S. Pat. No. 3,172,189.
Typically the above process is conducted by contacting 35 Various modifications of the thermal proceSS and chlorina
from 1.5 to 10 equivalents of alkenyl or alkylsuccinic acid tion proceSS are also well known, Some of which are
derivative (A) per mole of unsaturated acidic reagent described in U.S. Pat. Nos. 4,388,471; 4,450,281, 3,018,250
copolymer (B) and from 0.4 to 1.0 equivalents of amine (C) and 3,024,195. Free radical procedures for preparing alkenyl
per equivalent of alkenyl or alkylsuccinic acid derivative (A) Succinic anhydrides are, for example, described in U.S. Pat.
plus unsaturated acidic reagent copolymer (B). In conduct 40 Nos. 5,286,799 and 5,319,030. All of the above referenced
ing this reaction we have generally found it convenient to patents are hereby incorporated herein by reference in their
first add the alkenyl or alkylsuccinic acid derivative and the entirety.
unsaturated acidic reagent copolymer together and then add In accordance with the invention, the alkenyl or alkyl
the polyamine. It may be desirable to conduct the reaction in Succinic anhydride reactant is derived from a polyolefin
an inert organic Solvent. Optimum Solvents will vary with 45 having a Mn from 1000 to 5000 and a Mw/Mn ratio of 1:1
the particular copolymer and can be determined from litera to 5:1. In a preferred embodiment, the alkenyl or alkyl group
ture Sources or routine experimentations. For example, in the of the Succinimide has a Mn value from 1800 to 3000. Most
case of maleic anhydride poly C-olefin copolymers, we preferred are alkenyl or alkyl Substituents having a Mn of
from 2000 to 2500.
found that 100N diluent oil and mixtures of C aromatic
Solvents are acceptable Solvents. 50 Suitable polyolefin polymers for reaction with maleic
We have found that when less than 1.5 equivalents of anhydride include polymers comprising a major amount of
alkenyl or alkylsuccinic acid derivative (A) per mole of C. to C monoolefin, e.g., ethylene, propylene, butylene,
unsaturated acidic reagent copolymer (B) are used then the iso-butylene and pentene. The polymers can be
polymer Sometimes contains gels, which is undesirable. homopolymers, Such as polyisobutylene, as well as copoly
Typically, the reaction is conducted at temperatures in the 55 mers of two or more Such olefins, Such as copolymers of:
range of about from 140 to 180° C., preferably 150 to 170° ethylene and propylene, butylene, and isobutylene, etc.
C. for about from 1 to 10 hours, preferably 4 to 6 hours. Other copolymers include those in which a minor amount of
Typically the reaction is conducted at about atmospheric the copolymer monomers (e.g., 1 to 20 mole percent), is a C
preSSure; however, higher or lower preSSures can also be to C. nonconjugated diolefin, e.g., a copolymer of isobuty
used depending on the reaction temperature desired and the 60 lene and butadiene or a copolymer of ethylene, propylene
boiling point of the reactants or Solvent. and 1,4-hexadiene, etc.
AS above noted, the reaction product will typically be a A particularly preferred class of olefin polymers for
mixture, both because of the Secondary products or byprod reaction with maleic anhydride comprises the polybutenes,
ucts and also because the reactants will typically be mix which are prepared by polymerization of one or more of
tures. In theory, pure compounds could be obtained, for 65 1-butene, 2-butene and isobutene. Especially desirable are
example by using pure compounds as reactants and then polybutenes containing a Substantial proportion of units
Separating out the desired pure compounds from the reaction derived from isobutene. The polybutene may contain minor
 US 6,358,892 B1
11 12
amounts of butadiene, which may or may not be incorpo Poly(styrene-co-maleic anhydride) resins: These materi
rated in the polymer. These polybutenes are readily available als are known as SMACE) resins. There are two molecular
commercial materials well known to those skilled in the art. weight versions. The low molecular weight resin is called
Examples of procedures illustrating the preparation of Such SMA resin and is available from ARCO Chemical with
material can be found, for example, in U.S. Pat. Nos. styrene to maleic anhydride ratio’s of 1:1, 2:1, and 3:1. The
3,215,707; 3,231,587; 3,515,669; 3,579,450; 3,912,764 and high molecular weight resin is produced by Monsanto
4,605,808, hereby incorporated by reference for their dis (Lytron(R), ARCO (Dylark(R) or American Cyanamide
closures of Suitable polybutenes. (Cypress(R). Other names for SMA copolymers are
The alkenyl or alkylsuccinic anhydride may also be Styrolmol, Maron MS, and Provinal ST resins. In some
prepared using the So-called highly reactive or high methyl cases partially esterified resins are also available.
Vinylidene polyalkylene, most commonly polyisobutene, Poly(ethylene-co-maleic anhydride) resins: These mate
Such as described in U.S. Pat. Nos. 4,152,499; 5,071,919; rials are manufactured by Monsanto under the trade name
5,137,980; 5.286,823; 5,254,649; published International EMACE). They are also called Malethamer and Vinac resins.
Applications Numbers WO 93 24539-A1; WO9310063-A1; Poly(alpha olefin-co-maleic anhydride) resins are avail
and published European Patent Applications Numbers 15
able from Chevron Chemical as PA-18 (octadecene-1-co
0355895-A; 0565285A; and 0587381A, all of which are maleic anhydride), or can be prepared as in Preparation 1.
hereby incorporated by reference in their entirety. Other Alternately mixtures of alpha olefins can be used. These
polyalkenes can also be used including, for example, poly materials have been described in U.S. Pat. Nos. 3,461,108;
alkenes prepared using metallocene catalysts Such as for 3,560,455; 3,560,456; 3,560,457; 3,580,893; 3,706,704;
example described in published German patent application 3,729,450; and 3,729,451. Partially esterified olefin co
DE 4313O88A1 maleic anhydride resins can also be used. Some examples of
The Unsaturated Acidic Reagent Copolymer these types of resins are called Ketjenlube(E) resins available
from AKZO Co.
Reactant (B) Poly(isobutene-co-maleic anhydride) resins are called
25
The unsaturated acidic reagent copolymers used in the ISOBAMCR and are manufactured by Curaray Co. Ltd. They
present invention can be random copolymers or alternating are also available from Humphrey chemical Co. under the
copolymers, and can be prepared by known procedures. code K-66.
Further, in most instances, examples of each class are readily Poly(butadiene-So-maleic anhydride) resins are called
commercially available. Such copolymerS may be prepared MaldeneF) and are made by Borg-Warner Corp.
by the free radical reaction of an unsaturated acidic reagent Poly(methylvinylether-co-maleic anhydride) resins are
with the corresponding monomer of the other unit of the sold by GAF Corporation under the name Gantrey An. Other
copolymer. Thus, in the present case, the monomer will
correspond to R' in formula (I) plus a vinyl group, i.e., names are called Visco Frey.
R-CH=CH2. Hence, where R is phenyl the monomer will Poly(Vinylacetate-co-maleic anhydride) resins are avail
35
be styrene. Accordingly, the unsaturated acidic reagent able from Monsanto and are called Lytron 897, 898, and
copolymer can be prepared by the free radical reaction of an 899. They are also called Pouimalya resins in Europe.
unsaturated acidic reagent, preferably maleic anhydride, We have found that excellent results can be obtained using
With the corresponding Cs to Cs C-olefin, Cs to Cas a copolymer prepared by the free radical polymerization of
polyalkylene, ethylene, styrene, 1,3-butadiene, C. vinyl 40
maleic anhydride and C to Cs C.-olefins or olefin mixtures
alkyl ether, or C. Vinyl alkanoate. thereof.
We prefer to use alpha olefins from C to Cs because
these materials are commercially readily available, and The Polyamine Reactant (C)
because they offer a desirable balance of the length of the The polyamine reactant should have at least three amine
molecular weight tail, and the Solubility of the copolymer in 45 nitrogen atoms per mole, and preferably 4 to 12 amine
nonpolar Solvents. Mixtures of olefins, eg C, C, and Cs nitrogens per molecule. Most preferred are polyamines
are especially desirable. having from about 6 to about 10 nitrogen atoms per mol
The degree of polymerization of the copolymers can vary ecule. The number of amine nitrogen atoms per molecule of
over a wide range. In general copolymers of high molecular polyamine is calculated as follows:
weight can be produced at low temperatures and copolymers 50
of low molecular weight can be produced at high tempera Average number of nitrogen % Nx M
tures. It has been generally shown that for the polymers of atoms in molecule of polyamine T 14x100
this invention, we prefer low molecular weight copolymers,
i.e., low molecular weight (2000–5500 for example) because
higher molecular weight copolymers (greater than 10,000 55 wherein
for example) can Sometimes produce polymers that contain % N=percent nitrogen in polyamine or polyamine mixture
gels. M=number average molecular weight of the polyamine
The copolymerization is conducted in the presence of a or polyamine mixture
Suitable free radical initiator; typically a peroxide type Preferred polyalkylene polyamines also contain from
initiator, e.g. di(t-butyl) peroxide dicumyl peroxide or azo 60 about 4 to about 20 carbon atoms, there being preferably
type initiator, e.g., isobutylnitrile type initiators. Procedures from 2 to 3 carbon atoms per alkylene unit. The polyamine
for preparing poly C-olefin copolymers are, for example, preferably has a carbon-to-nitrogen ratio of from 1:1 to 10:1.
described in U.S. Pat. Nos. 3,560,455 and 4,240,916, hereby Examples of Suitable polyamines that can be used to form
incorporated by reference in their entirety. Both patents also the compounds of this invention include the following:
describe a variety of initiators. 65 tetraethylene pentamine, pentaethylene hexamine, Dow
Some examples of maleic anhydride C-olefin copolymers E-100R) heavy polyamine (number average M=303, avail
C. able from Dow Chemical Company, Midland, Mich.), and
 US 6,358,892 B1
13 14
Union Carbide HPA-X heavy polyamine (number average diluent, for example, toluene, Xylene. Examples of Suitable
M=275, available from Union Carbide Corporation, catalysts include, for example, phosphoric acid, boron
Danbury, Conn.). Such amines encompass isomers, Such as trifluoride, alkyl or aryl Sulfonic acid, alkali or alkaline
branched-chain polyamines, and the previously mentioned carbonate. Generally, the same Solvents or diluents as
Substituted polyamines, including hydrocarbyl-Substituted described above with respect to the preparation for the
polyamines. HPA-X heavy polyamine (“HPA-X”) contains co-polymer (A) or polymer (I) can also be used in the cyclic
an average of approximately 6.5 amine nitrogen atoms per carbonate post-treatment.
molecule. Such heavy polyamines generally afford excellent The reaction of polyamino alkenyl or alkyl Succinimides
results. with cyclic carbonates is known in the art and is described
The polyamine reactant may be a single compound but in U.S. Pat. No. 4,612,132, hereby incorporated by
typically will be a mixture of compounds reflecting com reference, in its entirety. Generally, the procedures described
mercial polyamines. Typically the commercial polyamine to post-treat polyamino alkenyl or alkyl Succinimides with
will be a mixture in which one or Several compounds cyclic carbonates can also be applied to post-treat the
predominate with the average composition indicated. For present polymers.
example, tetraethylene pentamine prepared by the polymer 15
A particularly preferred cyclic carbonate is 1,3-dioxolan
ization of aziridine or the reaction of dichloroethylene and 2-one (ethylene carbonate) because it affords excellent
ammonia will have both lower and higher amine members, results and also because it is readily commercially available.
e.g., triethylene tetramine ("TETA), Substituted piperazines The molar charge of cyclic carbonate employed in the
and pentaethylene hexamine, but the composition will be post-treatment reaction is preferably based upon the theo
largely tetraethylene pentamine and the empirical formula of
the total amine composition will closely approximate that of retical number of basic nitrogens contained in the polyamino
tetraethylene pentamine. Substituent of the Succinimide. Thus, when one equivalent of
Other examples of Suitable polyamines include admix tetraethylene pentamine (“TEPA") is reacted with one
tures of amines of various sizes, provided that the overall equivalent of Succinic anhydride and one equivalent of
mixture contains at least 4 nitrogen atoms per molecule. 25
copolymer, the resulting bis Succinimide will theoretically
Included within these Suitable polyamines are mixtures of contain 3 basic nitrogens. Accordingly, a molar charge of 2
diethylene triamine (“DETA) and heavy polyamine. A would require that two moles of cyclic carbonate be added
preferred polyamine admixture reactant is a mixture con for each basic nitrogen or in this case 6 moles of cyclic
taining 20% by weight DETA and 80% by weight HPA-X; carbonate for each mole equivalent of polyalkylene Succin
as determined by the method described above, this preferred imide or succinimide prepared from TEPA. Mole ratios of
polyamine reactant contains an average of about 5.2 nitro the cyclic carbonate to the basic amine nitrogen of the
gen atoms per mole. polyamino alkenyl Succinimide employed in the process of
Methods of preparation of polyamines and their reactions this invention are typically in the range of from about 1:1 to
are detailed in Sidgewick's THE ORGANIC CHEMISTRY OF about 4:1; although preferably from about 2:1 to about 3:1.
NITROGEN, Clarendon Press, Oxford, 1966; Noller's CHEM 35 As described in U.S. Pat. No. 4,612,132, cyclic carbon
ISTRY OF ORGANIC COMPOUNDS, Saunders, Philadelphia, 2nd ates may react with the primary and Secondary amines of a
Ed., 1957; and Kirk-Othmer's ENCYCLOPEDIA OF CHEMICAL polyamino alkenyl or alkyl Succinimide to form two types of
TECHNOLOGY, 2nd Ed., especially Volumes 2, pp. 99-116. compounds. In the first instance, Strong bases, including
unhindered amines Such as primary amines and Some Sec
Post-Treatments ondary amines, react with an equivalent of cyclic carbonate
40
We have found that the dispersancy of the present poly to produce a carbamic ester. In the Second instance, hindered
merS is generally further improved by reaction with a cyclic bases, Such as hindered Secondary amines, may react with an
carbonate. This may result in Some reduction in fluorocarbon equivalent of the same cyclic carbonate to form a hydroxy
elastomer compatibility. However, this generally can be alkyleneamine linkage. (Unlike the carbamate products, the
most than offset by reducing the concentration of the car 45 hydroxyalkyleneamine products retain their basicity.)
bonated post-treated polymer in light of the increased dis Accordingly, the reaction of a cyclic carbonate may yield a
perSancy. The cyclic carbonate post-treatment is especially mixture of products. When the molar charge of the cyclic
advantageous where the dispersant will be used in engines carbonate to the basic nitrogen of the Succinimide is about
which do not have fluorocarbon elastomer seals. The result 1 or less, a large portion of the primary and Secondary
ing modified polymer has one or more nitrogens of the 50 amines of the succinimide will be converted to hydroxy
polyamino moiety substituted with a hydroxy hydrocarbyl hydrocarbyl carbamic esters with Some hydroxyhydrocar
oxycarbonyl, a hydroxy poly(oxyalkylene)oxycarbonyl, a bylamine derivatives also being formed. AS the mole ratio is
hydroxyalkylene, hydroxyalkylenepoly-(oxyalkylene), or raised above 1 increased amounts of poly(oxyalkylene)
mixture thereof. polymers of the carbamic esters and the hydroxyhydrocar
The cyclic carbonate post-treatment is conducted under 55 bylamine derivatives are produced.
conditions Sufficient to cause reaction of the cyclic carbonate Both the polymers and post-treated polymers of this
with Secondary amino group of the polyamino Substituents. invention can also be reacted with boric acid or a similar
Typically, the reaction is conducted at temperatures of about boron compound to form borated dispersants having utility
from 0°C. to 250° C. preferably about from 100° C. to 200° within the scope of this invention. In addition to boric acid
C. Generally, best results are obtained at temperatures of 60 (boron acid), examples of Suitable boron compounds include
about from 150° C. to 180° C. boron oxides, boron halides and esters of boric acid. Gen
The reaction may be conducted neat, wherein both the erally from about 0.1 equivalents to 10 equivalents of boron
polymer and the cyclic carbonate are combined in the proper compound to the modified Succinimide may be employed.
ratio, either alone or in the presence of a catalyst (Such as an In addition to the carbonate and boric acids post
acidic, basic or Lewis acid catalyst). Depending on the 65 treatments both the compounds may be post-treated, or
Viscosity of the polymer reactant, it may be desirable to further post-treatment, with a variety of post-treatments
conduct the reaction using an inert organic Solvent or designed to improve or impart different properties. Such
 US 6,358,892 B1
15 16
post-treatments include those Summarized in columns 27-29 Combination of a hydrazine and carbon disulfide (e.g.
of U.S. Pat. No. 5,241,003, hereby incorporated by refer U.S. Pat. No. 3,519,564);
ence. Such treatments include, treatment with: Combination of an aldehyde and a phenol (e.g., U.S. Pat.
Inorganic phosphorous acids or anhydrates (e.g., U.S. Pat. Nos. 3,649,229; 5,030,249; 5,039,307);
5
Nos. 3,403,102 and 4,648,980); Combination of an aldehyde and an O-diester of dithio
Organic phosphorous compounds (e.g., U.S. Pat. No. phosphoric acid (e.g., U.S. Pat. No. 3,865,740);
3,502,677); Combination of a hydroxyaliphatic carboxylic acid and a
Phosphorous pentasulfides, boric acid (e.g., U.S. Pat. No. 4,554,086);
Boron compounds as already noted above (e.g., U.S. Pat. Combination of a hydroxyaliphatic carboxylic acid, then
Nos. 3,178,663 and 4,652,387); formaldehyde and a phenol (e.g., U.S. Pat. No. 4,636,
Carboxylic acid, polycarboxylic acids, anhydrides and/or 322);
acid halides (e.g., U.S. Pat. Nos. 3,708,522 and 4,948, Combination of a hydroxyaliphatic carboxylic acid and
386); then an aliphatic dicarboxylic acid (e.g., U.S. Pat. No.
Epoxides polyepoxiates or thioexpoxides (e.g., U.S. Pat. 15 4,663,064);
Nos. 3,859,318 and 5,026,495); Combination of formaldehyde and a phenol and then
Aldehyde or ketone (e.g., U.S. Pat. No. 3,458,530); glycolic acid (e.g., U.S. Pat. No. 4,699,724);
Carbon disulfide (e.g., U.S. Pat. No. 3,256,185); Combination of a hydroxyaliphatic carboxylic acid or
Glycidol (e.g., U.S. Pat. No. 4,617,137); Oxalic acid and then a diisocyanate (e.g. U.S. Pat. No.
Urea, thourea or guanidine (e.g., U.S. Pat. Nos. 3,312, 4,713,191);
619; 3,865,813; and British Patent GB 1,065,595); Combination of inorganic acid or anhydride of phospho
Organic sulfonic acid (e.g., U.S. Pat. No. 3,189,544 and rus or a partial or total Sulfur analog thereof and a boron
British Patent GB 2,140,811); compound (e.g., U.S. Pat. No. 4,857.214);
Alkenyl cyanide (e.g., U.S. Pat. Nos. 3,278,550 and 25 Combination of an organic diacid then an unsaturated
3.366,569); fatty acid and then a nitroSoaromatic amine optionally
Diketene (e.g., U.S. Pat. No. 3,546,243); followed by a boron compound and then a glycolating
A diisocyanate (e.g., U.S. Pat. No. 3,573,205); agent (e.g., U.S. Pat. No. 4,973,412);
Alkane Sultone (e.g., U.S. Pat. No. 3,749,695); Combination of an aldehyde and a triazole (e.g., U.S. Pat.
1,3-Dicarbonyl Compound (e.g., U.S. Pat. No. 4,579, No. 4,963.278);
675); Combination of an aldehyde and a triazole then a boron
compound (e.g., U.S. Pat. No. 4,981,492);
Sulfate of alkoxylated alcohol or phenol (e.g., U.S. Pat. Combination of cyclic lactone and a boron compound
No. 3,954,639); (e.g., U.S. Pat. Nos. 4,963,275 and 4,971,711).
Cyclic lactone (e.g., U.S. Pat. Nos. 4,617,138; 4,645,515; 35
4,668,246; 4,963,275; and 4,971,711); Lubricating Oil Compositions and Concentrates
Cyclic carbonate or thiocarbonate linear monocarbonate The compositions of this invention are compatible with
or polycarbonate, or chloroformate (e.g., U.S. Pat. Nos. fluorocarbon elastomer Seals, at concentrations at which
4,612,132; 4,647,390; 4,648,886; 4,670.170); 40 they are effective as detergent and dispersant additives in
Nitrogen-containing carboxylic acid (e.g., U.S. Pat. lubricating oils. When employed in this manner, the modi
4,971,598 and British Patent GB 2,140,811); fied polyamino alkenyl or alkyl Succinimide additive is
Hydroxy-protected chlorodicarbonyloxy compound (e.g., usually present in from 1 to 5 percent by weight (on a dry
U.S. Pat. No. 4,614.522); polymer basis) to the total composition and preferably less
Lactam, thiolactam, thiolactone or ditholactone (e.g., U.S. 45 than 3 percent by weight (on a dry or actives polymer basis).
Pat. Nos. 4,614,603 and 4,666.460); Dry or actives basis indicates that only the active ingredient
Cyclic carbonate or thiocarbonate, linear monocarbonate of this invention are considered when determining the
or plycarbonate, or chloroformate (e.g., U.S. Pat. Nos. amount of the additive relative to the remainder of a com
4,612,132; 4,647,390; 4,646,860; and 4,670,170); position (e.g., lube oil composition, lube oil concentrate,
Nitrogen-containing carboxylic acid (e.g., U.S. Pat. No. 50 fuel composition or fuel concentrate). Diluents and any
4,971,598 and British Patent GB 2.440,811); other inactives are excluded. Unless otherwise indicated, in
Hydroxy-protected chlorodicarbonyloxy compound (e.g., describing the lubricating oil and final compositions or
U.S. Pat. No. 4,614.522); concentrates, dry or active ingredient contents are intended
Lactam, thiolactam, thiolactone or dithiolactone (e.g., with respect to the polyalkylene Succinimides. This includes
U.S. Pat. Nos. 4,614,603, and 4,666.460); 55 the novel polyalkylene Succinimides of the present invention
Cyclic carbamate, cyclic thiocarbamate or cyclic dithio and also other reaction product or byproducts in the reaction
product mixture which function as dispersants.
carbamate (e.g., U.S. Pat. Nos. 4,663,062 and 4,666, The lubricating oil used with the additive compositions of
459); this invention may be mineral oil or synthetic oils of
Hydroxyaliphatic carboxylic acid (e.g., U.S. Pat. Nos. 60 lubricating Viscosity and preferably Suitable for use in the
4,482.464; 4,521,318; 4,713, 189); crankcase of an internal combustion engine. Crankcase
Oxidizing agent (e.g., U.S. Pat. No. 4,379,064); lubricating oils typically have a viscosity of about 1300 cSt
Combination of phosphorus pentasulfide and a polyalky at 0° F (-17.8° C) to 22.7 cSt at 210° F (99° C). The
lene polyamine (e.g., U.S. Pat. No. 3,185,647); lubricating oils may be derived from Synthetic or natural
Combination of carboxylic acid or an aldehyde or ketone 65 Sources. Mineral oil for use as the base oil in this invention
and sulfur or sulfur chloride (e.g., U.S. Pat. Nos. includes paraffinic, naphthenic and other oils that are ordi
3,390,086: 3,470,098); narily used in lubricating oil compositions. Synthetic oils
 US 6,358,892 B1
17 18
include both hydrocarbon Synthetic oils and Synthetic esters. about 3 to 8 carbon atoms, Such as isopropanol,
Useful synthetic hydrocarbon oils include liquid polymers of isobutylcarbinol, n-butanol and the like, in combination with
alpha olefins having the proper Viscosity. Especially useful hydrocarbon solvents are also suitable for use with the fuel
are the hydrogenated liquid oligomers of C to C alpha additive. The present fuel concentrate will typically contain
olefins Such as 1-decene trimer. Likewise, alkylbenzenes of about from 20 to 60 wt.% of the present composition or an
proper Viscosity Such as didodecyl benzene can be used. active ingredient basis.
Useful synthetic esters include the esters of both monocar PREPARATIONS AND EXAMPLES
boxylic acid and polycarboxylic acids as well as monohy
droxy alkanols and polyols. Typical examples are didodecyl A further understanding of the invention can be had in the
adipate, pentaerythritol tetracaproate, di-2-ethylhexyl following nonlimiting Preparations and Examples. Wherein
adipate, dilaurylsebacate and the like. Complex esters pre unless expressly Stated to the contrary, all temperatures and
pared from mixtures of mono and dicarboxylic acid and temperature ranges refer to the Centigrade System and the
mono and dihydroxy alkanols can also be used. term “ambient” or “room temperature” refers to about 20
Blends of hydrocarbon oils with synthetic oils are also C-25° C. The term “percent” or “%” refers to weight
useful. For example, blends of 10 to 25 weight percent 15
percent and the term “mole” or “moles” refers to gram
hydrogenated 1-decene trimmer with 75 to 90 weight per moles. The term “equivalent” refers to a quantity of reagent
cent 150 SUS (100 F) mineral oil gives an excellent equal in moles, to the moles of the preceding or Succeeding
lubricating oil base. reactant recited in that example in terms of finite moles or
Other additives which may be present in the formulation finite weight or Volume.
include detergents (overbased and non-overbased), rust Preparation 1
inhibitors, foam inhibitors, corrosion inhibitors, metal
deactivators, pour point depressants, antioxidants, wear Maleic Anhydride -Cls Alpha Olefin
inhibitors, Zinc dithiophosphates and a variety of other Copolymer Concentrate
well-known additives.
25 This example illustrates a Suitable procedure for preparing
It is also contemplated the modified Succinimides of this the title compound. In this example 170 grams of a mixture
invention may be employed as dispersants and detergents in
hydraulic fluids, marine crankcase lubricants and the like. of C, C, and Cls Olefins and 50 g of Co aromatic Solvent
When so employed, the modified succinimide is added at is heated to 300° F (149 C.) then sparged with nitrogen to
from 0.1 to 5 percent by weight (on a dry polymer basis) to remove entrained air and then cooled to 150 F. (66° C.). 75
the oil, and preferably at from 0.5 to 5 weight percent (on a grams of maleic anhydride is added and the temperature of
dry polymer basis). the mixture raised to 255° F (124° C). A total of 14 g of
Di-t-butyl peroxide is added in five equal portions at about
Additive concentrates are also included within the Scope 30-minute increments over a period of two hours. During the
of this invention. The concentrates of this invention usually additions the temperature is maintained between 255 F. to
include from 90 to 10 weight percent of an organic liquid 35
265° F and then allowed to slowly increase to 300° F (149
diluent and from 10 to 90 weight percent (on a dry polymer C.) and held at about this temperature for two hours and then
basis) of the additive of this invention. Typically, the con cooled affording a mixture of the title composition and
centrates contain Sufficient diluent to make them easy to solvent. This is used without further purification.
handle during Shipping and Storage. Suitable diluents for the
concentrates include any inert diluent, preferably an oil of 40 Preparation 2
lubricating Viscosity, So that the concentrate may be readily
mixed with lubricating oils to prepare lubricating oil com Preparation of Pibsa 2200 (Succinic Ratio=1.1)
positions. Suitable lubricating oils which can be used as A 35.186 Kg, 16 mole, of a 2200 Mn polybutene sold
diluents typically have Viscosities in the range from about 35 under the trademark Parapol 2200 by Exxon Chemical
to about 500 Saybolt Universal Seconds (SUS) at 100° F. 45 Company) is charged to a reactor and heated to 232 C.
(38 C.), although an oil of lubricating viscosity may be During this time, the reactor is preSSurized to 40 psig with
used.
nitrogen and then Vented three times to remove air. The
Fuel Compositions and Concentrates reactor is repressurized to 24.7 psia and 1500 g maleic
anhydride then added over a thirty-minute period. Following
Typically the fuel composition will about from 10 to 50 this, another 4581 g of maleic anhydride is added over a
10,000 weight parts per million, preferably from 30 to 2,000 4-hour period. The total charge mole ratio (CMR) of maleic
weight parts per million, of base fuel. This is based on active anhydride to polybutene is 3.88. After the maleic anhydride
ingredient including the other dispersant reaction products addition is completed, the reaction is held at 232 C. for 1.5
as well as the compounds of formula (I) but excluding hours and then cooled. Any unreacted maleic anhydride is
inactives for example diluent oil and any unreacted alkene or 55 removed by vacuum distillation at 0.4 psia a light neutral
poly C-olefins etc. carried through from the preparation of diluent oil is added to the Stripped product and heated to
Succinic anhydride (A) or copolymer (B). If other detergents 160 C. for 24 hours and was then filtered. This product was
are present, a lesser amount of the modified Succinimide found to contain 37.68 wt.% actives and had a saponifica
may be used. Optimum concentrations can vary with the tion number of 19.7 mg KOH/g sample. The succinic ratio
particular base oil and the presence of other additives, but, 60 was 1.1 based on a polybutene molecular weight of 2246
can be determined by routine procedures. determined by gel permeation chromatography (“GPC).
The compositions of this invention may also be formu
lated as a fuel concentrate, using an inert Stable oleophilic Preparation 3
organic solvent boiling in the range of about 150 F. to 400
F. Preferably, an aliphatic or an aromatic hydrocarbon sol 65 Preparation of Pibsa 1300 (Succinic Ratio=1.1)
vent is used, Such as benzene, toluene, Xylene or higher The procedure of Preparation 2 is repeated except that a
boiling aromatics or aromatic thinners. Aliphatic alcohols of 1300 Mn polybutene sold under the trademark Parapol 1300
 US 6,358,892 B1
19 20
by Exxon Chemical Company is used instead of Parapol analyzed and found to contain 0.82%N, 16.6 TBN, 0.98
2200 TM. After dilution with diluent oil and filtration, this TAN, a viscosity at 100° C. of 431.8 cSt and a specific
product was found to contain 49.6 wt.% actives and a gravity at 15 C. of 0.9149 The product contained about 40%
saponification number of 42.2 mg KOH/g sample. The active material.
Succinic ratio was 1.1 based on a polybutene molecular (b) Post-treatment
weight of 1300.
Preparation of Ethylene Carbonate-Treated BIS
Preparation 4 HPA-X Polyisobutenyl (Mn 2200) (Succinic ratio=
1.1)
Preparation of Pibsa 2200 (Succinic Ratio=1.5)
In this example 7.4 g of ethylene carbonate is added over
Parapol 2200TM, 42.8 Kg, 19.45 mol, is charged to a thirty minutes to 100.5 g of Bis HPA-X PIBSA 2200
reactor and the temperature increased to 150° C. During this (succinic ratio=1.1) at 100° C. The temperature of the
time, the reactor is pressurized to 40 psig with nitrogen and reaction mixture is increased to 165 C. over 2.5 hours and
then vented three times to remove oxygen. Then at 150 C., 15
then maintained at this temperature for 2 hours affording the
maleic anhydride, 4294 g., 43.82 mol, and di-t- title compound.
butylperoxide, 523 g, 3.58 mol, is added. The first 25% is
added over 30 minutes. The remainder is then added over Preparation C
11.5 hours. The CMR of maleic anhydride to polybutene is
2.25. The mixture is held at 150° C. for one hour and then Preparation of Polyalkylene Succinimide Using
heated at 190° C. for 1 hour to destroy any remaining Deta, Pibsa 950, and a C16 Alpha Olefin-maleic
di-t-butylperoxide. Then Vacuum is applied to the reactor Anhydride Copolymer
and the unreacted maleic anhydride is removed. This mate To a 3 liter round bottom flask equipped with a magnetic
rial is then diluted with a light neutral oil and filtered. The stirrer, Dean Startik trap, and nitrogen inlet was added 1950
product after filtration had a saponification number of 31.6
mg KOH/g sample and contained 45.62 wt.% actives. The 25 g PIBSA 950 T (1 mol), which had a SAP number of 57.5
Succinic ratio was 1.5 for this material based on a polybutene mg KOHAg Sample, and 1213 g Ce alpha olefin/maleic
molecular weight of 2200. anhydride copolymer (1.1 mol), dissolved in Co. aromatic
solvent, which had a SAP number of 102 mg KOH/g sample.
Preparation A The PIBSA 950 T/alpha olefin copolymer ratio was 48/52.
This was heated to 160° C. and to this was added over
Preparation of Teta Polyisobutenyl (MN 2200) twenty five minutes, 108 g diethylene triamine (1.05 mole)
Succinimide (Succinic Ratio=1.1) with stirring. The amine/PIBSACMR was 0.5. After 2 hours
(a) Succinimide heating, the Co aromatic Solvent was then removed in vacuo.
To a three neck flask equipped with an overhead Stirrer, A total of 2460 g product was recovered, which had 1.69%
nitrogen inlet tube and a Dean Stark trap was added 300.7 35 N, and a viscosity at 100° C. of 853.
g PIBSA (SAP no.=19.7 mg KOH/g sample, 0.0464 mol)
that was prepared using the procedure of preparation 2. To Example 1
this was then added at 130 C. 3.39 g TETA with stirring. Preparation of Polymeric Succinimide Using Pibsa
The mixture was heated for a total of 6.5 hrs. Then the
reaction was cooled. A total of 0.8 ml water was recovered. 40 (MN 2200), HPA, and C-C Alpha-Olefin
The analytical data for this compound is found in Table 1. Maleic Anhydride Copolymer
(b) Post treatment (a) Polymer
In this example, 658.4 (0.138 mol) of a polyisobutenyl
Preparation of Ethylene Carbonate-Treated BIS (Mn 2200) succinic anhydride having a succination ratio of
TETA Polyisobutenyl (Mn 2200) (Succinic ratio= 45 1.1 and a SAP number of 23.6 mg of potassium hydroxide/g
1.1) is added to a 2 L three neck flask equipped with a Dean Stark
trap and condenser followed by the addition of a solution of
In this example 3.33 g ethylene carbonate (0.0378 mol) containing 59.5 g (0.059 mol) of a C-C, C-olefin-maleic
was added to 100 g of the BIS TETA Polyisobutenylsuc anhydride copolymer in a C-9 ml of a Co aromatic Solvent
cinimide from preparation A. This was heated for 4 hours. 50 (a mixture of alkylbenzenes having nine carbon atoms). The
Then the reaction was cooled to give the title compound. The mixture is heated to 100° C. and 27.21 g (0.099 mol) of a
analytical data for this material is found in Table 1. heavy polyamine having an Mn of 275 containing an aver
Preparation B age of 6.5 amine nitrogen atoms per molecule Sold under the
Tradename HPA-X by Union Carbide Company. The tem
Preparation of Heavy Polyamine Polyisobutenyl 55 perature of the mixture is increased to 165 C. and main
(MN 2200) Succinimide (Succinic Ratio=1.1) tained at this temperature for six hours with stirring. The C9
(a) Succinimide aromatic Solvent is then removed by vacuum distillation
To a 1 L three-necked flask equipped with a Dean Stark affording a Viscous liquid product having a nitrogen content
trap is added 304.3 g (0.0469 mol) of PIBSA (SAP number= of 1.21 wt.%, a TBN of 22.64 mg KOH/g, a TAN of 0.60
17.3mg KOH/g Sample), prepared using the procedure from 60 mg/g and a viscosity 440 cSt at 100 C.
Preparation 2. This is heated to 130° C. under nitrogen with Example 1 EC
stirring and to this is added 6.45 g (0.02345 mol) of a heavy
amine sold under the trade name HPA-X, by Union Carbide Ethylene Carbonite-Post-Treated Polymeric
Company over 0.5 hours. The temperature was increased to Succinimide of Example 1
165 C. The amine/PIBSA CMR was 0.5. The reaction is 65
heated an additional 4 hours at 165 C while distilling off 33.06 g (0.376 mol) of ethylene carbonate is slowly added
water. A total of 0.8 cc water was removed. This product was to 304.3 g of the above reaction product above at 100° C.
 US 6,358,892 B1
21 22
The temperature is increased to 165 C. and maintained at copolymer and 0.6 mol of polyisobutylene (Mn 2200) Suc
this temperature for 3/2 hours. The resulting reaction prod cinic anhydride having a succination ratio of 1.1 at 100 C.
uct mixture had a nitrogen content of 1.15 wt.%, a TBN of in a flask equipped with a Dean Stark trap and condenser.
15.9 mg KOH/g, a TAN of 0.15 mg KOH/g and a viscosity The mixture is stirred at this temperature for six hours. The
of 81.2 cSt at 100° C. mixture is then distilled under vacuum to remove volatiles
affording the title compound as the principal product.
Example 2-6 b) Post-treatment
The reaction product is then mixed with 0.76 mol of
Examples 2-6 are prepared following the same proce ethylene carbonate for about four hours at about 160 C.
dures as described in Example 1 but varying the ratio of affording the ethylene carbonate post-treated derivative of
polyisobutenyl Succinic anhydride to copolymer based on the title composition.
Succinic anhydride equivalents or varying the particular Example 8
polyamine but not the mole ratio of polyamine; 0.5 moles of
the indicated polyamine were added per mole equivalent Tetraethylene Pentamine of Polyisobutylene (MN
Succinic anhydride in both the alkenylsuccinic anhydride 15
2200) Succinimide and Poly(Maleic Anhydride
and maleic anhydride copolymer regardless of the particular ethylene) Copolymer
polyamine. The nitrogen content, TBN, viscosity, and TAN a) Polymer
number for these examples and Example 1 are reported in The title compound can be prepared by admixing 0.5 mole
Table 1. In addition, for comparative purposes, the Table of tetraethylene pentamine to a mixture of 0.7 mole of
also lists a polyisobutenyl (Mn 2200) Succinimide prepared polyisobutylene (Mn 2200) succinic anhydride having a
by the same general procedure as illustrated by Preparation Succination ratio of 1.3 and 0.3 mol of poly(maleic anhy
A using either triethylenetetraamine or heavy polyamine dride ethylene) copolymer in 100 ml (solvent) at 1000 C. in
(HPA-X) and a mole ratio of 0.5 mole of polyamine per mole a flask equipped with a Dean Stark trap and condenser. The
of Succinic anhydride and the corresponding ethylene car mixture is Stored at this temperature for 6 hours and then
bonite post-treated derivatives prepared by the post 25
distilled to remove the solvent affording the title compound
treatment illustrated by Preparation B. In each case the as the principal product of the remaining mixture.
polyisobutenylsuccinic anhydride reactant was prepared by b) Post-treatment
the thermal proceSS using a conventional Mn 2200 poly 0.71 mol of ethylene carbonate is added to the polymer
isobutene such as Parapol 2200TM. reaction product and heat at about 165 C. for about four
TABLE 1.
ANALYTICAL DATA FOR POLYISOBUTENYLSUCCINIMIDE-MALEIC
ANHYDRIDE CA 18 OLEFIN COPOLYMER
Example Mole Ratio" N TBN mg Vis. at TAN mg
No. Amine PIBSA/Copolymer Wt. 9% KOH/g 1000C, cSt KOHig
1. HPA-X 70/30 1.21 22.6 440 O.6
1-EC HPA-X 70/30 1.15 15.9 812 O.15
2 TETA2 90/10 O.63 10.1 437 0.79
2-EC TETA 90/10 0.59 8.5 430 O.O7
3 HPA-X 90/10 O.93 21.6 443 0.44
3-EC HPA-X 90/10 0.95 13.6 662 O.09
4 TETA 70/30 O.77 11.2 439 O.43
4-EC TETA 70/30 0.78 9.2 441 O.OS
5 TETA 50/50 O.99 13.7 482 2.15
5-EC TETA 50/50 O.96 10.4 491 O.OS
6 HPA-X 50/50 1.59 26.3 567 1.33
6-EC HPA-X 50/50 1.46 18.7 2676 O.O7
COMPARISON PIB SUCCINIMIDES

A. TETA O.53 6.7 421 1.11

A-EC TETA O.39 3.9 395 O.O7
B HPA O.82 16.6 432 O.98
B-EC HPA O.76 8.8 599 O.09
C DETA 50/50 1.69 854

"Mole ratio of polyisobutenylsuccinic anhydride to copolymer based on Succinic anhydride

units in each
°Triethylenetetraamine
Ethylene carbonate treated
Heavy polyamine sold under this Trade Name by Union Carbide Company

Example 7 hours affording the ethylene carbonate post-treated deriva

Preparation of Polymeric Succinimide Using Pibsa 60 tive of the title compound.
(MN 2200), HPA, and a Styrene Maleic Anhydride Example 9
Copolymer of Polyisobutylene (MN 2200) and Poly
(Maleic Anhydride-styrene) Copolymer
a) Polymer Polyamine of Polyisobutylene (MN 1300)
The title compound can be prepared by admixing 0.6 mol 65 Succinimide and Poly(Maleic Anhydride-C. C.
of the same heavy polyamine described in Example 1 to a OLEFIN) Copolymer
mixture of 0.4 mol of poly(maleic anhydride-styrene) a) Polymer
 US 6,358,892 B1
23 24
The title compound can be prepared by admixing 0.5 mole mixture of 0.5 mole of polyisobutylene (Mn 2200) Succinic
of the same heavy polyamine described in Example 1 to a anhydride having a Succination ratio of 1.1:1 and 0.5 mol of
mixture of 0.7 mole of polyisobutylene (Mn 1300) Succinic poly(maleic anhydride-vinylacetate) copolymer in 200 ml
anhydride having a succination ratio of 1.5 and 0.3 mol of dimethyl fluoride at 100° C. in a flask equipped with a Dean
poly(maleic anhydride C24 C-olefin) copolymer in 150 ml 5 Stark trap and condenser. The mixture is Stored at this
(Co. aromatic, cholorobenzene, toluene or dioxane Solvent) at temperature for 6 hours and then distilled to remove the
100° C. in a flask equipped with a Dean stark trap and Solvent affording the title compound as the principal product
condenser. The mixture is Stored at this temperature for 6 of the remaining mixture.
hours and then distilled to remove the solvent affording the b) Post-treatment
title compound as the principal product of the remaining 0.71 mol of ethylene carbonate is added to the polymer
mixture. reaction product and heat at about 170° C. for about four
b) Post-treatment hours affording the ethylene carbonate post-treated deriva
0.71 mol of ethylene carbonate is added to the polymer tive of the title compound.
reaction product and heat at about 160° C. for about four Example 13
hours affording the ethylene carbonate post-treated deriva 15
tive of the title compound. Lubrication Oil Dispersancy
Example 10 The effectiveness of the compositions reported in Table I
Polyamine of Polyisobutylene (MN 2200) as was determined by the Panel Coker Bench Test and by the
Succinimide and Poly(Maleic Anhydride-1,3- Soot Thickening Test. The results of this testing are reported
in Table III.
Butadiene) Copolymer 1. Panel Coker Bench Test
a) Polymer In this test 200 g of the lubricating oil composition being
The title compound can be prepared by admixing 0.5 mole
of the same heavy polyamine described in Example 1 to a tested is weighed into a 400 ml beaker. The test composition
mixture of 0.6 mole of polyisobutylene (Mn 2200) Succinic 25 is a mixture of containing 8 wt. of the dispersant to be tested,
anhydride having a Succination ratio of 1.1 and 0.4 mol of 36 millimoles of an overbased phenate detergent and 18
poly(maleic anhydride-1,3-butadiene) copolymer in 50 ml millimoles of a zinc dithiophosphate wear inhibitor in Cit
(chlorobenzene) at 100° C. in a flask equipped with a Dean conF) 350 N diluent oil. To this is added 0.2 ml of a catalyst
Stark trap and condenser. The mixture is Stored at this solution. The catalyst solution consists of a mixture of 62.12
temperature for 6 hours and then distilled to remove the g of copper naphthenate Solution (7.88 wt.% copper) and
Solvent affording the title compound as the principal product 48.04 g iron naphtenate (6.12% iron) dissolved in pearl oil
of the remaining mixture. to 200 ml. This gave a copper content of 25 ppm and an iron
b) Post-treatment content of 15 ppm in the oil. The oil and catalyst Solution
0.71 mol of ethylene carbonate is added to the polymer then Stirred together for one minute. The test composition is
reaction product and heat at about 165 C. for about four 35 then poured into the Sump of the panel coker apparatus and
hours affording the ethylene carbonate post-treated deriva a new plate (weighed to 0.0001 g) is installed. The following
tive of the title compound. conditions are used for the panel coker test. The plate
temperature is 300° C., the Sump temperature is 18 C., the
Example 11 run time is 4 hours, the air flow rate is 60 cc/min. During the
40 test the spinner is on for 12 seconds then off for 78 seconds.
Polyamine of Polyisobutylene (MN 1300) During the time the Spiner is on the test composition is
Succinimide and Poly(Maleic Anhydride-methyl Splashed onto the plate. Then with the spinner off, the test
Vinyl Ether) Copolymer composition slowly drains off the surface of the plate. The
a) Polymer spinner on/off cycle is continued for 4 hours after which time
The title compound can be prepared by admixing 0.5 mole 45 the plate was removed, rinsed with hexane and dried. The
of the same heavy polyamine described in Example 1 to a plate is weighed to 0.0001 g and the weight gain is reported
mixture of 0.8 mole of polyisobutylene (Mn 1300) Succinic as weight of total deposit. Thus the lower the weight the
anhydride having a Succination ratio of 1.1:1 and 0.2 mol of better the result.
poly(maleic anhydride-methyl vinyl ether) copolymer in 2. Soot Thickening Test
200 ml n-methyl pyrrolidone at 100° C. in a flask equipped 50 In this test 98.0 g of the test lubricating oil composition
with a Dean Stark trap and condenser. The mixture is Stored is weighed and placed into a 250 milliliter beaker. The
at this temperature for 6 hours and then distilled to remove lubricating oil composition contained 8 wt.% on as is basis
the Solvent affording the title compound as the principal of the test dispersant 50 millimoles of an overbased phenate
product of the remaining mixture. detergent, 18 millimoles of a Zinc dithiophosphate wear
b) Post-treatment 55 inhibitor and 7.3 wt.% of a VI improver, in 85% 150N oil,
0.71 mol of ethylene carbonate is added to the polymer 15% 600N oil. To this is added 2.0 g Vulcan XC-72RTM
reaction product and heat at about 170° C. for about four carbon black from Cabot Co. The mixture is stirred and then
hours affording the ethylene carbonate post-treated deriva Stored for 16 hr in a desiccator. A Second Sample of the
tive of the title compound. lubricating oil composition, but without the carbon black, is
Example 12 60 mixed for 60 sec. using a Willems Polytron Homogenizer
Model PF 45/6 and then degased in a vacuum oven for 30
Polyamine of Polyisobutylene (MN 2200) minutes at 50–55 C. The viscosity of the two test compo
Succinimide and Poly(Maleic Anhydride Sitions is then measured at 100° C. using a capillary vis
vinylacetate) Copolymer cometer. The percent Viscosity increase is calculated by
a) Polymer 65 comparing the Viscosity in the presence and absence of
The title compound can be prepared by admixing 0.5 mole carbon black. Thus the lower the percent Viscosity increase
of the same heavy polyamine described in Example 1 to a the better the disperSancy of the dispersant.
 US 6,358,892 B1
25 26
TABLE III
DISPERSANCY
PANEL COKER AND SOOT THICKENING

Polyamine Mole Rate Panel Coker, Soot Thickening,

EXAMPLE No. Description PIBSA/Copolymer mg % Wis. Incr.
1. Bls HPA 70/30 156.8 117
1 EC ECBs HPA 70/30 61 24
2 Bis TETA 90/10 4 295
2 EC ECBs TETA 90/10 13.4 87
3 BIS HPA 90/10 29.4 146
3 EC ECBs HPA 90/10 4.3 25
4 Bis TETA 70/30 66.6 191
4 EC ECBs TETA 70/30 71.2 36
5 Bis TETA 50/50 120.2 173
5 EC ECBs TETA 50/50 311.7 37
6 Bls HPA 50/50 299.9 48
6 EC ECBs HPA 50/50 311.7 3O
COMPARISON SUCCINIMIDES

A. TETA 10.7 345

PIBSA 22OOT
A-EC TETA
PIBSA 22OOT
B HPA 7.5 310
PIB8A22OOT
B-EC HPA
PIBSA 22OOT

Example 14 intended to cover those various changes and Substitutions

Sequence VE Engine Test that may be made by those skilled in the art without
departing from the Spirit and Scope of the appended claims.
The ethylene carbonate treated reaction product of What is claimed is:
Example 1EC was formulated into a lubricating oil compo 1. A post-treated polymer prepared by treating a polymer
Sition with a mixture of 150N and 100N mineral oil at a
with a cyclic carbonate or a linear mono- or poly-carbonate
concentration of 5.3 wt.% (based on the reaction product under reactive conditions, wherein Said polymer is prepared
mixture). The lubricating oil composition also contained 35
by reacting a mixture under reactive conditions, wherein the
Small amounts of phenate and Sulfonate detergents, a Zinc mixture comprises:
dithiophosphate wear inhibitor and a Viscosity indeX
improver Such as conventionally used in passenger car (a) an alkenyl or alkylsuccinic acid derivative, wherein
crankcase lubrication oils. the alkenyl or alkyl substituent has a Mn of from 1800
The dispersant performance of the composition was tested 40 to 3000;
using the Sequence VE Engine test procedure defined in (b) an unsaturated acidic reagent copolymer of
ASTM proposed Method: 212. This test assesses a lubri (1) an unsaturated acidic reagent and
cant's ability to provide adequate wear and deposit control (2) an olefin having an average of from 14 to 30 carbon
under Stop-and-go conditions. The test measures rocker atoms, wherein the copolymer has a Mn of from
cover sludge (“RCS”); average engine sludge ("AES”), 45 2000 to 4800; and
piston skirt varnish (“PSV'); average engine vanish (c) a polyamine having at least three nitrogen atoms and
(“AEV") average cam wear (“ACW"), and maximum cam 4 to 20 carbon atoms; and
wear (“MCW). wherein said mixture contains from 1.5 to 10 equivalents of
The results of this testing is shown in Table IV. The pass Said alkenyl or alkylsuccinic acid derivative per equivalent
limits for each performance measure is also indicated in the 50 of Said unsaturated acidic reagent copolymer and from 0.4 to
table. As can be seen from the table, with the exception of 1.0 equivalents of Said polyamine per equivalent of alkenyl
example C which contains a 950 molecular weight poly or alkylsuccinic acid derivative plus unsaturated acidic
butene tail, the lubricating composition passed each perfor reagent copolymer.
ICC CSC. 2. The polymer of claim 1 wherein Said cyclic carbonate
55 is ethylene carbonate.
TABLE IV 3. A lubricating oil composition comprising a major
amount of an oil of lubricating Viscosity and a minor amount
Example No. RCS AES PSV AEV ACW MCW of the polymer of claim 1.
1 EC 9.17 9.15 7.20 6.84 1.12 1.OO 4. A concentrate comprising from 20 to 60 wt.% of the
Pass Limits 7.OO 9.OO 6.50 S.OO S.OO 15.OO 60 composition of claim 1 and from 80 to 40 wt.% of an
(min.) (min.) (min.) (min.) max in (max in organic diluent.
mils) mils) 5. A post-treated polymer prepared by treating a polymer
B-EC 8.56 9.15 7.17 6.55 O.89 1.25
C 1.9 4.8 6.6 4.7 5.0 11.2 under reactive conditions with a boron compound Selected
from the group consisting of boron oxide, boron halide,
65 boric acid, and esters of boric acid, wherein Said polymer is
While the present invention has been described with prepared by reacting a mixture under reactive conditions,
reference to specific embodiments, this application is wherein the mixture comprises:
 US 6,358,892 B1
27 28
(a) an alkenyl or alkylsuccinic acid derivative, wherein wherein said mixture contains from 1.5 to 10 equivalents of
the alkenyl or alkyl substituent has a Mn of from 1800 Said alkenyl or alkylsuccinic acid derivative per equivalent
to 3000; of Said unsaturated acidic reagent copolymer and from 0.4 to
(b) an unsaturated acidic reagent copolymer of 1.0 equivalents of Said polyamine per equivalent of alkenyl
(1) an unsaturated acidic reagent and or alkylsuccinic acid derivative plus unsaturated acidic
(2) an olefin having an average of from 14 to 30 carbon reagent copolymer.
atoms, wherein the copolymer has a Mn of from
2000 to 4800; and
(c) a polyamine having at least three nitrogen atoms and
4 to 20 carbon atoms; and