Note: Descriptions are shown in the official language in which they were submitted.
CA 02189208 1999-06-15
27088-02 (CIA
Title: ANTTWEAR ENIiANCING COMPOSITION FOR LUBRICANTS
AND :FUNCTIONAL FLUIDS
Technical Field_
This invention relates to additive compositions that are useful for enhancing
the
antiwear properties of lubricants and functional fluids, especially automatic
transmission fluids.
Background of the Invention
~s is a contunuing demand in the automotive and truck markets for automatic
transmissions that can operate under more severe conditions and for longer
periods of
time than was previously acceptable. The automatic transmissions that meet
these
standards require improved automatic transmission fluids that are
characterized by
enhanced antiwear properties. The present invention fulfills this need.
Summary of the Invention
This invention relates to a composition, comprising: (A) a boron-containing
overbased material; I;B) a phosphorus acid, ester or derivative thereof; and
(C) a
borated epoxide or t~orated fatty acid ester of glycerol. In one embodiment,
the
inventive composition. further comprises (D) a thiocarbamate. These
compositions are
u~~l in providing lubricants and functional fluids, particularly automatic
transmission
fluids, with enhanced antiwear properties. In one embodiment these
compositions also
provide such lubricants and functional fluids with enhanced extreme-pressure
and/or
friction-modifying properties.
Description of the Preferred Embodiments
As used in this specification and in the appended claims, the term
"hydrocarbyl" denotes a group having a carbon atom directly attached to the
remainder
of the molecule and having a hydrocarbon or predominantly hydrocarbon
character
within the context of this invention. Such groups include the following:
1
218920
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(1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or allo~yl),
alicyclic
(e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatio- and alicyclic-
substituted
aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like,
as well as
cyclic groups wherean the ring is completed through another portion of the
molecule
(that is, any two indic~te<i substituents may together form an alicyclic
group). Such
groups are lrnown to those sin the art. Examples include methyl, ethyl, octyl,
decyl, octadecyl, cyclohexyl, phenyl, etc.
(2) Substituted hydrocarbon groups; that is, groups containing
non-hydrocarbon subst~ts which, in the context of this invention, do not alter
the
predominantly hydrocarbon c~arac~ of the group. Those sla'lled in the art will
be
aware of suitable substituents. Examples include halo, hydroxy, vitro, cyano,
alkoxy,
aryl, etc.
C3) o groups; that is, groups which, while predominantly hydrocarbon
in character within tile context of this invention, contain atoms other than
carbon in a
chain or ring o~wise composed of carbon atoms. Suitable hetero atoms will be
apparent to those skilled in the art and include, for example, nitrogen,
oxygen and
sulfur.
In geneaal, no more than about three substituents or het~o atoms, and
preferably no more than one, will be preset for each 10 carbon atoms in the
hydmcar
byl group.
Teams such as "alkyl-based", "aryl~asad", and the like have meanings
analogous to the above with respect to alkyl groups, aryl groups and the like.
The teen "hydrocarbon-based" has the same meaning and can be used
interchangeably with the terrri hydrocarbyl when referring to molecular groups
having
a carbon atom attached directly to the nnmainder of a molecule.
The germ "lower" as used herein in conjunction with farms such as
hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is int~ded to desctbe such
groups
which contain a total of up to 7 carbon atoms.
The term "oil-soluble" refeas to a material that is soluble in mineral. oil to
the
extent of at least about one gram per liter at 25°C.
1
218208
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(A) Boron-Containing Overbased Material.
Overbased products are metal salts or complexes characterized by a metal
content in excess of that which would be present according to the
stoichiometry of the
metal and the particular acidic organic compound read with the metal, e.g., a
sulfonic acid. The term "metal ratio" is used herein to designate the ratio of
the total
chemical equivalents of the metal in the ova material (e.g., a metal sulfonate
or
carboxylate) to the chemical equivalents of the metal in the product which
would be
expected to result in the reaction between the organic material to be
overbased (e.g.,
sulfonic or carboxylic acid) and the metal-containing rea~ant (e.g., calcium
hydroxide,
barium oxide, etc.) according to the Irnown cheanical reiuxivity and
stoichiometry of
the two rea~nts.
The boron-containing overbased material (A) of this invention typically has a
metal ratio in excess of 1 and generally up to about 40 or more. In one
embodim~t,
the metal ratio for component (A) is from an excess of 1 up to about 35, and
in one
embodiment from an excess of 1 up to about 30. The metal ratio generally
ranges
from about 1.1 or about 1.5 to about 40, and in ~e embodiment about 1.1 or
about
1.5 to about 35, and in one embodiment about 1.1 or about 1.5 to about 30, and
in one
embodiment about 1.1 or about 1.5 to about 26. In one embodiment the meal
ratio is
from about 1.5 to about 30, and in one embodim~t about 6 to about 30, and in
one
embodiment about 10 to about 30, and in one embodiment about 15 to about 30.
In
one embodiment, the meal ratio is from about 20 to about 30. Here, as well as
throughout the specification, the range and ratio limits may be combined.
In one embodiment, the borated ovesbased material (A) is prepared by first
Preparing an overbased material then contacting that overbased material with
at least
one boron compound. The overbased material is prepared by contacting a reason
mixture comprising at least one organic material to be overbased, a reaction
medium
consisting essentially of at least one inert, organic solvent/diluent for said
organic
material to be overbased, a stoichiometric excess of at least one metal base
and at least
one promoter, with at least one acidic material. Methods for preparing the
overbased
materials as well as an extremely diverse group of overbased materials are
well Irnown
CA 02189208 1999-06-15
-4-
in the prior art and are disclosed, for example in the following U.S. patent
3,492,231.
The organic; material to be overbased is generally at Ieast one cuboxylic
acid,
sulfur-containing <~cid, phosphorus-containing aad, hydroxyammatic compound,
precursor of any of the foregoing compounds, or mixture of two or more of any
of the
foregoing compounds or precursors.
u~ AGds
The carboxylic acids useful as the organic ma~ial to be overbased may be
aliphatic or aznmatic, mono- or polycarboxylic acid or acid~roducing
compounds.
Throughout this spcxificabion and in the appended claims, any reference to
ca~oxylic
acids is intended to include the acid producing derivatives thereof such as
anhydrides,
esters, (lower, e.g. Cl~, alkyl esters), aryl halides, lactones and mixriues
thereof
unless otherwise spEx~ffically stated.
These carboxylic acids can have at least about 8, or at least about 12 carbon
atoms, or at least albut 16 carbon atoms, or at least about 20 carbon atoms,
or at least
about 30 carbon atoms, or at least about 50 carbon atoms. Generally, these
carboxylic
acids do not contain more than about 400 or about 500 carbon atoms per
molecule.
The monoc~rboxylic acids contemplated herein include and
unsaturated ;acids. The monocarboxylic acids include fatty acids having from
about 8 to about 30, or fiom about 10 to about 24 ca~fion atoms. F~camples of
such useful monocarboxylic acids include dodecxnoic acid, palmitic acid,
decanoic aciy, oleic acid, lauric acid, stearic acid, myristic acid, Iinoleic
acid,
linolenic acid, naphthenic acid, chlorostearic acid, tall oil acid, etc.
Anhydrides amd lower alkyl esters of these acids can also be used. N~ues of
two or more such agents can also be used. An extensive discussion of these
acids is found in Kirk-0thmer "Encyclopedia of Chemical Technology" Third
Edition, 19733, John Whey & Sons New York, pp. 814-871 .
The monocarboxylic acids include isoaliphatic acids, i.e., a;cids having one
or
more lower acyclic F~endant alkyl groups. Such acids often contain a principal
chain
2 o~2oa
_5-
having from about 14 to about 20 sat<uated, aliphatic carbon atoms and at
least one but
usually no more than about four pendant acyclic alkyl groups. The principal
chain of
the acid is exemplified by groups derived from tetradecane, pentadecane,
heRadecane,
heptadecane, octadecane, and ei~e. The pendant group is preferably a lower
alkyl
group such as methyl, ethyl, n propyl, isopropyl, n-butyl, isobutyl, tert-
butyl, n-hexyl,
or other groups having up to about 7 carbon atoms. The pendant group may also
be a
polar-substituted alkyl group such as chloromethyl, bromobutyl, methoxyethyl,
or the
like, but it preferably contains no more than one polar substituent per group.
Specific
examples of such isaaliphatic acids include 11-methyl-pentadecanoic acid,
3-ethyl-hexaderanoic acid, 6-methyl-octadecanoic acid, 16-methyl-odadecanoic
acid,
l5~thy1-heptxdecanoic acid, 3-chloromethyl-nonad~anoic acid,
7, 8,9,10-tetramethyl-octadecanoic acid, and 2,9,10-trimethyloctadecanoic
acid.
The isoaliphatic acids include mixt<ues of branch-chain acids prepared by the
isomerization of commercial fatty acids of, for example, about 16 to about 20
carbon
atoms. A useful method involves heating the fatty acid at a temperature above
about
250°C and a pressure between about 200 and 700 psi, distilling the
cxude isomeaized
acid, and hydrogenating the disttllate to produce a substantially saturated
isomeaized
acid. The isomerization can be promoted by a catalyst such as mineral clay,
diatomaceous earth, aluminum chloride, zinc chloride, ferric chloride, or some
other
Friedel-Crafts c~lyst. The oonoentration of the catalyst may be as low as
about
0.01 % , but more often from about 0.1 % to about 3 % by weight of the
isomerization
mixture. Water also promotes the isomerization and a small amount, from about
0.1 %
to about 5 % by weight, of water may thus be advantageously added to the
isomerization mixture. 1fie unsat<uated fatty acids from which the
isoaliphatic acids
may be derived include oleac acid, linoleic acid, linolenic acid, and
commercial fatty
acid mixtures such as tall oil acids.
In one embodim~t the carboxylic acid is at least one hydrocarbyl-substituted
carboxylic acid or anhydride. In one embodiment, die hydrocarbyl group has at
least
about 8 carbon atoms up to about 400, preferably at least about 12 to about
300, more
preferably at least about 16 to about 200 carbon atoms. In one embodiment, the
'~ 2189208
-6-
hydrocarbyl substituted carboxylic acid or anhydride is derived from the
reaction of an
w~riuated carboxylic reagent and a polyalkene. The unsa~uated carboxylic
reagent
includes mono, di , tri or tetracaiboxylic reagents. Specific examples of
useful mono-
basic unsaturated carboxylic acids are acrylic acid, methacrylic acid,
cinnamic acid,
S crotonic acid, 2 ph~ylpropenoic acid, and Iower alkyl esters thereof.
Exemplary
polybasic acids include malefic acid, malefic anhydride, fumaric acid,
mesaconic acid,
itaconic acid and citraconic acid. Genially, the unsaturated carboxylic neag~t
is
malefic anhydride, acid or lower ester, e.g. those containing less than eight
carbon
atoms.
14 The polyalinclude homopolymers and interpolymers of olefins having
from 2 to about 20 carbon atoms. The olefins include ethylene, Propylene, 1-
but~e,
isobutylene, I-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, i-
heptene,
1-octene, styrene, 1-none, 1-deoene, 1-iuideoene, 1-dodeoene, 1-trideoene,
1-tetradeceene, l~enta;deoene, 1-hexadene, 1-heptadeoene and 1-ocxadecene.
ITigh~
15 olefin mixt<ues such as olefins in the range of about 18 to about 24 carbon
atoms can
be used. The hydrorarbyl group, R, can be derived from at least one alpha-
olefin
fraction selecr~ from the group consisting of Cu.ia alpha-olefins, Clm6 alpha-
olefins,
Clø16 alpha-olefins, Cløl8 alpha-olefins and Clms alPha.~lefins. In one
embodiment,
R is an alkyl or an alkenyl group. Examples of polyalkenes include polybutene,
20 polyisobutylene, ethylene-propylene copolymer, polypropylene, and mixtures
of two or
more of any of these. Included in this group are those derived finm polybut~e
in
which at least about 50% of the total units derived from butenes is derived
from
isobutylene.
In one embodiment, the polyalkene is characterized by an Mn (number average
25 molecular weight) of at least about 200 or at least about 400. Generally,
the
polyalkene is characterized by having an Mn finm about 500 up to about 5000,
or
from about 700 up to about 3000, or from about 800 up to 2500, or from about
900 up
to about 2000. In another embodiment, Mn varies from about 500 up to about
1500,
or from about 700 up to about 1300, or from about 800 up to about 1200. In
another
30 embodiment, the polyalkenes have an Mn from about 1300 up to about 5000, or
from
CA 02189208 1999-06-15
_7_
about 1500 up to about 4500, or from about 1700 up to about 3000. In one
embodiment, the Fblyal~s have an Mw/Mn from about 1 to about 10, or from
about 1.5 to about :S, or from about 2.5 to about 4.
In another embodiment, the acylating agents may be prepay by rig one
or more of the ab~we described polyallcenes with an excess of maleac anhydride
to
provide substituted sua,~inic acylating agents wherein the number of succinic
groups for
each equivalent weight of substituent group, i.e., polyallaenyl group, is at
least 0.9.
The maximum number will generally not exceed 4.5. A suitable range is from
about
1.3 to 3.5 and or from about 1.5 to about 2.5 suaxnic groups per equivalent
weagllt of
substituent groups.
In one embodiment, the carboxylic acid is at least one substituted suocinic
acid
or anhydride, said substituted succanic acid or anhydride has a polybuteayl
group
characterized by an Mn value of about 1500 to about 2000 and an Mw/Mn value of
about 3 to about 4. These acids or anhydrides are characterized by the
presence within
their structure of ~~n aveaage of about 1.5 to about 2.5 succlnic groups for
each
equivalent weight of substituent groups. In another embodiment, the carboxylic
acid
or anhydrideis a polybutenyl suocinc anhydride wherein the polybutenyl group
has an
Mn value of about 1300 to about 1200; an Mw/Mn value of about 2 to about 3;
and is
characterized by the presence within their stru~u~e of an average of about 0.9
to about
1.2 succinic groups for each equivalent weight of substituent groups.
Hydmcarbyl-substituted carboxylic acids suitable for use as the organic
material
to be overbasad are described in detail in the following U.S. Patents: U.S.
Patents
3,219,666; and 4,234,435.
A useful group of carboxylic acids are the aromatic carboxylic acids. These
acids can be represented by the formula
Xi
II
(R).-(~') - C - X~i b (n
2. i 89208
wherein R is an aliphatic hydmcarbyl group of preferably-about 4 to about 400
carbon
atoms, a is a number in the range of zero to about 4, Ar is an aromatic group,
Xl and
X2 are independently sulfur or oxygen, and b is a number in the range of from
1 to
about 4, with the proviso that the sum of a and b does not exceed the number
of
unsatisfied valences of Ar. Preferably, R and a are such that there is an
average of at
least about 8 aliphatic carbon atoms provided by the R groups. The aromatic
gmups
Ar that are useful include the polyvalent aromatic gmups derived from benzene,
naphthalene, anthracene, phenanthrene, indene, fluorene, biphenyl, and the
like.
Generally, the Ar groups used herein are polyvalent nuclea derived from
beazene or
naphthal~e such as pheuyl~es and naphthylene, e.g., methylph~ylenes,
ethoxyphenylenes, nitrophenylenes, isopmpylphenylenes, hydroxyphenylenes,
merraptophenylenes, N,N-diethylaminophenylenes, chlor~ophenylenes, dipropoxy-
naphthylenes, taethylnaphthylenes, and similar tri-, tetra , pentavalent
nuclei thereof,
etc. These Ar groups may contain non~ydmcarbon substituents, for example, such
diverse substihients as lower alkoxy, lower alkyl m~apto, vitro, halo, alkyl
or alkenyl
groups of less than about 4 carbon atoms, hydroxy, memapto, and the lie.
F.xacnples
of the R groups include butyl, isobutyl, pentyl, octyl, ~ nonyl, dodecyl,
dooosyl,
tetzacontyl, 5-chlomhexyl, 4-ethoxypmtyl, 4-hexenyl, 3-cyclohexyloctyl,
4-~P-~°~Ph~Y'~ 2,3,5-tdrnethylhept~rl, 4~xhy15-methylodyl, and
substituents
derived from polymerized olefins such as polychlomprenes, polyethylenes,
PoIYP~PYl~es, polyisobutylenes, ethylenepropylene copolymers, chlorinated
olefin
polymers, oxidized ethylene-propylene copolymers, and the like.
A group of useful carboxylic acids are those of the formula
Xi
~ I
~c-x~,,
wherein R, Ar, Xl, X2, a and b are as defined in Formula I, X3 is oxygen or
sulfur,
and c is a number in the range of 1 to about 4, usually 1 to about 2, with the
proviso
CA 02189208 1999-06-15
-9-
that the sum of a, b and c does not exoead the unsatisfied-valences of Ar.
Within this
group are the carboxylic acids of the formula
(COOI~b
(OHM
wherein R is an aliphatic hydrocubyl group preferably containing from about 4
to
about 400 carbon atoms, a is a number in the range of from zero to about 4,
preferably
1 to about 3; b is a number in the range of 1 to about 4, preferably 1 to
about 2, c is a
number in the range of 1 to about 4, preferably 1 to about 2, and more
preferably 1;
with the proviso thax the sum of a, b and c does not exceed 6. Preferably, R
and a are
such that the acrd rnolecules contain ax least an average of about 12
aliphatic carbon
atoms in the aliphatic hydr~arbon substituents per acid molecule. Also useful
are the
aliphatic hydmru~~n-substituted salicylic acids wherein each aliphatic
hydrocarbon
substituent contains an average of at Ieast about 8 carbon atoms per
substituent and 1 to
3 substituents per molecule. Salts prepared from such salicylic acids wheaein
the
aliphatic hydrocarbcm substitue~rts are derived from polymerized olefins,
particularly
polymerized lower 1-mono-olefins such as polyethylene, polypropylene,
polyisobutylene, etlrylenelpropylene copolymers and the like and having
average
carbon contearts of about 30 to about 400 carbon atoms are particularly
useful. The
aromatic carboxylic acids corresponding to the above formulae are well known
or can
be prepared according to procedures known in the art. Carboxylic adds of the
type
illustrated by these l:ormulae and processes for preparing their neutral and
basic metal
salts are well lrnown and disclosed, for example, in U.S. Patents 2,197,832;
2,197,835; 2,252,6ti2; 2,252,664; 2,714,092; 3,410,798; and 3,595,791.
'' 2.189208
-lo-
Sulfur-Containing Acids
The sulfur-containing acids include the sulfonic, sulfamic, thiosulfonic,
sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosulfuric acids.
The sulfonic
acids include the mono- or polynuclear aromatic or cycloaliphatic compounds.
The
sulf°n~c adds and sulfonates can be represented for the most part by
the following
formulae:
~1s T-(s~~~'ta
or
(RZ-(S~~°Ma
In the above formulae, T is a cyclic nucleus such as, for example, b~zene,
naphthalene, anthraoene, pheaanthrene, diphenyl~e oxide, thianthrene,
phenothioxine,
diphenylene sulfide, phenothiazine, diphenyl oxide, Biphenyl sulfide,
diphenylamine,
cyclohexane, petroleum naphth~es, decahydronaphthalene, cyclopentane, etc.; Rl
is
an aliphatic group such as alkyl, allacnyl, allcoxy, aIkoxyalkyl,
carboallooxyallcyl, etc.;
a is at least 1, and Ri,+T contains a total of at least about 15 carbon atoms.
R2 is an
aliphatic hydrocarbyl group containing at least about 15 carbon atoms.
Faamples of R2
~ ~Yh ~Yh ~xY~y~ ~'boalkozyalkyl, etc. Specific examples of R2 are
groups derived from petrolatum, saturated and unsaturated paraffin wax, and
polyolefins, including polymeaized C.i, C3, C4, C5, C6, etc., olefins
containing from
about 15 to 7000 or more carbon atoms. The groups T, Rl, and R2 in the above
formulae can also contain other inorganic or organic substituents in addition
to those
enumerated above such as, for example, hydroxy, m~capto, halog~, nitm, amino,
nitroso, sulfide, disulfide, etc. M is hydrogen or a metal ration (e.g.,
alkali or allcaline
earth metal), and a, b, c and d are each at least 1.
The following oil soluble sulfonic acids are useful: mahogany sulfonic acids;
bright stock sulfonic acids; sulfonic acids deaived from lubricating oil
fiactions having
a Saybolt viscosity from about 100 seconds at 100°F to about 200
seconds at 210°F;
petrolatum sulfonic acids; mono- and poly-wax-substituted sulfonic and
polysulfonic
acids of, e.g., benzene, naphthalene, phenol, Biphenyl ether, naphthalene
disulfide,
diphenylamine, thiophene, alpha~hlomnaphthalene, etc.; other substituted
sulfonic
'' ?_.187208
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acids such as alkyl benzene sulfonic acids (where the alkyl group has at least
8 car-
bons), cetyiphenol mono-sulfide sulfonic acids, dicetyl thianthrene disulfonic
acids,
dilauryl beta naphthyl sulfonic acids, dicapryl nitronaphthal~e sulfonic
acids, and
alkaryl sulfonic acids such as dodecyl beazene "bottoms" sulfonic acids.
The latter are acids derived from benzene which has been alkylated with
propylene tetramers or isobutene trims to introduce l, 2, 3, or more branched-
chain
C12 substifuents on the b~zene ring. Dodecyl benzene bottoms, principally
miztures
of mono- and di-dodecyl b~z~,s, are available as by-products from the
manufa~ure
of household detergents. Similar products stained from alkylation bottoms
formed
during manufacture of linear alkyl sulfonates (LAS) are also useful. in
malting the
sulfonates used in this inv~tion.
Also included are aliphatic sulfonic acids such as paraffin wax sulfonic
acids,
undated paraffin wax sulfonic acids, hydrozy-substituted para~n wax sulfonic
acids, hexapropylene sulfonic adds, tetra amyl~e sulfonic acids, polyisobutene
sulfonic acids wherean the polyisobutene contains from 20 to 7000 or more
carbon
atoms, chlorn-substituted paraffin waz sulfonic acids, nitroparafhn wax
sulfonic acids,
etc.; cycloaliphatic sulfonic acids such as petroleum naphth~e sulfonic acids,
cetyl
cyclop~tyl sulfonic acids, lauryl cyclohearyl sulfonic acids, bis-(di-
isobutyl) cyclohezyl
sulfonic acids, mono- or poly wax substituted cyclohezyl sulfonic acids, etc.
With respect to the sulfonic acids or salts thereof described herein and in
the
appended claims, it is intended herein to employ the term "petroleum sulfonic
acids" or
°petroleum sulfonates" to cover all sulfonic acids or the salts thereof
derived from
petroleum products. A useful group of petroleum sulfonic acids are the
mahogany
sulfonic acids (so called because of thear reddish-brown color) obtained as a
by~r~oduct
from the manufacbue of petroleum white oils by a sulfuric acid process.
PhoSphOrus-Con aininø
The phosphorus-containing acids can be represented by the formula
2189208
-12-
3
Rl~l~a
P_X4H
R2~2
wherein Xi, X2, X3 and X4 are independently O, S or NR3 wh~~ein R3 is hydrogen
or
a hydrocarbyl group, preferably hydrogen or a lower alkyl group; a and b are
independently zero or one, and Ri and R2 are independently hydrogen or
hydmcarbyl
groups. These phosphorus~ontaining acids include the phosphorus- and sulfur-
oon-
taming acids. They include those acids wherein at least one X3 or X4 is
sulfur, and
more preferably both X3 and X4 are sulfur, at least one Xl or X2 is oxygen or
sulfur,
more preferably both X' and X2 are oxyg~, and a and b are each 1. ~xhues of
these
acids may be employed in aooordance with this invention. Rl and RZ are
independently
hY~°g~ °r hydmcarbyl groups that are preferably free from
acetylenic unsatiuation
and usually also from ethyl~ic un~adon. The total number of c~bon atoms in Rl
and R2 must be sufficient to render the compound soluble in the reaction
medium.
Generally this total is at least about 8 carbon atoms, and in one embodim~t at
least
about 12 carbon acorns, and in one embodiment at least about 16 carbon atoms,
and in
one embodiment at least about 20 carbon atoms. In one embodiment, Rl and R2
independ~tly have up to about 400 or about 500 carbon atoms. Each Rl and R2
can
be the same as the other, although mey may be different and either or both may
be
mixtures. Examples of useful Rl and RZ groups include t-butyl, isobutyl, amyl,
isooctyl, dacyl, dodecyl, eicosyl, dodec~yl, naphthyl, alkylphenyl,
alkylnaphthyl,
ph~Y~3'~ ~PhmY~3'1~ ~ylphenylalkyl, alkylnaphthylalkyl, and the like.
The phosphorus~ontaining acids can be at least one phosphate, phosphonate,
phosphinate or phosphine oxide. These pentavalent phosphorus derivatives can
be
represented by the formula
~- 2189208
-13-
Ry(O~ _
Rz-(O~ ~ P~
R3 -(Ok
wherein Rl, . RZ and R3 are independently hydrocarbyl groups, or hydrogen and
a, b
and c are independently zero or 1. The phosphorus-containing acid can be at
least one
phosphite, phosphonite, phosphinite or phosphine. These trivalent phosphorus
derivatives can be repres~ted by the formula
R -(O)
Rz-(Oh, P
R3 -(Ok
wherein Rl, R2 and R3 are independently hydrocarbyl groups, and a, b and c are
independently zerio or 1. The total number of carbon atoms in Rl, R2 and R3 in
each
of the above formulae must be sufficient to render the compound soluble in the
reaction medium. Geneaally, the total number of carbon atoms in RI, R2 and R3
is at
least about 8, and in one embodiment at least about 12, and in one embodiment
at least
about 16. There is no limit to the total number of carbon atoms in Rl, R2 and
R3 that
is required, but a practical upper limit is about 400 or about 500 carbon
atoms. In one
embodiment, Rl, R2 and R3 in each of the above formulae are independently
hydrocarbyl groups of preferably 1 to about 100 carbon atoms, or 1 to about 50
carbon
atoms, or 1 to about 30 carbon atoms, with the proviso that the total number
of
carbons is at least about 8. Fach Rl, R2 and R3 can be the same as the other,
although
~eY ~Y ~ ~~t. Examples of useful Rl, R2 and R3 groups include hydrogen, t
butyl, oisobutyl, amyl, isooctyl, decyl, dodecyl, eicosyl, 2-pentenyl,
dodeoenyl,
phenyl, naphthyl, alkylphenyl, alkylnaphthyl, pher~ylalkyl, naphthylalkyl,
alkylphenylalkyl, alkY~Ph~Y~YI~ ~d the like.
In another embodiment, the phosphorus acid is characterized by at least one
direct carbon-to-phosphorus linkage such as those prepared by the treatrnent
of an
olefin polymer, such as one or more of the above polyalkenes (e.g.,
polyisobut~e
21~920~
-14-
having a molecular weight of 1000) with a phosphorizing agent such as
phosphorus
trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus
trichloride
and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
Iivdroxyaromatic Compounds
The organic material to be overbased can be at least one
hydroxyaromatic compound represented by the formula: Ra Ar-(~,, , wheaean R is
an aliphatic hydrocarbyl group of generally about 4 to about 400 carbon atoms;
Ar is
an aromatic group; X is O, S, CH20 or CHzNRI, wherean RI is hydrog~ or a
hydrocarbyl group (preferably alkyl yr allaenyl) of generally 1 to about 30
carbon
atoms, and in one embodiment 1 to about 20 carbon atoms, and in one
eanbodimeut 1
to about 10 carbon atoms; a and b are independently numbers of at least one,
the sum
of a and b being in the range of two up to the number of displaceable
hydrogens on the
aromatic nucleus or nuclei of Ar. Generally, a and b are indep~dently numbers
in the
range of 1 to about 4, and in one embodiment 1 to about 2. R and a are such
that them
1 S is a sufficient number of aliphatic carbon atoms in the R groups to render
the
compound soluble in the reason medium. Generally, there is an average of at
least
about 8 aliphatic carbon atoms, and in one embodiment at least about 12 carbon
atoms,
provided by the R groups.
In one embodim~t, X is O and the fiuxfiionally-substituted aromatic compound
is a phenol. With such phenols, however, it is to be understood that the
aromatic
group Ar is not a limited benzene, as discussed below.
The R group is a hydrocatbyl group that is directly bonded to the aromatic
group Ar. R generally contains about 6 to about 80 carbon atoms, and in one
embodiment about 6 to about 30 carbon atoms, and in one embodiment about 8 to
about 25 carbon atoms, and advantageously about 8 to about 15 carbon atoms.
Examples of R groups include butyl, isobutyl, pentyl, oclyl, nonyl, dodecyl,
dodecosyl, tetracontyl, 5-chlorohexyl, 4~thoxypentyl, 4-hexenyl, 3-
cyclohexyloctyl,
4-(p~hlorophenyl)-octyl, 2,3,5-trimethylheptyl, 4-ethyl-5-methyloctyl, and
substituents
derived from polymerized olefins such as polychloroprenes, polyethylenes,
polypropylenes, polyisobutylenes, ethylene-propylene copolymers, chlorinated
olefin
218~2~8
-15-
polymers, oxidized ethylene-propYl~e copolymers, - PmPYlene tetramer and
tri(isobutene). In one embodiment, R is a hydrocarbyl group as defined above
for
caboxylic acids.
As will be appreaated from inspearon of the above formula, these compounds
contain at least one R group, as defined above, and at least one functional
group XH.
Each of the foregoing must be ato a carbon atom which is a part of an aromatic
nucleus in the Ar group. They need not, however, each be attached to the same
aromatic ring if mom than one aromatic nucleus is present in the Ar group.
It is to be undeastood that ~e aromatic group as represented by "Ar" in the
above formula, as well as elsewhea~e in other formulae in this specification
and in the
app~ded claims, can be mononuclear such as a ph~yl, a pyridyl, a thieayl, or
polynuclear. The polynuclear groups can be of the fused type wherein an
aromatic
nucleus is fused at two points to ano~er nucl~s such as found in naphthyl,
anthranyl,
azanaphthyl, etc. The polynuclear group can also be of the linked type wherein
at least
two nuclei (either mononuclear or poiynuclear) are linked through bridging
linkages to
each other. These bridging linkages can be chosen from the group consisting of
~bon-to-carbon single bonds, ether linkages, keto linkages, sulfide linkages,
polysulfide linkages of 2 to about 6 sulfur atoms, sulfinyl linkages, sulfonyl
linkages,
alkylene linkages, alkylid~e linkages, lower alkylene ether linkages, alkylene
keto
linkages, lower alkylene sulfur linkages, lower allrylene polysulfide linkages
of 2 to
about 6 carbon atoms, amino linkages, polyamino linkages and mixtures of such
dival-
ent bridging linkages. In certain insmnoes, more than one bridging linkage can
be
Present in Ar between two aromatic nuclei; for example, a fluor~e nucleus
having two
benzene nuclei linked by both a methylene linkage and a covalea~t bond. Such a
nucleus may be consid~ea~ed to have three nuclei but only two of them are
aromatic.
Normally, however, Ar will contain only carbon atoms in the aromatic nuclei
per se
(plus any alkyl or alkoxy substituent present).
The number of aromatic nuclei, fused, linked or both, in Ar can play a role in
determining the integer values of a and b in the above formula. For example,
when Ar
contains a single aromatic nucleus, the sum of a and b is from 2 to 6. When Ar
2 ~ ~~2oa
-16-
contains two aromatic nucl~, the sum of a and b is from -2 to 10. With a tri-
nuclear
Ar moiety, the sum of a and b is from 2 to 15. The value for the sum of a and
b is
limited by the fact that it cannot exceed the total number of displa~oeable
hydrogens on
the aromatic nucleus or nuclea of Ar.
In one embodiment, the organic material to be overbased is at least one phenol
represented by the formula
Oyy'b
v
l1~ c
wherein R is a hydmcarbyl group of about 4 to about 400 carbon atoms; R1 is a
lower
alkyl, lower alkoxyl, amino, aminomethyl, mercapto, amido, thioamido, vitro or
halo
group; a is a number in the range of 1 to about 3; b is 1 or 2; and c is 0 or
1. Usually
R is derived from a homo- or int~polymer of monoolefins having from 2 to about
20
carbon atoms and is in a position para to the -0H group. In one embodiment, R
is one
or more of the above polyalkene groups. Specific examples of the substituent R
are a
polypropylene group of about 60 too about 340 carbons, a
poly(ethylenelpropyl~e)
group of about 110 to about 260 carbons (equimolar monomer ratio), a
poly(isobutene)
group of about 70 to about 320 carbon atoms, and a poly(1-hexe~nell-ocxenell-
dame)
group of about 400 to about 750 carbons (equimolar monomer ratios).
Reaction Medium
The reaction medium used to prepare the overbased product (A) is a
substantially inert, organic solvent/diluea~t for the organic material to be
overbased.
Examples include the alkanes and haloalicanes of about 5 to about 18 carbons,
alkyl
ethos, alkanols, alkylene glycols, alkyl ethers of allrylene glycols and
polyalkyl~e
glycols, dibasic alkanoic acid diesters, silicate esters, and mixtures of
these. Specific
examples include pentane, hexane. octane_ cvl'.lnnPntanP r~vnlnt,AV",o
isopropylcyclohexane, cyclooctane, halobenzenes such as mono- and
polychlorobenzenes, mineral oils, isobutylether, methyl-n-amylether,
methoxybenzene,
2~'.'92~8
-17-
p-methoxytoluene, methanol, ethanol, propanol, isopropanol, hexanol, alkylene
glycols
such as ethylene glycol and propylene glycol, diethyl lcetone, methylbutyl
laetone,
dimethylformamide, dimethylacetamide, diisocxyl azelate, polyethyl~e glycols,
PoIYP~PYIene glycols, etc.
From the standpoint of availability, cost, and performance, the allcyl,
cycloalkyl, and aryl hydrocarbons represent a useful class of reaction
mediums. Liquid
petroleum fiactions represent another useful class. Included within these
classes are
benzenes and alkylated benzenes, cycloal>mnes and alkylatsd cycloalkanes,
cycloalkenes and alkylated cycloal>ornes such as found in naphthene_based
petroleum
fractions, and the alkanes such as found in the par~f n-based petroleum
fractions.
Petroleum ether, naphthas, mineral oils, Stoddard Solvent, toluene, xylene,
etc., and
mixtures thereof are examples of economical sources of suitable inert organic
liquids
which can function as the reaction medium. Particularly useful are those
containing at
least some mineral oil as a component of the reaction medium.
Meal Base
The metal base used in preparing the oveabased products is selected from the
group consisting of alkali metals, alkaline~arth metals, titanium, zirconium,
molybdenum, iron, copper, zinc, aluminum, mixttue of two or more thereof, or
basically reacring compounds thereof. The mdal can be an alkali metal,
alkaline-earth
metal, zinc, aluminum, or a mixdire of two or more thereof. Lithium, sodium,
Potassium, magae~um, calcium and barium are useful. The metal bases include
alkoxides, nitrites, carboxylates, phosphites, sulfites, hydrog~ sulfites,
carbonates,
hydrog~ carbonates, borates, hydroxides, oxides, alkoxides, and amides of one
or
more of the above metals. The nitrites, carboxylates, phosphites, alkoxides,
carbonates, borates, hydroxides and oxides are useful. The hydroxides, oxides,
alkoxides and carbonates are especially useful.
CA 02189208 1999-06-15
-18-
mo
The promoters, that is, the materials which permit the incorporation of the
excess metal into the overbased product, are also quite diverse and well
lrnown in the
art as evidenced by the cited patents. These materials must be less acidic
than the
acidic material usa3 in roiling the oveabased products. A particularly oowe
discussion of suitable promoters is found in U.S. Patents 2,777,874;
2,695,910; and
2,616,904. These iinclude the alcoholic and phenolic promoters which are
preferred.
The alcohol promoters include the alkanols of one to about 12 carbon atoms.
Examples
of the alcohols include methanol, ethanol, isopropanol, amyl alcohol,
cyclohexanol,
octanol, dodecanol" decanol, behenyl alcohol, ethylene glycol, diethylene
glycol,
triethylene glycol, monomethylether of ethylene glycol, trimethylene glycol,
hexamethylene glycol, glycerol, pentaerythritol, benzyl alcohol, phenylethyl
alcohol,
sorbitorl, nitropropanol, chloroethanol, aminoethanol, cinnamyl alcohol, allyl
alcohol,
and the like. Phenolic promoters include a variety of hydroxy-substituted
benzenes and
~phthalenes. A particularly useful class of phenols are the alkylated phenols,
such as
heptylphenol, octylphenol, nonlyphenol, dodecyl phenol, propylene tetramer
phenol, etc.
Mixtures of various promoters can be used.
Acidic Material
Suitable acidic materials are also disclosed in the above cited patents, for
example, U.S. Patent 2,616,904. Included within the lrnown group of useful
acidic
materials are c~rbamic acid, acetic acid, formic acid, boric acid,
trinitromethane, SCE,
C41, sources of said acids, and mixtures thereof. COi and SCE, and sources
thereof,
are useful. Usefrd sources of COi include urea, carbamates and ammonium
carbonates. Useful. sources of S02 include sulfurous acid, thiosulfuric acid
and
dithionous acid. CC~ is especially preferred.
Preparation of the Overbased Material
In one embodiment, the overbased materials are prepared by contacting a
mixture of the orgarnc material to be overbased, the reaction medium, the
metal base,
and the promoter, ~avith the acidic material. The tempera>xue at which the
acidic
..-- 2189208
-19-
material contacts the remainder of the reacrion mass depends to a large
measure upon
the promoter that is used. With a phenolic promoter, the temperature usually
ranges
from about 60°C to about 300°C, and often from about
100°C to about 200°C. When
an alcohol or m~tan is used as the promoter, the temperature usually does not
exceed the reflux teznpezxri~re of the reaction mixture and preferably does
not exceed
about 100°C. The exact nature of the resulting overbased mad is not
known.
However, it can be adequately deb for purposes of the present specification as
a
single phase homogeneous mixt<me of the reaction medium and (1) either a
metal.
complex formed from the metal base, the acidic mateaial, and the organic
material to
be overbased and/or (2) an amorphous metal salt formed from the reaction of
the acidic
material with the metal base and the organic material to be overbased. Thus,
if
mineral ofi is used as the reaction medium, p~sulfonic acid as the organic
material
which is ov~based, Ca(OH~ as the metal base, and carbon dioxide as the acidic
mateaiai, the resulting overbased mad ~n be described for purposes of this
1 S invention as an oil solution of either a metal containing complex of the
acidic material,
the metal base, and the petrosulfonic acid or as an oil solution of amorphous
calcium
carbonate and calcium petmsulfonate. Since ~e overbased materials are well
known
and as they are used merely as intermediates in the preparation of ~e boron-
containing
overbased rnateaials (A) employed herean, the exact nature of these materials
is not
critical to the present inv~tion.
Preparation of the Boron-Containing Overbased Materials
The boron-containing overbased mateaial (A) can be prepared by contacting at
least one overbased material with ~ l~ one boron compound. The boron compound
~ ~ b°~ °~de~ boron oxide hydrate, boron trioxide, boron
trifluoride, boron
tribromide, boron trichloride, boron acids such as boronic acid r.e., alkyl-
B(OH)2 or
aryl-B(OH~, boric acid ('~.e., H3B03), tetraboric acid ~.e., H2B40~),
metaboric acid
(i.e., HBO, boron anhydrides, and various esters of such boron acids. The use
of
complexes of boron irihalide with ethers, organic acids, inorganic acids, or
hydro
carbons is a convenient means of introducing the boron reac~nt into the
reaction
218~2Q~
-20.
The boron acid esters include especially mono-, di-, and tri-organic esters of
boric acid with alcohols or phenols such as, e.g., methanol, ethanol,
isopropanol,
cyclohexanol, cyclopentanol, 1-~odanol, 2-octanol,. ~yl alcohol, 2-butyl
cyclohex-
anol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol,
2,4-hexanediol, glycerol, triethylene glycol, tripropylene glycol, phenol,
naphthol,
p-butylphenol, o,p-diheptylpheaol, n-cyclohexylphenol, 2,2~is-(p-
hydroxyphenyl~
propane, o-chlorophenol, m-nitrophenol, 6-bmmooctanol, and 7 keto-decanoi.
Lower
alcohols, 1,2-glyools, and 1-3-glycols, i.e., those having less than about 8
carbon
atoms are especially useful for preparing the boric acid esters for the
purpose of this
invention.
Methods for preparing the esters of boron acid are lrnown and disclosed in the
~ (~~ ~ "c~ ~," pp. 959-1064, Vol. 56). Thus, one method involves
the reaction of boron tachloride with 3 moles of an alcohol or a phenol to
result in a
tri-organic borate. Another method involves the reaction of boric oxide with
an
alcohol or a phenol. Another method involves the direct esterification of
tetra boric
acid with 3 moles of an alcohol or a phenol. Still another method involves the
direct
esterification of boric acid with a glycol to form, e.g., a cyclic alkylene
borate.
The contacting of the overbased mat~iai with the boron compound can be
effected using smndard mixing techniques. The ratio of equivalents of the
boron
compound to equivalents of the overbasad material can range up to about 40:1
or
higher, and is typically in the range of about 0.05:1 to about 30:1, and is
often in the
range of about 0.2:1 to about 20:I. Equivalent ratios of about 0.5:1 to about
5:1, or
about 0.5:1 to about 2:1, and often about 1:1 can be used. For purposes of
this
invention, an equivalent of a boron compound is based upon the number of moles
of
boron in said compound. Thus, boric acid has an equivalent weight equal to its
molar
weight, while tetraboric acid has an equivalent weight equal to ona-fourth of
its molar
weight. An equivalent weight of an overbased material is based upon the number
of
equivalents of metal in said overbaseri material available to react with the
boron. An
equivalent of a metal is dependent upon its valence. Thus, one mole of a
monovalent
metal such as sodium provides one equivalent of the metal, whereas two moles
of a
21 ~9~i~8
21-
divalent metal such as calcium are inquired to provide one equivalent of such
metal.
This number can be measured using standard techniques (e.g., titration using
bromophenol blue as the indicator to measure total base number). Thus, an
overbased
material having one equivalent of metal available to react with the boron has
an
equivalent weight equal to its actual weight. An overbasad material having two
equivalents of metal available to react with the boron has an equivalent
weight equal to
one-half its actual weight.
The temperature can range from about room temperature up to the
decomposition tempeaa~ue of the rea~nts or desired products having the lowest
such
temperature, and is generally in the range of about 20°C to about
200°C, and in one
embodiment about 20°C to about 150°C, and in one embodiment
about 50°C to about
150°C, and in one embodiment about 80°C to about 120°C.
The contacting time is the time required to form the desired conc~tration of
metal borate (e.g., sodium borate) in the boron-containing oveabased material
(A).
This concentration can be measured using standard techniques (e.g.,
measurement of
the concentration of dissolved solids when the boron compound is a solid,
measurem~t of the water of reaction formed by the borating process, measurem~t
of
the displacement of acidic material , e.g., COi, from the overbased product
(A), etc.
Generally, the contacting time is from about 0.5 to about 50 hours, and often
is from
about 1 to about 25 hours, and in one embodiment about 1 to about 15 hours,
and in
one embodim~t about 4 to about 12 hours.
The following Example A illustrates the preparation of a boron-containing over-
based material (A) that is useful in accordance with the invention. Unless
otherwise
indicated in the examples as well as throughout the specification and the
appended
claims, all parts and percentages are by weight, all temperatures are in
degrees
centigrade, and all pressures are atmospheric.
Example A-1
Fart I:
A mixture of 1000 parts of alkyl benzene sulfonic acid in oil (24. 8 % oil),
771
parts of o-xylene, and 75.2 parts of polyisobutenyl (number average molecular
weight
2189208
-22-
= 950) suocinic anhydride is charged to a reaction vessel and the temperature
is
adjusted to 31.9°C. 87.3 parts magnesium oxide are added to the
mixture. 35.8 parts
of acetic acid are then added to the mixture. 31.4 parts of methanol and 59
parts of
water are added to the mixture. The mixture is carbonated, the temperature of
the
mixture being 34.7-40.2°C. 87.3 parts of magnesium oxide, 31.4 parts of
methanol
and 59 parts of water are added to the mixture, and the mixture is again
Carbonated.
87.3 parts of magnesium oxide, 31.4 parts of methanol and 59 parts of water
are again
added to the mixture, and the mixtiue is again carbonated. The total amount of
carbon
dioxide added is 232 parts. Methanol, o-xyl~e, and water are removed by
atmospheaic and vacuum flash stripping. The reaction mixture is cooled and
filtea~ed to
provide the de,9red overbased magnesium sulfonate having a metal ratio of 14.7
and a
diluent contest of 42~ by w~ght.
Part II:
A mixture of 5580 parts of the product from Part (n and 2790 parts of tolu~e
are charged to a r~ion vessel. A slow nitrogen purge is started. The mixture
is
stuTed and die t~pe~at<ue is adjusted to 45°C. 1395 parts of boric acid
are added to
the miztiu~e over a period of IO minutes. The mixture is heated from
45°C to 96°C
over a peaiod of 4.5 hours. The mixture is maintained at 80-96°C for 16
hours. The
mixture is heated from 80°C to 102°C over a period of 3 hours.
The mixtiu~e is the
heated from 102°C to 120°C over a peaiod of 5 hours. 310 parts
of water distillate are
removed. The toluene phase of the distillate is added back to the reaction
vessel. The
mixture is heated to 148°C ova a 5-hour period with full distivate
removal. 296 parts
of diatomaceous earth are added to the mixture and the mixture is filtered
over a two-
~Y period. The resulting product has a sulfur content of 1.29 qb by weaght, a
magnesium content of 8.28% by weaght, and a boron content of 4.66 by weight.
B) Phasnhorus Acid Fster or Derivative.
The lubricating compositions include at least one phosphorus acid, phosphorus
acid ester or phosphorus acid salt or derivatives thereof. The phosphorus
acids, esters,
salts or derivatives thereof include compounds selected from the group
consisting of
phosphorus acid esters or salts thereof, phosphites, phosphorus containing
amides,
CA 02189208 1999-06-15
phosphorus-containing carboxylic acids or esters, phosphorus containing ethers
and
mixtures thereof. lfncluded in this Section (B) are the phosphorus~ontaining
acids
listed above in Section (A).
The phosphorus acids include the phosphoric, phosphoric, phosphinic and
thiophosphoric acids including dithiophosphoric acid as well as the
monothiophosphor-
ic, thiophosphinic and thiophosphoric ands. Included in this group are the
phosphorus-containing ands desc~ed above under the subtitle 'Phosphorus
Containing Acids." Phosphosc aad is a preferred component of the compositions
of
this invention.
Eighty five peroeut phosphoric acid is the preferred compound for addition to
the fully formulated ATF package and is included at a level of about 0.01-0.3
weight
percent based on the weaght of the ATF.
The phosphorus acid esters can be prepared by reacting a phosphorus acid or
anhydride with an alcohol containing from 1 or about 3 carbon atoms up to
about 30,
1 S yr about 24, or about 12 carbon atoms. The phosphorus acid or anhydride is
generally
an inorganic phosphorus reagent such as phosphorus pentaoxide, phosphorus
trioxide,
phosphorus tetraoxide, phosphorus acid, phosphorus halide, or lower phosphorus
esters, and the like. Lower phosphorus acid esteas contain from 1 to about 7
carbon
atoms in each ester group. The phosphorus acid ester may be a mono, di- or
triphosphoric acid estea.
Alcohols used. to prepare the phosphorus acid esters include butyl, amyl,
hexyl,
octyl, oleyl, and cresol aloohols. Higher synthetic monohydric aloohols of the
type
formed by Oxo process (e.g., 2-ethylhexyl), the Aldol condensation, or by
organo
aluminum catalyzed oligomerizabion of alpha-olefins (especially ethylene),
followed by
oxidation and hydrolysis, also are useful. Examples of some preferred
monohydric
alcohols and alcohol mixtures include the commercially available "Alfol~
aYcohols
marketed by Continental Oil Corporation. Alfol 810 is a mixture of alcohols
containing primarily straight chain, primary aloohols having from 8 ' to 10
carbon
atoms. Alfol 12 is a mixture of alcohols containing mostly C12 fatty alcohols.
Alfol
1218 is a mixture of synthetic, primary, shaight-chain alcohols containing
primarily 12
CA 02189208 1999-06-15
,I"'"",
-24-
to 18 carbon atoms. The Alfol 20+ aloohols are mixt<u~es-of Cls-C~ primary
aloohols
having mostly, on an alcohol basis, Cm alcohols as determined by GLC
(~-~1~-~oaphY)~ The Alfol 22+ aloohols are Cls-C~ Primary aloohols
containing primarily, on an alcohol basis, C~ aloohols. These Alfol aloohols
can
contain a fairly large percentage (up to 40% by weight) of para~nic oompowrds
which
can be removed before the reaaron if deared.
Another example of a commerraally available alcohol mixriu~e is ~ 60 which
comprise',s about 75% by weight of a straight chain C~ primary alcohol, about
15% of
a Cio primary alcohol and about 8 % of Cl8 and Cu alcohols. Adol 320 comprises
predominantly oleyl alcohol. The Adol alcohols are marketed by Ashland
Chemical.
A of mixtures of monohydric fatty aloohols deaived from naturglly
ooauting t~iglYand ranging in chain length of from Cs to Cls are available
from
Pmctor & Gamble Company. These mixtures contain various amounts of fatty
aloohols containing mainly 12, 14, 16, or i8 carbon atoms. For example, CO-
1214 is
a fatty alcohol mixriu~e containing 0.5% of Clo alcohol, 66.0% of C12 alcohol,
26.0%
of C14 alcohol and 6.5% of C16 alcohol.
Another grcxip of commercially available mixtures include the "Neodol'~
products available from Shell Chemical Co. For example, Neodol 23 is a mixtiue
of
C12 ~d C13 ~hols; Neodol 25 is a mixture of C12 and Cu aloohols; and Neodol 45
is
a mixture of Cl~ to C~ linear aloohols. Neodol 91 is a mixture of Cg, Clo and
Cu
alcohols.
Fatty vicinal diols also are useful and these include those availabhe from
Ashland Oil under the general trade designation Adol 114 and Adol 158. The
former
is derived from a straight chain alpha ole5n fiaction of Cn-Ci4, and the
latter is
derived from a Cu-Cl$ fiction.
Examples of useful phosphorus acid esters include the phosphoric acid esters
prepared by reacting a phosphoric acid or anhydride with cresol alcohols. An
example
is tricresol phosphate.
In one ~nbodiment, the phosphorus acid ester is a monothiophosphoric acid
ester or a monothiophosphate. Monothiophosphates are pre~red by the region of
a
CA 02189208 1999-06-15
-25-
sulfur source and a hydrorubyl or aryl substituted phosphites. The sulfur
source may
be elemental sulfur;, a monosulfide, such as a sulfur coupled olefin or a
sulfur coupled
dithiophosphate. ):~emental sulfur is a prefeared sulfur sourre. The
preparation of
monothiophosphate;; is disclosed in U.S. Patent 4,755,311 and PCT Publication
WO
87/07638. A preferred monothiophosphate is triphenyl monothiophosphate.
Monothiophosphates may also be formed in the lubricant blend or functional
fluid by adding a hydrocarbyl or aryl phosphite to a lubricating composition
or
functional fluid conniving a sulfur source. The phosphate may react with the
sulfur
source under blending conditions ('Le., temperatures from about 30°C.
to about
100°C. or higher) to form the monothiophosphate.
In one embodiment, the phosphorus acid is a dithiophosphoric acid or
phosphorodithioic acid. The dithiophosphoric acid can be read with an e~OZide
or a
glycol to form an ir~te~mediate. The intermediate is then reacted with a
phosphorus
acid, anhydride, or :lower ester. The epoxide is generally an aliphatic
epoxide or a
styrene oxide. Examples of useful epoxides include ethylene oxide, propylene
oxide,
butene oxide, octene: oxide, dode~cane oxide, styrene oxide, etc. Propylene
oxide is
preferred. The glyoc~ls may be aliphatic glyools having from 1 to about i2,
preferably
about 2 to about 6,. more preferably 2 or 3 carbon atoms, or aromatic glycols.
Aliphatic glyools include e~ylene glycol, propylene glycol, triethylene glycol
and the
like. Aromatic glycols include hydroquinone, cate~hol, resorcinol, and the
IilGe.
These are din U.S. patent 3,197,405.
When the phosphorus acid esters are acidic, they may be read with an amine
compound or metallic; base to form the corresponding amine or metal salt. The
salts
may be formed separ,~tely and then the salt of the phosphorus acid ester is
added to the
lubricant or functional fluid composition. Alternatively, the salts may also
be formed
CA 02189208 1999-06-15
-26-
when the phosphorus acid ester is blended with other components to form the
lubricating composition. The phosphorus acid ester could then form salts with
basic
mateaials which am in the lubricant or functional fluid composition such as
basic
nitrogen containing compounds (e.g., carboxylic dispersants) and overbased ~.
The amine s;~lts of the phosphorus acid esters may be formed from ammonia, or
a primary, secondary or tertiary amine, or mixtures thereof. Useful amines
include
those amines disclosed in U.S. Patent 4,234,435 at Col. l, line 4, to Col. 27,
line 50.
The metal salts of the phosphorus acid esters are prepared by the reaction of
a
metal base with the ;phosphorus acid ester. The metal base may be in aay
oomrenient
form such as oxide, hydroxide, carbonate, sulfate, borate, or the line. The
metals of
the metal base include Group IA, IIA, IB through VI>B and VI>I metals (CAS
version
of the Periodic Table: of tile Elements). These metals include the alkali
metals, alkaline
earth metals and transition metals. In one embodiment, the metal is a Group
IIA meal
such as calcium or magnesium, Group IIB metal such as zinc, or a Group V~
metal
such as manganese. Preferably the metal is magnesium, calcium, manganese or
zinc,
more preferably mal~esium, calcium or zinc, more preferably magnesium or zux.
Specific examples of useful metal bases include those dabove under the
heading "Metal Base ".
The phosphorus acid ester can be a phosphite. In one embodiment, the
phosphite is a di- or trihydrocarbyl phosphite. Each hydrocarbyi group can
have from
1 to about 24 carbon atoms, or from 1 to about 18 carbon atoms, or from about
2 to
about 8 carbon atoms. Each hydrocarbyl group may be independently alkyl,
alkrnyl or
aryl. When the hydrncarbyl group is an aryl group, then it contains at least
about 6
carbon atoms; and in one embodiment about 6 to about 18 carbon atoms. Examples
of
~e ~yl or alkenyl gmups include propyl, butyl, hexyl, heptyl, octyl, oleyl,
linoleyl,
stearyl, etc. Eacamplex of aryl groups include phenyl, naphthyl, heptylphenol,
etc. In
one embodiment each hydrocarbyl group is independently propyl, butyl, pentyl,
hexyl,
heptyl, oleyl or phenyl, more preferably butyl, oleyl or phenyl. Phosphites
and their
preparation are knovm and many phosphites are available commercially. Useful
CA 02189208 1999-06-15
-27-
phosphites are dr'butylhydrogea phosphite (DBPH), trioleyl phosphite and
triphenyl
phosphite with DBPH being a preferred component.
In one embodiment, the phosphorus acid derivative is a phosphorus-containing
amide. The phosphorus~ontaining amides may be prepared by the reaction of a
phosphorus acid (e.g., a dithiophosphoric acid as described above) with an
unsaturated
amide. Examples of unsaturated amides include acrylamide, N,N methylene
bisacrylamide, metlaacrylamide, crotonamide, and the like. The reaction
product of
the phosphorus acidl with the unsaturated amide may be further reacted with
linking or
coupling compounds, such as formaldehyde or paraformaldehyde ,to form coupled
compounds. The plhosphorus-containing amides are known in the art and are
disclosed
in U.S. Patents 4"876,374, x,770,807 and 4,670,169 .
In one embodiment, the phosphorus acid ester is a phosphorus~ontaining
carboxylic ester. The phosphorus-containing carboxylic esters may be prepared
by
reaction of one of the above~iescribed phosphorus acids, such as a
dithiophosphoric
acid, and an unsatur,at~ed carboxylic acid or ester, such as a vinyl or allyl
acid or ester.
If the carboxylic edict is used, the ester may then be formed by subsequent
ruction
with an alcohol. _
The vinyl ester of a ~rboxylic acid may be represented by the formula
RCH=CH-0(O)CR~ wherein R is a hydrogen or hydmcarbyl group having from 1 to
about 30 carbon atoms, preferably hydrogen or a hydroc~rbyl group having 1 to
about
12, more preferably hydrogen, and Rr is a hydmrarbyl group having 1 to about
30
carbon atoms, or 1 to about 12, or 1 to about 8. Examples of vinyl esters
include
vinyl acetate, vinyl 2.-ethylhexanoate, vinyl butanoate, and vinyl crotonate.
In one embodiment, the unsahrrated carboxylic ester is an ester of an
unsaturated carboxylic acid, such as malefic, fumaric, acrylic, mettlacrylic,
itaconic,
citrioonic acids and the like. The ester can be represented by the formula RO-
(O)C-
HC=CH-C(O)OR v~rher~ein each R is independently a hydrocarbyl group having 1
to
about 18 carbon atoms, or 1 to about 12, or 1 to about 8 carbon atoms.
2189208
28-
Examples of unsaturated carboxylic esters that are useful include methyl-
~Y~~ ~Y~Y~~ 2~thylhexylacrylate, 2-hydroxyethylacrylate, ethyl_
methacrylate, 2-hydroxyethylmetha~crylate, 2-hydroxypropYlmethacrylate, 2_
hydroxypropylacryiate, ethylmaleate, butylmaleate and 2-ethylhexylmaleate. The
above Iist includes mono- as well as diesters of malefic, fumaric and
citraconic acids.
In one embodiment, the phosphorus acid is the region product of a
phosphorus acid and a vinyl ether. The vinyl ether is represented by the
formula R
CH2=CH-0RI wherein R is hydrogen or a hydroc~rbyl group having 1 to about 30,
preferably 1 to about 24, more preferably 1 to about 12 carbon atoms, and Rl
is a
hydmcarbyl group having 1 to about 30 carbon atoms, preferably 1 to about 24,
more
preferably 1 to about 12 carbon atoms. Examples of vinyl ethers include vinyl
methylether, vinyl propylether, vinyl 2-ethylhexylether and the li'he.
(C) Borated Enoxide or Borated Fatty Acid Ester of G~cerol and other
Fridaon Modifiers.
The borated epoxides are made by reacting at least one of boric acid or boron
trioxide with at least one epoxide having the formula
Ri \ / Rs
C j C
RZ ~ ~ ~ ~ Ra
wherein each of Rl, R2, R3 and R4 is hydrogen or an aliphatic radical, or any
two
thereof together with the epoxy carbon atom or atoms to which they are
attached form
a cyclic radical, said epoxide containing at least 8 carbon atoms. In one
embodiment
this reaction is conduc~eti in the presence of a minor amount of a heel of a
previously
obtained oil-soluble boron-containing composition prepared by reacting the
foregoing
reagents.
The boric acid that can be used can be any of the various forms of boric acid,
including metaboric acid (HBO, orthoboric acid (H3B03) and tetraboric acid
(HZB40.r). Boric acid and orthoboric acid are preferred.
2189208
29-
Each of the R groups in the above formula are most often hydrogen or an
aliphatic group with at least one beang an aliphatic group containing at least
6 carbon
atoms. The term "aliphatic group" includes aliphatic hydrocarbon groups (e.g.,
hexyl,
heptyl, octyl, decyl, dodecyl, tetradecyl, stearyl, hexenyl, oleyl),
preferably free from
acetylenic unsaturation; substituted aliphatic hydrocarbon groups including
substituents
such as hydroxy, ni>ro, c~rballcoxy, alkoxy and alkylthio (especially those
containing a
lower alkyl group; i.e., one containing 7 carbon atoms or less); and hetero
atom-
containing groups in which the heteno atoms may be, for example, oxygen,
nitrog~ or
sulfur. The aliphatic gmups are geneaally alkyl groups, and in one embodiment
those
containing from about 10 to about 20 carbon atoms. It is within the scope of
the
invention to use commercial mixtures of epoxides; for example, commercial
mixtures
of CIøis or Cløis epoxides and the like, wherein Ri is a mixture of alkyl
radicals
having two less carbon atoms than die epoxide.
In one embodim~t the borated epoxide (C) is a borated alpha-olefin epoxide
having about 10 to about 20 carbon atoms, and in one embodim~t about 14 to
about
18 carbon atoms.
Also within the scope of the invention is the use of epoxides in which any two
of the R groups together with the epoxy carbon atom or atoms to which they are
attached, form a cyclic group, which may be alicyclic or heterocyclic.
Examples
include n~utylcyclopentene oxide, n hexylcyclohex~e oxide, methyl~ecyclooctene
oxide and 2-methyl~~3-n-hexyltetcahydrofuran oxide.
The boratsd epoxides may be prepared by merely bleeding the boric acid or
boron trioxide and the epoxide and heating them at a temperature from about
80°C to
about 250°C, and in one embodiment fmm about 100°C to about
200°~, for a period
of time sufficient for ration to rake place. If desired, the reaction may be
effected in
the presence of a substantially inert, normally liquid organic diluent such as
toluene,
xylene, chlorobenzene, dimethylformamide or the like, but such diluents are
usually
unnecessary. During the reaction, water is frequently evolved and may be
removed by
distillation.
~- 2189208
-30-
The molar ratio of the boric acid or boron trioxide to the epoxide is
generally
between about 1:0.25 and about 1:4. Ratios between about 1:1 and about 1:3 are
useful.
In o~ embodiment it is advantageous to employ a catalytic amount of an
alkaline reagent to facilitate the reaction. Suitable allmline reagents
include inorganic
bases and basic salts such as sodium hydroxide, potassium hydroxide and sodium
~; ~ des such as sodium methoxide, potassium t-butoxide and
calcium edioxide; heterocyclic amines such as piperidine, morpholine and
pyridine;
and aliphatic amines such as n-butylamine, di-n-hexylamine and tri n-
butylamine.
Useful allmline reagents are the aliphatic and heterocyclic amines and
especially tertiary
amines.
The preparation of a borated epoxide useful in this inv~tion is illustrated by
the following example.
)~ramnle C-1
Part I:
A mixtin~e of 1500 parts (6.25 moles) of 1-hexade~ne oxide and 1 part of td-
n-butylamine is heated to 100-lI0°C under nitrogen, with stirring.
Boric acid, 193
parts (3.13 moles), is added incrementally over 15 minutes. Why boric acid
addition
is complete, the reaction mixture is heated to 185°C as water is
removed by
distillation. When water evolution ceases, the mixture is filtered while hot,
and the
filtrate is allowed to cool to a waxy solid melting at 60-65°C. This
solid is the
product; it contains 2.7% boron.
21 ~ 9 2 ~~~
-31-
Part II:
A blend of 193 parts (3.13 moles) of boric acid, 1 part of tri-n-butylamine
and
a "heel" comprising 402 parts of the product prepared as in Part I is heated
to 188°C,
with stirring, as volatiles are removed by distillation. After 8.5 hours, 1500
parts
(6.25 moles) of 1-hexa~deceae oxide is added over 5.5 hours at 186-
195°C, with
storing. Heating and storing are continued for 2 hours as volatiles are
removed. The
material is then vacuum shipped and filtered at 93-99°C. The filtrate
is the desired
product; it contains 2.1 % boron.
The borated fatty acid esters of glycerol are prepared by reacting a fatty
acid
ester of glycerol with a boric acid (e.g., boric acid, metaboric acid,
orthoboric acid,
tetraboric acid) with m~noval of the water of reaction. In one embodiment
there is
sufficient boron present such that each boron will react with from about 1.5
to about
2.5 hydroxyl groups present in the ration mixture.
The reaction may be out at a tempeiatme in the range of about 60°C
to
about 135°C, in the absence or presence of any suitable organic solvent
such as
methanol, b~ze~e, xylenes, toluene, neutral oil and the like.
Fatty acid esters of glycerol can be prepared by a variety of methods well
known in the art. Many of these esters, such as glycerol monooleate and
glycerol
tallowate, are manu~ured on a commercial scale. The esters useful for this
invention
are oil soluble and are preferably prepared from C8 to C~ fatty acids or
mixtures
thereof such as are found in natural products. The fatty acid may be saturated
or
unsaturated. Certain compounds found in acids from natural sources may include
licanic acid which contains one laeto group. Useful C8 to C~ fatty acids are
those of
the formula R-COOH wherein R is alkyl or alkenyl.
The faay acid monoester of glycerol is useful. M~xhues of mono and diesters
may be used. Nfixtures of mono- and diester can contain at least about 40% of
the
monoester. Mixtures of mono- and diesters of glycerol containing from about 40
% to
about 60% by weight of the monoester can be used. For example, commercial
glycerol monooleate containing a mixture of from 45 % to 55 % by weight
monoester
3 0 and from 55 % to 45 % diester can be used.
CA 02189208 1999-06-15
-32-
Useful fatty acids are oleic, stearic, isostearic, palmitic, myristic,
palmitoleac,
linoleic, lauric, lin~~lenic, and eleostearic, and the acids from the natural
products
tallow, palm oil, olive oil, peanut oil.
Friction modifiers are also well known to those skilled in the art. A useful
list
of friction modifiers are included in U.S. Pat. No. 4,792,410 . U.S. Patent
5,110,488
discloses metal salts of fatty .acids and especially zinc salts. Said list of
friction
modifiers includes:
fatty Phosphates
fatty acid amides
fatty epoxides
borated fatty epoxides
fatiy amines
~Y~
borated glycerol esters
allooxylated fatty amines
borated alhoxylated fatty amines
metal salts of fatty cads
strlfurrzad olefins
fatty imidazolines
and mixtures thereof.
The preferred friction modifier is a borated fatty epoxide as previously
mentioned as being included for its boron content. Friction modifiers are
included in
the compositions in the amounts of 0.1-10 weight percent and may be a single
fricxion
modifier or mixtures of two or more.
Friction modifiers also viclude metal salts of fatty acids. Preferred rations
are
zinc, magnesium, calcium, and sodium and_ any other alkali, or alkaline earth
metals
may be used. The salts may be overbased by including an excess of rations per
equivalent of amine. The excess rations are then treated with carbon dioxide
to form
the carbonate. The metal salts are prepared by reacting a suitable salt with
the acid to
21892~~8
-33-
form the salt, and where appropriate adding carbon dioxide to the reaction
mixture to
form the carbonate of any canon beyond that needed to form the salt. A
preferred
friction modifier is zinc oleate.
(D) lbiocarbamate.
The thiocarbamates (D) are compounds represented by the formula
RIRZN-C(X)S-(CR3R~,Y
where Rl, RI, R3 and R4 are independently hydrogen or hydrocxrbyl groups,
Provided
that at least one of Rl or RI is a hydrocarbyl group; X is oxygen or sulfur; a
is 1 or 2;
and Y is a hydrocarbyl group, a heteao group (that is, a group attached
through a
heteroatom such as O, N, or S), an additional -SC(X) NR1R2 group, or an
aarvating
group.
When a is 2, Y is an activating group, in describing Y as an "activating
1 S group, ° what is meant is a group which will activate an olefin to
which it is attached
toward nucleophilic addition by, e.g., CSI or COS derived inteamediates. (This
is
reflective of the method by which this material is normally prepared, by
reaction of an
activated olefin with CSI and an amine.) The activating group Y can be, for
instance,
an ester group, typically but not necessarily a c~boxylic ester group of the
struchme -
COORS. It can also be an ester group based on a non-carbon acid, such as a
sulfonic
or sulfinic ester or a phosphoric or phosphinic ester. The activating group
can also be
any of the acids corresponding to the aforementioned esters. Y can also be an
amide
group, that is, based on the condensation of an acid group, preferably a
carboxylic acid
group, with an amine. In that case the -(CR3R~,Y group can be derived from
acrylamide. Y can also be an ether group, -ORS; a carbonyl group, -C(O)-, that
is, an
aIdehyde or a Icetone group; a cyano group, -CN, or an aryl group. In one
embodiment Y is an ester group of the structure, -COORS, where RS is a
hydrocxrbyl
group. RS can comprise 1 to about 18 carbon atoms, and in one embodiment 1 to
about 6 carbon atoms. In one embodiment RS is methyl so that the activating
group is
-COOCH3.
CA 02189208 1999-06-15
-34-
When a is 1, Y need not be an activating group, because the molecule is
generally prepared b;y methods, descn'bed below, which do not involve
nucleophilic
addition to an activated double bond.
R3 and R4 can be, independently, hydrogen or methyl or ethyl groups. When a
is 2; at least one of R3 and R4 is normally hydrogen so that this compound
will be
R'R2N-C(S)S-CR3R4~CR3HCOORS. In one embodiment most or all of the R3 and R4
groups are hydrogcxi so that the thiocarbamate will be R1R2N-C-(S),S =CH2
CH2COOCH3. (These materials ran be derived from methyl methacrylate and
methylacrylate, respectively.) These and other materials containing
appropriate
activating groups are; disclosed in greater detail in U.S. Patent 4,758,362.
The substituer~ts Rr and R2 on the nitrogen atom are li>cewise hydrogen or
hydrocarbyl groups, but at least one should be a hydrocarbyl group. It is
generally
believed that at least one such hydmcarbyl group is desired in order to
provide a
measure of oil-solubility to the molecule. However, Rl and R2 cxn both be
hydrogen,
pm~~ ~e other R groups in the molecule provide sufficient oil solubility to
the
molecule. In practice; this means that at least one of the groups R3 or R4
should be a
hydrocarbyl group of at least 4 carbon atoms. R' or R2 are preferably alkyl
groups of
1 to about 18 cari~on atoms, and in one embodiment alkyl groups of 1 to about
8
carbon atoms. In one embodiment, both Rl and R2 are butyl groups. Thus, in one
embodiment, the thi~x~rbamate (D) is S-carbomethoxyethyl-N,N-dibutyl dithiocar-
bamate which can be represented by the formula
S O
~ N-C-S-CH2CH2C-0CH3
Briefly, these materials are prepared by reacting an amine, ~rbon disulfide or
carbonyl sulfide, or source materials for these reactants, and a reactant
containing an
activated, ethylenically-unsatural~ed bond or derivafives thereof. These
rea~ants are
charged to a reactor and stirred, generally without heating, since the
reaction is
CA 02189208 1999-06-15
-35-
norn~ally exothermic. Once the reaction reaches the teriiperature of the
exotherm
(typically 40-65~G~, the reaction mixture is held at the temperature to insure
compleae
reaction. After a reaction tune of typically 3-5 hours, the volatile materials
are
removed under reduced pressure and the residue is filtered to yield the final
product.
The relative ~~rnounts of the reactants used to prepare these compounds are
not
critical. The charge :ratios to the reactor can vary where economics and the
amount of
the product desued are controlling factors. Thus, the molar charge ratio of
the amine
to the CSl or COS rent to the ethylenically unsaturated reactant may vary in
the
ranges 5:1:1 to 1:5: I to 1:1:5. :(n one embodiment, the charge ratios of
these rea~nts
is 1:1:1.
In the case v~rhere a is I, the activating group Y is separated from the
sulfur
atom by a methylen~e group. hsaterials of this type can be prepared by
reaction of
sodium dithiocarbamate with .a chlorine-substituted material. Such ~ are
descn'bed in great,~a detail in U.S. Patent 2,897,152, .
U. S. Patents 4,758,362: and 4,997,969 describe dithiocubamate compounds
and methods of mating the same.
Concentraty, lubricating Comnos~itions and Flunctional Fluids.
The lubricant and functional fluid compositions of the present invention are
based on diverse oils of lubricating viscosity, including natural and
synthetic lubricating
0~ ~d ~e~f. The lubricating compositions may be lubricating oils and
greases usefiil in industrial applications and in automotive engines,
transmissions and
axles. These lubricating compositions are effective in a variety of
applications
including crankcase lubricating ails for spark ignited and compression-ignited
internal
combustion engines, including automobile and truck engines, two-cycle engines,
a~fion piston e:ngin.es, marine, and low-load diesel engines, and the like.
Also,
automatic transmission fluids, >ransaxle lubricants, gear lubricants,
metalworking
lubricants, hydraulic fluids, and other lubricating oil and grease
compositions can
benefit from the ina>rporation of the compositions of this invention. The
inventive
21892
-36-
functional fluids are particularly effective as automatic -transmission fluids
having
enhanced aniiwear properties.
The lubricants and functional fluid compositions of this invention employ an
oil
of lubricating viscosity which is g~eaally present in a major amount (i.e. an
amount
than about 50~ by weaght). Generally, the oil of lubricating vis~ity is
present in an amount greater than about 60%, or greater than about 709&, or
greater
than about 80~ by weight of the composition.
The natural oils useful in malting the inventive lubricants and functional
fluids
include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as
mineral
lubricating oils such as liquid petroleum oils and solvent treated or acid
treated mineral
lubricating oils of the parafbnic, naphthenic or mixed paraffinic-naphthenic
types. Oils
of lubricating viscosity delved from coal or shale are also useful. Synthetic
lubricating
oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as
polymerized and interpolymetized olefins (e.g., polybutylenes, polypropylenes,
propylene-isobutyleae copolymers, chlorinated polybutylenes, etc.); polY(I
hexes),
poly-(1-octenes), polY(1-decenes), etc. and mixtures thereof; alkyl-benzenes
(e.g.,
dodecylbenzenes, tebra~decylbe~zenes, dinonylbenzenes, di-(2-
ethylhexyl~benzenes,
etc.); PoIYPh~Y~ (e.g., bipherlyls, teaphenyls, allcylated polyphenyls, etc.);
alkylated
Biphenyl ethers and alkylated Biphenyl sulfides and the derivatives, analogs
and
homologs thereof and the h'ke.
Alkylene oxide polymers and interpolymers and derivatives thereof where the
terminal hydroxyl groups have beg modified by esterification, etheaification,
etc.,
constitute another class of known syn~etic lubricating oils that can be used.
These are
exemplified by the oils prepared through polymerization of ethylene oxide or
propylene
oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g.,
methyl polyisopropylene glyovl ether having an average molecular weight of
about
1000, Biphenyl ether of polyethylene glycol having a molecular weight of about
500-1000, diethyl ether of polypropylene glycol having a molecular weight of
about
1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the
acetic
218928
-37-
acid esters, mixed Cj.$ fatty acid esters, or the C~Oxo acid diester of
tettaethylene
gym.
Another suitable class of synthetic lubricating oils that can be used
comprises
the esters of dicarboxylic acids (e.g., phthalic acid, sucxinic acid, alkyl
succinic acids,
alkenyl succinic acids, malefic acid, azelaic acid, suberic acid, sebacic
acid, fumaric
acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids,
alkenyl
malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl
alcohol,
dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol
monoether,
propyl~e glycol, etc.) Specific examples of these esters include dibutyl
adipate,
di(2-ethylheacyl) sebacate, di n hexyl fumarate, dioclyl sebacate, diisooctyl
azelate,
diisodecyl azelate, dioctyl phthalate, didacyl phthalate, dieicosyl sebacate,
the
2-exhylhexyl diester of linoleac acid dimer, the complex ester formed by
reacting one
mole of sW acic acid with two moles of tetraethylene glycol and two moles of
2-ethylhexanoic acid and the lilae.
Esters useful as synthetic oils also include those made from CS to Cla
monocarboxylic acids and polyols and polyol ethers such as neap~tyl glycol,
trimethylol propane, pentaerythritol, dipentaerythritol, txipentaerythritol,
etc.
Silicon-based oils such as the polyalkyl-, polyaryl , polyalkoxy-, or
polyaryloxy-siloxane oils. and silicate oils comprise another useful class of
synthetic
lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-
ethylhexyl)silicate,
tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butylphenyl) silicate, hexyl-(4-
methyl-2-
pentoxy~isiloxane, poly(methyl) siloxanes, poly-(methylph~yl)siloxanes, etc.).
Other synthetic lubricating oils include liquid esters of phosphorus-
containing acids
(e.g., tricresyl phosphate, tiiocxyl phosphate; diethyl ester of decane
phosphoric acid,
etc.), polymeric tetrahydrofmans and the like.
Unrefined, refined and rerefined oils, either natural or synthetic (as well as
mixtures of two or more of any of these) of the type disclosed hereinabove can
be used
in the lubricants of the present invention. Unrefined oils are those obtained
directly
from a natural or synthetic source without further purification trealznent~
For example,
a shale oil obtained directly from retorting operations, a petroleum oil
obtained directly
~1~92~~
-38-
from primacy distillation or ester oil obtained directly from an
esterification process
and used without further treaanent would be an unrefined oil. Refined oils are
similar
to the unrefined oils except they have been further treated in one or more
purification
steps to improve one or more properties. Many such purification techniques are
lrnown to those skilled in the art such as solvent extraction, secondary
distillation, acid
or base extraction, filtration, percolation, etc. Rerefined oils are obtained
by processes
similar to those used to obtain refined oils applied to refined oils which
have been
already used in service. Such rerefined oils are also lmown as reclaimed or
reprocessed oils and often are a~itionally processed by techniques directed to
removal
I O of spent additives and oil breakdown products.
In one embodiment, me oil of lubricating viscosity is a poly alpha-olefin
(PAO). Typically, the polyalpha-olefins are derived from monomers having from
about 4 to about 30, or from about 4 to about 20, or from about 6 to about 16
carbon
atoms. Examples of useful PAOs include those deaived from dec~e. These PAOs
may have a viscosity firm about 3 to about 150, or from about 4 to about 100,
or from
about 4 to about 8 cSt ax 100°C. Examples of PAOs include 4 cSt poly
alpha~lefins,
6 cSt, poly-alpha-olefins, 40 cSt poly-alpha-olefins and 100 cSt poly-
alpha~lefins.
Mixtures of mineral oils with the foregoing poly-alpha-olefins can be useful.
Generally, the lubricants and functional fluids of the present invention
contain
2o an effective amount of the inv~tive composition ~.e., components (A), (B),
(C), and
(D)) to provide said lubricants and functional fluids with enhanced antiwear
pmpesties.
Normally the compositions of the present invention will be employed in such
lubricants
and functional fluids at a level in the range of about 0.01 % to about 20 % by
w~ght,
and in one embodim~t about 0.05 ~6 to about 10 % by weight of the total weight
of the
lubricant or functional fluid. The weight of substituents added to an oil to
form a
lubricant or functional fluid is given on a chemical basis. That is, the
composition or
component thereof is given on an oil-free basis.
The ranges for weight percents on an oil-free basis of components of the
inventive composition are given below on the basis of total weight of the
lubricant/functional fluid:
2.1 ~92.'~
-39-
(A)0.05-3.0 a boron-containing oveabased material;
tB)0.05-2.5 a phosphorus acid, ester or derivative;
(C~0.05-1.0 a borated epoxide or borated fatty
acid of glycerol;
tD)0.05-1.0 a thiocarbamate.
The inv~tion also contemplates the use of lubricants and functional fluids
containing other additives in addition to the compositions of this inv~tion.
Such
additives include, for example, detergents and dispersants, ion-inhibiting
agents,
antioxidants, visoosuy index improving agents, extreme pressure (E.P.) agents,
pour
point depressants, friction modifies, fluidity modifiers, seal swell agents,
color
stabilizers, dyes, anti foam agents, etc.
The inventive lubricating compositions and fiutctional fluids can contain one
or
more detergents or dispersants of the ash producing or ashless type. The
ash producing detergents are exemplified by oil-soluble neutral and basic
salts of alkali
or alkaline earth metals with sulfonic acids, carboxylic acids, or organic
phosphorus
acids. The most commonly used salts of such acids are those of sodium,
potassium,
lithium, calcium, magnesium, strontium and barium. These ash-producing
detergents
are described in greater detail above as beang among the oveabased materials
used in
Preparing the borated overbased materials (A) of the invention.
Ashless detergents and dispersants are so called despite the fact that,
depending
on its constitution, the dispersarit may upon combustion yield a non volatile
matezial
such as boric oxide or phosphorus p~toxide; however, it does not ordinarily
contain
metal and therefore does not yield a metal-containing ash on combustion. Many
types
are known in the art, and any of them are suitable for use in the lubricant
compositions
and functional fluids of this invention. The following are illustrative:
(1) Reaction products of carboxylic acids (or derivatives thereof) containing
at least about 34 and preferably at least about 54 carbon atoms with nitrogen
containing
compounds such as amine, organic hydroxy compounds such as ph~ols and
aloohols,
and/or basic inorganic materials. Examples of these "carboxylic dispersants"
are
described in many U.S. Patents including 3,219,666; 4,234,435; and 4,938,881.
These include the products formed by the reaction of a polyisobutenyl succinic
CA 02189208 1999-06-15
-40-
anhydride of the type: described above under the subtitle "Carboxylic Acids
(a)" with
an amine such as a polyethylene amine, as weu as such polyisobutenyl sua~nic
anhydride amine re3cxion products which have been post-treated with a boron
compound such as boric acid.
(2) Reaction products of relatively high molecular weight aliphatic or
alicyclic halides with amines, preferably oxyalkylene polyamines. These may be
W ara~~ized as "ami;ne dispersants" and examples thereof are described for
example,
in the following U.S. Patents: 3,275,554; 3,438,757; 3,454,555; and 3;565,804.
(3) Re~tion products of alkyl phenols in which the alkyl group contains at
least about 30 carbon atoms with aldehydes (especially formaldehyde) and
amines
(especially polyalkylene polyamines), which may be chararctrerized as "Mannish
dispersants". The materials described in the following U.S. Patents are
illustrative:
3,649,229; 3,697,574; 3,725,277; 3,725,480; 3,726,882; and 3,980,569.
(4) Produ~~s obtained by post treating the amine or Mannish dispe~nts
with such reagents a:c urea, thiounn., carbon disulfide, aldehydes, laetones,
carboxylic
acids, hydrocarbon substituted suocinic anhydrides, nitriles, epoxides, boron
compounds, phosphorus oompoiuids or the like. Exemplary materials of this kind
are
described in the following U.S. Patents: 3,639,242; 3,649,229; 3,649,659;
3,658,836; 3,697,574; 3,702,757; 3,703,536; 3,704,308; and 3,708,422.
(~ Interpolymers of oil solubilizing monomers such as decyl methacrylate,
vinyl decyl ether andl high molfxx~lar weight olefins with monomers containing
polar
substituents, e.g., aminoalkyl acrylates or acrylamides and.
poly-(oxyethylene)-substituted acrylates. These may be characterized as
"polymeric
dispersants" and ex~nples thereof are disclosed in the following U.S. Patents:
3,329,658; 3,449,250; 3,519,565; 3,666,730; 3,687,849; and 3,702,300.
The inventive lubricating compositions and functional fluids can contain one
or
more extreme pressure, corrosion inhl-bitors and/or oxidation inhibitors.
Extreme
pressure agents and a~rrosion- and oxidafion-inhibiting agents which may be
included
CA 02189208 1999-06-15
-41-
in the lubricants and functional fluids of the invention are exemplified by
chlorinated
aliphatic hydrocarbons such as chlorinated wax; organic sulfides and
polysulfides such
as benzyl disulfide; bis(chlorot~zyl)disulfide, dibutyl tetrasulfide,
sulfurized methyl
ester of oleic acid, s~uifurized altrylphenol, sulfurized dipentene, and
sulfurized terpene;
phosphosulfuriz~ed hydrocarbons such as the reaction product of a phosphorus
sulfide
with turpentine or methyl. oleate; metal thiocarbamates, such as zinc
dioctyldithiocarbamae, and barium heptylphenyl dithiocarbamate;
dithiocarbamate
esters from the reitction product of dithiocarbamic acid and acrylic,
methacrylic,
malefic, fumaric or itaconic esters; dithiorarbamate containing amides
prepared from
dithiocarbamic acid and an acrylamide; alkylene-coupled dithiocarbamates;
sulfur-
coupled dithiocartxunates. ~iroup II metal phosphorodithioates such as zinc
dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium
di(heptylphen-
yl)-phosphomdifhio~~te, cadmium dinonylphosphorodithioate, and the zinc salt
of a
phosphorodithioic a~~d produced by the reason of phosphorus pentasulfide with
an
equimolar mixriue of isopropyl alcohol and n-hexyl alcohol.
Zinc salts am added to lubricating compositions to provide antiwear
protection.
The zinc salts are normally added as zinc salts of phosphorodithioic acids.
Among the
prefen~ed compounds are zinc diisooctyl dithiophosphate and zinc dibenzyl
dithiophosphate. Also included in lubricating compositions in the same weight
percent
range as the zmc salts to give antiwear/extreme pressure performance is
dibutyl
hydrogen phosphite (DBPI~ and triphenyl monothiophosphate, and the
thiocarbamate
ester formed by reading dibutyl amine-carbon disulfide- and the methyl ester
of acrylic
acid. The thiocarbamate is des~~n'bed in U.S. Pat. No. 4,758,362 and the
phosphorus-
containing metal salts are described in U.S. Pat. No. 4,466,894.
Sp~ific oxidation-inhibitors that are useful include the mono- and di-
paraalkylated (e.g., ~:9) diphenylamines, hydroxythioether of t-dodecyl
mercaptan and
propylene oxide, and hydroxyelhyl dodecyl sulfide. Specific corrosion-
inhibitors that
are useful include tolyltriazole and the dialkylated (e.g., Cg) sulfur-coupled
dimercaptothiadiazoles.
CA 02189208 1999-06-15
-42-
The inventive lubricating compositions and functional fluids can contain one
or
more pour point depmssants, vi5oosity-indea~ improvers, color stabilizers,
dyes and/or
anti-foam agents. Pour point depressants are a particularly useful type of
additive often
included in the lubrio~ting oils and functional fluids described hen.an. The
use of such
pour point dt~ in oil-basil compositions to improve low tempeiahire properties
of oil-based compositions is well lmown in the art. See, for example, page 8
of
"Lubricant Additives" by C.V. Smalheer and R. Kennedy Smith (Ixzius-l~Ies Co.
publishers, Cleveland, Ohio, 19~.
Examples o:P useful pour point depressants are polymethacrylates;
polyacrylates; polyacxylamides; condensation products of haloparaffin waxes
and
aromatic compounds; vinyl carboxylate polymers; and terpolymers of diallrylfum-
arates, vinyl esters of fatty acids and allryl vinyl ethea~s. A specific pour
point
depressant that can be used i.4 the product made by alkylating naphthalene
with
polychlorinated paraffin and Cl~-Cl$ alpha-olefin. Pour point depressants
useful for
the purposes of this invention, techniques for their preparation and their
uses are
deseiibed in U.S. Patents 2,38'1,501; 2,015,748; 2,655,479; 1,815,022;
2,191,498;
2,666,746; 2,721,8T7; 2,721,878; and 3,250,715.
Examples of commercially available pour point depressants and their
chemical types are:
pour Point P~epressant Tradename ource
I. Polymethacrylates Acryloid~ 154-70, Rohm &
3004, 3007 Haas
LZ~ 7749B, 7742 Lubrizol
7748
TC 5301, 10314 Texaco
Viscoplex~ 1-31, Rohm
1-330, 5-557 GmbH
2189208
-43-
(Cont'd.)
Pour Point Depressant Tradename Source
2. Vinyl acetate/fumate ECA 11039, Exxon
or maleate copolymers 9153
(Paramins)
3. Styrene, maleate LZ~ 6662 Lubrizol
copolymers
Viscosity modifiers (VM) and dispersant viscosity modifiers (DVM) are
well known. Examples of VMs and DVMs are polymethacrylates,
polyacrylates, polyolefins, styrene-malefic ester copolymers, and similar
polymeric substances including homopolymers, copolymers and graft
copolymers.
In general, dispersant viscosity modifiers are polymers in which polar
groups have been added or included. The polar groups, which are often basic
in nature add dispersing properties to the viscosity modifiers.
Examples of commercially available VMs, DVMs and their chemical
types are listed below. The DVMs are designated by a (D) after their number.
Tradename and
Viscositx Modifiers Commercial Source
1. Polyisobutylenes Indopol~ Amoco
Parapol Exxon
(Paramins)
Polybutene Chevron
Hyvis~ British
Petroleum
2. Olefin copolymers Lubrizol~ 7060, 7065, 7067 Lubrizol
Paratone 8900, 8940, 8452 Exxon
8512 (Paramins)
CA 02189208 1999-06-15
-44-
(Cont'd.) Tradename and
Viscosity Modifiers Commercial Source
ECA-6911 Exxon
(Paramins)
TLA 347E, 555(D), 6723(D) Texaco
Trilene CP-40, CP-60 Uniroyal
3. Hydrogenated styrene-dieneShellvis 50, 40 Shell
copolymers LZ 7341, 7351, 7441 Lubrizol
4. Styrene, maleate copolymersLZ 3702(D), 3715(D), Lubrizol
3703(D)
5. Polymethacrylatea Acryloid~ 702, 954(D), Rohm &
985(D), 1019, 1265(D) Haas
TLA 388, 407, 5010(D), Texaco
5012(D)
Viscoplex~ 4-950(D), Rohm
6-500(D), 5151(D) GmbH
6. Olefin-graft-polymethacrylateViscopleX 2-500, 2-600 Rohm
polymers GmbH
7. Hydrogenated polyisopreneShellvis 200, 260 Shell
star
polymers
Recent summaries of viscosity modifiers can be found in U.S. patents
5,157,088, 5,256,752 and 5,395,539.
2189208
-45-
A specific preferred viscosity-index improver that can be used is Viscoplex
5151 which
is a product of Rohm GMBH identified as a polymethacrylate. In the preferred
mode of this
invention, a dispersant viscosity modifier is selected which provides the
compositions of the
invention with superior shear stability. For instance, when Visoplex 5151 is
used in the
formulations presented herein the kinematic 100°C viscosity dropped
from 7.52 cSt to only
7.41 cSt after 40 passes in the FISST apparatus used in ASTM D5275.
The shear stable dispersara viscosity mod~ers of this invention are selected
so that
their inclusion in a formulated automatic transmission fluid gives a
formulation wherein
kinematic viscosity at 100°C does not drop more than 10% when viscosity
is determined after
40 passes in the FISST apparatus used in ASTM 5275.
Anti-foam agents are used to reduce or prevent the formation of stable foam.
Typical
anti-foam agents include silicones or organic polymers. Additional anti-foam
compositions are
described in "Foam Control Agents", by Henry T. Kerner (Noyes Data
Corporation, 1976),
pages 125-162.
An example of a fluidity modifier is Hydrocal-38 which is a product Calumet
identified as a refined naphthenic oil. An example of a seal swell agent is
polyisobutyl-o-
aminophenol. Emery 2971, which is a product of Emery identified as a mixture
of di- and tri-
decyladipate, can function as both a fluidity modifier and a seal swell agent.
Ethomeen T/12,
which is a product of Armak identified as bis(2-hydroxyethyl) tallowamine, is
useful as a
friction modifier.
Each of the foregoing additives, when used, is used at a functionally
effective amount
to impart the desired properties to the lubricant or functional fluid. Thus,
for example, if an
additive is a dispersant, a functionally effective amount of this dispersant
would be an amount
sufficient to impart the desired dispersancy characteristics to the lubricant
or functional fluid.
Similarly, if the additive is an extreme-pressure agent, a functionally
effective amount of the
extreme-pressure agent would be a sufficient amount to improve the extreme-
pressure
characteristics of the lubricant or functional fluid. Generally, the
concentration of each of these
additives, when used, ranges from about 0.001 % to about 20% by weight, and in
one
embodiment about 0.01 % to about 10% by weight based on the total weight of
the lubricant or
functional fluid.
The lubricant compositions of the present invention may be in the form of a
grease in which any of the above-described oils of lubricating viscosity can
be
21892u~~
employed as a vehicle. Where the lubricant is to be used in the form of a
grease, the
lubricating oil generally is employed in an amount sufficient to balance the
total grease
composition and generally, the grease compositions will contain various
quantities of
thickening agents and other additive components to provide desirable
properties.
A wide variety of thick~ing ag~ts can be used in the preparation of the
greases of this invention. Included among the thickening ag~ts are alkali and
alkaline
earth metal soaps of fatty acids and fatty materials having from about 12 to
about 30
carbon atoms. The metals are typified by sodium, lithium, calcium and barium.
Examples of fatty materials include stearic acid, hydroxy stearic acid,
stearin, oleic
acid, palmitic acid, my~sbic acid, ooh oil acids, and hydrogenated fish oils.
Other thickening agents include salt and salt soap complexes as calcium
stearate-acetate (U.S. Patent 2,197,263), barium stearate a:~te (U.S. Pat~t
2,564,561), calcium stearate.-caprylate-mate complexes (U.S. Pat~t 2,999,06,
calcium caprylat~ao~ate t;U.S. Patrat 2,999,Ofi6), and calcium salts and soaps
of
low-, intermediate- and high_molecular weight acids and of nut oil acids.
In one embodiment, thick~ing agents employed in the grease compositions are
essentially hydrophilic in character, but which have been converted into a
hydrophobic
condition by the introduction of long gain hydrocarbon radicals onto the
surface of the
clay particles prior to their use as , a component of a grease composition,
as, for
example, by being subjected to a preliminary >xeahnent with an organic
cationic
surface-active agent, such as an opium compound. Typical opium compounds are
te>saalkylammonium chlorides, such as dimethyl dioc~decyl ammonium chloride,
dimethyl dibenzyl ammonium chloride and mixtures thereof. This method of
conversion, being well known to those skilled in the art, and is believed to
require no
further discussion. More specifically, the clays which are useful as starting
materials
in forming the thickening agents to be employed in the grease compositions,
can
comprise the naturally occurring chemically unmodified clays. These clays are
crystalline complex silicates, the exact composition of which is not subject
to precise
description, since they vary widely from one natural source to another. These
clays
can be described as complex inorganic silicates such as aluminum silicates,
magnesium
21892~~
-~7-
silicates, barium silicates, and the like, containing, in addition to the
silicate lattice, varying
amounts of ration-exchangeable groups such as sodium. Hydrophilic clays which
are
particularly useful for conversion to desired thickening agents include
montmorillonite clays,
such as bentonite, attapulgite, hectorite, illite, saponite, sepiolite,
biotite, vermiculite, zeolite
clays, and the like. The thickening agent is employed in an amount from about
0.5 % to about
30%, and in one embodiment from about 3% to about 15% by weight of the total
grease
composition.
Components (A), (B), (C) and (D) of the inventive compositions of this
invention can be
added directly to the lubricant or functional fluid. In one embodiment,
however, they are
diluted with a substantially inert, normally liquid organic diluent such as
mineral oil, naphtha,
benz,ne, toluene or xylene, to form an additive concentrate. These
concentrates usually
contain from about 10% to about 90% by weight of the inventive compositions
(that is, (A),
(B), (C) and (D)) and may contain, in addition, one or more other additives
known in the art or
described hereinabove. The remainder of the concentrate is the substantially
inert normally
liquid diluent.
Examples
The following Examples are provided in Table I below for the purpose of
illustrating
specific embodiments of the invention. Each of these examples consists of
automatic
transmission fluid formulations that are characterized by enhanced antiwear
properties. Test
results involving the following antiwear tests are also disclosed for
representative compositions
..
of each of these formulations in Table II: (1) Vane Pump Wear Test (ASTM D-
2882); (2)
Four-Ball Wear Test (ASTM D-4172); Falex EP Test (ASTM D-3233); Timken Wear
Test
(ASTM D-2782); and FZG Gear Wear Test. The disclosed test results demonstrate
the
enhanced antiwear properties of the inventive compositions. Column 4 of Table
II represents a
commercially-available ATF which is inferior in test results to those of this
invention. The
weight percent of each component added to a base oil is on an oil-free basis
and is based on the
weight of the lubricant/functional fluid.
The ATFs of this invention are blended to have Brool~eld viscosity values at -
40°C of less
than 20,Oi00 cP. Preferably the -40°C viscosity ranges from about 8,000
cP to about 13,000.
The ATFs of this invention are blended so that the 100°C kinematic
viscosity ranges for
the fluid range between about 6 and 8.5 cSt. The preferred 100°C
kinematic viscosity range is
roughly between 7 and 8.
CA 02189208 1999-06-15
-4g-
The antiwear ,properties of the fully formulated ATFs which meet the low
viscosity parameters outlined above are accomplished by use of components
listed
herein arid shown in examples 1 ~-3 arid S-7. Polysu~de compositions as
disclosed in
Schwind U.S. Pateru' 5,403,501 are spec~cally excluded from this invention.
Polysu~des as disclosed in 501 are too corrosive for use in ATFs, and would be
detrimental to an ATF's passing a copper corrosion test.
Table I reveals that both (B), a phosphorus acid, ester or derivative thereof
and
(D) a thiocarbamate are included in the three listed compositions. Preferred
embodiments for component (B) are listed below together with their weight
percent
~g~ on ~ oil-free basis in lubricating fluids.
(B)-1 Dibutyl hydrogen phosphite 0.05-2%
(B)-2 Triphenyl monothiaphosphate 0.01-2
(B)-3 85 % phosphoric acid 0.01-1.5
In another preferred embodiment, compounds (B)-1 and (B)-2 may be used
1 S ~,~,i~ ~) a ~~~.ate. Thus, compositions may embody (D) with (B) as shown
in
Table I where (B) may encompass (B)-1 through (B)-3 shown above, (D) may also
be
used in combination with only (13)-1 and (B)-2.
In still another preferred embodiment (B) may be used without (D) and in this
instance (B) may encompass (B)-1 through (B)-3.
Table III lists compositions 5-7. Composition 5 corresponds to a lubricating
composition with (D;1 and (B)-~I through (B)-3. Composition 6 corresponds to a
lubricating composition without (D) but with (B)-1 through (B)-3. Composition
7
corresponds to a composition having (D) with (B)-1 and (B)-2.
Further, the 5'01 patent discloses only SAE 90 as the base oil in its examples
which are used in determining antiwear properties of the compositions. SAE 90
oil
cannot meet the 100°C kinematic viscosity range or -40°C
Brookfield viscosity range of
the formulated ATFs c f this invention.
21892~~
-49
TABLE I
1 2 3
Base oil (75 % 6 cSt. poly-oc-olefinicabout
+
25 % 4 cSt. poly-a-olefin), 78-82 - --
v~rt. %
Base oil (85 % 4 cst. poly-a-olefin about
+
% 40 cSt. poly-a-olefin) - 78-82 -
10
Base oil (50% 90 N mineral about
oil + 50%
4 cSt. poly~c-olefin) - - 78-82
(A) Boratecl overbased magnesium
sulfonate
15 of Example A-1, v~rt. % 0.05-.200.05-.2 0.05-0.2
(B) Phophorus acid, ester or 0.2-0.6 0.2-0.6 0.2-0.5
derivative
thereof vvt. %
(C~ Borated C 16 -olefin epoxide0.15-0.30.15-0.3 0.15-0.3
vvt. %
(D) A thiocarbamate wt. % 0.05 0.05 0.05
Reaction productsof polyisobutenyl
succinic
anhydride and polyamines, v~rt.1.75-3.01.75-3.0 1.75-3.0
%
Borated reaction product of
polyisobutenyl
succinic anhydride and polyethylene
amines,
~ % 0.35-0.60.35-0.6 0.35-0.6
Friction modifiers wt. % 0.15-0.250.05-.15 0.05-0.15
Oxidation Inhibitors 0.75-1.250.75-1 0.75-1
3 Viscosity improver wt. % 0-4 2-4 3-7.5
5
Tolytriazole wt. % 0-0.03 0-0.03 0.01-0.03
Di-alkylated (Cg) sulfur coupled0-0,5 0-0.5 0.01-0.5
dimerc~ptothiadiawle wt.
21892J8
-50-
TABLE lI
1 2 ~ 4_
Vane Pump Wear Test, wt.
loss
(ASTM D-2882 at 80C, 6.9 0.2 1.6 14.0 8.0
MPa), mg.
(ASTM D-2882 at 150C, 6.9 2.9 9.7 14.8 > 1,000
MPa), mg.
Four-Ball Wear Test, 40 Kg.
load, 2 hrs.
(ASTM D-4172)
Average Wear Scar Diameter,
mm.
1200 RPM, 100C 0.38 0.41 0.43 0.57
, 1200 RPM, 150C 0.42 0.47 0.49 0.63
Average Wear Scar Diameter,
mm.
600 RPM, 100C 0.35 0.36 0.34 0.48
600 RPM, 150C 0.37 0.39 0.41 0.54
Falex EP Test
(ASTM D-3233)
No seizure load at 100C, 1750 1750 750,
1 min., lbs. 1000, 1000
1750
No seizure load at 150C, 1000 1000 1250 500,
1 min., lbs. 750
Timken Wear Test, burnish
width, mm.
(ASTM D-2782)
9 lb. load, 100C, 10 min. 0.58 0.43 0.75,
0.36
1.44
No Scoring No ScoringNo Scoring(Scoring
0.62 0.49 0.7, -
0.46
No Scoring No Scoring
FZG Gear Wear Test, Load
Stage Pass
1450 RPM, 15 min. at 100C > 12 > 12 11 10
start temp.
1450 RPM, 15 min. at 150C 11, 11 10 8
start temp. > 12
21~92J
-51
TABLE III
5 6 7
Base oil (75 % 6 cSt. poly-alpha
olefin +
25% 4 cSt. poly-alpha olefin), 79.83 -
wt. %
Base oil (50% 100 N mineral oil
+ 50%
4 cSt. poly alpha olefin) - -
Base oil (50 % 90 N mineral oil
+ 50 %
4 cSt. poly-alpha olefin) - 79.60 78.93
(A) Borated overbased magnesium
sulfonate
of Example A-1, wt. % 0.25 0.25 0.25
(B~1 Dibutyl hydrogen phosphite,0.25 0.25 0.25
wt. %
(B~2 Triphenyl monothiophosphate,0.10 0.10 0.10
wt. %
(B)-3 Phosphoric acid (85 % ), 0.04 0.04 -
vvt. %
(~ ~Cis ~p~ olefin epoxide, wt. 0.25 0.20 0.25
%
(D) S-carbomethoxyethyl-N,N-dibutyl-
~~~~~ ~ % 0.20 - 0.20
Reaction product of polyisobutenyl
succinic
anhydride and polyethylene amines,4.00 4.00 4.0
wt. %
Borated reaaron product of polyisobutenyl
succinic anhydride and polyethylene
amines,
~- % 0.50 0.50 0.5
C9 mono- and di paraalkylateti
diphenylamine
diluted with oil (16% oil), wt. 0.50 0.50 0.5
%
HY~xY ~oether of t-dodecyl mercaptan
and propylene oxide, wt. % 0.50 0.35 0
5
.
Tolyltriawle, wt. % 0.03 - 0.02
Di-alkylated (Cg) sulfur coupled
dimercapto
thiadiazole, wt. % - - 0.03
' ~- ~ 218920
-52
TABLE III (Cont' d)
6 7
5 Ethomeen T/12 (product of Arn~ak
identified
as bis(2-hydroxyethyl) tallowamine),0.12 0.12 0. I2
wt. %
Hydroxyethyl dodecyl sulfide, - 0.15 -
wt. %
Polyisobutyl-o-aminophenol, 1.80 0.60 0.60
v~rt. %
Emery 2971 (product of Emery
id~ti~fied as
di-, iri-decyladipate), wt. 5.00 - --
% .
Hydrocal-38 (product of Calumet
ideatified
as refined naphthenic oil), - 3.00 3.00
wt. %
Naphthalene alkylated with polychlo~nabad
parafOn and C16-Cl8 alpha olefin,- 0.30 0.30
wt. %
Viscoplex 5151 (product of Rohm
GMBH
identified as a polymexhacrylate),6.50 10.00 10.30
wt. %
Diluent oil, wt. % 0.06 0.04 -
Red dye, wt. % 0.025 0.025 -
Silicone antifoam agent, wt. 0.042 0.042 -
%
TEST RESULTS
Vane Pump Wear Test, wt. loss,
(ASTM D-2882 at 80°C, 6.9 MPa), mg. 0.5 12.3, 4.9 14.0
(ASTM D-2882 at 150°C, 6.9 MPa), mg. 9.4 I0.6, 13.7 I4.8
Four-Ball Wear Test, 40 Kg. load, 2 hrs.
(ASTM D-4172)
Average Wear Scar Diameter, mm.
1200 RPM, 100°C 0.42 0.54 0.43
1200 RPM, 150°C 0.44 0.56 0.49
' ~ 218928
-53-
TABLE III - TEST ~ ~TTrJTS ~
fCont'
6 7
Average Wear Scar Diameter,
mm.
600 RPM, 100C 0.36 0.38 0.34
600 RPM, 150C 0.38 0.41 0.41
Falex EP Test
(ASTM D-3233)
No seizure load at 100C, 1 min.,1500, 1000 1000
lbs. 2000
No seizure Ioad at 150C, 1 min.,1000 1000 1250
lbs.
Timkenk Wear Test, burnish width,
mm.
(ASTM D-2782)
9 lb. Ioad, 100C, 10 min. 0.52 0.74, 0.75,
0.8, 0.36
0.33
No ScoringNo ScoringNo Scoring
9 lb. load, 150C, 10 min. 0.58 0.82, 0.7,
0.68, 0.40
0.49
No ScoringNo ScoringNo Scoring
FZG Gear Wear Test, Load Stage
Pass
1450 RPM, 15 min. at 100C start10, > 10, > 10
temp. 12 12
1450 RPM, 15 min. at 150C start8, 9 11, 11 11
temp.
21892
While the invention has been explained in -relation to its preferred
embodiments, it is to be understood that various modifications thereof will
become
apparent to those skilled in the art upon reading the specification.
lfierefore, it is to be
understood that the inv~fion disclosed herein is intended to cover such
modifications
as fall within the scope of the appended claims.
