Title of Invention

A LUBRICATING OIL ADDITIVE COMPOSITION AND METHOD OF MAKING THE SAME

Abstract A post-treated polymeric dispersant which comprises reacting (I) a post-treating agent selected from a cyclic carbonate, a linear mono-carbonate, a linear poly-carbonate, an aromatic polycarboxylic acid or an aromatic polycarboxylic anhydride or an aromatic polycarboxylic acid ester and (II) an oil-soluble lubricating oil additive composition prepared by the process which comprises reacting a copolymer, with at least one ether compound and with at least one aliphatic compound capable of reacting with at least one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof.
Full Text FIELD OF THE INVENTION
The present invention is directed to an improved dispersant additive composition that is
used in engine oils; and it is also directed to the process of making the same.
BACKGROUND OF THE INVENTION
It is known to employ nitrogen containing dispersants and/or detergents in the formulation
of lubricating oil compositions. Many of the known dispersant/detergent compounds are
based on the reaction of an alkenylsuccinic acid or anhydride with an amine or polyamine
to produce an alkenylsuccinimide or an alkenyl succinamic acid as determined by selected
conditions of reaction. One problem facing the lubricant manufacturer is dispersancy of
particulate matter in internal combustion engines. Failure to have adequate particulate
matter dispersancy may result in filter plugging, sludge accumulation, and oil thickening.
DESCRIPTION OF THE RELATED ART
Liu et al., U.S. Patent No. 6,117,825, discloses a lubricating oil composition that
comprises a major amount of an oil of lubricating viscosity; and a minor amount of a
synergistic combination of an antioxidant-dispersant additive and a dispersant additive,
said combination comprising: (i) a polyisobutylene succinimide (PIBSAD) and (ii) an
ethylene-propylene succinimide (LEPSAD).
Nalesnik, U.S. Patent No. 5,139,688, discloses an additive composition comprising an
oxidized ethylene copolymer or terpolymer of a C3-C10 alpha-monoolefin and, optionally,
a non-conjugated diene or triene which has been reacted with a formaldehyde compound
and with an amino-aromatic polyamine compound.
GDnther et al., U.S Patent No. 6,512,055, discloses a copolymer obtained by free radical
copolymerization of at least one monoethylenically unsaturated C4.-C6dicarboxylic acid or
anhydride thereof, an oligomer, and one monoethylenically unsaturated compound.
Gwither et al., U.S Patent No. 6,284,716, discloses a lubricating oil composition
comprising a lubricant oil and a copolymer obtained by free radical copolymerization of at
2
least one monoethylenically unsaturated C4-C6 dicarboxylic acid or anhydride thereof, an
oligomer, and one monoethylenically unsaturated compound, wherein the copolymer is
further reacted with an amine.
Harrison et al., U.S. Patent No. 5,792,729, discloses a dispersant terpolymer
and polysuccinimide compositions derived from the terpolymers. The terpolymer
is obtained by free radical copolymerization of an unsaturated acidic reagent, a 1-olefin,
and a 1,1-disubstituted olefin in the presence of a free radical initiator.
Barr et al., U.S. Patent No. 5,670,462, discloses a lubricating oil additive composition that
is the reaction product of (i) a copolymerized olefin and unsaturated carboxylic acyiating
agent monomer with a free radical initiator and (ii) a succinimide prepared from an acyclic
hydrocarbyl substituted succinic acyiating agent and a polyamine wherein the hydrocarbyl
substituted succinic acyiating agent is prepared by reacting a polyolefin and an acyiating
agent under conditions such that at least 75 mole % of the starting polyolefin is converted
to the hydrocarbyl-substituted succinic acyiating agent.
Harrison et al., U.S. Patent No. 6,451,920, discloses copolymerizing a polyalkene and an
unsaturated acidic reagent, followed by reacting any unreacted polyalkene with the
unsaturated acidic reagent at elevated temperatures in the presence of a strong acid.
Chung et al., U.S. Patent Nos. 5,427,702 and 5,744,429, disclose a mixture of derivatized
ethylene-alpha olefin copolymers, wherein functional groups are grafted onto the
copolymer. The functionalized copolymer is mixed with at least one of an amine, alcohol,
including polyol, amino alcohol etc. to form multi-functional viscosity index improver
additive components.
Harrison et al., U.S. Patent No. 5,112,507, discloses novel copolymers of unsaturated
acidic reactants and high molecular weight olefins wherein at least 20% of the total high
molecular weight olefin comprises the alkylvinylidene isomer which copolymers are
useful as dispersants in lubricating oils and fuels and also may be used to prepare
polysuccinimides and other post-treated additives useful in lubricating oils and fuels.
3
Harrison et al., U.S. Patent No. 6,358,892 discloses a succinimide composition.
Harrison et al., U.S. Patent No. 6,451,920 discloses a process of making polysuccinimides.
Harrison, U.S. Patent No. 5,849,676 discloses a succinimide.
Harrison, U.S. Patent No. discloses a haze-free post-treated succinimide.
Frank et al., U.S. Patent No. 3,287,271 discloses a novel lubricating oil composition
containing a combined detergent-corrosion inhibitor.
Le Suer U.S. Patent No. 3,374,174 discloses nitrogen containing compositions obtained
from the reaction of an amine with a high molecular weight carboxylic acid such as a
monocarboxylic acid and alkylene or arylene dicarboxylic.
Liston U.S. Patent No. 3,692,681 discloses a terephthalic acid dispersed in a hydrocarbon
medium containing highly hindered acylated alkylene polyamines.
Durand et al. U.S. Patent No. 4,747,964 discloses a new dispersing additive composition.
Clark et al. U.S. Patent No. 6,255,258 discloses an oil-soluble dispersant.
Scattergood et al. EPA No. 0438848A1 discloses a method of lubricating mechanical
parts.
Michio et al., JP51130408 discloses lubricating oil additives.
SUMMARY OF THE INVENTION
In its broadest embodiment, the present invention is directed to a post-treated polymeric
dispersant prepared by the process comprising reacting (I) a post-treating agent selected
from a cyclic carbonate, a linear mono-carbonate, a linear poly-carbonate, an aromatic
polycarboxylic acid, an aromatic polycarboxylic anhydride or an aromatic polycarboxylic
4
acid ester and (II) a lubricating oil additive composition prepared by the process
comprising reacting
(A) at least one of the following copolymers:
(i) a copolymer obtained by free radical copolymerization of components comprising:
(a) at least one monoethylenically unsaturated C3 to C28 monocarboxylic acid or ester
thereof, or C4 to C28 dicarboxylic acid, anhydride or ester thereof;
(b) at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one
polyolefin comprising about 4 to 360 carbon atoms and having a terminal copolymerizable
group in the form of a vinyl, vinylidene or alkyl vinylidene group or mixtures thereof; and
(c) at least one monoolefin compound which is copolymerizable with the monomers of
(a) and (b) and is selected from the group consisting of:
(1) an alkyl vinyl ether and an allyl alkyl ether where the alkyl group is hydroxyl,
amino, dialkylamino or alkoxy substituted or is unsubstituted, and containing from about 1
to about 40 carbon atoms;
(2) an alkyl amine and an N-alkylamide of a monoethylenically unsaturated mono- or
dicarboxylic acid of from about 3 to about 10 carbon atoms where the alkyl substituent
contains from about 1 to about 40 carbon atoms;
(3) an N-vinylcarboxamide of carboxylic acids of from about 1 to about 8 carbon
atoms;
(4) an N-vinyl substituted nitrogen-containing heterocyclic compound; and
(5) at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one
polyolefin comprising about 4 to about 360 carbon atoms and having a terminal
5
copolymerizable group in the form of a vinyl, vinylidene or alkyl vinylidene group or
mixtures thereof, provided that the olefin employed is not the same as the olefin employed
in(i)(b);
(ii) a copolymer obtained by reacting compound (i)(a) and compound(i)(b) in the
presence of a free radical initiator;
(iii) a copolymer obtained by (a) reacting compound (i)(a) with compound (i)(b) or
(i)(c) in a non-free radical catalyzed reaction in the presence of copolymer (i) or
copolymer (ii) or both; or by (b) contacting copolymer (i) or copolymer (ii) or both with
the non-free radical catalyzed reaction product of compound (i)(a) and compound (i)(b) or
(i)(c); with
(B) at least one ether compound capable of being reacted with at least two
monocarboxylic acids or esters thereof, or with at least two dicarboxylic acids, anhydrides
or esters thereof, or mixtures thereof;
(C) at least one aliphatic compound having at least two functional groups, wherein one
of the functional groups is capable of reacting with at least one monocarboxylic acid or
ester thereof, or dicarboxylic acid, anhydride or ester thereof and wherein another
functional group is capable of reacting with at least one post-treating agent.
In one embodiment, the present invention is directed to a lubricating oil composition
comprising a major amount of an oil of lubricating viscosity and a minor amount of a posttreated
polymeric dispersant prepared by the process which comprises reacting (I) a posttreating
agent selected from a cyclic carbonate, a linear mono-carbonate, a linear polycarbonate,
an aromatic polycarboxylic acid or an aromatic polycarboxylic anhydride or an
aromatic polycarboxylic acid ester and (II) a lubricating oil additive composition prepared
by the process comprising reacting
(A) at least one of the following copolymers:
6
(i) a copolymer obtained by free radical copolymerization of
components comprising:
(a) at least one monoethylenically unsaturated
C3-C28 monocarboxylic acid or ester thereof, or
C4-C28 dicarboxylic acid, anhydride or ester thereof;
(b) at least one 1-olefin comprising about 2 to 40 carbon atoms
or at least one polyolefin comprising about 4 to 360 carbon
atoms and having a terminal copolymerizable group in the
form of a vinyl, vinylidene or alkyl vinylidene group or
mixtures thereof; and
(c) at least one monoolefin compound which is copolymerizable
with the monomers of (a) and (b) and is selected from the
group consisting of:
(1) an alkyl vinyl ether and an allyl alkyl ether where the
alkyl group is hydroxyl, amino, dialkylamino or
alkoxy substituted or is unsubstituted, and containing
from about 1 to about 40 carbon atoms;
(2) an alkyl amine and an N-alkylamide of a
monoethylenically unsaturated mono- or dicarboxylic
acid of from about 3 to about 10 carbon atoms where
the alkyl substituent contains from about 1 to about
40 carbon atoms;
(3) an N-vinylcarboxamide of carboxylic acids of from
about 1 to about 8 carbon atoms;
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an N-vinyl substituted nitrogen-containing
heterocyclic compound; and
at least one 1-olefin comprising about 2 to 40 carbon
atoms or at least one polyolefin comprising about 4 to
about 360 carbon atoms and having a terminal
copolymerizable group in the form of a vinyl,
vinylidene or alkyl vinylidene group or mixtures
thereof, provided that the olefin employed is not the
same as the olefin employed in (i)(b);
(ii) a copolymer obtained by reacting compound (i)(a) and
compound(i)(b) in the presence of a free radical initiator;
(iii) a copolymer obtained by (a) reacting compound (i)(a) with
compound (i)(b) or (i)(c) in a non-free radical catalyzed reaction in
the presence of copolymer (i) or copolymer (ii) or both; or by (b)
contacting copolymer (i) or copolymer (ii) or both with the non-free
radical catalyzed reaction product of compound (i)(a) and
compound (i)(b) or (i)(c); with
(B) at least one ether compound capable of being reacted with at least two
monocarboxylic acids or esters thereof, or with at least two dicarboxylic
acids, anhydrides or esters thereof, or mixtures thereof;
(C) at least one aliphatic compound having at least two functional groups,
wherein one of the functional groups is capable of reacting with at least
one monocarboxylic acid or ester thereof, or dicarboxylic acid,
anhydride or ester thereof and wherein another functional group is
capable of reacting with at least one post-treating agent.
(4)
(5)
8
In one embodiment, the present invention is directed to a method of making a post-treated
polymeric dispersant comprising reacting (I) a post-treating agent selected from a cyclic
carbonate, a linear mono-carbonate, a linear poly-carbonate, an aromatic polycarboxylic
acid or an aromatic polycarboxylic anhydride or an aromatic polycarboxylic acid ester and
(II) a lubricating oil additive composition which comprises reacting
(A) at least one of the following copolymers:
(i) a copolymer obtained by free radical copolymerization of
components comprising:
(a) at least one monoethylenically unsaturated
C3-C28 monocarboxylic acid or ester thereof, or a
C4-C28 dicarboxylic acid, anhydride or ester thereof;
(b) at least one 1-olefin comprising about 2 to 40 carbon atoms
or at least one polyolefin comprising about 4 to 360 carbon
atoms and having a terminal copolymerizable group in the
form of a vinyl, vinylidene or alkyl vinylidene group or
mixtures thereof; and
(c) at least one monoolefin compound which is copolymerizable
with the monomers of (a) and (b) and is selected from the
group consisting of:
(1) an alkyl vinyl ether and an allyl alkyl ether where the
alkyl group is hydroxyl, amino, dialkylamino or
alkoxy substituted or is unsubstituted, and containing
from about 1 to about 40 carbon atoms;
(2) an alkyl amine and an N-alkylamide of a
monoethylenically unsaturated mono- or
9
dicarboxylic acid of from about 3 to about 10 carbon
atoms where the alkyl substituent contains from
about 1 to about 40 carbon atoms;
(3) an N-vinylcarboxamide of carboxylic acids of from
about 1 to about 8 carbon atoms;
(4) an N-vinyl substituted nitrogen-containing
heterocyclic compound; and
(5) at least one 1-olefin comprising about 2 to 40 carbon
atoms or at least one polyolefin comprising about 4
to about 360 carbon atoms and having a terminal
copolymerizable group in the form of a vinyl,
vinylidene or alkyl vinylidene group or mixtures
thereof, provided that the olefin employed is not the
same as the olefin employed in (i)(b);
(iii) a copolymer obtained by reacting compound (i)(a) and
compound(i)(b) in the presence of a free radical initiator;
(iii) a copolymer obtained by (a) reacting compound (i)(a) with
compound (i)(b) or (i)(c) in a non-free radical catalyzed reaction in
the presence of copolymer (i) or copolymer (ii) or both; or by (b)
contacting copolymer (i) or copolymer (ii) or both with the non-free
radical catalyzed reaction product of compound (i)(a) and
compound (i)(b) or (i)(c); with
(B) at least one ether compound capable of being reacted with at least two
monocarboxylic acids or esters thereof, or with at least two dicarboxylic
acids, anhydrides or esters thereof, or mixtures thereof;
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(C) at least one aliphatic compound having at least two functional groups, wherein one
of the functional groups is capable of reacting with at least one monocarboxylic acid or
ester thereof, or dicarboxylic acid, anhydride or ester thereof and wherein another
functional group is capable of reacting with at least one post-treating agent.
Accordingly, the present invention relates to multi-functional lubricating oil additives
which are useful as dispersants in an internal combustion engine. The dispersants, which
are post-treated, have demonstrated improved dispersancy over dispersants which have not
been post-treated.
DETAILED DESCRIPTION OF THE INVENTION
While the invention is susceptible to various modifications and alternative forms, specific
embodiments thereof and are herein described in detail. It should be understood, however,
that the description herein of specific embodiments is not intended to limit the invention to
the particular forms disclosed, but on the contrary, the intention is to cover all
modifications, equivalents, and alternatives falling within the spirit and scope of the
invention as defined by the appended claims.
Definitions
The following terms used with the description are defined as such:
The term "PIB" is an abbreviation for polyisobutene.
The term "PIBSA" is an abbreviation for polyisobutenyl or polyisobutyl succinic
anhydride.
The term "polyPIBSA" refers to a class of copolymers employed within the scope of the
present invention which are copolymers of polyisobutene and a monoethylenically
unsaturated C3-C28 monocarboxylic acid or ester thereof, or a C4-C28 dicarboxylic acid,
anhydride or ester thereof which have carboxyl groups, preferably succinic groups, and
11
polyisobutyl groups. The preferred polyPIBSA is a copolymer of polyisobutene and
maleic anhydride having the general formula:
n
wherein n is one or greater; Ri, R2, R3 and R4 are selected from hydrogen, methyl and
polyisobutyl having at least about 8 carbon atoms, preferably at least about 30 carbon
atoms and more preferably at least about 50 carbon atoms wherein either R| and R2 are
hydrogen and one of R3 and R4 is methyl and the other is polyisobutyl, or R3 and R4 are
hydrogen and one of R| and R2 is methyl and the other is polyisobutyl. The polyPIBSA
copolymer may be alternating, block, or random.
The term "succinic group" refers to a group having the formula:
0
H
- C — c —w
C—c z
H II
o
wherein W and Z are independently selected from the group consisting of--OH, —CI, --0-
-alkyl or taken together are --0-- to form a succinic anhydride group. The term "—O—
alkyl" is meant to include alkoxy of from about 1 to about 40 carbon atoms, preferably
from about 1 to about 8 carbon atoms.
The term "degree of polymerization" refers to the average number of repeating structural
units in the polymer chain.
The term "terpolymer" refers to a polymer derived from the free radical copolymerization
of at least 3 monomers.
12
The term "1-olefin" refers to a monounsaturated olefin that has the double bond in the 1-
position. They can also be called alpha-olefins, and have the following structure:
CH2 = CHR
where R is the rest of the olefin molecule.
The term "1,1-disubstituted olefin" refers to a disubstituted olefin, also called a vinylidene
olefin, that has the following structure:
CH2 = CR5 R6
wherein R5 and R6 are the same or different, and constitute the rest of the olefin molecule.
Preferably, either R5 or R5 is a methyl group, and the other is not.
The term "succinimide" is understood in the art to include many of the amide, imide, etc.
species which are also formed by the reaction of a succinic anhydride with an amine. The
predominant product, however, is succinimide and this term has been generally accepted
as meaning the product of a reaction of an alkenyl- or alkyl-substituted succinic acid or
anhydride with an amine. Alkenyl or alkyl succinimides are disclosed in numerous
references and are well known in the art. Certain fundamental types of 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 disclosures of which are hereby incorporated by reference.
The term "polysuccinimide" refers to the reaction product of a succinic group-containing
copolymer with an amine.
The term "alkenyl or alkylsuccinic acid derivative" refers to a structure having the
formula:
O
H II
R7 C C L
H2C C M
O
13
wherein R7 is selected from hydrogen, methyl and polyisobutyl having at least about
8 carbon atoms, preferably at least about 30 carbon atoms and more preferably at least
about 50 carbon atoms; wherein L and M are independently selected from the group
consisting of -OH, —CI, --0-alkyl or taken together are - O - to form an alkenyl or
alkylsuccinic anhydride group.
The term "alkylvinylidene" or "alkylvinylidene isomer" refers to an olefin having the
following vinylindene structure:
CH2
wherein Rg is alkyl or substituted alkyl. Rg generally has at least about 5 carbon atoms,
preferably about 30 carbon atoms, and more preferably at least about 50 carbon atoms and
R9 is lower alkyl of from about 1 to about 6 carbon atoms.
The term "soluble in lubricating oil" refers to the ability of a material to dissolve in
aliphatic and aromatic hydrocarbons such as lubricating oils or fuels in essentially all
proportions.
The term "high molecular weight olefins" refers to olefins (including polymerized olefins
having a residual unsaturation) of sufficient molecular weight and chain length to lend
solubility in lubricating oil to their reaction products. Typically olefins having about 30
carbons or more suffice.
The term "high molecular weight polyalkyl" refers to polyalkyl groups of sufficient
molecular weight such that the products prepared having such sufficient molecular weight
are soluble in lubricating oil. Typically these high molecular weight polyalkyl groups have
at least about 30 carbon atoms, preferably at least about 50 carbon atoms. These high
molecular weight polyalkyl groups may be derived from high molecular weight
polyolefins.
14
The term "amino" refers to -NRIORI i wherein Rio and R| i are independently hydrogen or a
hydrocarbyl group.
The term "alkyl" refers to both straight- and branched-chain alkyl groups.
The term "lower alkyl" refers to alkyl groups having from about 1 to about 6 carbon atoms
and includes primary, secondary and tertiary alkyl groups. Typical lower alkyl groups
include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, npentyl,
iso-pentyl, n-hexyl and the like.
The term "polyalkyl" refers to an alkyl group that is generally derived from polyolefins
which are polymers or copolymers of mono-olefins, particularly l-mono-olefins, such as
ethylene, propylene, butylene, and the like. Preferably, the mono-olefin employed will
have from about 2 to about 24 carbon atoms, and more preferably, from about 3 to about
12 carbon atoms. More preferred mono-olefins include propylene, butylene, particularly
isobutylene, 1-octene and 1-decene. Preferred, polyolefins prepared from such monoolefins
include polypropylene, polybutene, especially polyisobutene.
The Lubricating Oil Additive Composition
One embodiment of the present invention is an oil-soluble lubricating oil additive
composition prepared by the process which comprises reacting
(A) at least one of the following copolymers:
(i) a copolymer obtained by free radical copolymerization of components
comprising:
(a) at least one monoethylenically unsaturated C3-C28 monocarboxylic
acid or ester thereof, or C4-C28 dicarboxylic acid, anhydride or ester
thereof;
15
(b) at least one 1-olefin comprising about 2 to 40 carbon atoms or at
least one polyolefin comprising about 4 to 360 carbon atoms and
having a terminal copolymerizable group in the form of a vinyl,
vinylidene or alkyl vinylidene group or mixtures thereof; and
(c) at least one monoolefin compound which is copolymerizable with
the monomers of (a) and (b) and is selected from the group
consisting of:
(1) an alkyl vinyl ether and an allyl alkyl ether where the alkyl
group is hydroxyl, amino, dialkylamino or alkoxy
substituted or is unsubstituted, and containing 1 to 40 carbon
atoms;
(2) an alkyl amine and an N-alkylamide of a monoethylenically
unsaturated mono- or dicarboxylic acid of 3 to 10 carbon
atoms where the alkyl substituent contains 1 to 40 carbon
atoms;
(3) an N-vinylcarboxamide of carboxylic acids of 1 to 8 carbon
atoms;
(4) an N-vinyl substituted nitrogen-containing heterocyclic
compound; and
(5) at least one 1 -olefin comprising about 2 to 40 carbon atoms
or at least one polyolefin comprising about 4 to about 360
carbon atoms and having a terminal copolymerizable group
in the form of a vinyl, vinylidene or alkyl vinylidene group
or mixtures thereof, provided that the olefin employed is not
the same as the olefin employed in (i)(b);
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(ii) a copolymer obtained by reacting compound (i)(a) and compound(i)(b) in
the presence of a free radical initiator;
(iii) a copolymer obtained by (a) reacting compound (i)(a) with compound (i)(b)
or (i)(c) in a non-free radical catalyzed reaction in the presence of
copolymer (i) or copolymer (ii) or both; or by (b) contacting copolymer (i)
or copolymer (ii) or both with the non-free radical catalyzed reaction
product of compound (i)(a) and compound (i)(b) or (i)(c); with
(B) at least one ether compound capable of being reacted with at least two
monocarboxylic acids, or esters, thereof, or dicarboxylic acids, anhydrides or esters
thereof, or mixtures thereof; and
(C) at least one aliphatic compound capable of reacting with at least two
monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester
thereof.
Copolymer (i)
(a) The Monoethylenically Unsaturated Monocarboxylic Acid or Ester Thereof or
Dicarboxylic Acid, Anhydride or Ester Thereof
In the present invention, at least one monoethylenically unsaturated C3-C28
monocarboxylic acid or ester thereof, or C4-C28 dicarboxylic acid, anhydride or ester
thereof is used to prepare the copolymers of copolymer (i). Preferably the at least one
monoethylenically unsaturated C3-C28 monocarboxylic acid or ester thereof, or C4-C28
dicarboxylic acid, anhydride or ester thereof is a dicarboxylic acid, anhydride or ester
thereof.
The general formula of the preferred dicarboxylic acid, anhydride or ester thereof is as
follows:
17
o o
C CH=CH C
X X'
wherein X and X' are the same or different, provided that at least one of X and X' is a
group that is capable of reacting to esterify alcohols, form amides or amine salts with
ammonia or amines, form metal salts with reactive metals or basically reacting metal
compounds and otherwise function as acylating agents. Typically, X and/or X' is —OH, -
O-hydrocarbyl, OM+ where M+ represents one equivalent of a metal, ammonium or
amine cation, --NH2, —CI, --Br, and taken together X and X' can be --0-- so as to form an
anhydride. Preferably X and X' are such that both carboxylic functions can enter into
acylation reactions. Maleic anhydride is a preferred reactant. Other suitable reactants
include electron-deficient olefins such as monophenyl maleic anhydride; monomethyl,
dimethyl, monochloro, monobromo, monofluoro, dichloro and difluoro maleic anhydride;
N-phenylmaleimide and other substituted maleimides, isomaleimides; fumaric acid,
maleic acid, alkyl hydrogen maleates and fumarates, dialkyl fumarates and maleates,
fumaronilic acids and maleanic acids; and maleonitrile and fumaronitrile.
Suitable monomers for (a) are monoethylenically unsaturated dicarboxylic acids or
anhydrides of from about 4 to 28 carbon atoms selected from the group consisting of
maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid,
citraconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride and
methylenemalonic anhydride and mixtures of these with one another, among which maleic
anhydride is preferred.
Other suitable monomers are monoethylenically unsaturated C3-C28-monocarboxylic acids
selected from the group consisting of acrylic acid, methacrylic acid, dimethacrylic acid,
ethylacrylic acid, crotonic acid, allylacetic acid and vinylacetic acid, among which acrylic
and methacrylic acid are preferred.
18
Another group of suitable monomers is C1-C40 alkyl esters of monoethylenecially
unsaturated C3-C10 mono- or C4-C10 dicarboxylic acids such as ethyl acrylate, butyl
acrylate, 2-ethyl acrylate, decyl acrylate, docedyl acrylate, loctadecyl acrylate and the
esters of industrial alcohol mixtures of from about 14 to 28 carbon atoms, ethyl
methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, octadecyl methacrylate,
monobutyl maleate, dibutyl maleate, monodecyl maleate, didodecyl maleate,
monooctadecyl maleate, and dioctadecyl maleate.
(b) The 1 -Olefin or Polyolefin
In the present invention at least one 1-olefin comprising about 2 to 40 carbon atoms or at
least one polyolefin comprising about 4 to 360 carbon atoms and having a terminal
copolymerizable group in the form of vinyl, vinylidene or alkyl vinylidene group is
employed.
Suitable 1-olefins for preparing copolymer (i) comprise from about 2 to about 40 carbon
atoms, preferably from about 6 to about 30 carbon atoms, such as decene, dodecene,
octadecene and mixtures of C20-C24 -1-olefins and C24-C28-I-olefins, more preferably from
about 10 to about 20 carbon atoms. Preferably 1-olefins, which are also known as alpha
olefins, with number average molecular weights in the range 100-4,500 or more are
preferred, with molecular weights in the range of 200-2,000 being more preferred. For
example, alpha olefins obtained from the thermal cracking of paraffin wax. Generally,
these olefins range from about 5 to about 20 carbon atoms in length. Another source of
alpha olefins is the ethylene growth process which gives even number carbon olefins.
Another source of olefins is by the dimerization of alpha olefins over an appropriate
catalyst such as the well known Ziegler catalyst. Internal olefins are easily obtained by the
isomerization of alpha olefins over a suitable catalyst such as silica. Preferably, 1-olefins
from C6-C30 are used because these materials are commercially readily available, and
because they offer a desirable balance of the length of the molecular tail, and the solubility
of the terpolymer in nonpolar solvents. Mixtures of olefins may also be employed.
Suitable polyolefins for preparing copolymer (i) are polyolefins comprising about 4 to
about 360 carbon atoms. These polymers have a number average molecular weight (Mn) of
19
from about 56 to about 5000 g/mol. Examples of these are oligomers of ethylene, of
butene, including isobutene, and of branched isomers of pentene, hexene, octene and of
decene, the copolymerizable terminal group of the oligomer being present in the form of a
vinyl, vinylidene or alkylvinylidene group, oligopropenes and oligopropene mixtures of
from about 9 to about 200 carbon atoms and in particular oligoisobutenes, as obtainable,
for example, according to DE-A 27 02 604, corresponding U.S. Patent No. 4,152,499, are
preferred. Mixtures of the stated oligomers are also suitable, for example, mixtures of
ethylene and other alpha olefins. Other suitable polyolefins are described in U.S. Patent
No. 6,030,930 which is herein incorporated by reference. The molecular weights of the
oligomers may be determined in a conventional manner by gel permeation
chromatography.
The copolymerizable polyolefin that is reacted with the unsaturated mono- or dicarboxylic
reactant are polymers comprising a major amount of C2 -C8 mono-olefin, e.g.,
ethylene, propylene, butylene, isobutylene and pentene. These polymers can be
homopolymers such as polyisobutylene as well as copolymers of 2 or more such olefins
such as copolymers of: ethylene and propylene, butylene, and isobutylene, etc.
The polyolefin polymer usually contains from about 4 to about 360 carbon atoms,
although preferably 8 to 200 carbon atoms; and more preferably from about 12 to about
175 carbon atoms.
Since the high molecular weight olefins used to prepare the copolymers of the present
invention are generally mixtures of individual molecules of different molecular weights,
individual copolymer molecules resulting will generally contain a mixture of high
molecular weight polyalkyl groups of varying molecular weight. Also, mixtures of
copolymer molecules having different degrees of polymerization will be produced.
The copolymers of the present invention have an average degree of polymerization of 1 or
greater, preferably from about 1.1 to about 20, and more preferably from about 1.5 to
about 10.
20
(c) The Mono-olefin Compound
The present invention employs at least one monoolefin compound which is
copolymerizable with the monomers of (a) and (b) and is selected from the group
consisting of:
(1) an alkyl vinyl ether and an allyl alkyl ether where the alkyl group is hydroxyl,
amino, dialkylamino or alkoxy substituted or is unsubstituted, and containing from
about 1 to about 40 carbon atoms;
Suitable monomers include the following: vinyl and allyl alkyl ethers where the alkyl
radical is of about 1 to about 40 carbon atoms are also suitable, and the alkyl radical may
carry further substituents, such as hydroxyl, amino, dialkyamino or alkoxy. Examples are
methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl
vinyl ether, decylvinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-
(diethylyamino)ethyl vinyl ether, 2-(di-n-butylamino)ethyl vinyl ether, and the
corresponding allyl ethers.
(2) an alkyl amine and an N-alkylamide of a monoethylenically unsaturated mono- or
dicarboxylic acid of from about 3 to about 10 carbon atoms where the alkyl
substituent contains from about 1 to about 40 carbon atoms;
Another group of monomers comprises C1-C40 alkyl amines and C1-C40 -N- alkylamides of
monoethylenically unsaturated C3 -C10 -mono- or dicarboxylic acids, such as
dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dibutylaminoethyl methacrylate,
acrylamide, methacrylamide, N-tert-butylacrylamide, N-octylacrylamide, N,N' -
dibutylacrylamide, N-dodecylmethacrylamide and N-octadecylmethacrylamide.
(3) an N-vinylcarboxamide of carboxylic acids of from about 1 to about 8 carbon
atoms;
Another group of monomers includes the following: N-vinylcarboxamides of
carboxylic acids of from about 1 to about 8 carbon atoms, such as N-
21
vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-Nmethylacetramide,
N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and
N-vinylpropionamide.
an N-vinyl substituted nitrogen-containing heterocyclic compound; Another group
of monomers includes the following: N-vinyl compounds of nitrogen-containing
heterocyles, such as N-vinylimidazole, N-vinylmethylimidazole, Nvinylpyrrolidone
and N-vinylcaprolactam.
at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one
polyolefin comprising from about 4 to about 360 carbon atoms and having a
terminal copolymerizable group in the form of a vinyl, vinylidene or alkyl
vinylidene group or mixtures thereof, provided that the olefin employed is not the
same as the olefin employed in (i)(b);
Suitable 1-olefins comprise about 2 to 40 carbon atoms, preferably from about 8 to
about 30 carbon atoms, such as decene, dodecene, octadecene and mixtures of C20-
C24 -1-olefins and C24-C28-I-olefins. Preferably 1-olefins, which are also known as
alpha olefins, with number average molecular weights in the range of from about
28 to about 560 are preferred, with molecular weights in the range of from about
112 to about 420 being more preferred. For example, alpha olefins obtained from
the thermal cracking of paraffin wax may be employed. Generally, these olefins
range from about 5 to about 20 carbon atoms in length. Another source of alpha
olefins is the ethylene growth process which gives even number carbon olefins.
Another source of olefins is by the dimerization of alpha olefins over an
appropriate catalyst such as the well known Ziegler catalyst. Internal olefins are
easily obtained by the isomerization of alpha olefins over a suitable catalyst such
as silica. Preferably, 1-olefins from C10-C30 are used because these materials are
commercially readily available, and because they offer a desirable balance of the
length of the molecular tail, and the solubility of the terpolymer in nonpolar
solvents. Mixtures of olefins are also suitable.
22
Preparation of Copolymer (i)
Copolymer reactant (i) may be prepared from well known methods which are described in
the art including, but not limited to, those methods which are disclosed in the following
patents, which are herein incorporated by reference: Harrison et al., U.S. Patent No.
5,792,729; Gunther et al., U.S. Patent No. 6,284,716; and Gunther et al., U.S. Patent No.
6,512,055.
In one embodiment of the present invention the copolymer reactant is a polyalkenyl
succinic anhydride terpolymer. These terpolymers are composed of at least one of
monomers (a) to (c) as described herein.
Typically, the terpolymers of this invention contain at least one monomer from each group
(a) to (c). In general, these components react to form terpolymers which can be random
terpolymers or alternating terpolymers or block terpolymers and can be prepared by
known procedures for making copolymers. Additionally, it is possible to form a small
percentage of copolymers which are composed of monomers (a) and (b) and monomers (a)
and (c). Component (a), the monocarboyxlic acid or ester thereof or dicarboxylic acid or
anhydride or ester thereof, is selected from those disclosed above, preferably maleic
anhydride. Component (b), the 1-olefin or polyolefin, is preferably polybutene.
Component (c), the mono-olefin, is preferably a linear alpha olefin containing from about
12 to 18 carbon atoms.
The degree of polymerization of the terpolymers can vary over a wide range. Preferably,
the degree of polymerization is from about 2 to about 10. In general, terpolymer degree of
polymerization decreases as the polymerization temperature increases.
The terpolymerization is conducted in the presence of a suitable free radical initiator.
Examples of suitable polymerization initiators are peroxide compounds, such as tertbutyl
perpivalate, tertbutyl perneocecanoate, tert-butylperethylhexanoate,
tertbutylperisobutyrate, di-tert-butyl peroxide, di-tert-amyl peroxide, diacetyl
peroxydicaronate and dicyclohexyldicaronate, or azo compounds, such as 2,2'
-azobisisobutyrontrile. The intiators may be used alone or as a mixture with one another.
23
Redox co-initiators may also be present. Preferably, the initiator is a peroxide type
initiator, e.g., di(t-butyl) peroxide, dicumyl peroxide or azo type initiator,
e.g., isobutylnitrile type initiators. Procedures for preparing poly 1-olefin copolymers are,
for example, described in U.S. Pat. Nos. 3,560,455 and 4,240,916, hereby incorporated by
reference in their entirety. Those procedures could be used to prepare terpolymers. Both
patents also describe a variety of initiators.
Copolymer (i), wherein a second olefin is employed in the reaction, can be prepared in the
same manner as copolymer (ii) which is described below.
Copolymer (ii)
In another embodiment of the present invention, the copolymer reactant is a copolymer
obtained by reacting (a) at least one monoethylenically unsaturated C3-C28
monocarboxylic acid or ester thereof, or a C4-C28 dicarboxylic acid, anhydride or ester
thereof and (b) at least one copolymerizable polymer composed of at least 3 olefin
molecules of propene or of a branched 1-olefin of from about 4 to about 10 carbon atoms,
having a number average molecular weight Mn of from about 112 to about 5000, and
having a terminal copolymerizable group in the form of a vinyl, vinylidene or alkyl
vinylidene group in the presence of a free radical initiator.
24
Thus, preferred copolymers of the present invention are prepared by reacting a "reactive"
high molecular weight olefin in which a high proportion of unsaturation, at least about
20% is in the alkylvinylidene configuration, e.g.,
CH2
wherein Rs and R9 are an alkyl or substituted alkyl of sufficient chain length to give the
resulting molecule stability in lubricating oils and fuels, thus Rg generally has at least
about 30 carbon atoms, preferably at least about 50 carbon atoms and R9 is a lower alkyl
of from about 1 to about 6 carbon atoms, with an unsaturated acidic reactant in the
presence of a free radical initiator.
Typically, the copolymer product has alternating polyalkylene and succinic groups and has
an average degree of polymerization of 1 or greater.
The preferred copolymers (ii) of the present invention have the general
formula:
w z1
0 = C C=0 R2 R4
-C C C C
H H II
Ri R„
' n
wherein W and Z' are independently selected from the group consisting of -OH, --0--
alkyl or taken together are --0-- to form a succinic anhydride group, n is one or greater;
and Ri, R2, R3 and R4 are selected from hydrogen, alkyl of from about 1 to about 40
carbon atoms, and high molecular weight polyalkyl wherein either Ri and R2 are hydrogen
and one of R3 and R4 is lower alkyl having from about 1 to about 6 carbon atoms and the
other is high molecular weight polyalkyl, or R3 and R4 are hydrogen and one of Ri and R2
is lower alkyl having from about 1 to 6 carbon atoms and the other is high molecular
weight polyalkyl.
25
Copolymer (ii) may be alternating, block, or random.
In a preferred embodiment, when maleic anhydride is used as the reactant, the reaction
produces copolymers predominately of the following formula:
R2 R4
C CR
1 R3
wherein n is from about 1 to about 100, preferably from about 2 to about 20, more
preferably from about 2 to about 10, and Ri, R2, R3 and R4 are selected from hydrogen,
lower alkyl of from about 1 to about 6 carbon atoms and higher molecular weight
polyalkyl, wherein either R\ and R2 are hydrogen and one of R3 and R4 is lower alkyl
having from about 1 to about 6 carbon atoms and the other is high molecular weight
polyalkyl or R3 and R4 are hydrogen and one of Ri and R2 is lower alkyl and the other is
high molecular weight polyalkyl.
Preferably, the high molecular weight polyalkyl group has at least about 30 carbon atoms
(more preferably at least about 50 carbon atoms). Preferred high molecular weight
polyalkyl groups include polyisobutyl groups. Preferred polyisobutyl groups include those
having number average molecular weights of from about 500 to about 5000, more
preferably from about 900 to about 2500. Preferred lower alkyl groups include methyl and
ethyl; especially preferred lower alkyl groups include methyl.
A particularly preferred class of olefin polymers comprises the polybutenes, which are
prepared by polymerization of isobutene. 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. Patent Nos. 4,152,499 and 4,605,808, which are herein
incorporated by reference for their disclosures of suitable polybutenes.
/ Yr
26
Preferably, 1,1-disubstituted olefins are used to provide a high molecular weight, oil
soluble tail in the terpolymer. Preferably the 1,1-disubstituted olefin has a number average
Mn of from about 500 to about 5000. One particularly useful 1,1-disubstituted olefin is a
1,1 -disubstituted polyisobutylene, such as methylvinylidene polyisobutylene.
Preferably the copolymerizable polymer comprises a high molecular weight polyalkyl
group which is derived from a high molecular weight olefin. The high molecular weight
olefins used in the preparation of the copolymers of the present invention are of
sufficiently long chain length so that the resulting composition is soluble in and
compatible with mineral oils, fuels and the like; and the alkylvinylidene isomer of the high
molecular weight olefin comprises at least about 20% of the total olefin composition.
Preferably, the alkyl vinylidene isomer comprises at least 50%, more preferably at least
70%, of the total olefin composition.
Such high molecular weight olefins are generally mixtures of molecules having different
molecular weights and can have at least one branch per 6 carbon atoms along the chain,
preferably at least one branch per 4 carbon atoms along the chain, and particularly
preferred that there be about one branch per 2 carbon atoms along the chain. These
branched chain olefins may conveniently comprise polyalkenes prepared by the
polymerization of olefins of from about 3 to about 6 carbon atoms, and preferably from
olefins of from about 3 to about 4 carbon atoms, and more preferably from propylene or
isobutylene. The addition-polymerizable olefins employed are normally 1-olefins. The
branch may be of from about 1 to about 4 carbon atoms, more usually of from about 1 to
about 2 carbon atoms and preferably methyl.
The preferred alkylvinylidene isomer comprises a methyl- or ethylvinylidene isomer, more
preferably the methylvinylidene isomer.
The especially preferred high molecular weight olefins used to prepare the copolymers of
the present invention are polyisobutenes which comprise at least about 20% of the more
reactive methylvinylidene isomer, preferably at least about 50% and more preferably at
least about 70%. Suitable polyisobutenes include those prepared using BF3 catalysis. The
27
preparation of such polyisobutenes in which the methylvinylidene isomer comprises a high
percentage of the total composition is described in U.S. Patent Nos. 4,152,499 and
4,605,808.
Preparation of Copolymer (ii)
As noted above, copolymer (ii) of the present invention is prepared by reacting an olefin
and an unsaturated acidic reactant in the presence of a free radical initiator. The process of
the preparation of copolymer (ii) is described in Harrison, U.S. Patent No. 5,112,507,
which is herein incorporated by reference in its entirety.
The reaction may be conducted at a temperature of about -30°C to about 210°C, preferably
from about 40°C to about 160°C. The degree of polymerization is inversely proportional
to temperature. Accordingly, for the preferred high molecular weight copolymers, it is
advantageous to employ lower reaction temperatures.
The reaction may be conducted neat, that is, both the high molecular weight olefin, acidic
reactant and the free radical initiator are combined in the proper ratio, and then stirred at
the reaction temperature.
Alternatively, the reaction may be conducted in a solvent. Suitable solvents include those
in which the reactants and free radical initiator are soluble and include acetone,
tetrahydrofuran, chloroform, methylene chloride, dichloroethane, toluene, dioxane,
chlorobenzene, xylenes, or the like. After the reaction is complete, volatile components
may be stripped off. When a solvent is employed, it is preferably inert to the reactants and
products formed and is generally used in an amount sufficient to ensure efficient mixing.
Alternatively, the reaction may be conducted in a diluent, such as mineral oil, as long as
the diluent does not contain constituents that interfere with the free radical polymerization,
e.g., sulfur compounds, antioxidants and the like.
28
In general, the copolymerization can be initiated by any free radical initiator. Such
initiators are well known in the art. However, the choice of free radical initiator may be
influenced by the reaction temperature employed.
The preferred free-radical initiators are the peroxide-type polymerization initiators and the
azo-type polymerization initiators. Radiation can also be used to initiate the reaction, if
desired.
The peroxide-type free-radical initiator can be organic or inorganic, the organic having the
general formula: R12 OORn where R12 is any organic radical and Rn is selected from the
group consisting of hydrogen and any organic radical. Both R\2 and Rn can be organic
radicals, preferably hydrocarbon, aryl, and acyl radicals, carrying, if desired, substituents
such as halogens, etc. Preferred peroxides include di-tert-butyl peroxide, dicumyl
peroxide, and di-tert-amyl peroxide.
Examples of other suitable peroxides, which in no way are limiting, include benzoyl
peroxide; lauroyl peroxide; other tertiary butyl peroxides; 2,4-dichlorobenzoyl peroxide;
tertiary butyl hydroperoxide; cumene hydroperoxide; diacetyl peroxide; acetyl
hydroperoxide; diethylperoxycarbonate; tertiary butyl perbenzoate; and the like.
The azo-type compounds, typified by alpha,alpha' -azobisisobutyronitrile, are also wellknown
free-radical promoting materials. These azo compounds can be defined as those
having present in the molecule group ~N=N~ wherein the balances are satisfied by
organic radicals, at least one of which is preferably attached to a tertiary carbon. Other
suitable azo compounds include, but are not limited to, p-bromobenzenediazonium
fluoroborate; p-tolyldiazoaminobenzene; p-bromobenzenediazonium hydroxide;
azomethane and phenyldiazonium halides. A suitable list of azo-type compounds can be
found in U.S. Patent No. 2,551,813, issued May 8, 1951 to Paul Pinkney.
The amount of initiator to employ, exclusive of radiation, of course, depends to a large
extent on the particular initiator chosen, the high molecular olefin used and the reaction
29
conditions. The usual concentrations of initiator are between 0.001:1 and 0.2:1 moles of
initiator per mole of acidic reactant, with preferred amounts between 0.005:1 and 0.10:1.
The polymerization temperature must be sufficiently high to break down the initiator to
produce the desired free-radicals. For example, using benzoyl peroxide as the initiator, the
reaction temperature can be between about 75°C and about 90°C, preferably between
about 80°C and about 85°C higher and lower temperatures can be employed, a suitable
broad range of temperatures being between about 20°C and about 200°C, with preferred
temperatures between about 50°C and about 150°C.
The reaction pressure should be sufficient to maintain the solvent in the liquid phase.
Pressures can therefore vary between about atmospheric and 100 psig or higher.
The reaction time is usually sufficient to result in the substantially complete conversion of
the acidic reactant and high molecular weight olefin to copolymer. The reaction time is
suitable between one and 24 hours, with preferred reaction times between 2 and 10 hours.
As noted above, the subject reaction is a solution-type polymerization reaction. The high
molecular weight olefin, acidic reactant, solvent and initiator can be brought together in
any suitable manner. The important factors are intimate contact of the high molecular
weight olefin and acidic reactant in the presence of a free-radical producing material. The
reaction, for example, can be conducted in a batch system where the high molecular
weight olefin is added all initially to a mixture of acidic reactant, initiator and solvent or
the high molecular weight olefin can be added intermittently or continuously to the
reactor. Alternatively, the reactants may be combined in other orders; for example, acidic
reactant and initiator may be added to high molecular weight olefin in the reactor. In
another manner, the components in the reaction mixture can be added continuously to a
stirred reactor with continuous removal of a portion of the product to a recovery train or to
other reactors in series. In yet another manner, the reaction may be carried out in a batch
process, wherein the high molecular weight olefin is added initially to the reactor, and then
the acidic reactant and the initiator are added gradually over time. The reaction can also
30
suitably take place in a tubular-type reactor where the components are added at one or
more points along the tube.
Copolymer (iii)
In one embodiment, copolymer reactant (iii) is obtained by a copolymer obtained by (a)
reacting compound (i)(a) with compound (i)(b) or (i)(c) in a non-free radical catalyzed
reaction in the presence of copolymer (i) or copolymer (ii) or both; or by (b) contacting
copolymer (i) or copolymer (ii) or both with the non-free radical catalyzed reaction
product of compound (i)(a) and compound (i)(b) or (i)(c).
Preparation of Copolymer (iii)
A process for the preparation of copolymer (iii) is described, for example, in Harrison et
al., U.S. Patent No. 6,451,920, which is herein incorporated by reference in its entirety.
In process step (a) above, any unreacted olefin, generally the more hindered olefins, i.e.,
the beta-vinylidene, that do not react readily with the monoethylenically unsaturated C3-
C28 monocarboxylic acid or ester thereof, or C4-C28 dicarboxylic acid or an anhydride or
ester thereof, under free radical conditions, are reacted with monoethylenically unsaturated
C3-C28 monocarboxylic acid or ester thereof, or C4-C28 dicarboxylic acid or an anhydride
or ester thereof, under thermal conditions, i.e., at temperatures of from about 180°C to
about 280°C. These conditions are similar to those used for preparing thermal process
PIBSA. Optionally, this reaction takes place in the presence of a strong acid, such as
sulfonic acid. See for example U.S. Patent No. 6,156,850.
Optionally, a solvent may be used to dissolve the reactants. The reaction solvent must be
one which dissolves both the acidic reactant and the high molecular weight olefin. It is
necessary to dissolve the acidic reactant and high molecular weight olefin so as to bring
them into intimate contact in the solution polymerization reaction. It has been found that
the solvent must also be one in which the resultant copolymers are soluble.
Suitable solvents include liquid saturated or aromatic hydrocarbons having from about 6 to
about 20 carbon atoms; ketones having from about 3 to about 5 carbon atoms; and liquid
31
saturated aliphatic dihalogenated hydrocarbons having from about 1 to about 5 carbon
atoms per molecule, preferably from about 1 to about 3 carbon atoms per molecule. By
"liquid" is meant liquid under the conditions of polymerization. In the dihalogenated
hydrocarbons, the halogens are preferably on adjacent carbon atoms. By "halogen" is
meant F, CI and Br. The amount of solvent must be such that it can dissolve the acidic
reactant and high molecular weight olefin in addition to the resulting copolymers. The
volume ratio of solvent to high molecular weight olefin is suitably between 1:1 and 100:1
and is preferably between 1.5:1 and 4:1.
Suitable solvents include the ketones having from about 3 to about 6 carbon atoms and the
saturated dichlorinated hydrocarbons having from about 1 to about 5, more preferably
from about 1 to about 3, carbon atoms.
Examples of suitable solvents include, but are not limited to:
1. ketones, such as: acetone; methylethylketone; diethylketone; and
methylisobutylketone;
2. aromatic hydrocarbons, such as: benzene; xylene; and toluene;
3. saturated dihalogenated hydrocarbons, such as: dichloromethane; dibromomethane;
l-bromo-2-chloroethane; 1,1-dibromoethane; 1,1-dichloroethane; 1,2-
dichloroethane; 1,3-dibromopropane; 1,2-dibromopropane; l,2-dibromo-2-
methylpropane; 1,2-dichloropropane; 1,1-dichloropropane; 1,3-dichloropropane;
1 -bromo-2-chloropropane; 1,2-dichlorobutane; 1,5-dibromopentane; and 1,5-
dichloropentane; or
4. mixtures of the above, such as: benzenemethylethylketone.
The copolymer is conveniently separated from solvent and any unreacted acidic reactant
by conventional procedures such as phase separation, solvent distillation, precipitation and
the like. If desired, dispersing agents and/or co-solvents may be used during the reaction.
32
The polyisobutenyl succinic anhydride (PIBSA), which may be directly added to
copolymer reactant (i) or (ii), is generally prepared by a number of well-known processes
including the method disclosed within. For example, there is a well-known thermal
process (see, e.g., U.S. Patent No. 3,361,673), an equally well-known chlorination process
(see, e.g., U.S. Patent. No. 3,172,892), a combination of the thermal and chlorination
processes (see, e.g., U.S. Patent No. 3,912,764), catalytic strong acid processes (see, e.g.,
U.S. Patent Nos. 3,819,660 and 6,156,850), and free radical processes (see, e.g., U.S.
Patent Nos. 5,286,799 and 5,319,030). Such compositions include one-to-one monomeric
adducts (see, e.g., U.S. Patent Nos. 3,219,666 and 3,381,022), as well as high succinic
ratio products, adducts having alkenyl-derived substituents adducted with at least
1.3 succinic groups per alkenyl-derived substituent (see, e.g., U.S. Patent No. 4,234,435).
Polyalkylene succinic anhydrides also can be produced thermally also from high
methylvinylidene polybutene as disclosed in U.S. Patent No. 4,152,499. This process is
further discussed in U.S. Patent No. 5,241,003 for the case where the succinic ratio is less
than 1.3 and in EP 0 355 895 for the case where the succinic ratio is greater than 1.3.
European Applications EP 0 602 863 and EP 0 587 381, and U.S. Patent No. 5,523,417
disclose a procedure for washing out the polymaleic anhydride resin from polyalkylene
succinic anhydride prepared from high methylvinylidene polybutene. A polyalkylene
succinic anhydride with a succinic ratio of 1.0 is disclosed. One advantage of polyalkylene
succinic anhydride from high methylvinylidene polybutene is that it can be prepared
essentially free of chlorine. U.S. Patent No. 4,234,435 teaches a preferred polyalkenederived
substituent group with a number average (Mn) in the range of from about 1500 to
about 3200. For polybutenes, an especially preferred number average (Mn) range is from
about 1700 to about 2400. This patent also teaches that the succinimides must have a
succinic ratio of at least 1.3. That is, there should be at least 1.3 succinic groups per
equivalent weight of polyalkene-derived substituent group. Most preferably, the succinic
ratio should be from 1.5 to 2.5.
33
Other suitable alkenyl succinic anhydrides includes those described in U.S. Patent
No. 6,030,930. Typical alkenyl used in the preparation are ethylene and 1-butene
copolymers.
(B) The Ether Compounds
In one embodiment of the present invention, the copolymer may further be reacted with an
ether compound capable of linking two succinimide groups. Suitable ether compounds
include, but are not limited to, the following:
Polyether Polyamines
Examples of suitable polyetheramines include compounds having the following structure:
R14 / R14 \ R14
I H2 / I H2 \ H2 I
H2N C C—\-0 C C—f-0 C C NH2
H I H I H l
^ ' Xwherein R)4 is independently hydrogen or a hydrocarbyl group having from about 1 to
about 4 carbons, and n is the degree of polymerization. Generally the polyether
polyamines suitable for use in the present invention will contain at least about one ether
unit, preferably from about 5 to about 100, more preferably from about 10 to about 50, and
even more preferably from about 15 to about 25 ether units.
The polyether polyamines can be based on polymers derived from C2-C6 epoxides such as
ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines
are sold under the Jeffamine® brand and are commercially available from Hunstman
Corporation located in Houston, Texas.
34
Other examples of suitable polyetheramines include polyoxytetramethylene polyamine
compounds having the following structure:
H2N-(H2C)3 0—(-(CH2)4-OH—(CH^-O (CH2)3-NH2
\ /n-1
wherein n is the degree of polymerization (i.e., number of monomer ether units).
Polyether Amine Derivatives
Furthermore, the copolymer reactant may be reacted with a polyether amino alcohol or
amino thiol.
Polyether Amino Alcohol
Typically, amino alcohols may be formed when the alcohol end groups of a compound are
not completely converted to amines during reactions, such as reductive amination. Also,
one may initiate a polymer chain (i.e. grow propylene or ethylene oxide) from an amino
group and therefore have an amino on one end of the polymer chain (i.e. initiator) and an
alcohol terminus, or an amine internally in the molecule with alcohol termini.
Examples of suitable polyetheramino alcohols include compounds having the following
structure:
R15 / R-I5 \ R-I5
H2N
wherein R15 is independently a hydrogen or hydrocarbyl group, having about 1 to about
4 carbons, and n is the degree of polymerization. Generally, the polyether amino alcohols,
suitable for use in the present invention will contain at least about one ether unit,
preferably from about 5 to about 100, more preferably from about 10 to about 50, and
even more preferably from about 15 to about 25 ether units.
Other examples of suitable polyetheramino alcohols include polyoxytetramethyleneamino
alcohol compounds having the following structure:
35
H2N-(H2C)3 O—HCH2)4-OH—(CH2)4-0 (CH2)4-OH
n-1
wherein n is the degree of polymerization.
Poly ether Amino Thiol
Examples of suitable polyetheramino thiols include compounds having the following
structure:
R-I6 / ^16 \ ^16
H2 / I H2 I H2
H2N C C—hO C C—hO C C SH
H H H
n
wherein Ri6 is independently a hydrogen or hydrocarbyl group, having from about 1 to
about 4 carbons and n is the degree of polymerization.
Other examples of suitable polyetheramino thiols include polyoxytetramethyleneamino
thiol having the following structure:
H2N-(H2C)3 0—j-(CH2)4-OH—(CH2)4-0 (CH2)4-SH
\ /n-1
wherein n is the degree of polymerization.
Generally, the polyetheramino thiols suitable for use in the present invention will contain
at least about one ether unit, preferably from about 5 to about 100, more preferably from
about 10 to about 50, and even more preferably from about 15 to about 25 ether units.
Ether Polvamines
Ether Diamines
In yet another embodiment of the present invention, the copolymer may be reacted with
ether diamines. Suitable diamines are reacted with the copolymer, such as decyloxypropyl-
1,3-diaminopropane, isodecyloxypropyl-l,3-diaminopropane,
36
isododecyloxypropyl-l,3-diaminopropane,
dodecyl/tetradecyloxypropyl-1,3-diaminopropane,
isotridecyloxypropyl-l,3-diaminopropane, tetradecyloxypropy-l,3-diaminopropane.
Ether Triamines
In yet another embodiment of the present invention, the copolymer may be reacted with
ether triamines. Suitable triamines include the following:
(i)
wherein R' isC)-C6;
wherein x+y+z = 1-85.
(ii)
H3C
wherein x+y+z = approx. 5-6;
37
Triamines of this type may be purchased from Huntsman Petrochemical Corporation,
Woodlands, Texas.
Polyether Polyol
In yet another embodiment of the present invention, the copolymer may be reacted with a
polyether containing at least two hydroxyl end groups to form an ester. The polyether
polyols have the following structure:
R17 / R17 \ R17
H2 / H2 \ H2
HO C C—V-0 C C—f-0 C C OH
H I H I H
/n
wherein R\7 is independently a hydrogen or hydrocarbyl group, having from about 1 to
about 4 carbons, and n is the degree of polymerization.
Other examples of suitable polyether polyols include polyoxytetramethylene polyol
compounds, such as those referred to as Terathane® which may be purchased from
DuPont Corporation, Wilmington, Delaware, having the following structure:
HO-(H2C)4 0—HCH2)4-CH—(CH2)4-OH
\ /n-1
wherein n is the degree of polymerization.
Suitable polyether polyols include, but are not limited to, the following:
polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, and
polyoxytetramethylene glycol.
The number average molecular weight of the presently employed polyether polyol will
generally range from about 150 to about 5000, preferably from about 500 to about 2000.
38
Generally, the polyether compounds suitable for use in the present invention will contain
at least one ether unit preferably from about 5 to about 100, more preferably from about 10
to about 50, and even more preferred from about 15 to about 25 ether units.
Generally, the polyether compounds suitable for use in the present invention may be
derived from only one ether type or a mixture of ether types, such as poly(oxyethylene-cooxypropylene)
diamine. The mixture of ether units may be block, random, or alternating
copolymers. The presently employed ether compounds are capable of reacting with at least
two carboxylic acid groups or anhydride derivatives thereof.
Generally, the copolymer may be reacted with a mixture of polyether polyamines,
polyether amino alcohols, polyether amino thiols, polyether polyols, or ether diamines to
form a mixture of imides, amides and esters.
(C) Aliphatic Compound
The aliphatic compound employed in the present invention has at least two functional
groups, wherein one of the functional groups is capable of reacting with at least
one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof
and wherein another functional group is capable of reacting with at least one post-treating
agent which is described hereinbelow. Preferably, the aliphatic compound will contain two
or more amino functional groups or two or more hydroxyl functional groups or both.
More preferably, the aliphatic compound will contain two or more amino functional
groups.
Amino Aliphatic Compound
In addition to the ether compound (i.e. polyether polyamine, polyether polyamine
derivative, polyether polyol, ether diamines and ether triamine) above, the copolymer is
also reacted with an aliphatic compound. The aliphatic compound employed may be an
amino aliphatic compound.
The amino aliphatic compound may be selected from (a) aliphatic diamines, (b) aliphatic
polyamines or (c) polyalkylene diamines and polyamines. The amino aliphatic compound
39
will have at least two reactive amino groups, that is, primary or secondary amino groups,
and preferably primary amino groups. Suitable examples include ethylenediamine,
diethylene triamine, triethylene tetraamine, hexamethylene diamine, aminoethyl
piperazine, tetraethylene pentamine, pentaethylene hexamine and heavy polyamine, HPA,
(available from Dow Chemical Company, Midland, Michigan). Such amines encompass
isomers such as branched-chain polyamines, cyclic polyamines and hydrocarbylsubstituted
polyamines.
Since more than one primary or secondary amino group is present, the reaction conditions
and/or stoichiometry should be such that oil solubility is maintained.
Hydroxy! Aliphatic Compound
In addition to the ether compound (i.e. polyether aromatic compound) above, optionally,
the copolymer may also be reacted with at least one aliphatic compound which may be a
hydroxyl aliphatic compound wherein the hydroxyl aliphatic compound has at least two
functional groups, wherein one of the functional groups is capable of reacting with at least
one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof
and wherein another functional group is capable of reacting with at least one post-treating
agent which is described hereinbelow.
The multifunctional hydroxyl compounds used according to the process of the present
invention may contain primary, secondary or tertiary alcohols.
Suitable hydroxyl aliphatic compounds include, but are not limited to, glycerol,
pentaerythritol, trimethylol propane and the like. Additionally, the hydroxyl aliphatic
compound could be a polyether containing at least two hydroxyl groups.
Aliphatic Compounds containing both an Amine Function and a Hydroxyl Function
In another embodiment of the present invention, the aliphatic compound may have at least
one amine group and at least one hydroxyl group. Examples of such compounds include,
but are not limited to, ethanol amine, diethanol amine, triethanol amine, and the like.
40
Method of Making the Lubricating Oil Additive Composition
The lubricating oil additive composition is prepared by a process comprising charging the
reactant copolymer (e.g., at least one of copolymers (i), (ii) and (iii) as described herein) in
a reactor, optionally under a nitrogen purge, and heating at a temperature of from about
80°C to about 170°C. Optionally, diluent oil may be charged optionally under a nitrogen
purge in the same reactor, thereby producing a diluted copolymer reactant. The amount of
diluent oil in the diluted copolymer is up to about 80 wt. %, more preferred from about 20
to about 60 wt. %, and most preferred from about 30 to about 50 wt. %. Both an aliphatic
compound and an ether compound are charged, optionally under a nitrogen purge, to the
reactor. This mixture is heated under a nitrogen purge to a temperature in range from
about 130°C to about 200°C. Optionally, a vacuum is applied to the mixture for about 0.5
to about 2.0 hours to remove excess water.
The lubricating oil additive composition can also be made using a process comprising
simultaneously charging all the reactants (reactant copolymer (i), (ii), or (iii); the aliphatic
compound; and the ether compound at the desired ratios into the reactor. One or more of
the reactants can be charged at an elevated temperature to facilitate mixing and reaction. A
static mixer can be used to facilitate mixing of the reactants as they are being charged to
the reactor. The reaction is carried out for about 0.5 to about 2 hours at a temperature from
about 130°C to about 200°C. Optionally a vacuum is applied to the reaction mixture
during the reaction period.
Since more than one functional group is present on the aliphatic compound, the reaction
conditions and/or stoichiometry should be such that oil solubility is maintained. For
example, since multifunctional aliphatic compounds are used, the linker group (i.e., the
polyether compound) and the copolymer are preferably charged to the reactor first and
allowed to react prior to addition of the multifunctional aliphatic compound. Furthermore,
the stoichiometry should be such that when the multifunctional aliphatic compound is
charged to the reactor, there is generally about one mole of reactive sites remaining per
mole of the multifunctional aliphatic compound. This reaction order and stoichiometry
reduces excessive crosslinking by limiting the number of un-reacted reactive sites in the
co-polymer relative to the number of reactive sites on the multifunctional aliphatic
41
compound. Reduction of excessive crosslinking may decrease the probability of gel
formation and therefore increase the probability of oil solubility.
Post-Treatment of the Lubricating Oil Additive Composition
In one embodiment of the present invention, the lubricating oil additive composition is
post-treated with a post-treating agent selected from a cyclic carbonate, a linear monocarbonate,
a linear poly-carbonate, an aromatic mono- or polycarboxylic acid, an aromatic
mono- or polycarboxylic anhydride, or an aromatic mono- or polycarboxylic acid ester.
Typical cyclic carbonates for use in this invention include the following: l,3-dioxolan-2-
one (ethylene carbonate); 4-methyl-l,3-dioxolan-2-one (propylene carbonate); 4-
hydroxymethyl-l,3-dioxolan-2-one; 4,5-dimethyl-l,3-dioxolan-2-one; 4-ethyl-l,3-
dioxolan-2-one; 4,4-dimethyl-l,3-dioxolan-2-one; 4-methyl-5-ethyl-l,3-dioxolan-2-one;
4,5-diethyl-l,3-dioxolan-2-one; 4,4-diethyl-l,3-dioxolan-2-one; l,3-dioxan-2-one; 4,4-
dimethyl-l,3-dioxan-2-one; 5,5-dimethyl-l,3-dioxan-2-one; 5,5-dihydroxymethyl-l,3-
dioxan-2-one; 5-methyl-l,3-dioxan-2-one; 4-methyl-l,3-dioxan-2-one; 5-hydroxy-1,3-
dioxan-2-one; 5-hydroxymethyl-5-methyl-l,3-dioxan-2-one; 5,5-diethyl-l,3-dioxan-2-one;
5-methyl-5-propyl-l,3-dioxan-2-one; 4,6-dimethyl-l,3-dioxan-2-one; 4,4,6-trimethyl-l,3-
dioxan-2-one and spiro[l,3-oxa-2-cyclohexanone-5,5'-l',3'-oxa-2'-cyclohexanone]. Other
suitable cyclic carbonates may be prepared from sacchrides such as sorbitol, glucose,
fructose, galactose and the like and from vicinal diols prepared from Ci -C30 olefins by
methods known in the art.
Several of these cyclic carbonates are commercially available such as l,3-dioxolan-2-one
or 4-methyl-l,3-dioxolan-2-one. Cyclic carbonates may be readily prepared by known
reactions. For example, reaction of phosgene with a suitable alpha alkane diol or an alkan-
1,3-diol yields a carbonate for use within the scope of this invention as for instance in U.S.
Pat. No. 4,115,206 which is incorporated herein by reference.
Likewise, the cyclic carbonates useful for this invention may be prepared by
transesterification of a suitable alpha alkane diol or an alkan-1,3-diol with, e.g., diethyl
carbonate under transesterification conditions. See, for instance, U.S. Pat. Nos. 4,384,115
42
and 4,423,205 which are incorporated herein by reference for their teaching of the
preparation of cyclic carbonates.
Typical linear mono-carbonates include diethyl carbonate, dimethyl carbonate, dipropyl
carbonate and the like. Typical linear poly-carbonates include poly(propylene carbonate)
and the like.
Typical aromatic polycarboxylic anhydrides include 2,3 - pyrazinedicarboxylic anhydride;
2,3 - pydridinedicarboxylic anhydride; 3,4 - pyridinedicarboxylic anhydride; diphenic
anhydride; isatoic anhydride; phenyl succinic anhydride; 1- naphthalene acetic anhydride;
1, 2, 4 - benzene tricarboxylic anhydride and the like. Typical aromatic polycarboxylic
acids include the acids of the aforementioned anhydrides.
Typical aromatic polycarboxylic acid esters include dimethyl phthalate, diethyl phthalate,
dimethylhexyl phthalate, mono methylhexyl phthalate, mono ethyl phthalate, and mono
methyl phthalate.
In one embodiment, the post-treating agent is a cyclic carbonate or a linear mono- or polycarbonate.
In another embodiment, the post-treating agent is an aromatic polycarboxylic
acid, anhydride or ester.
Preferably, the lubricating oil additive composition is post-treated with a post-treating
agent that is selected from ethylene-carbonate, phthalic anhydride, or naphthalic
anhydride.
Typically, the post-treating agent (i.e., ethylene carbonate, phthalic anhydride, or 1,8-
naphthalic anhydride) is added to the reactor containing the lubricating oil additive
composition and heated, thereby producing a post-treated lubricating oil additive
composition.
43
Other Additives
The following additive components are examples of some of the components that can be
favorably employed in the present invention. These examples of additives are provided to
illustrate the present invention, but they are not intended to limit it:
1. Metal Detergents
Sulfurized or unsulfurized alkyl or alkenyl phenates, alkyl or alkenyl aromatic
sulfonates, borated sulfonates, sulfurized or unsulfurized metal salts of
multi-hydroxy alkyl or alkenyl aromatic compounds, alkyl or alkenyl hydroxy
aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl naphthenates, metal
salts of alkanoic acids, metal salts of an alkyl or alkenyl multiacid, and chemical
and physical mixtures thereof.
2. Anti-Oxidants
Anti-oxidants reduce the tendency of mineral oils to deteriorate in service which
deterioration is evidenced by the products of oxidation such as sludge and
varnish-like deposits on the metal surfaces and by an increase in viscosity.
Examples of anti-oxidants useful in the present invention include, but are not
limited to, phenol type (phenolic) oxidation inhibitors, such as
4,4'-methylene-bis(2,6-di-tert-butylphenol), 4,4'-bis(2,6-di-tert-butylphenol),
4,4'-bis(2-methyl-6-tert-butylphenol),
2,2'-methylene-bis(4-rnethyl-6-tert-butylphenol),
4,4'-butylidene-bis(3-methyl-6-tert-butylphenol),
4,4'-isopropylidene-bis(2,6-di-tert-butylphenol),
2,2'-methylene-bis(4-methyl-6-nonylphenol),
2,2'-isobutylidene-bis(4,6-dimethylphenol),
2,2'-5-methylene-bis(4-methyl-6-cyclohexylphenol),
2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,4-dimethyl-6-tert-butyl-phenol, 2,6-di-tert-l-dirnethylamino-p-cresol,
2,6-di-tert-4-(N,N'-dimethylaminomethylphenol),
4,4'-thiobis(2-methyl-6-tert-butylphenol),
44
2,2'-thiobis(4-methyl-6-tert-butylphenol),
bis(3-methyl-4-hydroxy-5-tert-10-butylbenzyl)-sulfide, and
bis(3,5-di-tert-butyl-4-hydroxybenzyl). Diphenylamine-type oxidation inhibitors
include, but are not limited to, alkylated diphenylamine,
phenyl-alpha-naphthylamine, and alkylated-alpha-naphthylamine. Other types of
oxidation inhibitors include metal dithiocarbamate (e.g., zinc dithiocarbamate), and
15-methylenebis(dibutyldithiocarbamate).
3. Anti-Wear Agents
As their name implies, these agents reduce wear of moving metallic parts.
Examples of such agents include, but are not limited to, phosphates and
thiophosphates and salts thereof, carbamates, esters, and molybdenum complexes.
4. Rust Inhibitors (Anti-Rust Agents)
a) Nonionic polyoxyethylene surface active agents: polyoxyethylene lauryl
ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonyl phenyl
ether, polyoxyethylene octyl phenyl ether, polyoxyethylene octyl stearyl
ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate,
polyoxyethylene sorbitol mono-oleate, and polyethylene glycol
mono-oleate.
b) Other compounds: stearic acid and other fatty acids, dicarboxylic acids,
metal soaps, fatty acid amine salts, metal salts of heavy sulfonic acid,
partial carboxylic acid ester of polyhydric alcohol, and phosphoric ester.
5. Demulsifiers
Addition product of alkylphenol and ethylene oxide, polyoxyethylene alkyl ether,
and polyoxyethylene sorbitan ester.
6. Extreme Pressure Anti-Wear Agents (EP/AW Agents)
45
Sulfurized olefins, zinc dialky-1-dithiophosphate (primary alkyl, secondary alkyl,
and aryl type), diphenyl sulfide, methyl trich lorostea rate, chlorinated naphthalene,
fluoroalkylpolysiloxane, lead naphthenate, neutralized or partially neutralized
phosphates, dithiophosphates, and sulfur-free phosphates.
Friction Modifiers
Fatty alcohol, fatty acid (stearic acid, isostearic acid, oleic acid and other fatty
acids or salts thereof), amine, borated ester, other esters, phosphates, other
phosphites besides tri- and di-hydrocarbyl phosphites, and phosphonates.
Multifunctional Additives
Sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo
phosphorodithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate
amide, amine-molybdenum complex compound, and sulfur-containing
molybdenum complex compound.
Viscosity Index Improvers
Polymethacrylate type polymers, ethylene-propylene copolymers, styrene-isoprene
copolymers, hydrated styrene-isoprene copolymers, polyisobutylene, and
dispersant type viscosity index improvers.
Pour Point Depressants
Polymethyl methacrylate.
Foam Inhibitors
Alkyl methacrylate polymers and dimethyl silicone polymers.
46
12. Metal Deactivators
Disalicylidene propylenediamine, triazole derivatives, mercaptobenzothiazoles,
thiadiazole derivatives, and mercaptobenzimidazoles.
13. Dispersants
Alkenyl succinimides, alkenyl succinimides modified with other organic
compounds, alkenyl succinimides modified by post-treatment with ethylene
carbonate or boric acid, esters of polyalcohols and polyisobutenyl succinic
anhydride, phenate-salicylates and their post-treated analogs, alkali metal or mixed
alkali metal, alkaline earth metal borates, dispersions of hydrated alkali metal
borates, dispersions of alkaline-earth metal borates, polyamide ashless dispersants
and the like or mixtures of such dispersants.
Lubricating Oil Composition
The lubricating oil additive composition described above is generally added to a base oil
that is sufficient to lubricate moving parts, for example internal combustion engines, gears,
and transmissions. Typically, the lubricating oil composition of the present invention
comprises a major amount of an oil of lubricating viscosity and a minor amount of the
lubricating oil additive composition.
The base oil employed may be any of a wide variety of oils of lubricating viscosity. The
base oil of lubricating viscosity used in such compositions may be mineral oils or
synthetic oils. A base oil having a viscosity of at least 2.5 cSt at 40°C and a pour point
below 20°C, preferably at or below 0°C, is desirable. The base oils may be derived from
synthetic or natural sources.
Mineral oils for use as the base oil in this invention include, for example, paraffinic,
naphthenic and other oils that are ordinarily used in lubricating oil compositions. Synthetic
oils include, for example, both hydrocarbon synthetic oils and synthetic esters and
mixtures thereof having the desired viscosity. Hydrocarbon synthetic oils may include, for
example, oils prepared from the polymerization of ethylene, polyalphaolefin or PAO oils,
47
or oils prepared from hydrocarbon synthesis procedures using carbon monoxide and
hydrogen gases such as in a Fisher-Tropsch process. 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 1-decene trimer.
Likewise, alkyl benzenes of proper viscosity, such as didodecyl benzene, can be used.
Useful synthetic esters include the esters of monocarboxylic acids and polycarboxylic
acids, as well as mono-hydroxy alkanols and polyols. Typical examples are didodecyl
adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate, dilaurylsebacate, and the
like. Complex esters prepared from mixtures of mono and dicarboxylic acids and mono
and dihydroxy alkanols can also be used. Blends of mineral oils with synthetic oils are
also useful.
Thus, the base oil can be a refined paraffin type base oil, a refined naphthenic base oil, or a
synthetic hydrocarbon or non-hydrocarbon oil of lubricating viscosity. The base oil can
also be a mixture of mineral and synthetic oils.
Method of Use of the Present Invention
The lubricating oil additive composition of the present invention is added to an oil of
lubricating viscosity thereby producing a lubricating oil composition. The lubricating oil
composition contacts the engine, improving dispersancy. Accordingly, the present
invention is also directed to a method of improving soot dispersancy, sludge dispersancy
or both in an internal combustion engine which comprises operating the engine with the
lubricating oil composition of the invention.
Optionally, the lubricating oil additive composition described above may be used as a fuel
additive. When used in fuels, the proper concentration of the additive that is necessary to
achieve the desired detergency is 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, the range of concentration of the additive in the base fuel is 10 to 10,000 weight
parts per million, preferably from 30 to 5,000 parts per million of the additive. If other
detergents are present, a lesser amount of the additive may be used. The additives
described herein may be formulated as a fuel concentrate, using an inert stable oleophilic
48
solvent boiling in the range of about 150-400°F (65.6-204.4°C). Preferred solvents boil in
the gasoline or diesel fuel range. Preferably, an aliphatic or an aromatic hydrocarbon
solvent is used, such as a benzene, toluene, xylene or higher-boiling aromatics or aromatic
thinners. Aliphatic alcohols of about 3 to 8 carbon atoms, such as isopropanol,
isobutylcarbinol, 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 5 % by weight and generally not exceed 70 % by weight,
preferably from 5 to 50 and more preferably from 10 to 25 wt. %.
The following examples are presented to illustrate specific embodiments of this invention
and are not to be construed in any way as limiting the scope of the invention.
EXAMPLES
Example 1 (Comparative)
Polysuccinimide Derived from 1000 MW PolyPIBSA,
Polyetherdiamine and Heavy Polyamine
A 2 L glass reactor was charged with polyPIBSA derived from 1000 MW PIB (610.92 g;
available from Chevron Oronite, LLC) and Exxon 100N base oil (793.45 g). The solution
was heated under a nitrogen atmosphere to 160°C. Jeffamine® XTJ-501 polyetherdiamine
(151.60 g; available from Huntsman) was then added and mixture heated for 1 h. A
vacuum ( and then heavy polyamine (36.66 g) was added to the reactor. The mixture was heated at
160°C for 1 h. A vacuum ( Analysis of the final product found the following:
Viscosity at 100°C = 43.16 cSt
Nitrogen content = 1.09 wt %
Total Base Number (ASTM D 2896) = 25.77 mg KOH/g
49
Example 2
Phthalic Anhydride Post-Treated Polysuccinimide Derived
from 1000 MW PolyPIBSA/Polyetherdiamine/Heavy
Polyamine
A 500 mL glass reactor was charged with polysuccinimide (429.93 g) as prepared in
Example 1 and heated to 160°C under a nitrogen atmosphere. Phthalic anhydride (5.36 g;
available from Sigma-Aldrich) was added and the mixture was heated at 160°C for 2 h.
Analysis of the final product found the following:
Viscosity at 100°C = 702.2 cSt
Total Base Number = 19.64 mg KOH/g
Example 3
Ethylene Carbonate Post-Treated Polysuccinimide Derived
from 1000 MW PolyPIBSA/Polyetherdiamine/Heavy
Polyamine
A 500 mL glass reactor was charged with polysuccinimide (392.34 g) as prepared in
Example 1 and heated to 160°C under a nitrogen atmosphere. Ethylene carbonate (14.23 g)
was added over 1 h at 160°C. The mixture was heated at 160°C for additional 7 h.
Example 4 (Comparative)
Polysuccinimide Derived from 2300 MW PolyPIBSA,
Polyetherdiamine and Heavy Polyamine
A 2-L glass reactor was charged with polyPIBSA derived from 2300 MW PIB (1183.18 g;
available from Chevron Oronite, LLC) and Exxon 100N base oil (129.66 g). The solution
was heated under a nitrogen atmosphere to 160°C. Jeffamine® XTJ-501 polyetherdiamine
(141.71 g) was added and the mixture was heated at 160°C for 1 h. A vacuum ( Hg) was applied for 30 minutes at 160°C. The vacuum was released and then heavy
polyamine (34.27 g) was then added to the reactor. The mixture was heated at 160°C for 1
50
h. A vacuum ( product found the following:
Viscosity at 100°C = 577.8 cSt
Nitrogen content = 1.10 wt %
Total Base Number = 24.04 mg KOH/g
Example 5
Phthalic Anhydride Post-Treated Polysuccinimide Derived
from 2300 MW PolyPIBSA/Polyetherdiamine/Heavy
Polyamine
A 500 mL glass reactor was charged with polysuccinimide (351.48 g) as prepared in
Example 4 and heated to 160°C under a nitrogen atmosphere. Phthalic anhydride (4.38 g)
was added and the mixture was heated at 160°C for 2 h. Analysis of the final product
found the following:
Viscosity at 100°C = 696.2 cSt
Total Base Number = 18.44 mg KOH/g
Example 6
Ethylene Carbonate Post-Treated Polysuccinimide Derived
from 2300 MW PolyPIBSA/Polyetherdiamine/Heavy
Polyamine
A 500 mL glass reactor was charged with polysuccinimide (390.21 g) as prepared in
Example 4 and was heated to 160°C under a nitrogen atmosphere. Ethylene carbonate
(14.15 g) was added over 1 h at 160°C. The mixture was heated at 160°C for additional 5.5
h.
51
Example 7 (Comparative)
Polysuccinimide Derived from 2300 MW Terpolymer
PIBSA, Polyetherdiamine and Heavy Polyamine
A 1 L reactor was charged with terpolymer PIBSA derived from 2300 MW PIB (645.22 g;
available from Chevron Oronite, LLC). The solution was placed under a nitrogen
atmosphere and heated to 160°C. Jeffamine® XTJ-501 polyetherdiamine (84.59 g) was
then added over 15 minutes. The mixture was heated at 160°C for 1 h. A vacuum (22 mm
Hg) was applied at 160°C for 45 minutes. The vacuum was released and heavy polyamine
(20.56 g) was then added to the solution over 10 minutes. The mixture was heated at
160°C for 1 h and then a vacuum (24 mm Hg) was applied for 45 min at 160°C.
Example 8
Phthalic Anhydride Post-Treated Polysuccinimide Derived
from 2300 MW Terpolymer
PIBSA/Polyetherdiamine/Heavy Polyamine
The product of Example 7 was charged in a 1 L reactor and heated to 160°C under a
nitrogen atmosphere. Phthalic anhydride (8.31 g) was added and the mixture was heated at
160°C for 1 h. A vacuum (20 mm Hg) was then applied for 30 minutes.
Example 9
Naphthalic Anhydride Post-Treated Polysuccinimide
Derived from 2300 MW Terpolymer
PIBSA/Polyetherdiamine/HPA
A 0.5 L reactor was charged with terpolymer PIBSA derived from 2300 MW PIB (334.86
g); available from Chevron Oronite, LLC). The solution was placed under a nitrogen
atmosphere and heated to 160°C. Jeffamine® XTJ-501 polyetherdiamine (43.39 g) was
then added over 10 minutes. The mixture was heated at 160°C for 1 h. A vacuum ( mm Hg) was applied at 160°C for 30 minutes. The vacuum was released and heavy
polyamine (9.79 g) was then added to the mixture over 7 minutes. The mixture was heated
52
at 160°C for 1 h and then a vacuum ( vacuum was released and naphthalic anhydride (5.32 g) was added. The mixture was
heated at 160°C for 1 h and then heated at 180°C for 1 h. A vacuum ( then applied for 30 minutes.
Example 10 (Comparative)
Polysuccinimide Derived from 2300 MW Terpolymer
PIBSA, Polyetherdiamine and Diethylenetriamine (DETA)
A 1 L reactor was charged with terpolymer PIBSA derived from 2300 MW PIB (445.69 g)
available from Chevron Oronite, LLC). The mixture was placed under a nitrogen
atmosphere and heated to 160°C. Jeffamine® XTJ-501 polyetherdiamine (57.55 g) was
then added over 15 minutes. The mixture was heated at 160°C for 1 h. A vacuum ( mm Hg) was applied at 160°C for 30 minutes. The vacuum was released and the reactor
was cooled to 95°C. DETA (4.89 g) was then added to the mixture. The mixture was
heated to 160°C and this temperature was maintained for 1 h. Then a vacuum ( Hg) was applied for 37 min at 160°C.
Example 11
Phthalic Anhydride Post-Treated Polysuccinimide Derived
from 2300 MW Terpolymer
PIBSA/Polyetherdiamine/DETA
A 0.5 L reactor was charged with terpolymer PIBSA derived from 2300 MW PIB (296.53
g) available from Chevron Oronite, LLC). The solution was placed under a nitrogen
atmosphere and heated to 160°C. Jeffamine® XTJ-501 polyetherdiamine (38.29 g) was
then added over 8 minutes. The mixture was heated at 160°C for 1 h. A vacuum ( Hg) was applied at 160°C for 30 minutes. The vacuum was released and the reaction
mixture was cooled to 95°C. DETA (3.25 g) was then added to the mixture over 3
minutes. The mixture was heated to 160°C and temperature was maintained for 1 h. Then
a vacuum ( 53
phthalic anhydride (3.52 g) was added, and the mixture was heated at 160°C for 1.5 h. A
vacuum ( Example 12
Naphthalic Anhydride Post-Treated Polysuccinimide
Derived from 2300 MW Terpolymer
PIBSA/Polyetherdiamine/DETA
The 269.11 g of product of Example 10 was charged in a 0.5 L reactor and heated to
160°C under a nitrogen atmosphere. Naphthalic anhydride (3.78 g) was added and the
mixture was heated at 160°C for 1.5 h. A vacuum ( minutes.
Soot Thickening Bench Test Results
The polysuccinimides and post-treated polysuccinimides from Examples 1-12 were
reacted in the soot thickening bench test, which measures the ability of a formulation to
disperse and control viscosity increase resulting from the addition of carbon black, a soot
surrogate. In this test, 98.0 g of the test sample was weighed and placed into a 250 mL
beaker. The test sample contained 7.6 wt. % of the test dispersant, 50 millimoles of an
overbased phenate detergent, 18 millimoles of a zinc dithiophosphate wear inhibitor and
7.3 wt. % of a VI improver, in 85% 150N oil, 15% 600N oil. To this was added 2.0 g
Vulcan XC-72® carbon black from Cabot Co. The mixture was stirred and then stored for
16 hours in a dessicator. A second sample without the carbon black was mixed for 60
seconds using a Willems Polytron Homogenizer-Model PF 45/6 and then degassed in a
vacuum oven for 30 minutes at 50 to 55°C. The viscosity of the two samples was then
measured at 100°C using a capillary viscometer. The percent viscosity increase was
calculated by comparing the viscosity of the samples with and without carbon black. Thus,
the lower the percent viscosity increase the better the dispersancy of the dispersant. The
results from the soot thickening bench test are shown in Table 1.
54
TABLE 1
Example
1
2
3
4
5
6
7
8
9
10
11
12
Description
1000 MW PolyPIBSA/XTJ-501/HPA
1000 MW PolyPIBSA/XTJ-501/HPA
1000 MW PolyPIBSA/XTJ-501/HPA
2300 MW PolyPIBSA/XTJ-501/HPA
2300 MW PolyPIBSA/XTJ-501/HPA
2300 MW PolyPIBSA/XTJ-501/HPA
2300 MW Terpolymer PIBSA/XTJ-501/HPA
2300 MW Terpolymer PIBSA/XTJ-501/HPA
2300 MW Terpolymer PIBSA/XTJ-501/HPA
2300 MW Terpolymer PIBSA/XTJ-501/DETA
2300 MW Terpolymer PIBSA/XTJ-501/DETA
2300 MW Terpolymer PIBSA/XTJ-501/DETA
Post-
Treatment
-
PA1
EC2
.
PA
EC
.
PA
NA3
-
PA
NA
Soot Thickening
% Vise.
Increase
128.80
25.24
38.25
105.10
16.69
28.58
49.76
24.92
19.06
121.39
78.49
19.26
1 - phthalic anhydride
2 - ethylene carbonate
3 - naphthalic anhydride
As evidenced in Table 1, the results of the soot thickening bench test indicate that the
percent viscosity increase of formulated oils comprising phthalic anhydride, ethylene
carbonate or naphthalic anhydride post-treated polysuccinimides was significantly lower
than the percent viscosity increase in formulated oils that contain polysuccinimides that
are not post-treated. This test indicates that the lubricating oil additives of the present
invention have superior dispersant properties, as compared to the non-post treated
polysuccinimides.
It is understood that although modifications and variations of the invention can be made
without departing from the spirit and scope thereof, only such limitations should be
imposed as are indicated in the appended claims.
A post-treated polymeric dispersant wherein the at least one aliphatic compound has more
than one functional group capable of reacting with a monocarboxylic acid or ester thereof,
or dicarboxylic acid, anhydride or ester thereof.
55
A post-treated polymeric dispersant wherein the at least one ether compound (B) is a
polyether polyamine.
A post-treated polymeric dispersant wherein the polyether polyamine is a poiyoxyalkylene
diamine wherein each alkylene unit individually contains from about 2 to about 5 carbon
atoms.
A post-treated polymeric dispersant wherein the oxyalkylene moiety is oxyethylene or
oxypropylene, or mixtures thereof.
A post-treated polymeric dispersant wherein the copolymer is copolymer (i). A posttreated
polymeric dispersant wherein the copolymer is copolymer (ii). A post-treated
polymeric dispersant wherein the copolymer (ii) is polyPIBSA, obtained by the free
radical catalyzed reaction of maleic anhydride and polyisobutylene. A post-treated
polymeric dispersant wherein the copolymer is copolymer (iii).
A post-treated polymeric dispersant wherein the amino aliphatic compound is selected
from the group consisting of aliphatic diamines, aliphatic polyamines and polyalkylene
polyamines.
A post-treated polymeric dispersant wherein the aliphatic compound is an aliphatic
diamine.
A post-treated polymeric dispersant wherein the aliphatic diamine is ethylene diamine,
hexamethylene diamine, and butylene diamine.
A post-treated polymeric dispersant wherein the aliphatic compound is an polyalkylene
polyamine.
A post-treated polymeric dispersant wherein compound (i)(b) of copolymer (i) is
polyisobutene having a number average molecular weight (Mn) of from about 112 to about
5000.
56
A post-treated polymeric dispersant wherein the number average molecular weight (Mn) is
from about 500 to about 3000.
A post-treated polymeric dispersant wherein the number average molecular weight (Mn) is
from about 1000 to about 2500.
A post-treated polymeric dispersant wherein (i)(a) is a dicarboxylic acid, anhydride or
ester thereof.
A post-treated polymeric dispersant wherein (i)(a) is maleic anhydride or ester thereof.
A post-treated polymeric dispersant wherein the monoolefin of (i)(c) is a 1-olefin.
A lubricating oil composition wherein the at least one aliphatic compound has more than
one functional group capable of reacting with a monocarboxylic acid or ester thereof, or
dicarboxylic acid, anhydride or ester thereof.
A lubricating oil composition wherein in copolymer (iii)(b), said copolymer (i) or
copolymer (ii) or both are contacted with the non-free radical catalyzed reaction product of
compound (i)(a) and compound (i)(b) or (i)(c) in the presence of component (C).
A lubricating oil composition wherein the at least one ether compound (B) is a polyether
polyamine.
A lubricating oil composition wherein the polyether polyamine is a polyoxyalkylene
diamine wherein each alkylene unit individually contains from about 2 to about 5 carbon
atoms.
A lubricating oil composition wherein the oxyalkylene moiety is oxyethylene or
oxypropylene, or mixtures thereof.
A lubricating oil composition wherein the copolymer is copolymer (i).
57
A lubricating oil composition wherein the copolymer is copolymer (ii).
A lubricating oil composition wherein copolymer (ii) is polyPIBSA, obtained by the free
radical catalyzed reaction of maleic anhydride and polyisobutylene.
A lubricating oil composition wherein the copolymer is copolymer (iii).
A lubricating oil composition wherein the aliphatic compound is an amino aliphatic
compound.
A lubricating oil composition wherein the amino aliphatic compound is selected from the
group consisting of aliphatic diamines, aliphatic polyamines and polyalkylene polyamines.
A lubricating oil composition wherein the aliphatic compound is an aliphatic diamine.
A lubricating oil composition wherein the aliphatic diamine is ethylene diamine,
hexamethylene diamine, and butylene diamine.
A lubricating oil composition wherein the aliphatic compound is a polyalkylene
polyamine.
A lubricating oil composition wherein compound (i)(b) of copolymer (i) is polyisobutene
having a number average molecular weight (Mn) of from about 112 to about 5000.
A lubricating oil composition wherein the number average molecular weight (Mn) is from
about 500 to about 3000.
A lubricating oil composition wherein the number average molecular weight (Mn) is from
about 1000 to about 2500.
58
A lubricating oil composition wherein (i)(a) is a dicarboxylic acid, anhydride or ester
thereof.
A lubricating oil additive composition wherein (i)(a) is maleic anhydride or ester thereof.
A lubricating oil composition wherein the monoolefin of (i)(c) is a 1-olefin.
A method of making a post-treated polymeric dispersant wherein the post-treating agent is
a cyclic carbonate, a linear mono-carbonate or a linear poly-carbonate.
A method of making a post-treated polymeric dispersant, wherein the post-treating agent
is an aromatic polycarboxylic acid, an aromatic polycarboxylic anhydride or aromatic
polycarboxylic ester.
A method of making the post-treated polymeric dispersant wherein the post-treating agent
is ethylene carbonate, phthalic anhydride, or naphthalic anhydride.
59








I/WE CLAIM:
1. A post-treated polymeric dispersant prepared by the process comprising reacting
(I) a post-treating agent selected from a cyclic carbonate, a linear mono-carbonate, a linear
poly-carbonate, an aromatic polycarboxylic acid, an aromatic polycarboxylic anhydride or
an aromatic polycarboxylic acid ester and (II) a lubricating oil additive composition
prepared by the process comprising reacting
(A) at least one of the following copolymers:
(i) a copolymer obtained by free radical copolymerization of
components comprising:
(a) at least one monoethylenically unsaturated C3 to C28
monocarboxylic acid or ester thereof, or C4 to C28
dicarboxylic acid, anhydride or ester thereof;
(b) at least one 1 -olefin comprising about 2 to 40 carbon atoms
or at least one polyolefin comprising about 4 to 360 carbon
atoms and having a terminal copolymerizable group in the
form of a vinyl, vinylidene or alkyl vinylidene group or
mixtures thereof; and
(c) at least one monoolefin compound which is copolymerizable
with the monomers of (a) and (b) and is selected from the
group consisting of:
(1) an alkyl vinyl ether and an allyl alkyl ether where the
alkyl group is hydroxyl, amino, dialkylamino or alkoxy
substituted or is unsubstituted, and containing from about 1
to about 40 carbon atoms;
60
(2) an alkyl amine and an N-alkylamide of a
monoethylenically unsaturated mono- or dicarboxylic acid
of from about 3 to about 10 carbon atoms where the alkyl
substituent contains from about 1 to about 40 carbon atoms;
(3) an N-vinylcarboxamide of carboxylic acids of from
about 1 to about 8 carbon atoms;
(4) an N-vinyl substituted nitrogen-containing
heterocyclic compound; and
(5) at least one 1-olefin comprising about 2 to 40 carbon
atoms or at least one polyolefin comprising about 4 to about
360 carbon atoms and having a terminal copolymerizable
group in the form of a vinyl, vinylidene or alkyl vinylidene
group or mixtures thereof, provided that the olefin employed
is not the same as the olefin employed in (i)(b);
(ii) a copolymer obtained by reacting compound (i)(a) and
compound(i)(b) in the presence of a free radical initiator;
(iii) a copolymer obtained by (a) reacting compound (i)(a) with
compound (i)(b) or (i)(c) in a non-free radical catalyzed reaction in
the presence of copolymer (i) or copolymer (ii) or both; or by (b)
contacting copolymer (i) or copolymer (ii) or both with the non-free
radical catalyzed reaction product of compound (i)(a) and
compound (i)(b) or (i)(c); with
(B) at least one ether compound capable of being reacted with at least two
monocarboxylic acids or esters thereof, or with at least two dicarboxylic acids,
anhydrides or esters thereof, or mixtures thereof; and
61
(C) at least one aliphatic compound having at least two functional groups,
wherein one of the functional groups is capable of reacting with at least
one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester
thereof and wherein another functional group is capable of reacting with at least
one post-treating agent.
2. The post-treated polymeric dispersant of Claim 1 wherein the post-treating agent is
a cyclic carbonate, a linear mono-carbonate or a linear poly-carbonate.
3. The post-treated polymeric dispersant of Claim 1, wherein the post-treating agent
is an aromatic polycarboxylic acid, an aromatic polycarboxylic anhydride, or aromatic
polycarboxylic ester.
4. The post-treated polymeric dispersant of Claim 1 wherein the post-treating agent
is ethylene carbonate, phthalic anhydride, or naphthalic anhydride.
5. The post-treated polymeric dispersant of claim 1, wherein the at least one ether
compound (B) is selected from the group comprising an ether polyamine, a polyether
polyamine, a polyether amino alcohol, a polyether amino thiol, and a polyether polyol.
6. The post-treated polymeric dispersant of claim 1, wherein in copolymer (iii)(b),
said copolymer (i) or copolymer (ii) or both are contacted with the non-free radical
catalyzed reaction product of compound (i)(a) and compound (i)(b) or (i)(c) in the
presence of component (C).
7. The post-treated polymeric dispersant of claim 1 wherein the aliphatic compound is
an amino aliphatic compound.
8. A lubricating oil composition comprising a major amount of an oil of lubricating
viscosity and a minor amount of a post-treated polymeric dispersant prepared by the
process which comprises reacting (I) a post-treating agent selected from a cyclic
62
carbonate, a linear mono-carbonate, a linear poly-carbonate, an aromatic polycarboxylic
acid or an aromatic polycarboxylic anhydride or an aromatic polycarboxylic acid ester and
(II) a lubricating oil additive composition prepared by the process comprising reacting
(A) at least one of the following copolymers:
(i) a copolymer obtained by free radical copolymerization of
components comprising:
(a) at least one monoethylenically unsaturated
C3-C28 monocarboxylic acid or ester thereof, or
C4-C28 dicarboxylic acid, anhydride or ester thereof;
(b) at least one 1-olefin comprising about 2 to 40 carbon atoms
or at least one polyolefin comprising about 4 to 360 carbon
atoms and having a terminal copolymerizable group in the
form of a vinyl, vinylidene or alkyl vinylidene group or
mixtures thereof; and
(c) at least one monoolefin compound which is copolymerizable
with the monomers of (a) and (b) and is selected from the
group consisting of:
(1) an alkyl vinyl ether and an allyl alkyl ether where the
alkyl group is hydroxyl, amino, dialkylamino or
alkoxy substituted or is unsubstituted, and containing
from about 1 to about 40 carbon atoms;
(2) an alkyl amine and an N-alkylamide of a
monoethylenically unsaturated mono- or dicarboxylic
acid of from about 3 to about 10 carbon atoms where
63
the alkyl substituent contains from about 1 to about
40 carbon atoms;
(3) an N-vinylcarboxamide of carboxylic acids of from
about 1 to about 8 carbon atoms;
(4) an N-vinyl substituted nitrogen-containing
heterocyclic compound; and
(5) at least one 1-olefin comprising about 2 to 40 carbon
atoms or at least one polyolefin comprising about 4 to
about 360 carbon atoms and having a terminal
copolymerizable group in the form of a vinyl,
vinylidene or alkyl vinylidene group or mixtures
thereof, provided that the olefin employed is not the
same as the olefin employed in (i)(b);
(ii) a copolymer obtained by reacting compound (i)(a) and
compound(i)(b) in the presence of a free radical initiator;
(iii) a copolymer obtained by (a) reacting compound (i)(a) with
compound (i)(b) or (i)(c) in a non-free radical catalyzed reaction in
the presence of copolymer (i) or copolymer (ii) or both; or by (b)
contacting copolymer (i) or copolymer (ii) or both with the non-free
radical catalyzed reaction product of compound (i)(a) and
compound (i)(b) or (i)(c); with
(B) at least one ether compound capable of being reacted with at least two
monocarboxylic acids or esters thereof, or with at least two dicarboxylic acids,
anhydrides or esters thereof, or mixtures thereof; and
64
(C) at least one aliphatic compound having at least two functional groups, wherein
one of the functional groups is capable of reacting with at least
one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester
thereof and wherein another functional group is capable of reacting with at least
one post-treating agent.
9. The lubricating oil composition of Claim 8, wherein the post-treating agent is a
cyclic carbonate, a linear mono-carbonate or a linear poly-carbonate.
10. The lubricating oil composition of Claim 8, wherein the post-treating agent is an
aromatic polycarboxylic acid, an aromatic polycarboxylic anhydride, or an aromatic
polycarboxylic ester.
11. The lubricating oil composition of claim 8, wherein the post-treating agent is
ethylene carbonate, phthalic anhydride, or naphthalic anhydride.
12. The lubricating oil composition of claim 8, wherein the at least one ether
compound (B) is selected from the group comprising an ether polyamine, a polyether
polyamine, a polyether amino alcohol, a polyether amino thiol, and a polyether polyol.
13. A method of making a post-treated polymeric dispersant comprising reacting (I) a
post-treating agent selected from a cyclic carbonate, a linear mono-carbonate, a linear
poly-carbonate, an aromatic polycarboxylic acid or an aromatic polycarboxylic anhydride
or an aromatic polycarboxylic acid ester and (II) a lubricating oil additive composition
which comprises reacting
(A) at least one of the following copolymers:
(i) a copolymer obtained by free radical copolymerization of
components comprising:
65
(a) at least one monoethylenically unsaturated
C3-C28 monocarboxylic acid or ester thereof, or a
C4-C28 dicarboxylic acid, anhydride or ester thereof;
(b) at least one 1-olefin comprising about 2 to 40 carbon atoms
or at least one polyolefin comprising about 4 to 360 carbon
atoms and having a terminal copolymerizable group in the
form of a vinyl, vinylidene or alkyl vinylidene group or
mixtures thereof; and
(c) at least one monoolefin compound which is copolymerizable
with the monomers of (a) and (b) and is selected from the
group consisting of:
(1) an alkyl vinyl ether and an allyl alkyl ether where the
alkyl group is hydroxyl, amino, dialkylamino or
alkoxy substituted or is unsubstituted, and containing
from about 1 to about 40 carbon atoms;
(2) an alkyl amine and an N-alkylamide of a
monoethylenically unsaturated mono- or
dicarboxylic acid of from about 3 to about 10 carbon
atoms where the alkyl substituent contains from
about 1 to about 40 carbon atoms;
(3) an N-vinylcarboxamide of carboxylic acids of from
about 1 to about 8 carbon atoms;
(4) an N-vinyl substituted nitrogen-containing
heterocyclic compound; and
66
(5) at least one 1-olefin comprising about 2 to 40 carbon
atoms or at least one polyolefin comprising about 4
to about 360 carbon atoms and having a terminal
copolymerizable group in the form of a vinyl,
vinylidene or alkyl vinylidene group or mixtures
thereof, provided that the olefin employed is not the
same as the olefin employed in (i)(b);
(ii) a copolymer obtained by reacting compound (i)(a) and
compound(i)(b) in the presence of a free radical initiator;
(iii) a copolymer obtained by (a) reacting compound (i)(a) with
compound (i)(b) or (i)(c) in a non-free radical catalyzed reaction in
the presence of copolymer (i) or copolymer (ii) or both; or by (b)
contacting copolymer (i) or copolymer (ii) or both with the non-free
radical catalyzed reaction product of compound (i)(a) and
compound (i)(b) or (i)(c); with
(B) at least one ether compound capable of being reacted with at least two
monocarboxylic acids or esters thereof, or with at least two dicarboxylic acids,
anhydrides or esters thereof, or mixtures thereof;
(C) at least one aliphatic compound having at least two functional groups,
wherein one of the functional groups is capable of reacting with at least
one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester
thereof and wherein another functional group is capable of reacting with at least
one post-treating agent.
14. The method of making the post-treated polymeric dispersant of claim 13, wherein in
copolymer (iii)(b), said copolymer (i) or copolymer (ii) or both are contacted with the nonfree
radical catalyzed reaction product of compound (i)(a) and compound (i)(b) or (i)(c) in
the presence of component (C).
67
15. A method of improving soot dispersancy or sludge dispersancy or both in an
internal combustion engine which comprises operating the engine with a lubricating oil
composition comprising a major amount of oil of lubricating viscosity and an effective
amount of the post-treated polymeric dispersant of claim 1.
Dated this 12 day of November, 2010
To,
The Controller of Patents
The Patent office at New Delhi
%jb&fa
MALATHI LAKSHMIKUMARAN
Agent for the Applicant
68

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=jcdK94cNEj+022xWGE0XfA==&loc=+mN2fYxnTC4l0fUd8W4CAA==


Patent Number 278383
Indian Patent Application Number 8018/DELNP/2010
PG Journal Number 53/2016
Publication Date 23-Dec-2016
Grant Date 21-Dec-2016
Date of Filing 12-Nov-2010
Name of Patentee CHEVRON ORONITE COMPANY LLC
Applicant Address 6001 BOLLINGER CANYON ROAD, SAN RAMON, CA 94583 UNITED STATES OF AMERICA
Inventors:
# Inventor's Name Inventor's Address
1 RUHE, WILLIAM, R.. JR. 895 ROSE DRIVE, BENICIA, CA 94510 UNITED STATES OF AMERICA
PCT International Classification Number C10M 159/00
PCT International Application Number PCT/US2009/041631
PCT International Filing date 2009-04-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 12/110,248 2008-04-25 U.S.A.