[0001] The present invention relates to additives for improving the flow properties and
viscometric properties of certain oleaginous compositions and to oleaginous compositions
containing said additives. More particularly, the present invention relates to additives
for improving the low temperature flow properties and viscometric properties such
as viscosity index of lubricating oil compositions and to lubricating oil compositions
containing said additives. Still more particularly, the present invention relates
to improved lubricating oil compositions including such additives and exhibiting improved
low temperature flow properties and viscometric properties. The present invention
also relates to methods for improving the flow properties and viscometric properties
of oleaginous composition, particularly engine crankcase lubricant compositions.
[0002] A wide variety of compounds for use as lubricating oil or fuel oil additives are
known in this art. These include compounds variously referred to as pour point depressants,
viscosity index improving compositions, wax crystal modifiers, and the like. In particular,
Cashman et al., U.S. Patent No. 2,825,717, discloses the preparation of certain lubricating
oil additives by the copolymerization of polycarboxylic acid esters with other polymerizable
monomeric materials, including vinyl compounds such as vinyl acetate. The preferred
unsaturated polycarboxylic acid esters therein are fumaric acid esters produced from
C₁ through C₁₈ aliphatic alcohols.
[0003] Bartlett, U.S. Patent No. 2,618,602, discloses pour point depressing and/or viscosity
index improving materials obtained by polymerizing certain specified alkyl fumarate
esters. In particular this patentee discloses the use of polymerized fumarate esters
of C₁₂ to C₁₄ alcohols for such purposes. This patent specifically discloses that
the C₁₂ alcohol was more effective than the C₁₄ alcohol, although both polymerized
esters exhibited pour point depressing properties.
[0004] Rossi et al., U.S. Patent No. 4,089,589, discloses the use of specified mixtures
of lubricating oil pour point depressants which include polyesters consisting of a
polymeric ester of acrylic acid or methacrylic acid and a monohydric alcohol containing
from 10 to 18 carbon atoms, and/or interpolymers of a vinyl alcohol ester of a C₂
to C₁₈ alkanoic acid (e.g., vinyl acetate) and a di(C₆-C₁₈ alkyl) fumarate as one
of the components thereof for improving the viscosity index of high wax content lubricating
oils which also include viscosity index improving ethylene copolymers. Also, Wyman,
U.S. Patent No. 3,250,715, discloses terpolymers of dialkyl fumarates, vinyl esters,
and alkyl vinyl ethers for improving the pour point of lubricating oils, and most
particularly in which the dialkyl fumarates are prepared for various C₁₀ through C₁₈
alcohols including tetradecyl alcohol alone as well as alcohol mixtures averaging
from 12 to 14 carbon atoms.
[0005] There has also been disclosed in EP-A-153176 and EP-A-153177, the use in various
middle distillate fuel compositions for lowering the pour point and controlling the
size of wax crystals in these composition additives which specifically include polymers
and copolymers of specific dialkyl fumarate vinyl acetate copolymers. Most specifically,
these patent applications disclose the use of such additives in which the average
number of carbon atoms in the alkyl groups in the polymer or copolymer must be from
12 to 14. In addition these additives are also disclosed as being useful in combination
with the polyoxyalkylene esters, ethers, ester/ethers and mixtures thereof, as well
as with various other additives. Furthermore, British Patent No. 2,023,645 discloses,
for use in treating distillate fuel oils, various three-component systems which include
as a first component flow improvers having an ethylene backbone, such as various ethylene
polymers including ethylene polymerized with various mono- or diesters (e.g., vinyl
acetate; and C₁₃ fumarates), as a second component a lube oil pour depressant such
as various oil soluble esters and/or higher olefin polymers (e.g., dialkyl fumarate,
vinyl acetate copolymers), and as a third component various polar oil-soluble compounds
(e.g., phenates, sulfonates, phosphates, and carboxylates).
[0006] It is also disclosed in Lewtas's U.S. Patent Nos. 4,661,121 and 4,661,122 that the
size of wax crystals forming in fuels boiling in the range of 120°C to 500°C can be
controlled by an additive which includes the polymers and copolymers of mono- and
di-n-alkyl esters of mono-ethylenically unsaturated C₄ to C₈ mono- or dicarboxylic
acids, in which the average number of carbon atoms in the n-alkyl groups is from 14
to 18. These patents show a preference for copolymers of di-n-alkyl fumarates and
vinyl acetate, and specifically state that the fumarates can be made from single alcohols
or mixtures of alcohols, and when mixtures are used they are mixed prior to esterification.
Furthermore, these patents disclose the use of various ethylene unsaturated ester
copolymer flow improvers as co-additives therewith, but do not specify that these
additives are produced from alcohol mixtures. In EP-A-316108 there is disclosed as
a dewaxing aid a copolymer of dialkyl fumarate and vinyl acetate in which a large
proportion of the alkyl groups are C₂₀ to C₂₄ alkyl groups. In EP-A-269714 there is
disclosed a dual component flow improver additive composition for oleaginous compositions
which comprises (i) low molecular weight polymers and interpolymers (e . g., copolymers)
of unsaturated mono- or dicarboxy esters having the formula
in which R′ is either hydrogen or a COOR radical, and R is a C₁₄ alkyl group; and
(ii) low molecular weight lubricating oil flow improver (LOFI) comprising non-ethylene
containing polymers which are soluble or dispersable in these lubricating oils, preferably
interpolymers of dialkyl fumarates and vinyl esters in which the fumarates are esterified
with mixtures of C₆ through C₂₀ alcohols.
[0007] Various oil-soluble hydrocarbon polymeric materials such as ethylene-alpha-olefin
copolymers, e. g., ethylene-propylene copolymers, are known to be useful as viscosity
index improvers for oleaginous compositions such as lubricating oils.
[0008] While these various types of additive compositions have met with various degrees
of success in the particular environments in which they are employed it has been observed
that various lubricating oil compositions, such as those containing certain viscosity
improving additives such as copolymers of ethylene and propylene, as well as those
lubricating oil compositions containing lubricating oil flow improvers, nevertheless
experience difficulty in passing recently adopted, more stringent, low temperature,
slow cool performance tests designed to measure the low temperature pumpability of
crankcase lubricating oils. It is therefore an object of the present invention to
provide oleaginous compositions, particularly lubricating oil compositions, which
exhibit enhanced low temperature pumpability and viscometric properties.
SUMMARY OF THE INVENTION
[0009] In accordance with the present invention there is provided an oleaginous composition,
particularly a lubricating oil composition, exhibiting improved low temperature flow
properties and viscometric properties which comprises: (i) oleaginous material such
as lubricating oil; (ii) a first additive or component which is a lubricating oil
flow improver (LOFI) comprising low molecular weight, e.g., low number average molecular
weight (M
n), polymers and interpolymers (e.g., copolymers) of unsaturated mono- or dicarboxy
esters having the formula:
in which R′ is either hydrogen or a COOR radical, and R is a C₁₄ alkyl group; and
(iii) a second additive or component which is an oil soluble hydrocarbon polymeric
viscosity index improver, preferably an ethylene-alpha-olefin copolymer.
[0010] In a preferred embodiment of the present invention, the first additive, i.e., lubricating
oil flow improver, comprises a low molecular weight (M
n) interpolymer of at least one of the carboxy ester monomers of formula (1) above
interpolymerized with a variety of different comonomers such as a polymerizable vinyl
ester monomeric compound having the formula:
(II) CH₂ =
- O -
- R¹
in which R¹ is an alkyl group containing from about 1 to 18 carbon atoms, preferably
from about 1 to 6 carbon atoms, and most preferably 1 carbon atom. The preferred ester
monomer of formula (II) is vinyl acetate.
[0011] The second additive, i.e., the viscosity index improver, comprises an oil soluble
hydrocarbon polymer, preferably an ethylene-alpha-olefin copolymer, and more preferably
an ethylene-propylene copolymer.
DETAILED DESCRIPTION
[0012] The oleaginous compositions of the present invention comprise (i) oleaginous material,
preferably lubricating oil, generally in a major amount; (ii) first additive comprised
of polymers or interpolymers of unsaturated carboxy esters; and (iii) second additive
comprised of a hydrocarbon polymeric viscosity index improver.
[0013] The first additive of the present invention is a lubricating oil flow improver and
is comprised of a polymer or interpolymer represented by the formula
in which R′ is either hydrogen or the COOR radical, and in which R is a C₁₄ alkyl
group. The production of these ester and diester polymers includes an esterification
reaction between unsaturated mono- or dicarboxylic acids or their corresponding anhydrides,
as well as the polymerization of the esterified monomers, and is well known in the
art, as specifically disclosed beginning at column 2, line 35 of Cashman et al., U.S.
Patent No. 2,825,717, which disclosure is incorporated herein by reference.
[0014] While the alkyl group represented by R may be straight chain or slightly branched,
the straight chain alkyl group is preferred.
[0015] Some illustrative examples of compounds of formula I include
[0016] The first additive or component may be a homopolymer, e. g., a homopolymer derived
from monomers of formula I, or an interpolymer as defined hereinafter.
[0017] The first additive or component preferably includes the interpolymers of the diester
monomers of formula (I), wherein R′ is COOR, with certain specified polymerizable
monomeric compounds, namely vinyl esters, alpha-olefins, or styrenes such as styrene
itself. One of these copolymerizable compounds is a monomer of formula
(II) CH₂ =
- O -
- R¹
in which R¹ is an alkyl group containing from 1 to about 18 carbon atoms, preferably
from 1 to about 6 carbon atoms, and most preferably 1 carbon atom, preferably vinyl
acetate, which is interpolymerized with the diester of formula 1 in a reaction which
is carried out in the presence of free radical initiators, such as peroxide catalyst.
[0018] The first component is characterized by a low molecular weight, i.e., a number average
molecular weight (M
n) of not greater than about 40,000, and typically ranging from about 1,500 to about
40,000, and preferably from about 2,500 to about 15,000.
[0019] Alternatively, such molecular weights of the first component lubricating oil flow
improvers of the present invention are more conveniently expressed by the specific
viscosity exhibited by such polymers. Accordingly, such specific viscosities will
typically range from about 0.11 to about 2.2, preferably from about 0.2 to about 0.9,
and most preferably from about 0.2 to about 0.7.
[0020] Such specific viscosities are determined in accordance with the following equation:
wherein "K-vis of Solution" is the kinematic viscosity at 104°F (40°C) of a 2.0 mass/volume
percent solution of the polymer (a.i. basis) in mixed xylenes (solvent) available
commercially, using Ubbelohde-type viscometers with a viscometer constant of about
0.003 cSt/second; and the "K-vis of Solvent" is the corresponding kinematic viscosity
of the solvent alone at the same temperature. All specific viscosities reported herein
are determined by the above method.
[0021] When interpolymers of monomer components depicted by formulas (1) and (II) are employed
as the first component, the mole ratio employed for the polymerization of such monomers
can typically vary from about 1.3:1 to about 0.5:1, preferably from about 1.2:1 to
about 0.5:1, and most preferably from about 1.2:1 to about 1:1.
[0022] Furthermore, the details with respect to conditions for esterification, homopolymerization,
and interpolymerization reactions are essentially the same as set forth below with
reference to the esterification and interpolymerization of the dicarboxylic acid esters
described below in connection with the vinyl-ester-containing interpolymers of the
second component thereof.
[0023] The particular dicarboxylic acid or anhydride monomer which is preferred will depend
on the identity of its comonomer. Thus, when the comonomer is a vinyl ester, the preferred
dicarboxylic acid is fumaric acid. When the comonomer is an alpha-olefin or styrene,
the preferred dicarboxylic monomer is maleic anhydride.
[0024] Furthermore, whether it is preferable to esterify the dicarboxylic acid or anhydride
monomer first and then interpolymerize, or to first interpolymerize the free acid
or anhydride monomer and then esterify, depends on the particular identify of the
dicarboxylic monomer and its comonomer.
[0025] Thus, for example, it is conventional to first esterify the fumaric acid monomer
or any other dicarboxylic monomer, prior to interpolymerization with a vinyl ester.
[0026] In contrast, it is also conventional to polymerize maleic anhydride with styrene
or the alpha-olefins, and to then esterify.
[0027] Moreover, while it is preferred to achieve complete esterification of all of the
carboxyl groups of the dicarboxylic monomer, it is permissible to achieve only partial
esterification, of typically not less than about 70, and preferably not less than
about 80, mole of the available esterifiable carboxyl groups.
[0028] The lubricating oil flow improvers, i.e., first additive of component, are preferably
interpolymers, preferably copolymers, of certain unsaturated dicarboxy esters with
certain specified polymerizable monomeric compounds, namely, vinyl esters, alpha-olefins,
or styrene.
[0029] Suitable ethylenically unsaturated dicarboxylic acids or their anhydrides, which
are eventually esterified, have the carboxyl or anhydride groups located on vicinal
carbons, and have 4 to 30 carbons in the unesterified monomer molecule. Suitable dicarboxylic
acids or anhydrides thus include fumaric acid, maleic anhydride, mesaconic acid, citraconic
acid and anhydride, and itaconic acid and its anhydrides.
[0030] Accordingly, esterification is conducted with a C₁₄ alcohol, which alcohol can be
slightly branched or straight chain, preferably straight chains, and most preferably
straight chain alkyl. Thus, the alcohol used for esterification is selected from the
C₁₄ aliphatic alcohols. Primary alcohols are preferred over secondary and tertiary
alcohols, and the alcohols are preferably saturated, although some degree of unsaturation
(i.e., less than about 2 mole %) is permissible. Straight and lightly branched chain
alcohols are preferred over highly branched alcohols.
[0031] As indicated hereinafore, the dicarboxylic monomer of formula 1 can be interpolymerized
with a variety of different comonomers. The first of these comonomers, as indicated
hereinafore, is a vinyl ester represented by formula II, with the preferred ester
monomer of formula II being vinyl acetate. The preferred interpolymer of this class
of lubricating oil flow improvers is C₁₄ dialkyl fumarate/vinyl acetate copolymer.
[0032] The mole ratio of the unsaturated dicarboxyl monomer to vinyl ester in the polymerization
reaction mixture can vary typically from about 1.3:1 to 0.5:1, preferably from about
1.2:1 to 0.7:1, and most preferably from about 1.2:1 to 1:1.
[0033] These interpolymers can be prepared by conventional free radical polymerization techniques,
starting with a mixture of all of the constituent monomers which is essentially free
of polymer. Thus the polymers are random interpolymers and are not graft or block
interpolymers. Conventional free radical polymerization catalysts, such as azobis-(isobutyronitrile),
tert-butyl hydroperoxide, and benzoyl peroxide, can be used. Such polymerization techniques
can be conducted neat in the absence of solvent or in bulk.
[0034] Polymerization of the ester monomers is preferably carried out in an inert hydrocarbon
solvent, such as hexane or heptane, or low viscosity lubricating oils. Polymerization
is carried out in an oxygen-free reactor. The desired atmosphere can be maintained
by carrying out the polymerization in a nitrogen atmosphere as is known in the art.
Temperatures of about 65 to about 150°C, depending on the choice of initiator, can
be used. Polymerization is carried out at either atmospheric or super-atmospheric
pressure and on either a batch or a continuous basis. Polymerization can be stopped
when the described degree of polymerization is reached by known techniques, such as
adding inhibitors to the reaction mixture, or can be allowed to go to completion.
[0035] The second type of comonomer employed for interpolymerization with the unsaturated
dicarboxyl monomer is an alpha-olefin. Straight chain alpha-olefins are preferred
over branched chain alpha-olefins. Moreover, if branching occurs, it is preferred
that it occur at the beta-carbon, and that such branching contain not more than about
5, and preferably not more than about 2, carbons. Suitable alpha-olefins typically
contain between about 6 and 46, e.g., between about 10 and 22, and preferably about
18 carbon atoms per molecule. Mixtures of olefins may be used, e.g., a C₁₀-C₂₄ mixture.
[0036] Representative olefins include 1-hexene, 1-heptene, 1-nonene, 1-decene, 1-hexadecene,
1-octadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricontene, 1-tetracontene,
2-methyloctadecene, 2-ethyleicosene, and mixtures thereof.
[0037] The mole ratio of alpha-olefin to unsaturated dicarboxyl monomer employed in the
reaction mixture will typically range from about 1.2:1 to about 0.8:1, preferably
from about 1.1:1 to about 0.9:1, and most preferably about 1:1.
[0038] The preferred interpolymer of this class is an interpolymer of 1-octadecene and maleic
anhydride subsequently esterified with the aforedescribed C₁₄ alcohol in the manner
described hereinafter.
[0039] The third preferred comonomer for interpolymerization with the unsaturated dicarboxy
monomer is a styrene compound such as styrene.
[0040] In forming this preferred unesterified intermediate polymer, the molar ratio of styrene
to unsaturated dicarboxy-containing monomer (e. g., maleic anhydride) can typically
vary from about 3:1 to about 1:1, preferably from about 2:1, to about 1:1, and most
preferably from about 1.5:1 to about 1:1.
[0041] Most preferably, equal molar amounts of styrene and unsaturated carboxy containing
monomer (e.g., maleic anhydride) are employed. In addition, minor amounts of other
miscellaneous interpolymerizable comonomers can be included in the reaction mixture.
By minor amount is typically meant less than about 1, preferably less than about 0.3
mole of miscellaneous monomers per mole of carboxy containing monomer. Similar considerations,
vis-a-vis miscellaneous monomers, apply with respect to use of the alpha-olefins as
a comonomer for interpolymerization with the dicarboxy monomer.
[0042] Various methods of polymerizing styrene or the alpha-olefins and the dicarboxy-containing
monomers are known in the art and need not be discussed in detail herein. Such methods
include neat and bulk polymerization techniques.
[0043] The polymerization reaction for use of either the styrene or alpha-olefin comonomers
with the dicarboxy monomer is typically conducted to produce an unesterified interpolymer
having a number average molecular weight of less than about 25,000, preferably less
than about 15,000, as determined by membrane osmometry. Upon esterification, such
molecular weights will be as described generally above as well as the corresponding
specific viscosities.
[0044] The resulting interpolymer is then esterified with the C₁₄ alcohol of the type described
above with respect to esterification of the dicarboxy monomer.
[0045] The esterification reaction can be accomplished simply by heating the dicarboxy-containing
polymer and the C₁₄ alcohol under conditions typical for effecting esterification.
Such conditions usually include, for example, a temperature of at least about 80°C,
preferably from about 100°C to about 150°C, provided that the temperature be below
the decomposition point of the reaction mixture, and the water of esterification is
removed as the reaction proceeds. Such conditions may optionally include the use of
an excess of the alcohol reactant so as to facilitate esterification, the use of a
solvent or diluent such as mineral oil, toluene, benzene, xylene or the like, and
the use of an esterification catalyst such as toluene sulfonic acid, sulfuric acid,
phosphoric acid, or the like. These conditions and variations thereof are well known
in the art.
[0046] The first additive or component compositions 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 first additive
composition, for instance, is soluble or stably dispersible in oil to an extent sufficient
to exert its intended effect in the environment in which the oil is employed. Moreover,
the additional incorporation of other additives mad also permit incorporation of higher
levels of a particular first additive composition hereof, if desired.
[0047] The lubricating oil compositions of the present invention contain an amount of said
first additive or component composition which is effective to improve the flow properties,
particularly low temperature flow properties, of the lubricating oil composition,
i.e., a lubricating oil flow improving effective amount. Generally, this effective
amount may vary somewhat depending on the particular type of oil. Accordingly, while
any effective amount of the first additive composition can be incorporated into the
final, e. g., 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 first additive composition of typically from about 0.001 to about 1.5, preferably
from about 0.005 to about 1.0, and more preferably from about 0.01 to about 0.5 wt.
percent, based on the weight of said lubricating composition.
[0048] The second additive or component of the instant invention is a viscosity index improver
or modifier comprised of a hydrocarbon polymer.
[0049] These oil-soluble hydrocarbon polymeric viscosity index (V.I.) improver additives
contemplated to be compounded into the lubricating oil in accordance with this invention
are generally high molecular weight hydrocarbon polymers. The V.I. improvers may also
be derivatized to include other properties of functions, such as the addition of dispersancy
properties.
[0050] These oil soluble V.I. polymers will generally have number average molecular weights
of from about 20,000 to 1,000,000, preferably from about 40,000 to about 300,000,
as determined by gel permeation chromatography or membrane osmometry.
[0051] Examples of suitable hydrocarbon polymers include homopolymers and interpolymers
of two or more monomers of C₂ to C₃₀, e.g., C₂ to C₈ olefins, preferably ethylene
and C₃ to C₃₀ olefins, including both alpha-olefins and internal olefins, particularly
preferred being the copolymers of ethylene and propylene. Other polymers can be used
such as polyisobutylenes, homopolymers and interpolymers of C₆ and higher alpha-olefins,
atactic polypropylene, hydrogenated polymers and copolymers and terpolymers of styrene,
e.g., with isoprene and/or butadiene.
[0052] More specifically, other hydrocarbon polymers suitable as viscosity index improvers
in the present invention include those which may be described as hydrogenated or partially
hydrogenated homopolymers, and random, tapered, star or block interpolymers (including
terpolymers, tetrapolymers, etc.) of conjugated dienes and/or monovinyl aromatic compounds
with, optionally, alpha-olefins or lower alkenes, e.g., C₃ to C₁₈ alpha-olefins or
lower alkenes. The conjugated dienes include isoprene, butadiene, 2,3-dimethylbutadiene,
piperylene and/or mixtures thereof, such as isoprene and butadiene. The monovinyl
aromatic compounds include any of the following, or mixtures thereof, vinyl di- or
polyaromatic compounds, e.g., vinyl naphthalene, but are preferably monovinyl monoaromatic
compounds, such as styrene or alkylated styrenes substituted at the alpha-carbon atoms
of the styrene, such as alpha-methylstyrene, or at ring carbons, such as o-, m-, p-methylstyrene,
ethylstyrene, propylstyrene, isopropyl-styrene, butylstyrene, isobutylene, tert-butylstyrene
(e.g., p-tert-butylstyrene). Also included are vinylxylenes, methylethyl styrenes
and ethylvinylstyrenes. Alpha-olefins and lower alkenes optionally included in these
random, tapered and block copolymers preferably include ethylene, propylene, butene,
ethylene-propylene copolymers, isobutylene, and polymers and copolymers thereof.
As is also known in the art, these random, tapered and block copolymers may include
relatively small amounts, that is less than about 5 moles, of other copolymerizable
monomers such as vinyl pyridines, vinyl lactams, methacrylates, vinyl chloride, vinylidene
chloride, vinyl acetate, vinyl stearate, and the like.
[0053] Specific examples include random polymers of butadiene and/or isoprene and polymers
of isoprene and/or butadiene and styrene. Typical block copolymers include polystyrene-polyisoprene,
polystyrene-polybutadiene, polystyrene-polyethylene, polystyrene-ethylene propylene
copolymer, polyvinyl cyclohexane-hydrogenated polyisoprene, and polyvinyl cyclohexane-hydrogenated
polybutadiene. Tapered polymers include those of the foregoing monomers prepared by
methods known in the art. Star-shaped polymers typically comprise a nucleus and polymeric
arms linked to said nucleus, the arms being comprised of homopolymer of interpolymer
of said conjugated diene and/or monovinyl aromatic monomers. Typically, at least about
80% of the aliphatic unsaturation and about 20% of the aromatic unsaturation of the
star-shaped polymer is reduced by hydrogenation.
[0054] Representative examples of patents which disclose such hydrogenated polymers or interpolymers
include U.S. Patent Nos. 3,312,621; 3,318,813; 3,630,905; 3,668,125; 3,763,044; 3,795,615;
3,835,053; 3,838,049; 3,965,019; 4,358,565; and 4,557,849, the disclosures of which
are herein incorporated by reference.
[0055] The polymer may be degraded in molecular weight, for example by mastication, extrusion,
oxidation or thermal degradation, and it may be oxidized and contain oxygen. Also
included are derivatized polymers such as post-grafted interpolymers of ethylene-propylene
with an active monomer such as maleic anhydride which may be further reacted with
an alcohol, of amine, e.g., an alkylene polyamine or hydroxy amine, e.g., see U.S.
Patent Nos. 4,089,794; 4,160,739; 4,137,185; or copolymers of ethylene and propylene
reacted or grafted with nitrogen compounds such as shown in U.S. Patent Nos. 4,068,056;
4,068,058; 4,146,489; and 4,149,984.
[0056] Suitable hydrocarbon polymers are ethylene interpolymers containing from 15 to 90
wt. % ethylene, preferably 30 to 80 wt. % of ethylene and 10 to 85 wt. %, preferably
20 to 70 wt. % of one or more C₃ to C₈, alpha-olefins. While not essential, such interpolymers
preferably have a degree of crystallinity of less than 10 wt. %, as determined by
X-ray and differential scanning calorimetry. Copolymers of ethylene and propylene
are most preferred. Other alpha-olefins suitable in place of propylene to form the
copolymer, or to be used in combination with ethylene and propylene, to form a terpolymer,
tetrapolymer, etc., include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc.;
also branched chain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene,
5-methylpentene-1, 4,4-dimethyl-1-pentene, and 6-methyl-heptene-1, etc., and mixtures
thereof.
[0057] Terpolymers, tetrapolymers, etc., of ethylene, said C₃₋₈ alpha-olefin, and a non-conjugated
diolefin or mixtures of such diolefins may also be used. The amount of the non-conjugated
diolefin generally ranges from about 0.5 to 20 mole percent, preferably from about
1 to about 7 mole percent, based on the total amount of ethylene and alpha-olefin
present.
[0058] The second additive or component compositions 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 second additive composition, for instance, is soluble or stably dispersible in
oil to an extent sufficient to exert its intended effect in the environment in which
the oil is employed. Moreover, the additional incorporation of other additives may
also permit incorporation of higher levels of a particular first additive composition
hereof, if desired.
[0059] The lubricating oil compositions of the present invention contain an amount of said
second additive or component composition which is effective to improve the viscometric
properties, particularly viscosity index of the lubricating oil composition, e.g.,
a viscosity index improving effective amount. Generally, this effective amount may
vary somewhat depending upon the particular type of oil. Accordingly, while any effective
amount of the second additive composition can be incorporated into the final, e.g.,
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 second
additive composition of typically from about 0.01 to about 10, preferably from about
0.05 to about 5, and more preferably from about 0.1 to 2.5 (most preferably to 3.0)
wt. percent, based on the weight of said lubricating composition.
[0060] The additive compositions 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. Such blending
can occur at elevated temperatures. Alternatively, the additive compositions may be
blended with a base oil to form a concentrate, and the concentrate then blended with
lubricating oil base stock to obtain the final composition. Such concentrates will
typically contain the first additive composition in amounts of from about 0.5 to about
6, preferably from about 0.5 to about 5 percent by weight, based on the concentrate
weight, and the second additive composition in amounts of from about 0.5 to about
20, preferably from about 0.5 to about 12 percent by weight, based on the concentrate
weight.
[0061] It is to be noted that the amounts of the additive compositions of this invention
present in the fully formulated oil compositions or concentrates are on an active
ingredient basis (a.i.).
[0062] The lubricating oil base stock for the additive compositions of the present invention
typically is adapted to perform a selected function by the incorporation of other
additives therein to form lubricating oil compositions designated as formulations.
[0063] Representative other additives typically present in such formulations include corrosion
inhibitors, oxidation inhibitors, friction modifiers, dispersants, anti-foaming agents,
anti-wear agents, detergents, rust inhibitors and the like.
[0064] 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 phosphosulfurized 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 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. percent of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature
in the range of 150° to 600°F. Neutralization of the phosphosulfurized hydrocarbon
may be effected in the manner taught in U.S. Patent No. 1,969,324.
[0065] Oxidation inhibitors 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 alkyl phenolthioesters having preferably
C₅ to C₁₂ alkyl side chains, e.g., calcium nonylphenol sulfide, barium t-octylphenyl
sulfide, dioctylphenylamine, phenylalpha-naphthylamine, phosphosulfurized or sulfurized
hydrocarbons, etc.
[0066] Friction modifiers serve to impart the proper friction characteristics to lubricating
oil compositions such as automatic transmission fluids.
[0067] Representative examples of suitable friction modifiers are found in U.S. Patent No.
3,933,659 which discloses fatty acid esters and amides; U.S. Patent No. 4,176,074
which describes molybdenum complexes of polyisobutenyl 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
No. 3,778,375 which discloses reaction products of a phosphonate with an oleamide;
U.S. Patent No. 3,852,205 which discloses 5-carboxyalkylene hydrocarbyl succinimide,
S-carboxyalkylene hydrocarbyl succinamic acid and mixtures thereof; U.S. Patent No.
3,879,306 which discloses N-(hydroxyalkyl)alkenyl-succinamic acids or succinimides;
U.S. Patent No. 3,932,290 which discloses reaction products 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 thiobisalkanols such as described in U.S. Patent
No. 4,344,853.
[0068] 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 succinates,
the reaction product of oil-soluble polyisobutylene succinic anhydride with ethylene
amines such as tetraethylene pentamine and borated salts thereof.
[0069] Foam control can be provided by an antifoamant of the polysiloxane type, e.g., silicone
oil and polydimethyl siloxane.
[0070] Anti-wear agents, as their name implies, reduce wear of metal parts. Representatives
of conventional anti-wear agents are zinc dialkyldithiophosphate and zinc diaryldithiosphate.
[0071] 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 salts,
such as highly basic alkaline earth metal sulfonates (especially Ca and Mg salts)
are frequently used as detergents. Representative examples of such materials, and
their methods of preparation, are found in EP-A-208560, the disclosure of which is
hereby incorporated by reference.
[0072] 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.
[0073] Compositions when containing these conventional additives are typically blended into
the base oil in amounts which are effective to provide their normal attendant function.
Representative effective amounts of such additives are illustrated as follows:
|
% Active Ingredient By |
Additive |
Volume |
Weight |
Corrosion Inhibitor |
0.01-1 |
0.01-1.5 |
Oxidation Inhibitor |
0.01-1 |
0.01-1.5 |
Dispersant |
0.1-7 |
0.1-8 |
Anti-Foaming Agents |
0.001-0.1 |
0.001-0.15 |
Anti-Wear Agents |
0.001-1 |
0.001-1.5 |
Friction Modifiers |
0.01-1 |
0.01-1.5 |
Detergent/Rust Inhibitors |
0.01-2.5 |
0.01-3 |
Mineral Oil Base |
Balance |
Balance |
[0074] When other additives are employed, it may be desirable, although not necessary, to
prepare additive concentrates comprising concentrated solutions or dispersions of
the dual additive composition (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-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 first
and second additive compositions of the instant invention 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 additive composition 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.
[0075] The final formulations may employ typically about 10 wt. % of the additive-package
with the remainder being base oil.
[0076] All of said weight and volume 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.
[0077] Neither the oleaginous compositions nor the additive concentrates of the instant
invention contain, i. e., are free of, the second component lubricating oil flow improvers
described in EP-A-296714. These second component lubricating oil flow improvers are
comprised of:
(i) polymers of ethylenically unsaturated dicarboxylic acids or their anhydrides having
the carboxyl or anhydride groups located on vicinal carbons and having 4 to 10 carbons
in the unesterified monomer molecule, esterified with a mixture of C₁ to C₂₀ aliphatic
alcohols, preferably mixtures of alcohols in the C₄ to C₂₀ average carbon number range,
more preferably in the C₈ to C₁₈ carbon range;
(ii) interpolymers of (a) ethylenically unsaturated dicarboxylic acids or their anhydrides
having the carboxyl or anhydride groups located on vicinal carbons and having 4 to
10 carbons in the unesterified monomer molecule, esterified with a mixture of C₁ to
C₂₀ aliphatic alcohols, preferably mixtures of alcohols in the C₄ to C₂₀ average carbon
number range, more preferably in the C₈ to C₁₈ carbon range, and (b) vinyl esters,
alpha-olefins or styrene;
(iii) polymers of unsaturated monoesters, preferably polymers of long side chain unsaturated
mono- esters, and interpolymers of long and short side chain unsaturated monoesters.
The unsaturated esters are generally acrylate or 2-alkylacrylate mono-esters represented
by the formula:
wherein R₂ is hydrogen or a C₁ to C₅ alkyl group; and R₃ is a COOR₄ group wherein
R₄ is a C₁ to C₂₀, preferably a C₁₀ to C₁₈ alkyl group. A 2-alkylacrylate is one wherein
R₂ is alkyl. The hydrocarbyl groups constituting R₄ represent the hydrocarbyl residues
of mixtures of alcohols from which the same are prepared, which alcohols are preferably
saturated, although some degree of unsaturation is permissible when mixtures of alcohols
are employed, e.g., less than about 2 mole % of the alcohols in the mixture can be
unsaturated. Straight chain or lightly branched alcohols are preferred over highly
branched alcohols. The mixture of alcohols employed are those containing from C₁ to
about C₂₀ carbons which can be employed in such proportions that the average number
of carbons in the alcohol residue of the monomer molecule is preferably between about
10 and about 18. Furthermore, it is preferred that at least 60 mole %, most preferably
at least 80 mole % of the alcohols present in such mixture contain between 10 and
18 carbon atoms.
[0078] Illustrative non-limiting examples of (i) are polymers of dialkyl fumarates wherein
the fumarates are esterified with mixtures of C₆ through C₂₀ alcohols. An illustrative
non-limiting example of (ii) are interpolymers of dialkyl fumarates and vinyl esters,
preferably vinyl acetate, in which the fumarates are esterified with mixtures of C₆
through C₂₀ alcohols.
[0079] The following examples are given as specific illustrations of the claimed invention.
It should be understood, however, that the invention is not limited to the specific
details set forth in the examples. All parts and percentages in the examples, as well
as in the remainder of the specification, are by weight unless otherwise specified.
[0080] The following Comparative Examples fall outside the scope of the instant invention
and are presented for comparative purposes only.
COMPARATIVE EXAMPLE 1
[0081] A fully formulated 15W-40 lubricating base oil (designated Base Oil A) was prepared
containing mineral oil base stock oil (i.e., a mixture of 150N and 750N); no lubricating
oil flow improver (LOFI); a conventional detergent/inhibitor package containing ashless
dispersant, anti-oxidant, anti-wear additive, and overbased sulfonate; and 0.85 wt.
% (a.i.) of a V.I. improver comprised of ethylene-propylene copolymer having a Thickening
Efficiency of about 2.0, a ratio of weight average molecular weight to number average
molecular weight greater than 2, and an ethylene content of about 48 wt.
COMPARATIVE EXAMPLE 2
[0082] Comparative Example 1 was repeated except that the base oil contained 0.19 wt. %
(a.i.) of lubricating oil flow improver composition falling outside the scope of the
instant invention - LOFI B (di-C₁₀ alkyl fumarate-vinyl acetate copolymer wherein
the fumarate was derived from a C₁₀ alkanol and the fumarate: vinyl acetate mole ratio
employed in the synthesis of said LOFI B composition was 1:0.8). With the exception
of the presence of LOFI B, the types and amounts of other additives were the same
as in Comparative Example 1.
COMPARATIVE EXAMPLE 3
[0083] Comparative Example 2 was repeated except that the lubricating oil flow improver,
LOFI B, of Comparative Example 2 was replaced with 0.19 wt. % (a.i.) of another lubricating
oil flow improver falling outside the scope of the instant invention - LOFI C (di-C₁₂
alkyl fumaratevinyl acetate copolymer wherein the fumarate: vinyl acetate mole ratio
employed in the synthesis of LOFI C composition was 1:0.8). With the exception of
the lubricating oil flow improver, the types and amounts of other additives were the
same as in Comparative Example 2.
COMPARATIVE EXAMPLE 4
[0084] Comparative Example 2 was repeated except that the lubricating oil flow improver,
LOFI B, of Comparative Example 2 was replaced with 0.19 wt. % (a.i.) of another lubricating
oil flow improver falling outside the scope of the instant invention - LOFI D (di-C₁₆
alkyl fumaratevinyl acetate copolymer wherein the fumarate: vinyl acetate mole ratio
employed in the synthesis of said LOFI D composition was 1:0.8). With the exception
of the lubricating oil flow improver, the types and amounts of other additives were
the same as in Comparative Example 2.
COMPARATIVE EXAMPLE 5
[0085] Comparative Example 2 was repeated except that the lubricating oil flow improver,
LOFI B, of Comparative Example 2 was replaced with 0.19 wt. % (a.i.) of another lubricating
oil flow improver falling outside the scope of the instant invention - LOFI E (di-C₁₈
alkyl fumaratevinyl acetate copolymer wherein the fumarate: vinyl acetate mole ratio
employed in the synthesis of said LOFI E composition was 1:0.8). With the exception
of the lubricating oil flow improver, the types and amounts of other additives were
the same as in Comparative Example 2.
[0086] The following Examples illustrate the compositions of the instant invention.
EXAMPLE 6
[0087] A fully formulated 15W-40 lubricating base oil (designated Base Oil A) was prepared
containing mineral oil base stock oil (i.e., a mixture of 150N and 750N); about 0.19
wt. % (a.i.) of first additive composition of the instant invention - LOFI A (di-C₁₄
alkyl fumarate - vinyl acetate copolymer wherein the di-alky fumarate was derived
from C₁₄ alcohol and wherein the fumarate: vinyl acetate mole ratio employed in the
synthesis of said first additive composition was 1:0.8); about 0.85 wt. % (a.i.) of
the second additive composition comprised of V.I. improver comprised of ethylene-propylene
copolymer having a Thickening Efficiency of about 2.0, a ratio of weight average molecular
weight to number average molecular weight greater than 2, and an ethylene content
of about 48 wt. %; and a conventional detergent/inhibitor package containing ashless
dispersant, anti-oxidant, anti-wear additive, and overbased sulfonate.
[0088] Thickening Efficiency (T.E.) is defined as the ratio of the weight percent of a polyisobutylene
(sold as an oil solution by Exxon Chemical Co. as Paratone N), having a Staudinger
Molecular Weight of 20,000, required to thicken a solvent-extracted neutral mineral
lubricating oil, having a viscosity of 150 SUS at 37.8°C, a viscosity index of 105
and an ASTM pour point of 0°F, (Solvent 150 Neutral) to a viscosity of 12.4 centistokes
at 98.9°C, to the weight percent of a test copolymer required to thicken the same
oil to the same viscosity at the same temperature. T.E. is related to M
n and is a convenient, useful measurement for formulation of lubricating oils of various
grades.
EXAMPLE 7
[0089] Example 6 was repeated, except that a different 15W-40 mineral oil base stock was
employed. The base oil, fully formulated in accordance with Example 6, was designated
Base Oil B and contained the same types and amounts of additives as Base Oil A of
Example 6.
EXAMPLE 8
[0090] Example 6 was repeated except that a different 15W-40 mineral oil base stock was
employed. The base oil, fully formulated in accordance with Example 6, was designated
Base Oil C and contained the same types and amounts of additives as Base Oil A of
Example 6.
EXAMPLE 9
[0091] Example 6 was repeated except that a different 15W-40 mineral oil base stock was
employed. The base oil, fully formulated in accordance with Example 6, was designated
Base Oil D, and contained the same types and amounts of additives as Base Oil A of
Example 6.
EXAMPLE 10
[0092] Example 6 was repeated, except that a different 15W-40 mineral oil base stock was
employed. The base oil, fully formulated in accordance with Example 6, was designated
Base Oil E and contained the same types and amounts of additives as Base Oil A of
Example 6.
EXAMPLE 11
[0093] Example 6 was repeated, except that a different 15W-40 mineral oil base stock was
employed. The base oil, fully formulated in accordance with Example 6, was designated
Base Oil F and contained the same types and amounts of additives as Base Oil A of
Example 6.
EXAMPLE 12
[0094] Example 6 was repeated, except that a different 15W-40 mineral oil base stock was
employed. The base oil, fully formulated in accordance with Example 6, was designated
Base Oil G and contained the same types and amounts of additives as Base Oil A of
Example 6.
[0095] The flow properties of Comparative Examples 1-5 and of Examples 6-12 were tested
by the Mini Rotory Viscometer (MRV) procedure, and the results are summarized in TABLE
I. The analysis of the flow properties was conducted by testing the lubricating oil
formulations in a Mini Rotory Viscometer after subjecting each sample to a temperature
profile controlled in accordance with ASTM D4684 over about a 40 to 44 hour cooling
cycle. More specifically, this test is used by the SAE (J300 Specification-JUN87)
for determining the low temperature pumpability of a crankcase oil. In the test procedure
itself, the temperature is gradually lowered to -20°C, and then at that temperature
the yield stress (YS) is measured in pascals, and the apparent viscosity (VIS) is
measured in pascal seconds. The latter is required because this is a two-phase system,
so that a true viscosity measurement cannot be made. Thus, in accordance with SAE
requirements for 15W-40 oils, the target values of less than 35 pascals (YS) and not
greater than 300 pascal seconds (VIS) are considered acceptable in order to provide
a pumpable composition at -20°C, i.e., to maintain fluidity. For purposes of the instant
application a sample is considered to "fail" if either the YS is greater than 35 pascals
or the viscosity is greater than 300 pascal seconds.
[0096] As illustrated by the data in TABLE I, the combination of the first and second additive
compositions of the present invention provide lube oil formulations (Examples 6-12)
which meet, with the exception of the composition of Example 9, the target for SAE
15W-40 oil with a variety of different base oils. As discussed hereinafore, different
types of oils may generally require different amounts of first and/or second additives
of the instant invention, i.e., lubricating oil flow improvers and viscosity index
improvers or modifiers. Thus, while the amounts of the instant additives utilized
in the compositions of Examples 6-12 were effective in improving the low temperature
flow properties and viscometric properties of oils A-C and E-G, they were not adequate
to improve the viscometric properties of oil D (Example 9) sufficiently to meet the
SAE requirements for 15W-40 oil. In contrast, using lubricating oil flow improvers
other than those of the instant invention (Comparative Examples 2-8), or using no
lubricating oil flow improvers at all (Comparative Example 1) results in lube oil
formulations which fail to meet the target for SAE 15W-40 oil. It is to be noted that
LOFIs B-E of Comparative Examples 2-5 differ from LOFI A of Examples 6-12 in that
the di-alkyl fumarate is derived from an alcohol different from the C₁₄ alcohol of
LOFI A.
[0097] Although the invention herein has been described with reference to particular embodiments,
it is to be understood that these embodiments are merely illustrative of the principles
and applications of the present invention. It is therefore to be understood that numerous
modifications may be made to the illustrative embodiments and that other arrangements
may be devised without departing from the spirit and scope of the present invention
as defined by the appended claims.