Note: Descriptions are shown in the official language in which they were submitted.
- 1 133S095
FIELD OF THE INVENTION
This invention relates to oil soluble dispersant
additives useful in fuel and lubricating oil compositions
including concentrates containing said additives, and methods
for their manufacture and use. The dispersant additives of
the instant invention are comprised of the reaction products
of (1) nitrogen or ester containing adduct and (2)
polyepoxide.
BACKGROUND OF THE INVENTION
Multigrade lubricating oils typically are identified
by two numbers such as lOW30, 5W30 etc. The first number in
the multigrade designation is associated with a maximum low
temperature (e.g. -20 C.) viscosity requirement for that
multigrade oil as measured typically by a cold cranking
simulator (CCS) under high shear, while the second number in
the multigrade designation is associated with a minimum high
temperature (e.g. lOO-C) viscosity requirement. Thus each
particular multigrade oil must simultaneously meet both strict
low and high temperature viscosity requirements in order to
qualify for a given multigrade designation. Such requirements
are set e.g., by ASTM specifications. By "low temperature" as
used herein is meant temperatures of typically from about
-30-to about -5-C. By "high temperature" as used herein is
meant temperatures of typically at least about 100C.
The minimum high temperature viscosity
requirement, e.g., at lOO-C, is intended to prevent the oil
from th;nn;ng out too much during engine operation which can
lead to excessive wear and increased oil consumption.
. . ~
1335095
-2-
The maximu~ low temperature viscosity requirement is
intended to facilitate engine starting in cold weather and
to ensure pumpability, i.e., the cold oil should readily
flow or slump into the well for the oil pump, otherwise the
engine can be damaged due to insufficient lubrication.
In formulating an oil which efficiently meets both
low and high temperature viscosity requirements, the
formulator may use a single oil of desired viscosity or a
blend of two lubricating oil~ of different viscosities, in
conjunction with manipulating the identity and amount of
additives that must be present to achieve the overall
target properties of a particular multigrade oil including
its viscosity requirements.
The natural viscosity characteristic of a
lubricating oil i9 typically expressed by the neutral
number of the oil (e.g. S150N) with a higher neutral number
being associated with a higher natural viscosity at a given
temperature. ~n some instances the formulator will find it
desirable to blend oils of two different neutral numbers,
and hence vi~cositites, to achieve an oil having a
visco~ity intermediate between the viscosity of the
components of the oil blend. Thu~m the neural number
designation provide~ the formulator with a simple way to
achieve a desired based oil of predictable viscosity.
Unfortunately, merely blending oils of different viscosity
characteristic~ does not enable the formulator to meet the
low and high temperature viscosity requirements of
multigrade oils. The
- 3 - 1 3 35 09~
~ormulator,~ primary tool for achieving this goal is an
additive conventionally referred to as a viscosity index
improver (i.e., V.I. improver).
The V. I . improver is conventionally an
oil-soluble long chain polymer. The large size of these
polymQrs enables them to significantly increase kinematic
ViSCo~itiQ~ of base oils even at low concentrations.
How-ver , because solution~ of high polymers are
non-Newtonian they tend to give lower viscosities than
expected in a high shear environment due to the alignment
of the polymer. Consequently, V.I. improvers impact
(i.e., incrsasQ) the low temperature (high shear)
viscositie~ (i.e. CCS viscosity) of the base oil to a
les~er extent than they do the high temperature (low shear)
viscosities.
The aforesaid viscosity requirements for a
multigrade oil can therefore be viewed as beinq
increa~ingly antagonistic at increasingly higher levels of
V.I. improver. For example, if a large quantity of V.I.
improver is used in order to obtain high viscosity at high
temperatures, the oil may now exceed the low temperature
requirement. In another example, the formulator may be
able to readily meet the requirement for a lOW30 oil but
not a 5W30 oil, with a particular ad-pack (additive
package) and base oil. Under these circumstances the
formulator may attempt to lower the viscosity of the base
oil, ~uch as by increasing the proportion of low viscosity
oil in a blend, to compensate for the low temperature
visco~ity increase induced by the V.I. improver, in order
to m~et the desired low and high temperature viscosity
requirements. However, increasing the proportion of low
viscosity oils in a blend can in turn lead to a new set of
limitations on the formulator, as lower viscosity base oils
are considerably less desirable in diesel engine use than
the heavier, more viscous oils.
Further complicating the formulator,s task is the
effect that dispersant additive~ can have on the viscosity
I 335095
characteristics of multigrade oils. Dispersants are
frequently present in quality oils such as multigrade oils,
together with the V.I. improver. The primary function of a
dispersant is to maintain oil insolubles, resulting from
oxidation during use, in suspension in the oil thus
preventing sludge flocculation and precipitation.
Consequently, the amount of dispersant employed is dictated
and controlled by the effectiveness of the material for
achieving its dispersant function. A high quality 10W30
commercial oil might contain from two to four times as much
dispersant as V.I. improver (as measured by the respective
dispersant and V.I. improver active ingredients). In
addition to dispersancy, conventional dispersants can also
increase the low and high temperature viscosity
characteristics of a base oil simply by virtue of their
polymeric nature. In contrast to the V.I. improver, the
dispersant molecule is much smaller. Consequently, the
dispersant is much less shear sensitive, thereby
contributing more to the low temperature CCS viscosity
(relative to its contribution to the high temperature
viscosity of the base oil) than a V.I. improver. Moreover,
the smaller dispersant molecule contributes much less to the
high temperature viscosity of the base oil than the V.I.
improver. Thus, the magnitude of the low temperature
viscosity increase induced by the dispersant can exceed the
low temperature viscosity increase induced by the V.I.
improver without the benefit of a proportionately greater
increase in high temperature viscosity as obtained from a
V.I. improver. Consequently, as the dispersant induced low
temperature viscosity increase causes the low temperature
viscosity of the oil to approach the maximum low temperature
viscosity limit, the more difficult it is to introduce a
sufficient amount of V.I. improver effective to meet the
high temperature viscosity requirement and still meet the
low temperature viscosity requirement. The formulator is
thereby once again forced to shift to the
_ 5_ 1335095
undesirable expedient of using higher proportions of low
viscosity oil to permit addition of the requisite amount of
V.I. improver without exceeding the low temperature
viscosity limit.
In accordance with the present invention,
dispersants are provided which have been found to possess
inherent characteristics such that they contribute
considerably less to low temperature viscosity increases
than dispersants of the prior art while achieving similar
high temperature viscosity increases. Moreover, as the
concentration of dispersant in the base oil is increased,
this beneficial low temperature viscosity effect becomes
increasingly more pronounced relative to conventional
dispersants. This advantage is especially significant for
high quality heavy duty diesel oils which typically require
high concentrations of dispersant additive. Furthermore,
these improved viscosity properties facilitate the use of
V.I. improvers in forming multigrade oils spanning a wider
viscosity requirement range, such as 5W30 oils, due to the
overall effect of lower viscosity increase at low
temperatures while maintaining the desired viscosity at high
temperatures as compared to the other dispersants. More
significantly, these viscometric properties also permit the
use of higher viscosity base stocks with attendant
advantages in engine performance. Furthermore, the
utilization of the dispersant additives of the instant
invention allows a reduction in the amount of V.I. improvers
required.
The materials of this invention are thus an
improvement over conventional dispersants because of their
effectiveness as dispersants coupled with enhanced low
temperature viscometric properties. These materials are
particularly useful with V.I. improvers in formulating
multigrade oils.
~,~
- 6 1335095
SUMMARY OF THE INVENTION
The present invention is directed to improved oil
soluble dispersants comprising nitrogen or ester, preferably
nitrogen, containing conventional dispersants or adducts
which are post-reacted with at least one polyepoxide. The
nitrogen or ester containing adducts or intermediates which
are reacted with the polyepoxide to form the improved
dispersants of this invention comprise members selected from
the group consisting of (i) oil soluble salts, amides,
imides, ozazolines and esters, or mixtures thereof, of long
chain hydrocarbon substituted mono and dicarboxylic acids or
their anhydrides; (ii) long chain aliphatic hydrocarbon
having a polyamine attached directly thereto; and (iii)
Mannich condensation products formed preferably by
condensing about a molar proportion of long chain
hydrocarbon substituted phenol with about 1 to 2.5 moles of
formaldehyde and about 0.5 to 2 moles of polyalkylene
polyamine.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention there are
provided oil soluble dispersant compositions. These
dispersants exhibit a high temperature to low temperature
viscosity balance or ratio which is more favorable than that
of conventional dispersant materials. That is to say the
instant dispersant materials possess inherent
characteristics such that they contribute less to low
temperature viscosity increase than dispersants of the prior
art while increasing the contribution to the high
temperature viscosity increase. They also exhibit enhanced
or improved dispersancy characteristics. This is believed
to be due, inter alia, to the presence of hydroxyl groups
formed as a result of the ring opening of the oxirane rings
in their reaction with the reactive amino groups or hydroxyl
groups of the nitrogen or ester containing adducts as
described hereinafter.
Y
- 7 - 133~09~
Tha improved dispersantJ of the instant invention
are co~prised of the oil soluble reaction products of:
(I) nitrogen or ester containing adducts selected
from the group consisting of (i) oil soluble salts, amides,
imide~, oxazoline~ and eaters, or mixtures thereof, of long
chain hydrocarbon sub~tituted mono and dicarboxylic acids
or their anhydride~; (ii) long chain aliphatic hydrocarbon
having a polyamine attached directly thereto: and (iii)
Mannich condensation product~ formed by condensing a long
chain hydrocarbon sub~tituted phenol with an aldehyde and a
polyalkylene polyamine, wherein ~aid long chain hydrocarbon
group in (i), (ii), and (iii) is a polymer of a C2 to
Clo, e.g., C2 to C5 monoolefin, said polymer having a
number average molecular weight of about 500 to about 6000;
and
(II) a polyepoxide.
The molecular weight of the product is increased
by the coupling or linking of two or more molecules of the
adduct by or through the polyepoxide moieties.
The long chain hydrocarbyl substituted dicar-
boxylic acid producing material, e.g., acid, anhydride, or
ester, used in the invention or produce the nitrogen or
ester containing adducts classified as (i) above includes a
long chain hydrocarbon substituted typically with an
average of at least about 0.7, usefully from about 0.7-2.0
(e.g. 0.9-1.6), preferably about 1.0 to 1.3 (e.g. 1.1 to
1.2) mole~, per mole of hydrocarbon, of a C4 to C10
dicarboxylic acid, anhydride or ester thereof, such as
succinic acid, succinic anhydride, dimethyl methyl-
succinate, etc., and mixtures thereof.
The hydrocarbyl substituted dicarboxylic acid
materials, as well as methods for their preparation, are
well known in the art and are amply described in the patent
133509~
literature. They may be obtained, for example, by the Ene
reaction between a polyolefin and an alpha-beta unsaturated
C4 to C10 dicarboxylic acid, anhydride or ester
thereof, such as fumaric acid, itaconic acid, maleic acid,
maleic anhydride, chloromaleic acid, dimethyl fumarate,
etc.
The hydrocarbyl substituted dicarboxylic acid
materials function as acylating agents for the adducts such
as those comprised of a nitrogen containing moiety, e.g.,
polyamine, to form the acylated nitrogen derivatives of
hydrocarbyl substituted dicarboxylic acids, anhydrides, or
esters which are subsequently reacted with the polyepoxides
to form the dispersants of the present invention.
Preferred olefin polymers for reaction with the
unsaturated dicarboxylic acid, anhydride, or ester are
polymers comprising a major molar amount of C2 to C18,
e.g. C2 to C5, monoolefin. Such olefins include
ethylene, propylene, butylene, isobutylene, pentene,
octene-l, styrene, etc. The polymers can be homopolymers
such as polyisobutylene and isobutylene; propylene and
isobutylene; etc. Other copolymers include those in which
a minor molar amount of the copolymer monomers, e.g., 1 to
10 mole %, is a C4 to C18 non-conjugated diolefin,
e.g., a copolymer of isobutylene and butadiene; or a
copolymer of ethylene, propylene and l,4-hexadiene; etc.
In some cases the olefin polymer may be completely
saturated, for example an ethylene-propylene copolymer made
by a Ziegler-Natta synthesis using hydrogen as a moderator
to control molecular weight.
The olefin polymers will usually have number
average molecular weights (Mn) within the range of about
500 and about 6000, e.g. 700 to 3000, preferably between
about 800 and about 2500. An especially useful starting
material for a highly potent dispersant additive made in
accordance with this invention is polyisobutylene.
133509~
Processes for reacting the olefin polymer with the
C4-C10 unsaturated dicarboxylic acid, anhydride or ester are
known in the art. For example, the olefin polymer and the
dicarboxylic acid material may be simply heated together as
disclosed in U.S. Pat. Nos. 3,361,673 and 3,401,118 to
cause a thermal "ene" reaction to take place.
Alternatively, the olefin polymer can be first halogenated,
for example, chlorinated or brominated to about 1 to 8 wt.
~, preferably 3 to 7 wt. % chlorine or bromine, based on the
weight of polymer, by passing the chlorine or bromine
through the polyolefin at a temperature of 25 to 160-C,
e.g., 120-C, for about 0.5 to 10, preferably 1 to 7 hours.
The halogenated polymer may then be reacted with sufficient
unsaturated acid or anhydride at 100 to 250 C, usually about
180 to 220 C, for about 0.5 to 10 hours, e.g. 3 to 8 hours,
so the product obtained will contain an average of about 0.7
to 2.0 moles, preferably 1.0 to 1.3 moles, e.g., 1.2 moles,
of the unsaturated acid per mole of the halogenated polymer.
Processes of this general type are taught in U.S. Patents
3,087,436; 3,172,892; 3,272,746 and others.
Alternatively, the olefin polymer and the
unsaturated acid material are mixed and heated while adding
chlorine to the hot material. Processes of this type are
disclosed in U.S. Patents 3,215,707; 3,231,587; 3,912,764;
4,110,349; 4,234,435; and in U.K. 1,440,219.
By the use of halogen, about 65 to 95 wt. ~ of the
polyolefin, e.g. polyisobutylene, will normally react with
the discarboxylic acid material. Upon carrying out a
thermal reaction without the use of halogen or a catalyst,
then usually only about 50 to 85 wt. ~ of the
polyisobutylene will react. Chlorination helps increase the
'~ ~
- lO 1~35095
reactivity. For convenience, all of the aforesaid
functionality ratios of dicarboxylic acid producing units to
polyolefin, e.g. 1.0 to 2.0, etc. are based upon the total
amount of polyolefin, that is, the total of both the reacted
and unreacted polyolefin, present in the resulting product
formed in the aforesaid reactions.
Amine compounds useful as reactants with the
hydrocarbyl substituted dicarboxylic acid material, i.e.,
acylating agent, are those containing at least two reactive
amino groups, i.e., primary and secondary amino groups. -
They include polyalkylene polyamines, of about 2 to 60 (e.g.
2 to 30), p~eferably 2 to 40, (e.g. 3 to 20) total carbon
atoms and about 1 to 12 (e.g., 2 to 9), preferably 3 to 12,
and most preferably 3 to 9 nitrogen atoms in the molecule.
These amines may be hydrocarbyl amines or may be hydrocarbyl
amines including other groups, e.g., hydroxy groups, alkoxy
groups, amide groups, nitriles, immidazoline groups, and the
like. Hydroxy amines with 1 to 6 hydroxy groups, preferably
1 to 3 hydroxy groups are particularly useful. Such amines
should be capable of reacting with the acid or anhydride
groups of the hydrocarbyl substituted dicarboxylic acid
moiety and with the oxirane rings of the polyepoxide moiety
through the amino functionality or a substituent group
reactive functionality. Since tertiary amines are generally
unreactive with anhydrides and oxirane rings, it is
desirable to have at least two primary and/or secondary
amino groups on the amine. It is preferred that the amine
contain at least one primary amino group, for reaction with
the acylating agent, and at least one secondary amino group,
for reaction with the polyepoxide. Preferred amines are
aliphatic saturated amines, including those of the general
formula:
RIV _ N - R~
R'' (I)
V
~, ~,
11 1335095
RI ~ H2)s - N-(CH2~ N ~IV (Ia)
R' ~ R''' t R'
wherein RIV~ R', R'' and R''' are independently
select-d fro~ the group consisting of hydrogen; C1 to
C2s ~traight or branched chain alkyl radicals; C1 to
C12 alkoxy C2 to C6 alkylene radicals; C2 to C12
hydroxy amino alkylene radicals; and Cl to C12 alkyl-
amino C2 to C6 alkylene radicals; and wherein R'' and
R''' can additionally comprise a moiety of the formula
(CH2)~ - N H
I t'
R' (Ib)
wherein R' is as defined above, and wherein each s and s'
can be the same or a different number of from 2 to 6,
preferably 2 to 4; and t and t' can be the same or dif-
ferent and are each numbers of typically from O to 10,
preferably about 2 to 7, most preferably about 3 to 7, with
the proviso that t + t' is not greater than 10. To assure
a facile reaction it is preferred that RIV, R', R'',
R''', (s), (g'), (t) and (t') be selected in a manner
sufficient to provide the compounds of formula I wit~
typically at least two primary and/or secondary amino
group-. This can be achieved by selecting at least one of
said RIV~ R', R", or R''' groups to be hydrogen or by
letting (t) in formula Ia be at least one when R''' is H or
when the (Ib) moiety possesses a secondary amino group. The
most preferred amines of the above formulas are represented
by formula Ia and contain at least two primary amino groups
and at least one, and preferably at least three, secondary
amino groups.
- 12 - 1335UY~
Non-limiting examples of suitable amine compounds
include: l,2-diaminoethane~ l,3-~iaminopropane;
l,4-diaminobutane; l,6-diaminohexane; polyethylene amines
such as diethylene triamine; triethylene tetramine;
tetraethylene pentamine; polypropylene amines such as
l,2-propylene diamine; di-(l,2-propylene) triamine;
di-(l,3-propylene) triamine; N,N'-dimethyl-l,
3-diaminopropane; N,N'-di-(2-aminoethyl) ethylene diamine;
N,N'-di(2-hydroxyethyl)-l,3-propylene diamine;
N-dodecyl-l,3propan- diamine; t ri~
hydroxymethylaminomethane (THAM); diisopropanol amine;
diethanol amine; triethanol amine: mono-, di-, and
tri-tallow amines; amino morpholines such as
N-(3-aminopropyl) morpholine; and mixtures thereof.
Other useful amine compound~ include: alicyclic
diamines such as l,4-di(aminoethyl) cyclohexane, and
N-aminoalkyl piperazines of the general formula:
~CH2--C~2_ 1
H-N~-(C~2)Pl--N N -(CH2) NHI H
_ ~ CH2 CH~ ~ - P2 n (II)
wherein Pl and P2 are the same or different and are
each integer~ of from l to 4, and nl, n2 and n3 are
the same or different and are each integers of from l to 3.
Commercial mixtures of amine compounds may
advantageously be used. For example, one process for
preparing alkylene amines invol~es the reaction of an
alkylenQ dihalide (such as ethylene dichloride or propylene
dichloride) with ammonia, which results in a complex
mixtur- of alkylene amines wherein pairs of nitrogens are
joined by alkylene groups, forming such compounds as
diethylene triamine, triethylenetetramine, tetraethylene
pentamine and corresponding piperazines. Low cost
poly(ethyleneamine) compounds averaging about s to 7
nitrogen atoms per molecule are available commercially
under trade names such as "Polyamine H", "Polyamine 400",
"Dow Polyamine E-lOO", etc.
~ 13 ~ 13~095
Useful amines also include polyoxyalkylene
polyamines such as those of the formulae:
NH2 alkyl-n~ ~ 0-alkylene ~ NH2 ~III)
where m has a value of about 3 to 70 and preferably 10 to
35; and
RV ~ alkylen~ ~ 0-alkylene ~ NH2) (IV)
where n has a value of about 1 to 40, with the provision
that the sum of all the n's is from about 3 to about 70,
and preferably from about 6 to about 35, and RV is a
substituted saturated hydrocarbon radical of up to 10
carbon atoms, wherein the number of substituents on the
RV group is from 3 to 6. The alkylene groups in either
formula (III) or (IV) may be straight or branched chains
containing about 2 to 7, and preferably about 2 to 4 carbon
atoms.
The polyoxyalkylene polyamines of ~ormulas ( r ~ r )
or (IV) above, preferably polyoxyalkylene diamines and
polyoxyalkylene triamines, may have number avera~e
molecular weights ranging from about 200 to about 4000 and
preferably from about 400 to about 2000. The preferred
polyoxyalkylene polyamines include the polyoxyethylene and
polyoxypropylene diamines and the polyoxypropylene tri-
amines having average molecular weights ranging from about
200 to 2000. The polyoxyalkylene polyamines are
commercially available and may be obtained, for example,
from the Jefferson Chemical Company, Inc. under the trade
name "Jeffamines D-230, D-400, D-1000, D-2000, T-403", etc.
- l4 ~ 133509~
The amine is readily reacted with the dicarboxylic
acid material, e.g. alkenyl succinic anhydride, by heating
an oil ~olution containing 5 to 95 wt. % of dicarboxylic
acid material to about 100 to 200-C. J preferably 125 to
175~C., generally for 1 to 10, e.g. 2 to 6 hours until the
desired amount of water is removed. The heating is
preferably carried out to favor formation of imides or
mixtures of imides and amides, rather than amides and
salts. Reaction ratios of dicarboxylic acid material to
equivalents of amine as well as the other nucleophilic
reactants described herein can vary considerably, depending
upon the reactants and type of bond~ formed. Generally from
0.1 to 1.0, preferably about 0.2 to 0.6, e.g. 0.4 to 0.6,
moles of dicarboxylic acid moiety content (e.g. grafted
maleic anhydride content) is used, per equivalent of
nucleophilic reactant, e.g. amine. For example, about 0.8
mole of a pentamine (having two primary amino groups and 5
equivalents of nitrogen per molecule) is preferably used to
convert into a mixture of amides and imides, the product
formed by reacting one mole of olefin with sufficient
maleic anhydride to add 1.6 moles of succinic anhydride
groups per mole of olefin, i.e. preferably the pentamine is
used in an amount sufficient to provide about 0.4 mole
(that is 1.6/[0.8x5] mole) of succinic anhydride moiety per
nitrogen equivalent of the amine.
Tris(hydroxymethyl) amino methane (THAM) can be
reacted with the aforesaid acid material to form amides,
imides Or ester type additives as taught by U.K. 984,409,
or to form oxazoline compounds and borated oxazoline
compounds as described, for example, in U.S. 4,102,798;
4,116,876 and 4,113,639.
The adducts may also be esters derived from the
aforesaid long chain hydrocarbon substituted dicarboxylic
acid material and from hydroxy compounds such as monohydric
and polyhydric alcohols or aromatic compounds such as
phenols and naphthols, etc. The polyhydric alcohols are
the mo~t p re fer red hyd roxy c omp oun ds.
_ 15 - l 335 095
Suitable polyol co~pounds which can be used
inclu~Q aliphatic polyhydric alcohols containing up to
abo~t l00 carbon atoms and about 2 to a~cut l0 hydroxyl
groups. These alcohols can be quite diverse in structure
and chemical composition, for example, they can be
substituted or unsubstitued, hindered or unhindered,
branched chain or straight chain, etc. as desired. Typical
alcohols are alkylene glycols such as ethylene glycol,
propylene glycol, tremethylene glycol, butylene glycol, and
polyglycol such as diethylene glycol, triethylene glycol,
tetraethylene glycol, dipropylene glycol, tripropylene
glycol, dibutylene glycol, tributylene glycol, and other
alkylene glycols and polyalkylene glycols in which the
alkylene radical contains from two to about eight carbon
atoms. Other useful polyhydric alcohols include glycerol ,
monomethyl ether of glycerol, pentaerythritol,
d ipe nta e ryth ritol, t rip enta e ryth r itol,
9,l0-dihydroxystearic acid, the ethyl ester of
9,l0-dihydroxystearic acid, 3-chloro-l, 2-propanediol,
l,2-butanediol, l,4-butanediol, 2,3-hexanediol, pinacol,
tetrahydroxy pentane, erythritol, arabitol, sorbitol,
mannitol, l,2-cyclohexanediol, l,4-cyclohexanediol,
l,4-(2-hydroxyethyl)-cyclohexane, l,4-dihydroxy-2-
nitrobutane, l,4-di-(2-hydroxyethyl)-benzene, the
carbohydrates such as glucose, rhamnose, mannose,
glyceraldehyde, and galactose, and the like, amino alcohols
such as di-(2-hydroxyethyl) amine, tri-(3 hydroxypropyl)
amine, N,N,-di-(hydroxyethyl) ethylenediamine, copolymer of
allyl alcohol and styrene, N,N-di-(2-hydroxylethyl~ glycine
and esters thereof with lower mono-and polyhydric aliphatic
alcohols etc.
Included within the group of aliphatic alcohols
are those alkane polyols which contain ether groups such as
polyethylene oxide repeating units, as well as those
polyhydric alcohols containing at least three hydroxyl
- 16 - 13~5~95
~LU~3~ at least one of which has been esterified with a
mono-carboxylic acid having from eight to about 30 carbon
atoms such as octanoic acid, oleic acid, stearic acid,
linoleic acid, dodecanoic acid, or tall oil acid. Examples
of such partially esterified polyhydric alcohols are the
mono-oleate of sorbitol, the mono-oleate of glycerol, the
mono-stearate of glycerol, the di-stearate of sorbitol, and
the di-dodecanoate of erythritol.
A preferred class of ester containing adducts are
those prepared from aliphatic alcohols containing up to 20
carbon atoms, and especially those containing three to 15
carbon atoms. This class of alcohols includes glycerol,
erythritol, pentaerythritol, dipentaerythritol,
tripentaerythritol, gluconic acid, glyceraldehyde, glucose,
arabinose, 1,7-heptanediol, 2,4-heptanediol,
1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol,
2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol,
quinic acid, 2,2,6,6-tetrakis(hydroxymethyl)-cyclohexanol,
1,10-decanediol, digitalose, and the like. The esters
prepared from aliphatic alcohols containing at least three
hydroxyl groups and up to fifteen carbon atoms are
particularly preferred.
An especially preferred class of polyhydric
alcohols for preparing the ester adducts used as starting
materials in the present invention are the polyhydric
alkanols containing 3 to 15, especially 3 to 6 carbon atoms
and having at least 3 hydroxyl groups. Such alcohols are
exemplified in the above specifically identified alcohols
and are represented by glycerol, etythritol,
pentaerythritol, mannitol, sorbitol, 1,2,4 hexanetriol, and
tetrahydroxy pentane and the like.
The ester adducts may be di-esters of succinic
acids or acidic esters, i.e., partially esterified succinic
acids; as well as partially esterified polyhydric alcohols
or phenols, i.e., esters having free alcohols or phenolic
hydroxyl radicals. Mixtures of the above illustrated
esters likewise are contemplated within the scope of this
inv ent ion.
_ 17 _ 1 3350~5
The ester adduct may be prepared by one of several
known methods as illustrated for example in U.S. Patent 3,
381,022. The ester adduct may also be borated, similar to
the nitrogen containing adduct, as described herein.
Hydroxyamines which can be reacted with the
aforesaid long chain hydrocarbon substituted dicarboxylic
acid material to form adducts include 2-amino-2-methyl-1-
propanol, p-(beta-hydroxyethyl)-aniline, 2-amino-1-
propanol, 3-amino-1-propanol, 2-amino-2-methyl-
1,3-propane-diol, 2-amino-2-ethyl-1,3-propanediol,
N-(beta-hydroxypropyl)-N'-(beta-amino-ethyl)piperazine,
tris(hydrocymethyl) amino-methane (also known as
trismethylolaminomethane), 2-amino-1-butanol, ethanolamine,
diethanolamine, triethanolamine, beta-(beta-hydroxy-
ethoxy)-ethylamine and the like. Mixtures of these or
similar amines can also be employed. The above description
of nucleophilic reactants suitable for reaction with the
hydrocarbyl substituted dicarboxylic acid or anhydride
includes amines, alcohols, and compounds of mixed amine and
hydroxy containing reactive functional groups, i.e.
amino-alcohols.
Also useful as nitrogen containing adducts which
are reacted with the polyepoxide to form the improved
dispersants of this invention are the adducts of group (ii)
above wherein a nitrogen containing polyamine is attached
directly to the long chain aliphatic hydrocarbon as shown
in U.S. Patents 3,275,554 and 3,565,804 where the halogen
group on the halogenated hydrocarbon is displaced with
various alkylene polyamines.
Another class of nitrogen containing adducts which
are reacted with the polyepoxide to produce the dispersants
of this invention are the adducts of group (iii) above
which contain Mannich base or Mannich condensation products
as they are known in the art. Such Mannich condensation
products generally are prepared by condensing about 1 mole
of a high molecular weight hydrocarbyl substituted hydroxy
- 18 - 1335095
aromatic compound (e.g., having a number average molecular
weight of 700 or greater) with about l to 2.5 moles of an
aldehyde such as formaldehyde or paraformaldehyde and about
0.5 to 2 moles polyalkylene polyamine as disclosed, e.g., in
U.S. Patents 3,442,808; 3,649,229 and 3,798,165. Such
Mannich condensation products may include a long chain, high
molecular weight hydrocarbon on the phenol group or may be
reacted with a compound containing such a hydrocarbon, e.g.,
polyalkenyl succinic anhydride as shown in said
aforementioned U.S. Patent 3,442,808.
The hydrocarbyl substituted hydroxy aromatic
compounds used in the preparation of the Mannich base
include those compounds having the formula
R20
I x
R2ly - Ar - (OH)z
wherein Ar represents
R2ox R20
~ q or ~L
wherein q is l or 2, R21 is a long chain hydrocarbon, R20 is a
hydrocarbon or substituted hydrocarbon radical having from l
to about 3 carbon atoms or a halogen radical such as the
bromide or chloride radical y is an integer from l to 2, x
is an integer from 0 to 2, and z is an integer from l to 2.
Illustrative of such Ar groups are phenylene,
biphenylene, naphthylene and the like.
The preferred long chain hydrocarbon substituents
are olefin polymers comprising a major molar amount of C2 to
C8, e.g. C2 to C5 monoolefin. Such olefins
- 1335095
-- 19
include ethylene, propylene, butylene, pentene, octene-l,
styrene, etc. The polymers can be homopolymers such as
polyisobutylene, as well as copolymers of two or more of
such olefins such as copolymers of: ethylene and propylene;
butylene and isobutylene; propylene and isobutylene; etc.
Other copolymers include those in which a minor molar amount
of the copolymer monomers, e.g., a copolymer of isobutylene
and butadiene; or a copolymer of ethylene, propylene and
1,4-hexadiene; etc.
In some cases, the olefin polymer may be
completely saturated, for example an ethylene-propylene
copolymer made by a Ziegler-Natta synthesis using hydrogen
as a moderator to control molecular weight.
The olefin polymers will usually have a number
average molecular weight (Mn) within the range of about 700
to about 10,000, more usually between about 700 and about
5,000. Particularly useful olefin polymers have number
average molecular weight within the range of about 700 to
about 3,000, and more preferably within the range of about
900 to about 2,500 with approximately one terminal double
bond per polymer chain. An especially useful starting
material for a highly potent dispersant additive made in
accordance with this invention is polyisobutylene. The
number average molecular weight for such polymers can be
determined by several known techniques. A convenient method
for such determination is by gel permeation chromatography
(GPC) which additionally provides molecular weight
distribution information, see W. W. Yau, J. J. Kirkland and
D. D. Bly, "Modern Size Exclusion Liquid Chromatography",
John Wiley and Sons, New York, 1979.
Processes for substituting the hydroxy aromatic
compounds with the olefin polymer are known in the art and
may be depicted as follows:
~ ~r
~ 1335095
- 20 -
OH BF3 OH
(~20~ ~ + yR21 - 3 (R22) ~ (R21)y
where R20, R2l, y and x are as previously defined, and BF3 is
an alkylating catalyst. Processes of this type are
described, for example, in U.S. Patents 3,539,633 and
3,649,229.
Representative hydrocarbyl substituted hydroxy
aromatic compounds contemplated for use in the present
invention include, but are not limited to, 2-polypropylene
phenol, 3-polypropylene phenol, 4-polypropylene phenol,
2-polybutylene phenol, 3-polyisobutylene phenol,
4-polyisobutylene phenol, 4-polyisobutylene-2-chlorophenol,
4-polyisobutylene-2-methylphenol, and the like.
Suitable hydrocarbyl-substituted polyhydroxy
aromatic compounds include the polyolefin catechols, the
polyolefin resorcinols, and the polyolefin hydroquinones,
e.g., 4-polyisobutylene-1,2-dihydroxybenzene,
3-polypropylene-1,2-dihydroxybenzene,
5-polyisobutylene-1,3-dihydroxybenzene,
4-polyamylene-1,3-dihydroxybenzene, and the like.
Suitable hydrocarbyl-substituted naphthols include
l-polyisobutylene-5-hydroxynaphthalene, 1-polypropylene-3-
hydroxynaphthalene and the like.
The preferred long chain hydryocarbyl substituted
hydroxy aromatic compounds to be used in this invention can
be illustrated by the formula:
OH
R22~
wherein R22 is hydrocarbyl of from 50 to 300 carbon atoms,
and preferably is a polyolefin derived from a C2 to Cl0
(e.g., C2 to Cs) mono-alpha-olefin.
.~,~ .~
.
- 133S095
- 21 -
The aldehyde material which can be employed in the
production of the Mannich case is represented by the
formula:
R23CHo
in which R23 is a hydrogen or an aliphatic hydrocarbon
radical having from 1 to 4 carbon atoms. Examples of
suitable aldehydes include formaldehyde, paraformaldehyde,
acetaldehyde and the like.
In a preferred embodiment of the instant invention
the adducts which are reacted with the polyepoxide to form
the dispersants of this invention are the nitrogen
containing adducts of group (i) above, i.e., those derived
from a hydrocarbyl substituted dicarboxylic acid forming
material (acids or anhydrides) and reacted with polyamines.
These types of adducts are nomenclatured, in the
specification and claims, as acylated nitrogen derivatives
of hydrocarbyl substituted dicarboxylic acid materials, with
the hydrocarbyl substituted dicarboxylic acid forming
material being nomenclatured as an acylating agent or
material. Particularly preferred adducts of this type are
those derived from polyisobutylene substituted with succinic
anhydride groups and reacted with polyethylene amines, e.g.
tetraethylene pentamine, pentaethylene hexamine,
polyoxyethylene and polyoxypropylene amines, e.g.
polyoxypropylene diamine, trismethylolaminoethane and
combinations thereof.
Utilizing this preferred group of nitrogen
containing adducts the dispersants of the instant invention
may be characterized as acylated nitrogen derivatives of
hydrocarbyl substituted dicarboxylic materials comprising
the reaction products of:
- 22 - 1335095
(Aj reaction products of (1) a long chain
hydrocarbyl substituted dicarboxylic acid
producing material, and (2) a polyamine;
subsequently reacted with
(B) a polyepoxide.
The polyepoxides are compounds containing at least
two oxirane rings, i.e. - C - C -. These oxirane rings are
connected or joined by hydrocarbon moieties or hydrocarbon
moieties cont~;n;ng at least one hetero atom or group. The
hydrocarbon moieties generally contain from 1 to about 100
carbon atoms. They include the alkylene, cycloalkylene,
alkenylene, arylene, aralkenylene and alkarylene radicals.
Typical alkylene radicals are those containing from 1 to
about 100 carbon atoms, more typically from 1 to about 50
carbon atoms. The alkylene radicals may be straight chain
or branched and may contain from 1 to about 100 carbon
atoms, preferably from 1 to about 50 carbon atoms. Typical
cycloalkylene radicals are those containing from 4 to about
16 ring carbon atoms. The cycloalkylene radicals may
contain alkyl substituents, e.g., Cl - C8 alkyl, on one or
more ring carbon atoms. Typical arylene radicals are those
containing from 6 to 12 ring carbons, e.g., phenylene,
naphthylene and biphenylene. Typical alkarylene and
aralkylene radicals are these containing from 7 to about 100
carbon atoms, preferably from 7 to about 50 carbon atoms.
The hydrocarbon moieties joining the oxirane rings may
contain substituent groups thereon. The substituent groups
are those which are substantially inert or unreactive at
ambient conditions with the oxirane ring. As used in the
specification and appended claims the term "substantially
inert and unreactive at ambient conditions" is intended to
mean that the atom or group is substantially inert to
chemical reactions at ambient temperatures and pressure with
the oxirane ring so as not to materially interfere in an
'f
1 335095
- 23 -
adverse manner with the preparation and/or functioning of
the compositions, additives, compounds, etc. of this
invention in the context of its intended use. For example,
small amounts of these atoms or groups can undergo minimal
reaction with the oxirane ring without preventing the making
and using of the invention as described herein. In other
words, such reaction, while technically discernable, would
not be sufficient to deter the practical worker of ordinary
skill in the art from making and using the invention for its
intended purposes. Suitable substituent groups include, but
are not limited to, alkyl groups, hydroxyl groups, tertiary
amino groups, halogens, and the like. When more than one
substituent is present they may be the same or different.
It is to be understood that while many substituent
groups are substantially inert or unreactive at ambient
conditions with the oxirane ring, they will react with the
oxirane ring under conditions effective to allow reaction of
the oxirane ring with the reactive amino groups of the
acylated nitrogen derivatives of hydrocarbyl substituted
dicarboxylic materials. Whether these groups are suitable
substituent groups which can be present on the polyepoxide
depends, in part, upon their reactivity with the oxirane
ring. Generally, if they are substantially more reactive
with the oxirane ring than the oxirane ring is with the
reactive amino group, particularly the secondary amino
group, they will tend to materially interfere in an adverse
manner with the preparation of the improved dispersants of
this invention and are, therefore, unsuitable. If, however,
their reactivity with the oxirane ring is less than or
generally similar to the reactivity of the oxirane ring with
the reactive amino groups, particularly a secondary amino
group, they will not materially interfere in an adverse
manner with the preparation of the dispersants of the
present invention and may be present on the polyepoxide,
particularly if the epoxide groups are present in excess
relative to the substituent groups. An example of such a
,
-~ X
Il
- 24 - 1335~95
reactive but suitable group is the hydroxyl group. An
example of an unsuitable substituent group is a primary
amino group.
The hydrocarbon moieties containing at least one
hetero atom or group are the hydrocarbon moieties described
above which contain at least one hetero atom or group in the
chain. The hetero atoms or groups are those that are
substantially unreactive at ambient conditions with the
oxirane rings. When more than one hetero atom or group is
present they may be the same or different. The hetero atQms
or groups are separated from the carbon atom of the oxirane
ring by at least one intervening carbon atom. These hetero
atom or group containing hydrocarbon moieties may contain at
least one substituent group on at least one carbon atom.
These substituent groups are the same as those described
above as being suitable for the hydrocarbon moieties.
Some illustrative non-limiting examples of
suitable hetero atoms or groups include:
oxygen atoms (i.e, -O- or ether linkages in the
carbo chain);
sulfur atoms (i.e. -S- or thioether linkages in
the carbon chain);
carboxy groups (i.e., - C - O -);
sulfonyl group (i.e., - ~
ketone group (i.e, - C -);
13~5095
sulflnyl group (i.e., - S -);
/o\
an oxirane ring (i.e., ~ -); and
nitro group.
As mentioned hereinafore the polyepoxides of the
present invention contain at least two oxirane rings or
epoxide moieties. It is critical that the polyepoxide
contain at least two oxirane rings in the same molecule.
Preferably, these polyepoxides contain no more than about
10 oxirane rings, preferably no more than about 5 oxirane
rings. Preferred polyepoxides are the diepoxides, i.e.,
those containing two oxirane rings.
The polyepoxides useful in the instant invention
are well known in the art and are generally commercially
available or may readily be prepared by conventional and
well known methods.
The polyepoxides include those represented by the
general formula/
O~ \
l \
R30 _------ C - C - R
\ R3 R2
s
wherein:
R30 is a s valent hydrocarbon radical, a
substituted s valent hydrocarbon radical, a s valent
hydrocarbon radical containing at least one hetero atom or
group, and a substituted s valent hydrocarbon radical
containing at least one hetero atom or group; R1 - R3
are as described herein below; and s is an integer having a
value of at least 2, preferably rom 2 to about 10, more
preferablly from 2 to about 5. In this generic formula
R30 has the same meaning as R in Formula V below except
that it is s valent rather than divalent.
- 26 - 13~ ~ O ~ ~
Among the polyepoxides described hereinafore are
those repre~ented by the general formula.
O O
V. R6 _ C - C - R - C - C -
R5 R4 R R
wherein:
R is a divalent hydrocarbon radical, a substituted
divalent hydrocarbon radical, a divalent hydrocarbon
radical containing at least one hetero atom or group, and a
substituted divalent hydrocarbon radical containing at
lea~t one hetero atom or group.;
Rl and R6 are independently selected from
hydrogen, monovalent hydrocarbon radicals, substituted
monovalent hydrocarbon radicals, monovalent hydrocarbon
radicals containing at least one hetero atom or group,
substituted monovalent hydrocarbon radicals containing at
lea~t one hetero atom or group, and oxirane containing
radicals;
R2 and R3 are independently selected from
hydrogen, monovalent hydrocarbon radicals, substituted
monovalent hydrocarbon radicals, monovalent hydrocarbon
radicals containing at least one hetero atom or group,
substituted monovalent hydrocarbon radicals containing at
least one hetero atom or group, monovalent oxirane
containing radicals, divalent hydrocarbon radicals, and
sub~tituted divalent hydrocarbon radicals, with the proviso
that i~ R2 or R3 is a divalent hydrocarbon radical or
substituted divalent hydrocarbon radical then both R2 and
R3 must be divalent hydrocarbon radicals or substituted
divalent hydrocarbon radicals that together with the two
carbon atoms of the oxirane ring form a cyclic structure;
a nd
. - 27 - 1 3 3 ~o 9~
R4 and R5 are independently selected from
hydrogen, monovalent hydrocarbon radicals, substituted
monovalent hydrocarbon radicals, monovalent hydrocarbon
radicals containing at least one hetero atom or group,
substituted monovalent hydrocarbon radicals containing at
least one hetero atom or group, monovalent oxirane
containing radicals, divalent hydrocarbon radicals, and
sub~tltuted divalent hydrocarbon radicals, with the proviso
that if R4 or RS is a divalent hydrocarbon radical or
substituted divalent hydrocarbon radical then both R4 and
R5 must be divalent hydrocarbon radicals or substituted
divalent hydrocarbon radicals that together with the two
carbon atoms of the oxirane ring form a cyclic structure.
The monovalent hydrocarbon radical~ represented by
R1 _ R6 generally contain from 1 to about 100 carbon
atoms. These hydrocarbon radicals include alkyl, alkenyl,
cycloalkyl, aryl, aralkyl, and alkaryl radicals. The alkyl
radicals may contain from 1 to about 100, preferably from l
to about 50, carbon atoms and may be straight chain or
branched. The alkenyl radicals may contain from 2 to about
lOO carbons, preferably from 2 to about 50 carbon atoms,
and may be straight chain or branched. Preferred
cycloalkyl radicals are those containing from about 4 to
about 12 ring carbon atoms, e.g., cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, etc. These cycloalkyl radicals
may contain substituent groups, preferably alkyl groups, on
the ring carbon atoms, e.g., methylcyclohexyl,
1,3-dimethylcyclopentyl, etc. The preferred alkenyl
radicals are those containing from 2 to about 30 carbon
atom~, e.g., ethenyl, l-propenyl, 2-propenyl, etc. The
preferred aryl radicals are those containing from 6 to
about 12 ring carbon atoms, i.e., phenyl, naphthyl, and
biphenyl. The preferred aralkyl and alkaryl radicals are
those containing from 7 to about 30 carbon atoms, e.g.,
p -tol yl, 2,6-xylyl, 2,4,6-trimethylphenyl,
2-isopropylphenyl, benzyl, 2-phenylethyl, 4-phenylbutyl,
etc.
- 28 - 13 3509S
The substituted monovalent hydrocarbon radicals
represented by Rl - R6 are the monovalent hydrocarbon
radicals described hereinafore which contain at least one
sub~ti~uent group thereon. The substituent groups are such
that they are substantially unreactive under ambient
conditions with the oxirane moieties. When more than one
~ubstituent group i~ present they may be the same or
di f ~erent .
Th- monovalent hydrocarbon rad$cals containing at
least one hetero atom or group are the monovalent
hydrocarbon radicals described hereinafore which contain at
lea~t one hetero atom or group in the carbon chain. The
hetero atom or group is separated from the carbon of the
oxirane ring by at least one intervening carbon atom. When
more than one hetero atom or group is present they may be
the same or different. The hetero atom~ or groups are
those that are substantially unreactive under ambient
conditions with the oxirane ring. These hetero atoms or
groups are those described hereinafore.
The substituted monovalent hydrocarbon radicals
containing at least one hetero atom or group are the
substituted monovalent hydrocarbon radicals containing at
1 east one hetero atom or group described above wh ich
contain at least one substituent group on at least one
carbon atom. The substituent groups are those described
hereinafore .
The oxirane radicals represented by R1 _ R6
may be repre~ented by the formula
VI. -R10 - C - C - R7
19 18
R R
wherein:
R7 has the same meaning as Rl, R8 _ R9
have the same meaning as R2 _ R3, and R10 has the
same meaning as R in Formula V .
-29 - 133S09S
The divalent hydrocarbon radicals represented by
R2 _ Rs and R3 _ R9 generally are aliphatic acyclic radicals
and contain from 1 to about S carbon atoms. Preferred
divalent hydrocarbon radicals are the alkylene radicals.
Preferred alkylene radicals are those that, together with
the two carbon atoms of the oxirane ring, form a cyclic
structure containing from 4 to about 8 ring carbon atoms.
Thus, for example, if R3 and R4 are both ethylene radicals
the resultant cyclic structure formed with the two carbon
atoms of the oxirane ring is a cyclohexylene oxide i.e.,
j C - C
C -- C
H2 H2
The divalent substituted hydrocarbon radicals
represented by R2 _ R5 and R3 _ R~ are the divalent
hydrocarbon radicals described above which contain at least
one substituent group on at least one carbon atom. Thus,
for example, if R3 and R4 are both hydroxy substituted
ethylene radicals, the resultant cyclic structure formed
with the two carbon atoms of the oxirane ring may be
represented by the formula.
/o\
~C -- C\--
H2C~ ~CH2
C --C
/~ r\
~ OH H OH
The divalent hydrocarbon radicals represented by R
and R10 generally contain from 1 to about 100 carbon atoms,
preferably from 1 to about 50 carbon atoms. They may be
aliphatic, aromatic or aliphatic-aromatic. If they
~ 30 - 133S095
are aliphatic they may be saturated or unsaturated, acyclic
or alicyclic. They include alkylene, cycloalkylene,
alkenylene, arylene, aralkylene, and alkarylene radicals.
The alkylene radicals may be straight chain or branched.
Preferred alkylene radicals are those containing from 1 to
about 50 carbon atoms. Preferred alkenylene radicals are
those containing from 2 to about 50 carbon atoms. Preferred
cycloalkylene radicals are those containing from 4 to about
12 ring carbon atoms. The cycloalkylene radicals may
contain substituents, preferably alkyls, on the ring carbon
atoms.
It is to be understood that the term "arylene" as
used in the specification and the appended claims is not
intended to limit the divalent aromatic moiety represented
by R and Rl to benzene. Accordingly, it is to be understood
that the divalent aromatic moiety can be a single aromatic
nucleus such as a benzene nucleus, a pyridine nucleus, a
thiophene nucleus, a 1,2,3,4-tetrahydronaphthalene nucleus,
etc., or a polynuclear aromatic moiety. Such polynuclear
moieties can be of the fused type; that is, wherein at least
one aromatic nucleus is fused at two points to another
nucleus such as found in naphthalene, anthracene, the
azanaphthalenes, etc. Alternatively, such polynuclear
aromatic moieties can be of the linked type wherein at least
two nuclei (either mono- or polynuclear) are linked through
bridging linkages to each other. Such bridging linkages can
be chosen from the group consisting of carbon-to-carbon
single bonds, ether linkages, keto linkages, sulfide
linkages, polysulfide linkages of 2 to 6 sulfur atoms,
sulfinyl linkages, sulfonyl linkages, methylene linkages,
alkylene linkages, di-(lower alkyl)-methylene linkages,
lower alkylene ether linkages, alkylene keto linkages, lower
alkylene sulfur linkages, lower alkylene polysulfide
linkages of 2 to 6 carbon atoms, amino linkages, polyamino
linkages and mixtures of such divalent bridging linkages.
X
~ _
- 31 - 1335095
When the divalent aromatic moiety, Ar, is a linked
polynuclear aromatic moiety it can be represented by the
general formula
- Ar(Lng-Ar~w
wherein w is an integer of l to about lO, preferably l to
about 8, more preferably l, 2 or 3; Ar is a divalent
aromatic moiety as described above, and each Lng is a
bridging linkage individually chosen from the group
consisting of carbon-to-carbon single bonds, ether linkages
(e.g. -O-), keto linkages (e.g.,
01
-- C--),
sulfide linkages (e.g., -S-), polysulfide linkages of 2 to 6
sulfur atoms (e.g., -S2-), sulfinyl linkages (e.g.,
-S (O) -), sulfonyl linkages (e.g., --S (O) 2 - ~, lower
alkylene linkages (e.g.,
-CH2 -, - CH2 - CH2-, - CH2 - CH -, etc.),
R*
di (lower alkyl) - methylene linkages (e.g., - CR*2-), lower
alkylene ether linkages (e.g.,
- CH2 - O -, -CH2 - O - CH2 -, -CH2 - CH2- O -,
-CH2CH20CH2CH2 -, -CH2CHOCH2CH - -
R* R*
- CH2CHOC~HCH2--
R* R*
:~,
- 32 - 133 ~ 095
etc.) lower alkylene sulfide linkages (e.g., wherein one or
more -O-,s in the lower alkylene ether linkages is replaced
with an -S- atom), lower alkylene polysulfide linkages
(e.g., wherein one or more -O-'s is replaced with a -S2to
-S6- group), with R~ being a lower alkyl group.
Illustrative of such linked polynuclear aromatic
moieties are those represented by the formula
(~13) ( 12) 1
_~ _ R~
wherein R12 and R13 are independently selected from
hydrogen and alkyl radicals, preferably alkyl radicals
containing from 1 to about 2 O carbon atoms; Rll is
selected from alkylene, alkylidene, cycloalkylene, and
cycloalkylidene radicals; and u and ul are independently
selected from integers having a value of from 1 to 4.
The divalent substituted hydrocarbon radicals
represented by R and R10 are those divalent hydrocarbon
radicals described above which contain at least one
substituent group of the type described hereinafore. Thus,
for example, if the divalent hydrocarbon radical is a C5
alkylene, the corresponding divalent substitute hydrocarbon
radical, e.g., hydroxyl substituted radical, may be
OH
2 CH2 - CH - CH2 - CH
When more than one substituent group is present they may be
the same or different.
The divalent hydrocarbon radicals containin~ at
least one hetero atom or group are those divalent
hydrocarbon radicals described hereinafore which contain at
least one hetero atom or group. These hetero atoms or
groups are those described hereinafore. Some illustrative
non-limiting examples of divalent hydrocarbon radicals
containing at least one hetero atom or group include:
1335095
- CH2 - O - CH2;-
-CH2 - O - CH2 - CH2 - O - CH2 - ;
CH3
CH2 ~ o - C - o {~ CH2 -
CH3
CH2 OE) o CH2
_CH2 Ic f CH2
H H
H
CH2 ~ ~ ~ C - ~ - O - CH
O~ I O
H2C - C - CH2 - -<~)- C - ~ - O - CH2 - C - CH2
H H H
- CH2 - O - CH2 - CH - CH2 - o - CH2 -
,CH2
O o
~ \
CH2 - C - CH2
H
The divalent substituted hydrocarbon radicals
containing at least one hetero atom or group are those
divalent hydrocarbon radicals containing at least one
hetero atom or group described above which contain at least
one substituent group of the type described hereinafore.
- 34 - 1335095
Some illustrative non-limiting examples of divalent
substituted hydrocarbon radicals containing at least one
hetero atom or group include:
OH
~ CH2 ~ CH2 - O - CH2 - CH - CH2 - O - CH2 - CH2 -
CH3 CH3
- CH2 - O - ~ - C - ~ - O - CH2 - CH - CH2 - O - ~ -~$ -
CH3 OH CH3
_ ~ _ o - CH ~ ;
OH /O\ OH
-CH2 - CH - CH2 - C - C - CH2 - CH - CH2 - ; and
H H
OH loj ,CO2CH3
- CH2 - CH - S - CH - CH2-
Also included within the scope of the polyepoxidesof the instant invention are these represented by the
formula
VIII. R15 - C/ - \ C - R14
~ X
- wherein:
t, X
~ - 3S - 1~35095
R and R1-R3 are as defined hereinafore; Rl4 and R15
independently have the same meaning as R1; X is an aromatic
moiety; R16 and R17 are independently selected from divalent
aliphatic acyclic hydrocarbon radicals and divalent
substituted aliphatic acyclic hydrocarbon radicals which
together with the two carbon atoms of the oxirane ring and
the two adjacent ring carbon atoms of the aromatic moiety X
form a cyclic structure;
m and ml are independently zero or one with the
proviso that the sum of m plus ml is at least one; and p-is
zero or one.
The aromatic moieties represented by X are
preferably those containing from 6 to 12 ring carbon atoms,
e.g., benzene, napthalene, and biphenyl. The aromatic
moieties may contain one or more substituents on one or more
ring carbon atoms. These substituents are those which are
substantially unreactive at ambient conditions, e.g.,
temperature and pressure, with the oxirane ring. They
include, for example, alkyl, hydroxyl, nitro, and the like.
Also falling within the scope of the polyepoxides
of the instant invention are those represented by the
formula:
IX. R15- C -\C - R14 0
/ \
R13_______----(R)p - C - C - R
R3 R4
,
wherein:
R, R1-R3, R14-R15 and p are as defined hereinafore;
and R13 is independently selected from divalent hydrocarbon
radicals or a substituted divalent hydrocarbon radicals
which together with the two carbon atoms of the oxirane ring
forms a cyclic preferably cylcoaliphatic, structure.
- 1335095
- 36 -
The divalent hydrocarbon or substituted divalent
hydrocarbon radicals represented by Rl8 preferably contain
from 2 to about 14 carbon atoms so as to form, together with
the two carbon atoms of the oxirane ring, a 4 to about 16
membered ring structure, preferably a cycloaliphatic ring.
The preferred divalent hydrocarbon radicals are the divalent
aliphatic hydrocarbon radicals, preferably the alkylene
radicals.
The divalent aliphatic hydrocarbon radicals
represented by Rl3 may contain one or more substituent groups
on one or more ring carbon atoms. The substituents are
selected from those that are substantially unreactive under
ambient conditions with the oxirane ring, e.g., alkyl,
hydroxyl, and the like.
Preferred polyepoxides of the instant invention
are those wherein at least two of the oxirane rings,
preferably the two terminal or end oxirane rings, are
unhindered. By unhindered is meant that the oxirane ring
contains one secondary carbon atom, i.e., having two
hydrogens bonded thereto, and preferably contains one
secondary carbon atom and one tertiary carbon atom, i.e.,
having one hydrogen bonded thereto. Thus, for example, an
unhindered polyepoxide of Formula I is one wherein Rl, R2,
R~, and R6 are hydrogen, preferably one wherein Rl-R3 and R4-R6
are all hydrogen.
Some illustrative non-limiting Examples of the
polyepoxides of the instant invention include:
/o~ /o ~
H2C - C - CH2 - O - CH2 - CH2 - O - CH2 - C - CH2;
H H
0~ O
H2C - C~ - CH2 - O - (CH2) 4 - O - CH2 - C - CH2
H H
. ~
A~
- 37 - 1 3 3 5 ~ 9~
/~ ,o~
H2c - f - CH2 - s - ~H2 - CH2 - s CH2 - C - CH2
H H
p~ O O O
/ \ 11 11 / \
H2C - C - CH2 - O - C - (CH2) 4 - C - O - CH2 - Cl - CH2
H H
. H2C - f - CH2 - o - C - CH2 - CH2 C - o - CH2 - lC - CH2
H H
H2 c Ic cH2 0 e CH ~ CH - C - O - CH2 - C -\CH2
~0~ 0
H2 c - c - CH2 CH2 - CH2 - CH2 f CH2
H H
~0~ ~ 0~
H2C - lC - CH2 - O - CH2 - CH - CH2 - O - CH2 - f CH2
H CH2 H
O ~0~
CH2 - C - CH2
o CH2 f - CH2
--( ' /\
o - CH2 -, lC - CH2
/o\ o a ~o\
H2C - lC - CH2 - O - C - CH2 - CH2 - C - O - CH2 - C - CH2
H H
- 38 -
13~5095
~o\ ~ o
H
O O O
~- CH2 - O - C - ~/
/0\ 0 01 O
H2C lC CH2 - O - ~ - ~ - C - O - CH2 - C - CH2
Ol /O
C - O - CH2 - I - CH2
H2C/-\C - CH2 - O - C ~ H
~ /0\
C - O - CH2 - bC - CH2
H C/ \C - CH - O - ~ - C - ~ - O - CH2 - IC - CH2 ; and
H H H
H2 C - C - CH2 - {~> O CH2 - I - CH2
H H
H2C - C - CH2 - O ~>- C -~- O - CH2 - C - CH2
H H H
The polyepoxides useful in the instant invention
also include the epoxy resins. These epoxy resins are well
known in the art and are generally commercially available.
They are described, for example, in Billmeyer, F. W. Jr.,
Textb oo k o f Polyme r Sc ience, 2nd edition,
1335095
- 39 -
Wiley-Interscience, New York, 1971, pp. 479-480; Lee, H and
Neville, K., "Epoxy Resins", pp. 209-271 in Mark, H. F.,
Gaylord, N. G. and Bikales, N. M., eds., Encyclopedia of
Polymer Science and Technology, Vol. 6, Interscience Div.,
John Wiley and Sons, New York, 1967; and in U.S. Patent Nos.
3,477,990 and 3,408,422.
The epoxy resins (or polyepoxides) include those
compounds possessing one or more vicinal epoxy groups.
These polyepoxides are saturated or unsaturated, aliphatic,
cycloaliphatic, aromatic or heterocyclic, and are
substituted, if desired, with non-interfering substituents,
such as halogen atoms, hydroxyl groups, ether radicals, and
the like.
Preferred polyepoxides are the glycidyl polyethers
of polyhydric phenols and polyhydric alcohols, especially
the glycidyl polyethers of 2,2-bis(4-hydroxyphenyl) propane
having an average molecular weight between about 300 and
3,000 and an epoxide equivalent weight (WPE) between about
140 and 2,000. Especially preferred are the diglycidyl
polyethers of 2,2-bis(4-hydroxyphenyl) propane having a WPE
between about 140 and 500 and an average molecular weight of
from about 300 to about 900.
Other suitable epoxy compounds include those
compounds derived from polyhydric phenols and having at
least one vicinal epoxy group wherein the carbon-to-carbon
bonds within the six-membered ring are saturated. Such
epoxy resins may be obtained by at least two well-known
techniques, i.e., by the hydrogenation of glycidyl
polyethers of polyhydric phenols or (2) by the reaction of
hydrogenated polyhydric phenols with epichlorohydrin in the
presence of a suitable catalyst such as Lewis acids, i..e.,
boron trihalides and complexes thereof, and subsequent
dehydrochlorination in an alkaline medium. The method of
preparation forms no part of the present invention and the
resulting saturated epoxy resins derived by either method
are suitable in the present compositions. -
~ c~ ~
1335095
- 40 -
Briefly, the first method comprises the
hydrogenation of glycidyl polyethers of polyhydric phenols
with hydrogen in the presence of a catalyst consisting of
rhodium and/or ruthenium supported on an inert carrier at a
temperature below about 50 C. This method is thoroughly
disclosed and described in U.S. Pat. No. 3,336,241, issued
Aug. 15, 1967.
The hydrogenated epoxy compounds prepared by the
process disclosed in U.S. Pat. No. 3,336,241 are suitable
for use in the present compositions.
The second method comprises the condensation of a
hydrogenated polyphenol with an epihalohydrin, such as
epichlorohydrin, in the presence of a suitable catalyst such
as BF3, followed by dehydrohalogenation in the presence of
caustic. When the phenol is hydrogenated Bisphenol A, the
resulting saturated epoxy compound is sometimes referred to
as "diepoxidized hydrogenated Bisphenol A," or more properly
as the diglycidyl ether of 2,2-bis(4-cyclohexanol) propane.
In any event, the term "saturated epoxy resin", as
used herein shall be deemed to mean the glycidyl ethers of
polyhydric phenols wherein the aromatic ring structure of
the phenols have been or are saturated.
Preferred saturated epoxy resins are the
hydrogenated resins prepared by the process described in
U.S. Pat. No. 3,336,241. More preferred are the
hydrogenated glycidyl ethers of 2,2-bis(4-hydroxyphenyl)
propane, sometimes called the diglycidyl ethers of
2,2-bis(4-cyclohexanol) propane.
One class of useful epoxy resins are those
prepared by condensing epichlorohydrin with bisphenol-A.
They include resins represented by the general structural
formula
~r
1335095
(R )v (~ )w (~)v (R21~
Q I CH3 1oH R5 I CH3
R5 R4 C~3- R - R - ~ - ~ ~3
/0
- 0~2C - C -
R3 R2
wh-rein:
R1-R6 are defined hereinafore, and preferably
are all hydrogen;
R20 is independently selected from alkyl
radicals, preferably alkyl radicals containing from 1 to
about 10 carbon atoms, hydroxyl, or halogen radicals:
R21 is independently selected from alkyl
radicals, preferably alkyl radicals containing from 1 to
about 10 carbon atoms, hydroxyl, or halogen radicals:
v is independently selected from integers having a
value of from 0 to 4 inclusive;
w is independently selected from integers havinq a
value of from 0 to 4 inclusive; and
f has a value of at least one, and varies
according to the molecular weight of the resin, with the
upper-limit Or f preferably not exceeding about 10, more
pr-f-rably not exceeding about 5.
Preferred compounds of Formula X are those wherein
Rl _ R6 are all hydrogen, and v and w are all zero.
An exampls of commercially available and useful
epoxy resins are the EPON resins of Shell Oil Company
As mentioned hereinafore those polyepoxides,
including the epoxy reins, wherein the two carbon atoms of
the oxirane ring are bonded to three hydrogen atoms, e.g.,
wherein R1-R6 in Formula V are all hydrogen, are
preferred. Preferred polyepoxides of this type are those
- 42 - 1 3 3 50 9 5
wherein the hydrocarbon moieties bridging the epoxide
moieties, e.g., R in Formula V, contain polar groups or
atoms. These polar groups or atoms include, but are not
limited to, the polar hetero atoms or groups described
hereinafore. Particularly preferred polyepoxides are the
epoxy resins, especially those devised from polyhydric
phenols .
These polyepoxides are reacted with the nitrogen
or ester containing adducts selected from the group
consisting of (i) oil soluble salts, amides, imides,
oxazolines and esters, or mixtures thereof, of long chain
hydrocarbon substituted mono and dicarboxylic acids or
their anhydrides; (ii) long chain aliphatic hydrocarbon
having a polyamine attached directly thereto; and (iii)
Mannich condensation products formed by condensing about a
molar proportion of long chain hydrocarbon substituted
phenol with about 1 to 2.5 moles of formaldehyde and about
0.5 to 2 moles of polyalkylene polyamine, to form the
improved dispersants of the present invention. In the case
of nitrogen containing adducts these adducts that are
further reacted with the polyepoxides in accordance with
the present invention contain sufficient unreacted residual
reactive amino groups, i.e., primary and/or secondary amino
groups, to enable the desired reaction with the
polyepoxides to take place. This reaction involves a ring
opening of the oxirane ring whereby different molecules of
the adduct are joined or coupled by the ring opened oxirane
moietie~ on the same polyepoxide molecule.
In a preferred embodiment the nitrogen containing
adduct is of group (i). Such an adduct, as discussed
hereinafore, may be characterized as an acylated nitrogen
derivative of hydrocarbyl substituted dicarboxylic acid
producing materials. While the following discussion is
directed to this preferred embodiment, it is to be
understood that, with minor modifications, it is equally
applicable to the other adducts of groups (i)-(iii) which
may be used in the instant invention.
_ 43 - 1 3 3 ~ O 9 5
The polyepoxides of the present invention are
react~d with the acylated nitrogen derivatives of
hydrocarbyl substituted dicarboxylic acid materials. The
acylated nitrogen derivatives that are further reacted with
th~ polyepoxide~ in accordance with the present invention
contain sufficient unreacted residual reactive amino
nitrogens, e.g., secondary amino nitrogens, to enable the
desired reaction with the polyepoxides to take place. This
reaction is between the remaining reactive nitrogen~ of the
acylated nitrogen derivatives and the ox~rane rings of the
polyepoxide, and involve~ ring opening o~ th~ oxirane rings
whereby different molecule~ of the acylated nitrogen
derivatives are joined or coupled by the ring opened
oxirane moieties on the same polyepoxide molecule. That i~
to say different oxirane rings on the same polyepoxid-
molecule react with amino groups on different molecules of
the acylated nitrogen derivatives, thereby coupling or
linking these different acylated nitrogen derivative
molecules.
Reaction may be carried out by adding an amount of
polyepoxide to the acylated nitrogen derivative which is
effective to link or chain extend at least some of the
molecules of the acylated nitrogen derivative, i.e., chain
extending effective amount. It will be apparent to ~hose
skilled in the art that the amount of polyepoxide utilized
will depend upon (i) the number of reactive nitrogen atoms
pr-aent in the acylated nitrogen derivative, (ii) the
number Or oxirane rings present in the polyepoxide, (iii)
any participation from other functional groups present on
the polyepoxide in the reaction and, (iv) the number of
such groups which it is desired to react, i.e., the degree
of coupling or cross-linking it is desired to obtain.
Generally, however, it is preferred to utilize an
amount of polyepoxide such that there are present from
about 0.01 to about 5, preferably from about 0.05 to about
2, and more preferably from about 0.1 to about 1 equivalent
_ ~4 - 1 3 ~ 5 0 9 S
o~ ~poxide per equi~alent of reactive residual amino group
in th~ acylated nitrogen derivative.
The temperature at which the reaction is carried
out generally ranges from about 50-C. to the decomposition
temperature of the mixture, preferably from about 50 C. to
about 250-C., and more preferably from about 100-C., to
about 200-C. While superatmospheric pressures are not
excluded, the reaction generally proceeds at atmospheric
pres~ure. Th~ reaction may b~ conducted using a mineral
oil, e.g., 100 neutral oil as a solvent. An inert organic
co-solvent, e.g., xylene or toluene, may also be used. The
reaction time generally ranges from about 0.5 - 24 hours.
The products of this embodiment are formed as a
result of bonding i.e. formation of a carbon to nitrogen
bond, of different oxirane moieties on the same polyepoxide
molecule with a reactive amino group , preferably a
secondary amino group, on different molecules of the
acylated nitrogen derivative. The product may, for
purposes of illustration and examplification only, be
represented by the following formula and reaction scheme:
/o~ /~
Y - CH - fH2 + H2C - C - R - C - CH2----~
2 O = C C = O H H
\ N
CH2
CH2
N - H
~H2
Y - fH--fH2 Y - fH--CH2
o = C C = o o = C C = o
\N'/ \ /
fH2 CH2
f 2 4 1 OH H CH2
N - C - C - R - C - C - N
CH2 H H H H {CH2
- 45 - 1 33 S O 9~
wherein Y i~ independently selected from olefin polymers
containing at lea~t 30 carbon atoms. This type of product
i~ o~tained fro~ the reaction of an acyla~ed nitrogen
derivative containing only one residual react.ve amino
group per molecule, e.g., secondary amino group, and a
polyepoxide containing only two oxirane rings per
molecule. If the acylated nitrogen derivative contains
more than one re~idual reactive amino group per molecule
and/or the polyepoxide contains more than two oxirane rings
per molecule then the products will be more complex, e.g.,
a polyepoxide containing three oxirane rings per molecule
may join or couple three different acylated nitrogen
derivative molecules containing one residual reactive amino
group per molecule.
If the acylated nitrogen derivative contains more
than one re~idual reactive amino group per molecule, e.g.,
two secondary amino groups, and the polyepoxide contains
two oxirane rings, then one acylated nitrogen derivative
molecule could, depending on the stoichiometry of the
reaction, be be joined to two other acylated nitrogen
derivative molecules by two polyepoxide molecules. This
may be illustrated by the following structure:
Y - CH- CH2 Y - CH- CH Y - CH -c
t I , ~ 2 ~ ,
O = C C = O O = C C = O o = c . = o
N N N
ICH2 C,H2 CH,
CH2 CH2 H OHOH H CH ?
NH N - C~ c -R- C -c- N
CIH2 CH2 H H H H CH~
CH2 CH2 CH
~ H OH OH H ¦ NH
N ~ C - C -R -C-C- N CH2
s
CH2 H H ~ 2
- 46 - 1 3 3 5 0 9 5
T~e polyepoxide ig, in effect, a chain extender or
cros~-linking agent serving to join together two or more
molecules of acylated nitrogen derivative. The product,
since it contain~ two or more acylated nitrogen derivative
mol~cules bonded together, has a higher molecular weight
and may be characterized as an oligomer or even a polymer.
The molecular weight of the product will depend, inter
alia, upon the number of reactive amino groups per molecule
of acylated nitrogen derivative, the number of oxirane
rings per molecule of polyepoxide, and the amount of
polyepoxide present in the reaction mixture o~ polyepoxide
and acylated nitrogen derivative. For example, if an
acylated nitrogen derivative containing only one residual
reactive amino group, preferably a secondary amino group,
per molecule is reacted with a diepoxide the product will
be a dimer of the acylated nitrogen derivative. In such a
situation increasing the amount of the diepoxide will
generally not result in an increase in the molecular weight
of the resultant dimer molecule but will yield more dimer
molecules. On the other hand, if an acylated nitrogen
derivative containing more than one residual reactive amino
group per molecule is reacted with a diepoxide, the
molecular weight of the product molecule may be increased
in addition to the production of more cross-linked
molecules.
Further aspects of the present invention reside in
the formation of metal complexes and other post-treatment
derivatives, e.g., borated derivatives, of the novel
additives prepared in accordance with this invention.
Suitable metal complexes may be formed in accordance with
known techniques of employing a reactive metal ion species
during or after the formation of the present dispersant
materials. Complex-forming metal reactants include the
nitrates, thiocyanates, halides, carboxylates, phosphates,
thio-phosphates, sulfates, and borates of transition metals
such as iron, cobalt, nickel, copper, chromium, manganese,
- 47 -
13~095
~olybdenum, tungsten, ruthenium, palladium, platinum,
cadmium, lead, silver, mercury, antimony and the like.
Prior art disclosures of these complexing reactions may be
found in U.S. Patents 3,306,908 and Re. 26,443.
Po~t-treatment compositions include those formed
by reacting the novel additive~ Or the present invention
with one or more post-treating reagents, usually selected
from the group consisting of boron oxide, boron oxide
hydrate, boron halide~, boron acid-~, sulfur, sulfur
chlorides, phosphorous sulfides and oxides, carboxylic acid
or anhydride acylating agents, epoxides and episulfides and
acrylonitrile~. The reaction of such post-treating agents
with the novel additives of this invention is carried out
using procedures known in the art. For example, boration
may be accomplished in accordance with the teachings of
U.S. Patent 3,254,025 by treating the additive compound of
the present invention with a boron oxide, halide, ester or
acid. Treatment may be carried out by adding about 1-3 wt.
% of the boron compound, preferably boric acid, and heating
and stirring the reaction mixture at about 135 C to 165-C
for l to 5 hours followed by nitrogen stripping and
filtration, if desired. Mineral oil or inert organic
solvents facilitate the process.
The compositions produced in accordance with the
present invention have been found to be particularly useful
as fuel and lubricating oil additives.
When the compositions of this invention are used
in normally liquid petroleum fuels, such as middle
distillates boiling from about 150- to 800-F. including
kerosene, diesel fuels, home heating fuel oil, jet fuels,
etc., a concentration of the additi-ve in the fuel in the
range of typically from 0.001 wt. % to 0.5 wt. %,
preferably 0.005 wt. % to 0.2 wt. %, based on the total
weight of the composition, will usually be employed. These
additives can contribute fuel stability as well as
dispersant activity and/or varnish control behavior to the
fuel.
- 48 - 1 ~ 3 S O 9 5
The compounds of this invention find their primary
utility, however, in lubricating oil compositionS, which
employ a base oil in which the additives arP dissolved or
dispersed. Such base oils may be natural or synthetic.
Thus, base oils suitable for use in preparing the
lubricating compositions of the present invention include
those conventionally employed as crankcase lubricating oils
~or spark-ignited and compression-ignited internal
combustion engines, such as automobile and truck engines,
marine and railroad diesel enginQs, and the like.
Advantageous results are also achieved by employing the
additives of the present invention in base oils
conventionally employed in and/or adapted for use as power
transmitting fluids such as automatic transmission fluid~,
tractor fluids, universal tractor fluids and hydraulic
fluids, heavy duty hydraulic fluids, power steering fluids
and the like. Gear lubricants, industrial oils, pump oils
and other lubricating oil compositions can also benefit
from the incorporation therein of the additives of the
present invention.
Thus, the additives of the present invention may
be suitably incorporated into synthetic base oils such as
alkyl esters of dicarboxylic acids, polyglycols and
alcohols; polyalpha-olefins, polybutenes, alkyl benzenes,
organic esters of phosphoric acids, polysilicone oils, etc.
selected type of lubricating oil composition can be
included as desired.
The additives of this invention are oil-soluble,
dissolvable in oil with the aid of a suitable solvent, or
are stably dispersible materials. Oil-soluble,
dissolvable, or stably dispersible as that terminology is
used herein does not necessarily indicate that the
materials are soluble, dissolvable, miscible, or capable of
being suspended in oil in all proportions. It does mean,
however, that the additives, for instance, are soluble or
stably dispersible in oil to an extent sufficient to exert
_ 49 - ~ 5~95
th~ir intended effect in the environment in which the oil
Ls emplcyed. Moreover, the additional incorporation of
ot~er additive may also per~it incorporaticn of higher
level~ of a particular polymer adduct hereof, if desired.
Accordingly, while any dispersant effective amount
of the~e additives can be incorporated into the fully
formulated lubricating oil composition, it is contemplated
that such effective amount be sufficient to provide said
lube oil composition with an amount of the additive of
typically from 0.01 to about 10, e.g., 0.1 to 6.0, and
preferably from 0.25 to 3.0 wt. %, based on the weight of
said composition.
The additives of the present invention can be
incorporated into the lubricating oil in any convenient
way. Thus, they can be added directly to the oil by
dispersing, or dissolving the same in the oil at the
desired level of concentration, typically with the aid of a
suitable solvent such as toluene, cyclohexane, or
tetrahydrofuran. Such blending can occur at room
temperature or elevated.
Natural base oils include mineral lubricating oils
which may vary widely as to their crude source, e.g.,
whether paraffinic, naphthenic, mixed, paraffinic-
naphthenic, and the like; as well as to their formation,
e.g., distillation range, straight run or cracked,
hydrofined, solvent extracted and the like.
More specifically, the natural lubricatin~ oil
bas~ stock~ which can be used in the compositions of this
invention may be straight mineral lubricating oil or
distillates derived from paraffinic, naphthenic, asphaltic,
or mixed base crudes, or, if desired, various blends oils
may be employed as well as residuals, particularly those
from which asphaltic constituents have been removed. The
oils may be refined by conventional methods using acid,
alkali, and/or clay or other agents such as aluminum
chloride, or they may be extracted oils produced, for
~ ~ ~ 1335095
ex~pla, by 301vent extraction with solvent~ of the type of
ph~ncl, sul~ur dioxide, furfural, dichlorod.2thyl ether,
nitrobenzene, crotonaldehyde, etc.
The lubricating oil base stock conveniently has a
viscosity of typically about 2.5 to about 12, and
preferably about 2.5 to about 9 cSt. at lOO C.
Thus, the additives of the present invention can
be employed in a lubricating oil composition which
comprises lubricating oil, typically in a major amount, and
the additive, typically in a minor amount, which is
effective to impart enhanced dispersancy relative to the
absence o~ the additive. Additional conventional additives
selected to meet the particular requirements of a
temperatures. In this form the additive per se is thus
being utilized as a 100% active ingredient form which can
be added to the oil or fuel formulation by the purchaser.
Alternatively, these additives may be blended with suitable
oil-soluble solvent and base oil to form concentrate, which
may then be blended with a lubricating oil base stock to
obtain the final formulation. Concentrates will typically
contain from about 2 to 80 wt. %, by weight of the
additive, and preferably from about S to 40% by weight of
the additive.
The lubricating oil base stock for the additive of
the present invention typically is adapted to perfor~
selected function by the incorporation of additives thereln
to form lubricating oil compositions (i.e., formulations).
Representative additives typically present in such
formulations include viscosity modifiers, corrosion
inhibitors, oxidation inhibitors, friction modifiers, other
dispersants, anti-foaming agents, anti-wear agents, pcur
point depressants, detergents, rust inhibitors and the
like.
Viscosity modifiers impart high and low
temperature operability to the lubricating oil and permit
it to remain shear stable at elevated temperatures and also
- 51 -
133~095
exhi~it acc~ptable viscosity or fluidity at low temper-
atur-s. These viscoaity modifier~ are generally high
molecular weight hydrocarbon polymers including
polyssters. The viscosity modifiers may also be
derivatized to include other properties or functions, such
as the addition of dispersancy properties.
These oil soluble viscosity modifying polymers
will generally have weight average molecular weights of
from about 10,000 to 1,000,000, preferably 20,000 to
500,000, as determined by gel permeation chromatography or
light scattering methods.
Representative examples of suitable viscosity
modifiers are any of the types known to the art including
polyisobutylene, copolymers of ethylene and propylene,
polymethacrylates, methacrylate copolymers, copolymers of
an unsaturated dicarboxylic acid and vinyl compound,
interpolymers of styrene and acrylic esters, and partially
hydrogenated copolymers of styrene/isoprene,
styrene/butadiene, and isoprene/butadiene, as well as the
partially hydrogenated homopolymers of butadiene and
isoprene.
Corrosion inhibitors, also known as anti-corrosive
agents, reduce the degradation of the metallic parts
contacted by the lubricating oil composition. Illustrative
of corrosion inhibitors are phosphosulfurized hydrocarbons
and the products obtained by reaction of a phospho-
sulfurized hydrocarbon with an alkaline earth metal oxide
or hydroxide, preferably in the presence of an alkylated
phenol or of an alkylphenol thioester, and also preferably
in the presence of an alkylated phenol or of an alkylphenol
thioester, and also preferably in the presence of carbon
dioxide. Phosphosulfurized hydrocarbons are prepared by
reacting a suitable hydrocarbon such as a terpene, a heavy
petroleum fraction of a C2 to C6 olefin polymer such as
polyisobutylene, with from 5 to 30 wt. % of a sulfide of
phosphorus for 1/2 to 15 hours, at temperature in the range
_ 52 - 1335~95
of about 66 to about 316-C. Neutralization of the
phosphosulfurized hydrocarbon may be effected in the manner
taught in U.S. Patent No. 1,969,324.
Oxidation inhibitors, or antioxidants, reduce the
tendency of mineral oils to deteriorate in service which
deterioration can be evidenced by the products of oxidation
such as sludge and varnish-like deposits on the metal
surfaces, and by viscosity growth. Such oxidation
inhibitors include alkaline earth metal salts of
alkylphenolthioesters having preferably C5 to Cl2 alkyl side
chains, e.g., calcium nonylphenol sulfide, barium
toctylphenyl sulfide, dioctylphenylamine,
phenylalphanaphthylamine, phospho-sulfurized or sulfurized
hydrocarbons, etc.
Other oxidation inhibitors or antioxidants useful
in this invention comprise oil-soluble copper compounds.
The copper may be blended into the oil as any suitable oil
soluble copper compound. By oil soluble it is meant that
the compound is oil soluble under normal blending conditions
in the oil or additive package. The copper compound may be
in the cuprous or cupric form. The copper may be in the
form of the copper dihydrocarbyl thio- or dithio-phosphates.
Alternatively, the copper may be added as the copper salt of
a synthetic or natural carboxylic acid. Examples of same
thus include C10 to C18 fatty acids, such as stearic or
palmitic acid, but unsaturated acids such as oleic or
branched carboxylic acids such as napthenic acids of
molecular weights of from about 200 to 500, or synthetic
carboxylic acids, are preferred, because of the improved
handling and solubility properties of the resulting copper
carboxylates. Also useful are oil-soluble copper
dithiocarbamates of the general formula (R30R31, NCSS)zCu
(where z is 1 or 2, and R30 and R3l, are the same or
different hydrocarbyl radicals containing from 1 to 18,
and preferably 2 to 12, carbon atoms, and including
radicals such as alkyl, alkenyl, aryl,
~.
- 53 -
13~509~
aralkyl, alkaryl and cycloaliphatic radica]s. Particularly
pre~erred as R30 and R31, groups are alkyl groups of
from 2 to 8 carbon atoms. Thus, the radicals may, for
example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl,
decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl,
butylphenyl, cyclohexyl, methylcyclopentyl, propenyl,
butenyl, etc. In order to obtain oil solubility, the total
number of carbon atoms (i.e., R30 and R31,) will
generally be about 5 or greater. Copper sulphonates,
phenate~, and acetylacetonates may also be used.
Exemplary of useful copper compounds are copper
CuI and/or CuII salts of alkenyl succinic acids or
anhydrides. The salt~ themselves may be basic, neutral or
acidic. They may be formed by reacting (a) polyalkylene
succinimides (having polymer groups of Mn of 700 to 5,000)
derived from polyalkylene-polyamines, which have at least
one free carboxylic acid group, with (b) a reactive metal
compound. Suitable reactive metal compounds include those
such as cupric or cuprous hydroxides, oxides, acetates,
borates, and carbonates or basic copper carbonate.
Examples of these metal salts are Cu salts of
polyisobutenyl succinic anhydride, and Cu salts of
polyisobutenyl succinic acid. Preferably, the selected
metal employed is its divalent form, e.g., Cu+2. The
preferred substrates are polyalkenyl succinic acids in
which the alkenyl group has a molecular weight greater than
about 700. The alkenyl group desirably has a Mn from about
900 to 1,400, and up to 2,500, with a Mn of about 950 being
most preferred. Especially preferred is polyisobutylene
succinic anhydride or acid. These materials may desirably
be dissolved in a solvent, such as a mineral oil, and
heated in the presence of a water solution (or slurry) of
the metal bearing material. Heating may take place between
70-C and about 200 C. Temperatures of lOO C to 140 C are
entirely adequate. It may be necessary, depending upon the
- 54 - 1 3 3~ 0 9~
salt produced, not to allow the reaction to remain at a
tQD~p~raturQ above a~out 140 C for an extended perlod of
time, e.g., longer than 5 hours, or decomposition of the
salt may occur.
The copper antioxidants (e.g., Cu-polyisobutenyl
succinic anhydride, Cu-oleate, or mixtures thereof) will be
generally employed in an amount of froDI about 50 to 500 ppm
by weight of the metal, in the final lubricating or fuel
composition.
Friction modifiers serve to impart the proper
friction characteristics to lubricating oil compositions
such as automatic transmission fluid~.
Representative examples of suitable friction
modifiers are found in U.S. Patent No. 3,933,659 which
disclose~ fatty acid esters and amides; U.S. Patent No.
4,176,074 which describes molybdenum complexes of poly-
isobutyenyl succinic anhydride-amino alkanols; U.S.
Patent No. 4,105,571 which discloses glycerol esters of
dimerized fatty acids; U.S. Patent No. 3,779,928 which
discloses alkane phosphonic acid salts; U.S. Patent ~o.
3, 778, 375 which discloses reaction products o~ a
phosphonate with an oleamide; U.S. Patent No. 3,852,205
which discloses S-carboxyalkylene hydrocarbyl succinimide,
S-carboxyalkylene hydrocarbyl succinamic acid and mixtlres
thereo f; U.S. Patent No. 3,879,306 which discloses
N(hydroxyalkyl) alkenyl succinimic acids or succinimides:
U.S. Patent No. 3,932,290 which discloses reaction
product~ of di- (lower alkyl) phosphites and epoxides; and
U.S. Patent No. 4,028,258 which discloses the alkylene
oxide adduct of phosphosulfurized N-(hydroxyalkyl) alkenyl
succinimides. The disclosures of the above references are
herein incorporated by reference. The most preferred
friction modifiers are succinate esters, or metal salts
thereof, of hydrocarbyl substituted succinic acids or
anhydrides and thiobis-alkanols such as described in U.S.
Patent 4,344,853.
133509S
Dispersants maintain oil insolubles, resulting
from oxidation during use, in suspension in the fluid thus
preventing sludge flocculation and precipitation or
deposition on metal parts. Suitable dispersants include
high molecular weight alkyl succinimides, the reaction
product of oil-soluble polyisobutylene succinic anhydride
with ethylene amines such as tetraethylene pentamine and
borated salts thereof.
Pour point depressants, otherwise known as lube
oil flow improvers, lower the temperature at which the fluid
will flow or can be poured. Such additives are well known.
Typically of those additives which usefully optimize the low
temperature fluidity of the fluid are C8-Cl8 dialkylfumarate
vinyl acetate copolymers, polymethacrylates, and wax
naphthalene. Foam control can be provided by an antifoamant
of the polysiloxane type, e.g., silicone oil and
polydimethyl siloxane.
Anti-wear agents, as their name implies, reduce
wear of metal parts. Representatives of conventional
antiwear agents are zinc dialkyldithiophosphate and zinc
diaryldithiosphate.
Detergents and metal rust inhibitors include the
metal salts of sulphonic acids,~alkyl phenols, sulfurized
alkyl phenols, alkyl salicylates, naphthenates and other oil
soluble mono- and di-carboxylic acids. Highly basic (viz.
overbased) metal sales, such as highly basic alkaline earth
metal sulfonates (especially Ca and Mg salts) are frequently
used as detergents. Representatives examples of such
materials, and their methods of preparation, are found in
co-pending Canadian Serial No. 512,917.
Some of these numerous additives can provide a
multiplicity of effects, e.g., a dispersant-oxidation
inhibitor. This approach is well known and need not be
further elaborated herein.
_ 56 - 1 3 35 0 9 5
Compositions when containing these conventional
additives are typically blended into the base oil in
a~ounts which are effective to provide their normal
attendant function. Representative effective amounts of
such additives are illustrated as follows:
A~Aitive Wt.~ a.i. Wt. % a.i.
(Broad) (Preferred)
Viscosity Modifier 0.01-12 0.01-4
Corrosion Inhibitor 0.01-5 0.01-1.5
oxidation Inhibitor 0.01-5 0.01-1.5
Dispersant 0.1-20 0.1-8
Pour Point Depressant 0.01-5 0.01-1.5
Anti-Foaming Agents 0.001-3 0.001-0.15
Anti-Wear Agents 0.001-5 0.001-1.5
Friction Modifiers 0.01-5 0.01-1.5
wt.% a.i. wt.% a.i.
(Broad) (Preferred)
Detergents/Rust Inhibitors0.01-10 0.01-3
Min-ral Oil Base Balance Balance
When other additives are employed it may be
desirable, although not necessary, to prepare additive
concentrates comprising concentrated solutions or
dispersions of the dispersant (in concentrate amounts
hereinabove described)~ together with one or more of said
other additives (said concentrate when constituting an
additive mixture being referred to herein as an additive
1 33~095
package) whereby several additives can be added
simultaneously to the base oil to form the lubricating oil
composition. Dissolution of the additive concentrate into
the lubricating oil may be facilitated by solvents and by
mixing accompanied with mild heating, but this is not
essential. The concentrate or additive-package will
typically be formulated to contain the dispersant additive
and optional additional additives in proper amounts to
provide the desired concentration in the final formulation
when the additive-package is combined with a predetermined
amount of base lubricant. Thus, the products of the
present invention can be added to small amounts of base oil
or other compatible solvents along with other desirable
additives to form additive-packages containing active
ingredients in collective amounts of typically from about
2.5 to about 90%, and preferably from about 5 to about 75%,
and most preferably from about 8 to about 50% by weight
additives in the appropriate proportions with the remainder
being base oil.
All of said weight percents expressed herein are
based on active ingredient (a.i.) content of the additive,
and/or upon the total weight of any additive-package, or
formulation which will be the sum of the a.i. weight of
each additive plus the weight of total oil or diluent.
This invention will be further understood by
reference to the following examples, wherein all parts are
parts by weight and all molecular weights are number weight
average molecular weights as noted, and which include
preferred embodiments of the invention.
The following examples illustrate the preparation
of the oil soluble dispersants of the-instant invention.
- 58 - 1 3 3 5 0 9 ~
EXAMPLE 1
A mixture of 300 grams of SlSON minerai oil
solution containing about 50 wt % of polyisobutenyl
succinic anhydride-polyamine adduct (having a ratio of
about 1.2 succinic anhydride moieties per polyisobutylene
molecule of about 2,200 Mn~ the polyamine being a
polyethylene polyamine having from about 5 to 7 nitrogens),
said oil solution containing about l wt. % nitrogen and
having a viscosity at lOO-C of 960 centistokes, and 17.42
grams (0.1 mol) of ethylene glycol diglycidyl ether is
heated, under a nitrogen blanket, at 150- C for 5 hours.
The reaction mixture is stripped by heating at 150- C with
nitrogen blowing for one hour. The residue is a S150N
mineral oil solution of the dispersant, said oil solution
having a viscosity at 100 C of 5437 centistokes.
EXAMPLE 2
The procedure of Example 1 is repeated except that
the 17.42 grams of ethylene glycol diglycidyl ether of
Example l are replaced with 20.2 grams (0.1 mol) of
1,4-butanediol diglycidyl ether. The residue is a S150N
mineral oil solution of the dispersant, said oil solution
having a viscosity at 100 C of 5664 centistokes.
EXAMPLE 3
The procedure of Example 1 is repeated except that
the 17.42 grams of ethylene glycol diglycidyl ether of
Example l are replaced with 14.2 grams (0.1 mol) of
1,2,7,8-diepoxyoctane. The residue is a S150N mineral oil
solution of the dispersant, said oil solution having a
viscosity at 100 C of 3588 centistokes.
EXAMPLE 4
A mixture of 300 grams of S150N mineral oil
solution containing about 50 wt. % polyisobutenyl succinic
anhydride-polyamine adduct (having a ratio of about 1.3
succinic anhydride moieties per polyisobutylene molecule of
1300 Mn~ the polyamine being a polyethylene polyamine
- 59 - 1 3 3 5 0 9 ~
having from about 5 to 7 nitrogens), said oil solution
containing about 1.5 wt. % nitrogen and having a viscosity
at 100- C of 350 centistokes, and 20 grams of ethylene
glycol diglycidyl ether is heated, under a nitrogen
blanket, at 150- C for 5 hours. The reaction mixture is
stripped by heating at 150- C with nitrogen blowing for one
hour. The residue is a S150N solvent neutral mineral oil
solution of the dispersant, said oil solution having a
viscosity at 100- C of 1745 centistokes.
EXAMPLE 5
A mixture of 500 grams of S150N mineral oil
solution containing about 50 wt. % of polyisobutenyl
succinic anhydride-polyamine adduct (having a ratio of
about 1.1 succinic anhydride moieties per polyisobutylene
molecule of about 2,200 Mnl the polyamine being a
polyethylene polyamine containing from about 5 to 7
nitrogens), said oil solution containing about 1 wt. %
nitrogen and having a viscosity at 100-C of 729
centistokes, and 10 grams of EPON Resin 828 (an epoxy resin
available from Shell Oil Company which is a diglycidyl
polyether of 2,2-bis(4-hydroxyphenyl) propane having an
average molecular weight of about 380 and a weight per
epoxy of about 180-195) is heated under nitrogen at 150- C
for 5 hours. To this reaction mixture are added 125 grams
of S150N mineral oil. This mixture is blended until
substantially homogeneous. This resultant solution is a
S150N mineral oil solution of the dispersant, said oil
solution having a viscosity at 100- C of 395.1 centistokes.
EXAMPLE 6
The procedure of Example 5 is repeated except that
15 grams of the EPON Resin 828 are utilized. The resultant
S150N oil solution of the dispersant has a viscosity at
100- C of 513.0 centistokes.
_ 60 - 1 3 3 5 0 9 5
~ XAMPLE 7
The procedure of Example 5 is repeated except that
20 grams of the EPGN Resin 828 are utilized. The resultant
S150N oil solution of the dispersant has a viscosity at
lO0- C of 707.1 centistokes.
EXAMPLE 8
The procedure of Example 5 is repeated except that
25 grams of the EPON Resin 828 are utilized. The resultant
S150N oil solution of the dispersant has a viscosity at
100- C of 1015 centistokes.
Various aforedescribed polyisobutenyl succinic
anhydride-polyamine adduct reactants, which are the
precursors of the instant dispersants, as well as various
dispersants of the instant invention described above are
tested to determine their sludge inhibition (via the SIB
test) and varnish inhibition (via the VIB test) properties,
as described below, and the results are set forth in Tables
I - II.
The SIB test has been found, after a large number
of evaluations, to be an excellent test for assessing the
dispersing power of lubricating oil dispersant additives.
The medium chosen for the SIB test was a used
crankc a s e m inera l lubr icat ing o i l compos it ion hav ing an
original viscosity of about 325 SUS at 38~C that had been
used in a taxicab that was driven generally for short trips
only, thereby causing a buildup of a high concentration of
sludge precursors. The oil that was used contained only a
ref ined base mineral lubricating oil, a viscosity index
improver, a pour point depressant and z inc
dialkyldithiophosphate anti-wear additive. The oil
contained no sludge dispersant. A quantity of such used
oil was acquired by draining and refilling the taxicab
crankcase at 1000-2000 mile intervals.
133509~
The SIB test ig conducted in the following
manner: the aforesaid u5ed crankcase oil, which is milky
brown in color, is freed of sludge by centrifuging for one
hour at about 39,000 gravities (gs.). The resulting clear
bright red supernatant oil i9 then decanted from the
insoluble sludge particles thereby separated out. However,
th- supernatant oil still contain~ oil-soluble sludge
precursors which on heating under the conditions employed
by this test will tend to form additional oil-insoluble
deposit~ of sludge. The sludge inhibiting properties of
the additives being tested are determined by adding to
portions of the supernatant used oil, a small amount, such
a~ 0.5, 1 or 2 weight percent, o~ the particular additive
being tested. Ten grams of each blend being tested are
placed in a stainless steel centrifuge tube and are heated
at 135-C for 16 hours in the presence of air. Following
the heating, the tube containing the oil being tested is
cooled and then centrifuged for about 30 minutes at room
temperature at about 39,000 gs. Any deposits of new sludge
that form in this step are separated from the oil by
decanting the supernatant oil and then carefully washing
the sludge deposits with 25 ml of heptane to remove all
remaining oil from the sludge and further centrifuging.
The weight of the new solid sludge that has been formed in
the test, in milligrams, is determined by drying the
residue and weighing it. The results are reported as
amount of precipitated sludge in comparison with the
pr-cipitated sludge of a blank not containing any
additional additive, which blank is normalized to a rating
of 10. The less new sludge precipitated in the presence of
the additive, the lower the SIB value and the more
effective is the additive as a sludge dispersant. In other
words, if the additive gives half as much precipitated
sludge as the blank, then it would be rated 5.0 since the
blank will be normalized to 10.
- 62 - 1 3 3 i 0 9 ~
The VIB test was used to determine v~ rnish
inhibi~lon. Here, each test sample consisted of 10 grams
o~ lubricating oil containing a small amount of the
additive being tested. The test oil to which the additive
is admixed is of the same type as used in the
a~ove-doscribed SIB test. Each ten gram sample was heat
-oak~ overnight at about 140-C and thereafter centrifuged
to remove the sludge. The supernatant fluid of each sample
was sub~ected to heat cycling from about 150-C to room
temperature over a period o~ 3.5 hours at a fre~uency of
about 2 cycles per minute. During the heating phase, gas
which was a mixture of about 0.7 volume percent S02, 1.4
volume percent NO and balance air wa~ bubbled through the
test ~amples. During the cooling phase, water vapor was
bubbled through the test samples. At the end of the test
period, which testing cycle can be repeated as necessary to
determine the inhibiting effect of any additive, the wall
surface of the test flasks in which the samples were
contained are visually evaluated as to the varnish
inhibition. The amount of varnish imposed on the walls is
rated to values of from 1 to 11 with the higher number
being the greater amount of varnish, in comparison with a
blank with no additive that was rated 11.
10.00 grams of SIB test oil were mixed with
varying amounts of the products of the Examples as
described in Tables I - II below and tested in the
afored-scribed SIB and VIB tests. The amounts of additives
listed in Tables I - II are not the neat active ingredient
but ar~ solutions of the various polyisobutenyl succinic
anhydride-polyamine adducts or dispersants of the instant
invention in S150N mineral oil as described in the
corresponding Examples. Thus, for example, the amount of
the polyisobutenyl succinic anhydride-polyamine adduct of
Bxample 1 added to the lubricating oil refers not to the
neat polyisobutenyl succinic anhydride-polyamine adduct but
to the SlSON neutral mineral oil solution containing about
- 63 - 1 3 3 ~ O 9 5
50 wt. % of polyisobutenyl succinic anhvdride-polyamine
adduct on an active ingredient basis.
~able I
Wt. % (gms)
of Oil Solution
~itive of additive ~I~ VIB
PIBSA-PAM 0.5 3.37 5
adduct of
Example 4
Dispersant 0.5 1.68 3
of Example 4
Table II
Wt. % (gms)
of Oil Solution
Additive of additive SIB VIB
PIBSA-PAM 0.03 5.44 7
adduct of
Example 5
PIBSA-PAM 0.04 3.25 6
adduct of
Example 5
Dispersant of 0.03 4.69 8
Example 5
Dispersant of 0.04 3.38 5
Example 5
Wt. % (gms)
of Oil Solution
A~tive of additive SIB VIB
Dispersant of 0.03 4.25 8
Example 6
Dispersant of 0.04 2.5 6
Example 6
Dispersant of 0.03 4.13 6
Example 8
Dispersant of 0.04 0.56 4
Example 8
- 64 -
133~095
In Tables I and I~ the "PIBSA-PAM adduct of
Example 4" and the "PIBSA-PAM adduct of Example 5" fall
outside the scope of the present invention and are
presented for comparative purposes only.
Furthermore, in Table II while the oil solution of
the comparative "PIBSA-PAM adduct of Example 5" contains
about 50 wt. % of active ingredient, i.e., polyisobutenyl
succinic anhydride-polyamine adduct, the oil solutions of
the dispersants, i.e., the reaction product of a
polyepoxide and the polyisobutenyl succinic anhydride-
polyamine adduct, of Examples 5, 6 and 8 are about 25% more
dilute because of the added mineral oil.
Examples 9 and 10 further illustrate the
dispersants of the present invention.
EXAMPLE 9
A mixture of 500 grams of S150N mineral oil
solution containing about 50 wt. % polyisobutenyl succinic
anhydride polyamine adduct (having a ratio of about 1.3
succinic anhydride moieties per polyisobutylene molecule of
1,300 Mn~ the polyamine being a polyethylene polyamine
having from about 5 to 7 nitrogens), said oil solution
containing about 1.5 wt. % nitrogen and having a viscosity
at 100'C of 350 centistokes, and 30 grams of EPON Resin 828
is heated, under a nitrogen blanket, at 120-C for one
hour. The resultant oil solution contains the dispersant
product.
EXAMPLE 10
A mixture of 500 grams of S150N mineral oil
solution containing about 50 wt. % of polyisobutenyl
succinic anhydride-polyamine adduct (having a ratio of
about 1.2 succinic anhydride moieties per polyisobutenyl
molecule of about 2,200 Mn~ the polyamine being a
polyethylene polyamine having from about 5 to 7 nitrogens),
_ 65 - 1 3 3 ~ 0 9 5
said cil solution containing ab~ut 1 wt. % nitrogen and
hav~ng a VLscosity at lOO C of 960 c~ntistokes, and 30
gram~ of EPON Resin 828 is heated, under a nitrogen
blanket, at 120-C for one hour. The resultant oil solution
contains the dispersant product.
COMPARATIVE EXAMPLE 11
A fully formulated lOW40 crankcase motor oil is
prepared containing 3 . 6 wt. % of the oil solution of the
polyisobutenyl succinic anhydride-polyamine adduct of
Example 10, together with a base oil containing an
overbased sulfonate detergent, a zinc dialkyl
dithiophosphate, an antioxidant, and 11.8 wt. % of an
ethylene propylene copolymer viscosity index improver.
This motor oil composition is tested for its viscosity
characteristics at lOO-C in centistokes, and for cold
cranking properties in a Cold Cranking Simulator (CCS)
according to ASTM-D-2607-72 method at -20-C for viscosity
in centipoise. The results are summarized in Table III.
EXAMPLE 12
A fully formulated lOW40 crankcase motor oil is
prepared substantially in accordance with the procedure of
Example 11 except that the 3.6 wt.% of the oil solution of
the polyisobutenyl succinic anhydride-polyamine adduct of
Example 10 is replaced with 3. 6 wt. % of the oil solution
of the dispersant product of Example 10 and it contains 11
wt. % of the viscosity index improving ethylene-propylene
copolymer. The mineral lubricating oil in the base oil is
66 . 7 wt. % S150N oil and 11 wt. % SlOON oil.
This motor oil composition is tested for its
viscosity characteristics as in Comparative Example 11 and
the results are summarized in Table III.
- 6~ -
133509S
Table III
XV at CCS at
100- C -20- C
Formulation (cSt) ~cP)
Comparative Example 11 14.5 3193
Example 12 21.9 3068
It is evident from the data in Table III tha~
despite substantial increa~es in kinematic viscosity of the
formulation of the inRtant invention (Example 12) relative
to that Or Comparative Example 11 CCS viscosity dropped
slightly. Example 12 embodies a formulation within the
scope of the instant invention while Comparative Example 11
embodies a formulation falling outside the scope of the
in~tant invention. Comparative Example 11 is presented for
comparative purposes only.
The following Example 13 illustrates a borated
dispersant of the instant invention.
EXAMPr~ 13
A mixture of 2S00 gram~ of S150N mineral oil
solution containing about 50 wt. % of polyisobutenyl
succinic anhydride-polyamine adduct (having a ratio of
about 1.2 succinic anhydride moieties per polyisobutylene
molecule of about 2,200 Mn~ the polyamine being a
polyethylene polyamine having from about 5 to 7 nitrogen
ato~;) said oil solution containing about 1 wt. % nitrogen
and having a viscosity at lOO-C of 960 centistokes, 150
gram~ of EPON 828 resin, and 625 grams of S150N mineral oil
is heated, under a nitrogen blanket, at 120-C for 7 hours.
At the end of this 7 hour heating period an additional 375
gram~ of S150N mineral oil is added to the reaction mixture
and the reaction mixture i8 heated to 163-C. Into this
reaction mixture are charged, over a 2-hour period and
under a nitrogen sparge, 37.7 grams of boric acid
crystals. The reaction mixture is then stripped for 2
hours at 163-C at a rate of approximately 1000 cc/min. and
filtered. The resultant oil solutlon contains 44.6 wt. %
_ 67 - 1335095
active ingredien's, i.e., borated dispersant prGduct, has a
kinematic viscosity at lOO C of 2772 centi~tokes, and
contains 0.724 wt. % nitrogen and 0.201 wt. % boron.
E~MPT~ 14
A fully formulated lOW40 crankcase motor oil is
prepared containing 5 wt. % of the oil solution of the
borated dispersant product of Example 13, together with a
base oil containing an overbased sulfonate detergent, a
zinc dialkyl dithiophosphate, an antioxidant, and 7.5 wt. %
of an ethylene-propylene copolymer viscosity index
improver. The mineral lubricating oil in the base oil i~
S140N oil.
This lubricating oil composition is tested for it~
viscosity characteristics as in comparative Example 11 and
the results are summarized in Table IV. This lubricating
oil composition is also tested in a Caterpillar 1-H2 test,
but for 120 hours rather than the full 480 hour test
described in ASTM Document for Single Cylinder Engine Test
for Crankcase Lubricants, Caterpillar l-H2 Test Method,
Part 1, STP 509A. This test evaluates the ability of
diesel lubricants to curtail accumulation of deposits on
the piston while operating in high severity diesel
engines. The results are summarized in Table V.
COMPARATIVE EXAMPLE 15
A fully formulated lOW40 crankcase oil is prepared
substantially in accordance with the procedure of Example
14 except that the 5 wt. % of the oil solution of the
borated dispersant product of Example 13 is replaced with 5
wt. % of an oil solution (containing about 50 wt. ~ active
ingredients) of a conventional borated dispersant (a
borated polyisobutenyl succinic anhydride-polyamine adduct
having a ratio of about 1.2 succinic anhydride moieties per
polyisobutylene molecule of about 2,200 Mn~ the polyamine
being a polyethylene polyamine having from about 5 to 7
- 68 - 1 3 3 5 0 9 S
n~trogens), and it cor.tains 10.4 wt. % of the
ethylene-propylene copolymer, viscosity index improver) and
the mineral lubricating oil in the base oil is S130N oil.
Thi~ lubricating oil co~osition is tested for its
viscosity characteristics as in Comparative Example 11 and
in a Caterpillar l-H2 test and the results are summarized
in Tables IV and V respectively.
TART F IV
Kv at CCS at
lOO-C -20-C
~le ~o. (cstl (CP
Example 14 14.00 3152
Comparative
Example 15 13.89 3225
~ABLE V
Caterpillar l-H2 Test - 120 Hours
lOW40 Lubricants
Comparative
Exam~le 14 Example 16
Weighed Total Demerits 75.7 150.4
Top Groove Fill 35 49
It is evident from the data in Table IV that
despite an increase in kinematic viscosity of the lube oil
formulation containing the dispersant of the instant inven-
tion (Example 14) relative to that of a lube oil formula-
tion containing a conventional prior art dispersant
(Comparative Example 15), CCS viscosity dropped slightly.
Thi~ was achieved with the lube oil formulation of Example
14 containing less viscosity index improver (7.5 wt. %) and
a higher viscosity oil (S140N) relative to the lube oil
formulation of Comparative Example 15 (10.4 wt. % VI
improver and S13ON oil).
- 69 - 1 3 3 5 0 9 5
The data in Table V shows that the dispersant of
the present invention was superivr in Top Groove Fill and
Weighed Total Demerits, i.e., deposits, cGmpared with the
known conventional dispersant of Comparative Example 15.
It i~ to be understood that the examples present
in the foregoing specification are merely illustrative of
this invention and are not intended to limit it in any
mann e r.
