Note: Descriptions are shown in the official language in which they were submitted.
2~2~
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Title: LUBRlCATING COMPOSlTIONS WlTH IMPROVED OXlDATION
RESISTANCE CONTAINING A DISPERSANT AND AN
ANTIOXIDANT
Technical Field of the I~vention
This invention relates to a lubricating composition having improved oxidation
inhibition properties.
,
Background of the Invention ~ ~-
Lubricating compositions serve to remove heat from operating equipment.
These compositions also act to reduce metal-metal contact which lead to wearirng.
Today many pieces of equipment are reduced in size, which in turn has lead to higher ~ `~
operating temperatures for the equipment. These higher temperatures may lead to
increased oxidation of the lubricating composition.
Today the drain intervals for lubricants have increased. When a lubricant has
to operate for longer periods at higher temperatures, the lubricant is prone to ;
viscosily increase. The viscosity increase is believed to be caused by polymerization ~ ~ ~
of oxidized components of the lubncants. This increased viscosity renders the ~ -
lubricant unfit for use. ~t is desirable to have lubricants with improved oxidation
resistance. More particularly, it is desirable to have lubricants which will withstand ~ -
long periods of operation at high temperatures. ~ ;
... ..
`- 21~7238
S Summary of the Invention
This invention relates to a lubricating composition comprising a major arnount of
an oil of lubricating viscosity with an iodine number less than about 9, (A) one or more
antioxidant, and (B) from about 0.01% to about 3~6 by weight of at least one dispersant
or detergent, wherein the total arnount of antioxidant is at least about 2% by weight.
The additives are useful act controlling oxidation of lubricants. Further, these lubricants
have reduced viscosity increase caused by oxidation, while maintaining favorablecarbon/varnish ratings.
DescFipticn of the Preferred Embodiments
The term "hydrocarbyl" includes hydrocarbon as well as substantially hydrocarbongroups. Substanbally hydrocarbon describes groups which contain heteroatom
substituents that do not alter the predominantly hydrocarbon nature of the substituent.
Examples of hydrocarbyl groups include the following~
(1) hydrocarbon substituents, i.e., aliphatic (e.g., aLIcyl or alkenyl) and
alicyclic (e.g., cycloal~yl, cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-
substituted aromatic substituents and the like as well as cyclic substituents wherein the
ring is completed through another portion of the molecule (that is, for example, any two
indicated substituents may together form an alicyclic radical);
(2) substituted hydrocarbon substituents, i.e., those substituents containing
non-hydrocarbon groups which, in the context of this invention, do not alter thepredominantly hydrocarbon nature of the substituent; those skilled in the art will be
aware of such groups (e.g., halo (especially chloro and fluoro), hydroxy, mercapto,
nitro, nitroso, sulfoxy, etc.);
(3) heteroatom substituents, i.e., substituents which will, while having a
predominantly hydrocarbon character within the context of this invention, contain an
atom other than carbon present in a ring or chain otherwise composed of carbon atoms
(e.g., aLlcoxy or alkylthio). Suitable heteroatoms will be apparent to those of ordinary
skill in the art and include, for example, sulfur, oxygen, nitrogen and such substituents
as, e.g. parietal, furyl, thienyl, imidazolyl, etc.
~''
- 2147238 : -
In general, no more than about 2, preferably no more than one heteroatom
substituent will be present for every ten carbon atoms in the hydrocarbyl group.Typically, there will be no such heteroatom substituents in the hydrocarbyl group.
Therefore, the hydrocarbyl group is purely hydrocarbon.
As described above, the lubricating composition contains an oil of lubricating
viscosity which has an iodine value of less than about 9. Iodine value is determined
according to ASTM D-460. In one embodiment, the oil of lubricating viscosity has a
iodine value less than about 8, or less than about 6, or less than about 4. The oil of
lubricating viscosity includes natural or synthetic lubricating oils and mixtures thereof.
Natural oils include animal oils, mineral lubdcating oils, and solvent or acid treated
mineral oils. Synthetic lubricating oils include hydrocarbon oils (polyalpha-olefins),
halo-substituted hydrocarbon oils, alkylene oxide polymers, esters of dicarboxylic acids
and polyols, esters of phosphorus-containing acids, polymedc tetrahydrofurans and
silicon-based oils. Preferably, the oil of lubdcating viscosity is a hydrotreated mineral
oil or a synthetic lubricating oil, such a polyolefin. Examples of useful oils of
lubdcating viscosity include XHVI basestocks, such as lOON isomerized wax basestock
(0.01 % sulfur/ 141 VI), 120N isomerized wax basestock (0.01 % sulfur/ 149 VI), 170N
isomerized wax basestock (0.01 % sulfur/ 142 VI), and 250N isomerized wax basestock
(0.01% sulfur/ 146 Vl); refined basestocks, such as 250N solvent refined paraffinic
mineral oil (0.16% sulfur/89 VI), 200N solvent refined naphthenic mineral oil (0.2%
sulfur/ 60 VI), lOON solvent refined/ hydrotreated paraffinic mineral oil (0.01%sulfur/98 VI), 240N solvent refined/ hydrotreated paraffinic mineral oil (0.01% sulfur/
98 VI), 80N solvent refined/ hydrotreated paraffinic mine~al oil (0.08% sulfur/ 127 VI),
and l50N solvent refined/ hydrotreated paraffinic mineral oil (0.17% sulfur/ 127 VI).
A descAption of oils of lubAcating viscosity occurs in U.S. Patent 4,582,618 (column
2, line 37 through column 3, line 63, inclusive), herein incorporated by reference for its
disclosure to oils of lubAcating viscosity.
In one embodiment, the oil of lubAcating viscosity is a polyalpha-olefin (PAO).
Typically, the polyalpha~lefins are dedved from monomers having from about 4 to
about 30, or from about 4 to about 2~, or from about 6 to about 16 carbon atoms.
`" 214723~
S Examples of useful PAOs include those derived from decene. These PAOs may have a
viscosity from about 3 to about 150, or from about 4 to about 100, or from about 4 to -
about 8 cSt at lOO C. Examples of PAOs include 4 cSt polyolefins, 6 cSt polyolefins, :
40 cSt polyolefins and 100 cSt polyalphaolefins.
Table 1 contains exarnples of oils of lubricating viscosi~. The iodine value forthe oils and oil mixtures is detern~ined by ASTM D~60. .
~, . . . .
,.~ ~ . . . ' -
~ 21~23~
xl I I I I I I I I 1'~'1~ lo 1~ . ~;-
~XI I I I I I I I lolo~ I I loll ~
Xl I Igl lol I~LI rl r~
~T ~
U~ ~ o ~ ~ I .
E~ 3
æ
` 21~238
In one embodiment, the oil of lubricating viscosity are selected to provide
lubricating compositions with a kinematic viscosity of at least about 3.5 cSt, or at
least about 4.0 cSt at 100C. In one embodiment, the lubricating compositions have
an SAE gear viscosity number of at least about SAE 70W, or at least about SAE
75W. The lubricating composition may also have a s~called multigrade rating suchas SAE 75W-80, 75W-90, 75W-90, 75W-140, 80W-90, or 80W-140. Multigrade
lubricants may include a viscosity improver which is formulated with the oil of
lubricating viscosity to provide the above lubricant grades. Useful viscosity
improvers include but are not limited to polyolefins, such as ethylene-propylenecopolymers, or polybutylene rubbers, including hydrogenated rubbers, such as
styrene-butadiene or styrene-isoprene rubbers; or polyacrylates, including
polymethacrylates. In one embodiment, the viscosity improver is a polyolefin or
polymethacrylate. Viscosi~ improvers available commercially include Acryloidn'
viscosity improvers available from Rohm & Haas; Shellvis~ rubbers available fromShell Chemical; Trilenen' polymers, such as Trilene~ CP-40, available commercially
from Uniroyal Chemical Co., and Lubrizol 3100 series and 8400 series polymers,
such as Lubrizol 3174 avai1able from The Lubrizol Corporation.
In one embodiment, the oil of lubricating viscosity includes at least one ester
of a dicarboxylic acid. Typically the esters containing from about 4 to about 30,
preferably from about 6 to about 24, or from about 7 to about 18 carbon atoms ineach ester group. Here, as well as elsewhere, in the specification and claims, the
range and ratio lin~its may be combined. Examples of dicarboxylic acids include
glutaric, adipic, pimelic, suberic, azelaic and sebacic. Example of ester groupsinclude hexyl, octyl, decyl, and dodecyl ester groups. The ester groups include linear
as well as branched ester groups such as iso arrangements of the ester group. A
particularly useful ester of a dicarboxylic acid is diisodecyl azelate.
In another embodiment, the oil of lubricating viscosity is selected to provide
lubricating compositions for crankcase applications, such as for gasoline and diesel
engines. Typically, the lubricating compositions are selected to provide an SAE
crankcase viscosity number of lOW, 20W, or 30W lubricants. The lubricating
composition may also have a so called multi-grade rating such as SAE SW-30, lOW-30, lOW~0, 20W-50, etc. As described above, multigrade lubricants include a
.``'` ~ ~
. ~
.
21~7~
~ iscosity improver which is formulated with the oil of lubricating viscosity to provide
the above lubricant grades.
(A) Antioxidant
The lubricating compositions also include one or more antioxidants which are
present in a total amount of at least about 2% by weight. Gene~ally, the antioxidants
are present in an amount fTom about 2.2% up to about 10%, or from about 2.5% up
to about 8%, or from about 3% up to about 7% by weight. The antioxidants includeamine antioxidants, dithiophosphoric esters, phenol antioxidants, dithiocarbamates,
aromatic phosphites, and sulfurized fatty oils and olefins. In one embodiment, the
antioxidant (A) is a sulfur free antioxidant, preferably an amine antioxidant, or a
dithiocarbamate, preferably an alkylene coupled dithiocarbarnate.
Amine antioxidants include alkylated aromatic amines and heterocyclic amines.
The aLkylated aromatic amines include compounds represented by the formula Ar'-
N~-Ar2, wherein Arl and AT2 are independently mononuclear or polynuclear,
substituted or unsubstituted aromatic groups; and R, is hydrogen, halogen, OH, NH2,
SH, NO2 or a hydrocarbyl group having from 1 to about 50 carbon atoms. The
aromatic group as represented by "Arn, as well as elsewhere in other forrnulae in this
specification and in the appended claims, may be mononuclear or polynuclear.
Examples of mononuclear Ar moieties include benzene moieties, such as 1,2,4-
benzenetriyl; 1,2,3-benezenetriyl; 3-methyl-1,2,4-benzenetriyl; 2-methyl-5-ethyl-
1,3,4-benænetriyl; 3-propoxy-1,2,4,5-benzenetetrayl; 3-chloro-1,2,4-benzenebiyl;1,2,3,5-benzenetetrayl; 3-cyclohexyl-1,2,4-benzenetriyl; and 3-azocyclopentyl-1,2,5-
benzenetriyl, and pyridine moieties, such as 3,4,5-azabenzene; and ~methyl-3,4,5-
azabenzene. The polynuclear groups may be those where an aromatic nucleus is
fused at two points to another aromatic nucleus, such as naphthyl and anthracenyl
groups. Specific examples of fused ring aromatic moieties Ar include: 1,4,8-
naphthylene; 1,S,8-naphthylene; 3,~dime~hyl~,5,8(1-azonaphthalene); 7-methyl-9-
methoxy-1,2,5, 9-anthracenetetrayl; 3,10-phenathrylene; and 9-methoxy-
benz(a)phenanthrene-5,6,8, 12-yl. The polynuclear group may be those where at least
two nuclei (either mononuclear or polynuclear) are linl~d through bridging linkages.
These bridging linkages may be chosen from the group consisting of aL~cylene
linkages, ether linkages, keto linkages, sulfide linkages, and polysulfide linkages of
2 to about 6 sulfur atoms. Specific examples of Ar when it is linked polynucleas
.
c~
~ - , :: , : -
.. ~ , . . ..
2~47238
aromatic moiety include: 3,3',4,4',5-bibenzenetetrayl; di(3,4-phenylene)ether; 2,3-
phenylene-2,~naphthylenemethane; and 3-rnethyl,9H-fluorene-1,2,4,5,8-yl; 2,2-
di(3,4-phenylene)propane; sulfur-coupled 3-methyl-1,2,4-benzatriyl (having 1 to about
10 thiomethylphenylenegroups); and amino-coupled 3-methyl-1,2,4-benzatriyl (having
1 to about 10 aminomethylphenylene groups). Typically Ar is a benzene nucleus,
lower alkylene bridged benzene nucleus, or a naphthalene nucleus.
In another embodiment, the alkylated aromatic amine is represented by the
formula R2-Ar-NH-Ar-R3, wherein R~ and ~3 are independently hydrogen or
hydrocarbyl groups having from 1 to about 50, or from about 4 to about 20 carbonatoms. E~camples of aromatic amines include p,p'~ioctyldiphenylamine; octylphenyl-
beta-naphthylamine; octylphenyl-alpha-naphthylamine, phenyl-alpha-naphthylamine;phenyl-beta-naphthylamine; p-octylphenyl-alpha-naphthylamine and 4-octylphenyl-1-
octyl-beta-naphthylamine and di(nonylphenyl)amine, with di(nonylphenyl)amine pre-
ferred. U.S. Patents 2,558,285; 3,601,632; 3,368,975; and 3,505,225 disclose
diarylamines useful as antioxidant (A). These patents are incorporated herein byreference.
In another embodiment, the antioxidant (A) may be a phenothiazine.
Phenothiazines include phenothiazine, substituted phenothiazine, or derivatives, such
as those represented by the formula
::
IR4s(o)~Rs
~ N (I)
(R6)b -- ~S(~}~)b .`. ~
wherein R4 is an alkylene, alkenylene or an aralkylene group, or mixtures thereof,
R5 is selected from the group consisting of higher alkyl groups, or an aIkenyl, aryl,
alkaryl or aralkyl group and mixtures thereof; each R6 is independently alkyl, aLtcenyl,
aryl, aLkaryl, arylalkyl, halogen, hydroxyl, al~oxy, alkylthio, arylthio, or fused
aromatic rings, or mixtures thereof; a and b are each independently 0 or greater. In
one embodiment, R4 contains from about 2 to about 8, or two or three carbon atoms.
Rs typically contains from about 3 to zbout 30, or from about 4 to about 15 carbon
21~7~3~
g ::
S atoms. R6 contains from 1 to about 50, or from about 4 to about 30, or from 6 to
about 20 carbon atoms.
In another embodiment, the phenothiazine derivatives may be represented by
the formula
~ S~O~ :
R4
~S(O). (I~
~
wherein R4, R6, a and b are as defined with respect to Formula I.
The above-described phenothiazine derivatives, and methods for their
preparation are described in U.S. Patent 4,785,095, and the disclosure of this patent
is hereby incorporated by reference for its teachings of such methods and compounds.
In one embodiment, a dialkyldiphenylamine is treated with sulfur at an elevated -
temperature such as in the range of 145C to 205C for a sufficient time to complete
the reaction. A catalyst such as iodine may be utilized to establish the sulfilr bridge. ~ -
Phenothiazine and its various deAvatives may be converted to the above
compounds by contacting the phenothiazine compound containing the free NH group ;
with a thioalcohol of the formula R5SR40 H where R4 and R5 are defined with respect
to Formula I. The thioalcohol may be obtained by the reaction of a mercaptan, such
as hexanethiol, octanethiol and dodecanethiol, with an aL~ylene oxide, sueh as
ethylene or propylene oxide under basic conditions. Alternatively, the thioalcohol ~ ;
may be obtained by reacting a terminal olefin, such as those described herein, with ~ ~ -
..-:
mercaptoethanol under free radical conditions.
When it is desired to prepare compounds of the type represented by Formulae
I and II wherein a is 1 or 2, i.e., sulfones or sulfoxides, the derivatives prepared by
~ ':
`" 21~723~
the reaction with the thioalcohols described above are oxidized with an oxidizing
agent, such as hydrogen peroxide, in a solvent such as glacial acetic acid or ethanol
under an inert gas blanket. The partial oxidation takes place convenien~y at from
about 20C to about 150C. The foUowing examples iUustrate the preparation of
phenothiazines .
~ In one embodiment, the antioxidant may be a phosphorus ester. The ester
includes reaction products of a phosphorus acid with an unsaturated compound. The
phosphorus acids include the phosphoric, phosphonic, phosphinic and thiophosphoric
acids, including dithiophosphoric acid, as weU as the monothiophosphoric acid,
thiophosphinic and thiophosphonic acids. The phosphorus acid is typicaUy prepared
by reacting one or more phosphorus acid or anhydride with an alcohol containing
from one to about 30, or from two to about 24, or from about 3 to about 12 carbon
atoms. The phosphorus acid or anhydride is generaUy an inorganic phosphorus
reagent, such as phosphorus pentoxide, phosphorus trioxide, phosphorus tetroxide,
phosphorous acid, phosphoric acid, phosphorus halide, Cl 7 phosphorus esters, or a
phosphorus sulfide which includes phosphorus pentasulfide, phosphorus sesquisulfide,
phosphorus heptasulfide and the like. Alcohols used to prepare the phosphorus acid
esters include butyl, amyl, 2-ethylhexyl, hexyl, octyl, oleyl, and cresol alcohols.
Examples of commerciaUy available alcohols include Alfol 810 (a mixture of
primarily straight chain, primary alcohols having from 8 to 10 carbon atoms); Alfol
1218 (a mixture of synthetic, primary, straight-chain alcohols containing 12 to 18
carbon atoms); Alfol 20+ alcohols (mixtures of Cl8-C28 primary alcohols having
mostly C20 alcohols as determined by GLC (gas-~iquid-chromatography)); and Alfol22+ alcohols (C,8-C28 primary alcohols containing primarily C22 alcohols). Alfolalcohols are available from Continental Oil Company. Another exarnple of a
commercially available alcohol mixtures are Adol 60 (about 75% by weight of a
straight chain C22 primary alcohol, about 15% of a C20 primary alcohol and about 8%
of Cl8 and C2, alcohols) and Adol 320 (oleyl alcohol). The Adol alcohols are
marketed by Ashland Chemical.
A variety of mixtures of monohydric fatty alcohols derived from natu~ally
occurring triglycerides and ranging in chain length of from C8 to Cl8 are available
from Procter & Gamble Company. These mixtures contain various amounts of fatty
alcohols containing mainly 12, 14, 16, or 18 carbon atoms. For exarnple, CO-1~14
, .. . ........ . . .
- '~14723~ `
S is a fatty alcohol mL~ture containing 0.5% of Cl0 alcohol, 66.0% of C,2 alcohol,
26.0% of Cl4 alcohol and 6.5% of C,6 alcohol.
Another group of commercially available mixtures include the "Neodol"
products available from Shell Chemical Co. For example, Neodol 23 is a mixture
of C12 and Cl3 alcohols; Neodol 25 is a mixture of Cl2 and Cl5 alcohols; and Neodol
45 is a mixture of Cl4 to Cl5 linear alcohols. Neodol 91 is a n~ixture of C9, Clo and
Cll alcohols.
Fatty vicinal diols also are useful and th~se include those available from
Ashland Oil under the general trade designation Adol 114 a ld Adol 158. The former
is derived from a straight chain alpha-olefin fraction of Cll-C14, and the latter is
derived from a Cls-C,8 alpha-olefin fraction.
In one embodiment, the phosphorus acid is a thiophosphorus acid or salt
thereof. The thiophosphorus acid or salt may be prepared by reacting one or morephosphorus sulfides, such as those described above with alcohols, such as those
described above. The thiophosphorus acid esters may be mono- or dithiophosphorusacid esters. Thiophosphorus acid esters are also referred to generally as
dithiophosphates.
In one embodiment, the phosphorus acid is a monothiophosphoric acid.
Monothiophosphic acids may be prepared by the reaction of a sulfur source with adihydrocarbyl phosphite. The sulfur source may ~or instance be elemental sulfur, or
a sulfide, such as a sulfur coupled olefin or a sulfur coupled dithiophosphate.
Elemental sulfur is a preferred sulfur source. The preparation of monothiophosphoAc
acids is disclosed in U.S. Patent 4,755,311 and PCT Publication WO 87/07638,
which are incorporated herein by reference for their disclosure of monothiophosphoric
acids, sulfur sources, and the process for making monothiophosphoric acids
Monothiophosphoric acids may also be formed in the lubricant blend by adding a
dihydrocarbyl phosphite to a lubricating composition containing a sulfur source, such
as a sulfurized olefin. The phosphite may react with the sulfur source under blending
conditions (i.e., temperatures from about 30C to about 100C, or higher) to fonn
the monothiophosphoAc acid.
In another embodiment, the phosphorus acid is a dithiophosphoric acid or
phosphorodithioic acid. The dithiophosphoric acid may be represented by the formula
(R7O)2PSSH, wherein each R7 is independently a hydrocarbyl group containing from
~ ~ .
` 214723~
S about 3 to about 30, or from about 3 up to about 18, or from about 4 up to about 12,
or up to about 8 carbon atoms. Examples of R7 include isopropyl, isobutyl, n-butyl,
sec-butyl, amyl, n-hexyl, methylisobutyl carbinyl, heptyl, 2~thylhexyl, isooctyl,
nonyl, behenyl, decyl, do~ecyl, tridecyl, alkylphenyl groups, or mLxtures thereof.
Illustrative lower alkylphenyl R7 groups include butylphenyl, amylphenyl, and
heptylphenyl and mixtures thereof. Examples of mixtures of R7 groups include:
l-butyl and l-octyl; l-pentyl and 2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl and
isoamyl; 2-propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl; and isopropyl and
isooctyl.
As described above, the phosphoric acids are reacted with an unsaturated
compound to form the phosphorus esters. The unsaturated compounds include
unsaturated amides, esters, acids, epoxides, and ethers. Examples of unsaturatedamides include acrylamide, N,N'-methylene bis(acrylamide), methacrylamide,
crotonamide, and the like. The reaction product of the phosphorus acid and the
unsaturated amide may be further reacted with a lin~ng or a coupling compound,
such as formaldehyde or paraformaldehyde. Examples of phosphorus containing
amides include the reaction product of di(methylarnyl) dithiophosphoric acid andacrylamide and the reaction product of di(amyl) dithiophosphoric acid, acrylamide and
paraformaldehyde. The phosphorus containing amides are known in the art and are
disclosed in U.S. Patents 4,670,169, 4,770,807, and 4,876,374 whlch are
incorporated by reference for their disclosures of phosphorus amides and their
preparation.
In another embodiment, the unsaturated compound is an unsaturated carboxylic
acid or ester. Examples of unsaturated carboxylic acids and anhydrides include
acrylic acid or esters, methacrylic acid or esters, itaconic acid or esters, fumaric acid
or esters, and maleic acid, anhydride, or esters. The esters may be represented by
one of the formulae R8C=C(R9)C(O)ORIo, or RloO-(O)C-HC=CH-C(O)ORIo,
wherein each R8 and Rlo are independently hydrogen or a hydrocarbyl group havingfrom one to about eighteen, or from one to about twelve, or from one to about eight
carbon atoms, R9 is hydrogen or an alkyl group having from one to about SLlC carbon
atoms. In one embodiment, R9 is preferably hydrogen or a methyl group. 13xamplesof unsaturated carboxylic esters include methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl
` ^` 21~7238
13
methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, ethyl maleate, butyl maleate and 2-ethylhexyl maleate.
The above list includes mono- as well as diesters of maleic, fumanc and citraconic
acids. If the carboxylic acid is used, the ester may then be formed by subsequent
reaction of the phosphoric acid-unsaturated carboxylic acid adduct with an alcohol,
such as those described above. Examples of phosphorus containing esters are the
reaction product of isobutyl, amyl dithiophosphoric acid and methyl acrylate anddi(amyl)dithiophosphoric acid and butyl methacrylate.
In another embodiment, the unsaturated compound is a vinyl ether. The vinyl
ether is represented by the formula RIl-CH2=CH-ORl2, wherein R,l and Rl2 are
independently hydrogen or a hydrocarbyl group having from 1 up to about 30, Dr
from 1 up to about 24, or from 2 up to about 12 carbon atoms. Examples of vinyl
ethers include methyl vinyl ether, propyl vinyl ether, 2-ethylhexyl vinyl ether and the
like.
In another embodiment, the unsaturated compound is a vinyl ester. The vinyl
ester may be represented by the formula Rl3CH=CH-O(O)CRl4, wherein Rl3 is a
hydrocarbyl group having from 1 to about 30, or from 1 to about 12 carbon atoms,preferably hydrogen, and Rl4 is a hydrocarbyl group having 1 to about 30, or from
1 to about 12, or from 1 to about 8 carbon atoms. Examples of vinyl esters include
vinyl acetate, vinyl 2-ethylhexanoate, vinyl butanoate, etc.
In another embodiment, the antioxidant (A) is at least one phenol antioxidant.
The phenol antioxidants include metal and metal free hindered phenols. AL~ylene
coupled derivatives of hindered phenols and phenol sulfides or sulfur coupled phenols
may also be used. Hindered phenols are defined as those containing a sterically
hindered hydroxyl group, and these include those derivatives of dihydroxy aryl
compounds wherein the hydroxyl groups are in the ~ or ~position to each other.
The metal-free hindered phenols may be represented by the following formulae:
- ` 2147238
.
14
~H
Rl5 ~ Rl7
~0 J
R16
(~H ~H
R,5~_RI5 (IV)
0 16 16
~)H ~;)H
R,s ~--C(RI8)2~Rl5 (V)
R-6 R16
wherein each R~s is independently a hydrocarbyl group contail~Lng from 3 to about 9
15 carbon atoms, each R,6 is hydrogen or a hydrocarbyl group, Rl7 is hydrogen or a
hydrocarbyl group containing from 1 to about 9 carbon atoms, and each Rl8 is
independently hydrogen or a methyl group. In one embodiment, Rl6 is an alkyl group
containing from about 3 to about 50, or from about 6 to about 20, or from about 6
to about 12 carbon atoms. In one embodiment alkyl groups are derived from
20 polymers of ethylene, propylene, l-butene and isobutene, preferably propylenetetramer or trimer. Examples of such groups include hexyl, heptyl, octyl, decyl,dodecyl, tripropenyl, tetrapropenyl, etc. Examples of Rl5, Rl6 and Rl7 groups include
propyl, isopropyl, butyl, sec-butyl, tert-butyl, heptyl, octyl, and nonyl. In another
embodiment, each Rl5 and Rl7 are tertiary groups, such as tert-butyl or tert-amyl
25 groups. The phenol~c compounds may be prepared by various techniques, and in one
embodiment, such phenols are prepared in stepwise manner by first preparing the
para-substituted alkylphenol, and thereafter alkylating thepara-substituted phenol in
the 2- and/or ~position as desired. When it is desired to prepare coupled phenols of
the type represented by Formulae IV and V, the second step alkylation is conducted
30 under conditions which result in the alkylation of only one of the positions ortho to
723~
the hydroxyl group. Examples of useful phenolic materials include:
2-t-butyl-4-heptylphenol; 2-t-butyl-4-octylphenol; 2-t-butyl-4-dodecylphenol; 2,~di-t-
butyl-4-butylphenol; 2,~di-t-butyl-4-heptylphenol; 2,~di-t-butyl~-dodecylphenol;2,6-di-t-butyl-tetrapropenylphenol; 2-methyl-~di-t-butyl~-heptylphenol; 2,6-di-t-
butyl-tripropenylphenol; 2,4-dimethyl-~t-butylphenol; 2,~t-butyl-4-ethylphenol; 4-t-
butylcatechol; 2,4-di-t-butyl-p-cresol; 2,~di-t-butyl4-methylphenol; and 2-methyl-~
di-t-butyl-4-dodecylphenol. Examples of the ortho coupled phenols include:
2,2'-bis(6-t-butyl-4-heptylphenol); 2,2'-bis(6-t-butyl-4-octylphenol); 2,6-bis-(1'-
methylcyclohexyl)-4-methylphenol; and 2,2'-bis(~t-butyl~-dodecylphenol).
Alkylene-coupled phenolic compounds may be prepared from the phenols by
reaction of the phenolic compound with an aldehyde, typically those containing from
one to about eight carbon atoms, such as formaldehyde or acetaldehyde, aldehyde
precursors, such as paraforrnaldehyde or trioxane, or a ketone, such as acetone. The
alkylene-coupled phenols may be obtained by reacting from 0.3 to about 2 moles aphenol with 1 equivalent of an aldehyde or ketone. Procedures for coupling of
phenolic compounds with aldehydes and ketones are known to those in the art.
Examplesofphenoliccompoundsinclude2,2'-methylenebis(6-t-butyl~-heptylphenol);
2,2'-methylenebis(6-t-butyl-4-octylphenol); 2,2'-methylenebis(4-
dodecyl-6-t-butylphenol); 2,2'-methylenebis(4-octyl-6-t-butylphenol);
2,2'-methylenebis(4-octylphenol); 2,2'-methylenebis(4-dodecylphenol);
2,2'-methylenebis(4-heptylphenol); 2,2'-methylenebis(~t-butyl-4~odecylphenol);
2,2'methylenebis(~t-butyl~-tetrapropenylphenol); and2,2'methylenebis(~t butyl~-
butylphenol).
In another embodiment, the antioxidant (A) is a metal-free (or ashless)
alkylphenol sulfide or sulfur coupled phenols. The alkylphenols from which the
3~ sulfides are prepared also may comprise phenols of the type discussed above and
represented by Formula III wherein Rl7 is hydrogen. For example, the alkylphenols
which can be converted to alkylphenol sulfides include: 2-t-butyl-4-heptylphenol;
2-t-butyl-4-octylphenol; and 2-t- butyl-4-dodecylphenol; 2-t-buty-4-
tetrapropenylphenol. The term "alkylphenol sulfides" is meant to include
di-(alkylphenol) monosulfides, disulfides, and polysulfides, as well as other products
obtained by the reaction of the alkylphenol with sulfur monochloride, sulfur dichlor-
ide or elemental sulfur. One mole of phenol typically is reacted with about 0.5-1.5
-" 2147238
16
S moles, or higher, of sulfur compound. For example, the alkylphenolsulfides are
readily obtained by mixing, one mole of an alkylphenol and 0.5-2.0 moles of sulfur
dichloride. The reaction mixture is usually maintained at about 100C for about 2-5
hours, after which time the resulting sulfide is dried and filtered. When elemental
sulfur is used, temperatures from about 15~250C or higher are typically used. It
is also desirable that the drying operation be conducted under nitrogen or a similar
inert gas. A particularly useful alkylphenol sulfide is thio-bis(tetrapropenylphenate).
Suitable basic alkylphenolsulfides are disclosed, for example, in U.S. Patents
3,372,116; 3,410,798; and 4,021,419, which are hereby incorporated by reference.These sulfur-containing phenolic compositions described in U.S. Patent 4,021,419 are
obtained by sulfurizing a substituted phenol with sulfur or a sulfur halide and
thereafter reacting t~e sulfurized phenol with formaldehyde or an aldehyde precursor,
e.g., paraformaldehyde or trioxane. Alternatively the substituted phenol may be first
reacted with forrnaldehyde or paraformaldehyde and thereafter reacted with sulfur or
a sulfur halide to produce the desired al~ylphenol sulfide.
In another embodiment, the antioxidant (A) is a dithiocarbamate antioxidant.
The dithiocarbamate antioxidants include reaction products of a dithiocarbamic acid
or salt and one or more of the above described unsaturated compounds, such as
unsaturated amides, carboxylic acids, anhydrides, or esters, or ethers; alkylene-
coupled dithiocarbamates; and bis(S-alkyldithiocarbamoyl) disulfides. In one
embodiment, the dithiocarbamate compounds are ashless, i.e. metal free. The
dithiocarbamic acid or salts may be prepared by simultaneously reacting an amine,
carbon disulfide and one or more of the above unsa~urated compounds. Generally,
the reaction occurs at a temperature from about 25C, or from about 50C to about
125C, or to about 100C. U. S. Patents 4,758,362 and 4,997,969 describe
dithiocarbamate compounds and methods of making the same. These patents are
hereby incorporated by reference for their disclosure of dithiocarbarnate compounds
and method of making the same.
The dithiocarbamic acid or salt may be prepared by reacting an amine with
carbon disulfide. The amine may be a pAmary or a secondary amine. The amine
may be a mono-or polyamine, such as those described herein. The amines may be
primary or secondary amines, with secondary amines preferred. The amines
~'. ' " .'~
```~ 21~7238
generally may contain hydrocarbyl groups independently having from 1 up to about40, or from about 2 up to about 30, or from 3 up to about 24, or eYen up to about
12 carbon atoms. In one embodiment, the amines are primary amines. Exarnples of
primary amines useful in the present invention include ethylarnine~ propylamine,butylamine, 2-ethylhexylamine, octylamine, and dodecylamine.
In one embodiment, the primary amine is a fatty arnine, such as those
containing from about 8 to about 30, or from about 12 to about 24 carbon atoms.
The fatty a nines include n-octylamine, n-decylamine, n~odecylamine, n-tetradecyl-
amine, n-hexadecylamine, n-octadecylamine, oleyamine, etc. Also useful fatty
amines include commercially available fatty amines such as "Armeen" amines
(products available from Akzo Chemicals, Chicago, Illinois~, such as Akzo's Armeen
C, Armeen O, Armeen OL, Armeen T, Armeen Hl, Armeen S and Armeen SD,
wherein the letter designation relates to the fatty group, such as cocoa, oleyl, tallow,
or stearyl groups.
Other useful primary amines include primary ether amines, such as those
represented by the formula, R~8(ORI9)xNH2 ~ wherein R,8 is a divalent alkylene group
having about 2 to about 6 carbon atoms; x is a number from one to about 150, or
from about one to about five, or one; and R,9 is a hydrocarbyl group from about 5
to about 150, or from 1 to about 24 carbon atoms. An example of an ether amine is
available under the name SURFAM~ amines produced and marla~ted by Mars
Chemical Company, Atlanta, Georgia. Etheramines include those identified as
SURFAM P14B (decyloxypropylamine), SURFAM P16A ~inear C,63, and SURFAM
P17B (tridecyloxypropylamine). The carbon chain leng hs (i.e., Cl4, etc.) of theSURFAMS described above and used hereinafter are approximate and include the
oxygen ether linkage.
In another embodiment, the primary amine is a tertiary-aliphatic pnmary
amine. Generally, the aliphatic group, and in one ernbodiment an alkyl group,
contains from about 4 to about 30, or from about 6 to about 24, or from about 8 to
about 22 carbon atoms. Usually the tertiary alkyl primary amines are monoarninesrepresented by the formula R20-C(R2,')2-NH2, wherein R20 is a hydrocarbyl group
containing from 1 to about 28 carbon atoms and R2,' is a hydrocarbyl group
containing from 1 to about 12 carbon atoms. Such amines are illustrated by
tert-butylamine, tert-hexylamine, l-methyl-l-zmino-cyclohexane, tert octylamine,
~1~723~
18
S tert-decylamine, tert-dodecylamine, teIt-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, and tert~ctacosanylamine.
Mixtures of amines are also useful for the purposes of this invention.
Illustrative of amine mixtures of this type are ~Primene 81R" which is a mixture of
Ctl-C,4 tertiary alkyl primary amines and "Primene JMT" which is a similar mixture
of C,8-Cn tertiary alkyl primary amines (both are available from Rohm and Haas
Company). The tertiary alkyl primary amines and methods for their preparation are
known to those of ordinary skill in the art. The tertiary alkyl primary amine useful
for the purposes of this invention and methods for their preparation are described in
U.S. Patent 2,945,749, which is hereby incorporated by reference for its teaching in
this regard.
In another embodiment, the amine is a secondary amine. Specific examples
of secondary amines include dimethylamine, diethylamine, dipropylamine,
dibutylarnine, diamylamine, dihexylamine, diheptylarnine, methylethylamine,
ethylbutylamine, ethylamylamine and the like. In one embodiment, the secondary
amines may be cyclic amines such as piperidine, piperazine, morpholine, etc.
In one embodiment, the dithiocarbamate compound (A) is prepared by reacting
one or more dithiocarbamic acids or salts with one or more of the above unsaturated
amides. If the reaction products of the dithiocarbamic acid or salt and an unsaturated
amide has at least one additional NH group which are capable of reacting, then the
reaction product may be further reacted with a linking or a coupling compound, such
as formaldehyde or parafor naldehyde. The reaction products of dithiocarbamic acids
and salts with unsaturated amides are disclosed in U.S. Patents 4,758,362 (Butke) and
4,997,969 (Luciani), which patents are incorporated by reference for their disclosures
of dithiocarbamic acids and salts, unsaturated amides and their reaction products
including coupled products.
In one embodiment, the dithiocarbamate compound (A) is a reaction product
of a dithiocarbamic acid or salt with one or more of the above described unsaturated
acids, anhydrides or esters. If an unsaturated carboxylic acid or anhydride is used,
an ester may then be formed by subsequent reaction of the dithiocarbamate~
unsaturated carboxylic acid or anhydride adduct with an alcohol, such as those
alcohols discussed above. In one embodiment, the dithiocarbamate acid or salt is
'''""~'';'''
21~723~
S formed from diethylamine or dibutylamine and carbon disulfide. The resulting
dithiocarbamic acid is then reacted with methyl acrylate.
In one embodiment, the dithiocarbamate compound (A) is an alkylene-coupled
dithiocarbamate. The dithiocarbamate may be represented by the Formula:
Rn(R23)N-C(S)-S-R2~-S-C(S)-N(R23)R22; wherein each R22 is independently a
hydrogen; a hydrocarbyl group having from 1 to about 18 carbon atoms, or from 1
to about 10, or from 1 to about 6; or R22 taken together with R23 and a nitrogen atom
form a five, six or seven member heterocyclic group; each R23 is independently ahydrocarbyl group having from 1 to about 18 carbon atoms, or R23 taken together
with R22 and a nitrogen atom form a five, six or seven member heterocyclic group;
and R~4 is a hydrocarbylene group having from 1 to about 10, or from 1 to about 4
carbon atoms. In one embodiment, each R22 is independently a hydrogen or a propyl,
butyl, arnyl or hexyl group, or a butyl group. The above list encompasses all stereo
arrangements of thesei groups, including isopropyl, n-propyl, isobutyl, sec-butyl, and
n-butyl. When R7~ is a hydrocarbyl group, it is defined the same as when R~2 is a
hydrocarbyl group. When R~ and R23 are taken together with a nitrogen atom to
form a five, six or seven member heterocyclic group, the heterocyclic group is apyrrolidinyl, a piperidinyl, a morpholinyl or a piperazinyl group. The heterocyclic
group may contain one or more, or from one to three alkyl substituents on the
heterocyclic ring. The alkyl substituents generally contain from about one to about
six carbon atoms. Examples of heterocyclic groups include 2-methylmorpholinyl,
3-methyl-S-ethylpiperidinyl,3-hexylmorpholinyl,tetramethylpyrrolidinyl,piperazinyl,
2,5-dipropylpiperazinyl, piperidinyl, 2-butylpiperazinyl, 3,4,5-triethylpiperidinyl,
3-hexylpyrrolidinyl, and 3-ethyl-S-isopropylmorpholinyl groups. In one embodiment,
the heterocyclic group is a pyrrolidinyl or piperidinyl group.
Examples of R~ groups include an alkylene, arylene, aLkarylene, and
arylalkylene. In one embodiment, Rn is a methylene or ethylene group. In anotherembodiment, R~4 is an arylene group, alkarylene group, or arylalkylene group having
from 6 to about 10, or from 6 to about 8 carbon atoms. In one embodiment, R~4 isa phenylmethylene, phenylethylene, phenyldiethylene, phenylene, or tolylene group.
U.S. Patent 3,876,550, issued to Holubec, describes lubricant compositions
containing allylene dithiocarbamic compounds. U.S. Patents 1,726,647 and
1,736,429, issued to Caldwell, describe phenylmethylenebis(dithiocarbamates) and
--` 2147238
S methods for making the same. These patents are incorporated by reference for their
teachîngs relating to dithiocarbamate compounds and methods for preparing the same.
A particularly useful dithiocarbamate is methylenebis(di-n-butyldithiocarbamate).
In another embodiment, the dithiocarbamate compound is a bis(S-
alkyldithiocarbamoyl) disulfide. These materials have previously been referred to as
sulfur-coupled dithiocarbamates. The disulfides are prepared by (A) reacting a sulfur
halide with about a stoichiometric equivalent of (i) at least one olefinic hydrocarbon,
or (ii) an aldehyde or ketone, at a temperature and for a period of time sufficient to
produce a di(halohydrocarbyl)sulfur intermediate or a dialdehyde or diketo sulfur
intermediate, and (B) reacting the intermediate with a salt of a dithiocarbamate in an
amount sufficient generally to replace both halo groups with the dithiocarbamategroups or to react with both carbonyl groups of the dialdehyde or diketone. The
sulfur halide utilized in the first step (A) may be sulfur monochloride (i.e., S2Cl2),
sulfur dichloride, sulfur monobromide, sulfur dibromide, or mixtures of any of the
above sulfur halides with elemental sulfur in varying amounts.
The sulfur halide utilized in the first step (A) may be sulfur monochloride
(i.e., S2Cl2), sulfur dichloride, sulfur monobromide, sulfur dibromide, or mixtures
of any of the above sulfur halides with elemental sulfur in varying amounts. Various
olefins and olefin mixtures may be used as the starting material in step (A). The
olefins are disclosed below. Specific examples of aldehydes that may be reacted with
sulfur halides include, for example, acetaldehyde, propionaldehyde, butyraldehyde,
isobutyraldehyde, 2-ethyl-hexanal, and cyclohexanecarboxaldehyde. Examples of
ketones include dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl
isopropyl ketone, methyl isobutyl ketone, etc.
The bis(S-alkyldithiocarbamoyl) disulfides also may be prepared by a process
which comprises the steps of (A) reacting an olefinic hydrocarbon with a halogen to
produce a halogen-containing intermediate, and (B) reacting said intermediate with
an alkali metal sulfide and a salt of a dithiocarbamate in an amount sufficient to
replace the halogen groups present partially with dithiocarbamate groups and/or
partially with sulfide groups. The bis(S-alkyldithiocarbamoyl) disulfides are described
in U.S. Patent 2,599,350, issued to Rudel et al. This patent is incorporated by
reference for its disclosure of bis(S-alkyldithiocarbamoyl) disulfide and methods of
making the same.
~ . .. - - . . . : :
1'.' ' . . ' , . . ~ ' . -:
21~2~$
21
S ~B) Dispersant or Detergent
As descAbed above, the lubAcating compositions contain from about 0.01%
to about 3% by weight of at least one dispersant or detergent. Generally, the
dispersant or detergent is present in an amount from about 0.1% to about 3%,
preferably ~rom about 0.2 % to about 2 %, more preferably from about 0.3 % to about
1.5% by weight of the lubAcating composition. The dispersants include acylated
amines, carboxylic esters, Mznnich reaction products, hydrocarbyl substituted amines,
and mixtures thereof. In one embodiment, the dispersant or detergent is a boron
containing dispersant or detergent.
The acylated amines include reaction products of one or more carboxylic
acylating agent and one or more amine. The carboxylic acylating agents include fatty
acids, isoaliphatic acids, dimer acids, addition dicarboxylic acids, trimer acids,
addition tAcarboxylic acids, and hydrocarbyl substituted carboxylic acylating agents.
In one embodiment, the carboxylic acylating agent is a fatty acid. The fatty acids
generaUy contain from about 8 to about 30, or from about 12 to about 24 carbon
atoms. Examples of fatty acids include palmitoleic acid, oleic, linoleic, linolenic,
erucic acid, lard oil acid, soybean oil acid, taU oil and rosin acid.
In another embodiment, the carboxylic acylating agents include isoaliphatic
acids. Such acids contain a principal saturated, aliphatic chain typicaUy having from
about 14 to about 20 carbon atoms and at least one, but usually no more than about
four, pendant acyclic lower alkyl groups. Specific examples of such isoaliphatic acids
include 10-methyl-tetradecanoic acid, 3-ethyl-hexadecanoic acid, and
8-methyl-octadecanoic acid. The isoaliphatic acids include branched-chain acids
prepared by oligomerization of commercial fatty acids, such as oleic, linoleic and tall
oil fatty acids.
The dimer acids include products resulting from the dimerization of
unsaturated fatty acids and generally contain an average from about 18 to about 44,
or from about 28 to about 40 carbon atoms. Dimer acids are described in U.S.
Patents 2,482,760, 2,482,761, 2,731,481, 2,793,219, 2,964,545, 2,978,468,
3,157,681, and 3,256,304, the entire disclosures of which are incorporated herein by
reference.
In another embodiment, the carboxylic acylating agents are addition carboxylic
acylating agents, which are addition (4+2 and 2+2) products of an unsaturated fatty
~^
. ' ` : ~ , ', ' ' '
,~ , . . .
7 .~ 3 ~
acid, such æ tall oil acids and oleic acids, with one or more unsaturated carboxylic
reagents, which are described below. These acids are taught in U.S. Patent No.
2,444,328, the disclosure of which is incorporated herein by reference.
In another embodiment, the carboxylic acylating agent is a hydrocarbyl
substituted carboxylic acylating agent. The hydrocarbyl substituted carboxylic
acylating agents are prepared by a reaction of one or more olefins or polyalkenes with
one or more unsaturated carboxylic reagent. The unsaturated carboxylic reagents
include unsaturated ~arboxylic acids per se and functional denvatives thereof, such
æ anhydrides, esters, arnides, imides, salts, acyl halides, and nitriles. The
unsaturated carboxylic reagent include mono, di, tri or tetracarboxylic reagents.
Specific examples of useful monobasic unsaturated carboxylic acids are acrylic acid,
methacrylic acid, cinnamic acid, crotonic acid, 2-phenylpropenoic acid, etc.
Exemplary polybasic acids include maleic acid, maleic anhydride, fumaric acid, mesa~
conic acid, itaconic acid and citraconic acid. Generally, the unsaturated carboxylic
reagent is maleic anhydride, acid or lower ester, e.g. those containing less than eight
carbon atoms.
The hydrocarbyl group generally contains from about 8 to about 300, or from
about 12 up to about 200, or from about 16 up to about 150, or from about 30 to
about 100 carbon atoms. In one embodiment, the hydrocarbyl group contains from
about 8 up to about 40, or from about 10 up to about 30, or from about 12 up to
about 24 carbon atoms. The hydrocarbyl group may be derived from an olefin. The
olefins typically contain from about 3 to about 40, or from about 4 to about 24 carbon
atoms. These olefins are preferably alpha-ole~ms (sometimes referred to as mono-l-
olefins or terminal olefins) or isomerized alpha-olefins. Examples of the alpha-olefins
include l-octene, l-nonene, l-decene, l-dodecene, l-tridesene, l-tetradecene, 1
pentadecene, l-hexadecene, l-heptadecene, l-octadecene, l-nonadecene, l-eicosene,
l-heneicosene, l-docosene, l-tetracosene, etc. CommerciaUy available alpha-oleIin
fractions that can be used include the Cls ,8 alpha-olefins, C,2 ,6 alpha-olefins, Cl~,6
alpha-olefins, C,~,8 a,lpha-olefins, C,6 l8 alpha-olefins, Cl620alpha-olefins, C,8 24 alpha-
olefins, C22-28 alpha-olefins, etc.
In another embodiment, the hydrocarbyl group is derived from a polyalkene.
The polyalkene includes homopolymers and inteIpolymers of polymerizable olefin
monomers having from 2 up to about 16, or from 2 up to about 6, or from 2 to about
~ -:
`- 21~723~
23
4 carbon atoms. The olefins may be monoolefins, such as ethylene, propylene,
l-butene, isobuten~, and l-octene, or polyolefinic monomers, including diolefinic
monomers, such l,3-butadiene and isoprene. In one embodiment, the interpolymer
is a homopolymer. In one embodiment, the homopolymer is a polybutene, such as
a polybutene in which about 50% of the polymer is derived from butylene. The
polyalkenes are prepared by conventional procedures. In one embodiment, the
polyalkene is characterized as containing from about 8 up to about 300, or from about
30 up to about 200, or from about 35 up to about 100 carbon atoms. In one
embodiment, the polyalkene is characterized by an Mn (number average molecular
weight) of at least about 400 or at least about 500. Generally, the polyalkene is
characterized by having an Mn from about 500 up to about 5000, or from about 700up 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.
The abbreviation Mn is the conventional symbol representing number average
molecular weight. Gel permeation chromatography (GPC) is a method which
provides both weight average and number average molecular weights as well as theentire molecular weight distribution of the polymers. For purpose of this invention
a series of fractionated polymers of isobutene, polyisobutene, is used as the
calibration standard in the GPC. The techniques for determining Mn and Mw valuesof polymers are well known and are described in numerous books and articles. Forexample, methods for the determination of Mn and molecuL~r weight distribution of
polymers is descri~ed in W.W. Yan, J.J. Kirkland and D.D. Bly, ~Modern Size
Exclusion Liquid Chromatographs", J. Wiley & Sons, Inc., 1979.
In another embodiment, the polyalkenes have a Mn from about 1300 up to
about 5000, or from about 1500 up to about 4500, or from about 1700 up to about
3000. The polyalkenes also generally have a Mw/Mn from about 1.5 to about 4, or
from about 1.8 to about 3.6, or from about 2.5 to about 3.2. The hydrocarbyl
substituted carboxylic acylating agents are described in U.S. Patent 3,219,666 and
4,234,435, the disclosures of which is hereby incorporated by reference.
In another embodiment, the acylating agents may be prepared by reacting one
or more of the above described polyalkenes with an excess of maleic anhydride toprovide substituted succinic acylating agents wherein the number of succinic groups
-`~ 21~723~
24
S for each equivalent weight of substituent group, i.e., polyaLkenyl group, is at least
1.3. The maximum number will generally not exceed 4.5. A suitable range is from
about 1.3 to 3.5 and or from about 1.4 to about 2.5 succinic groups per equivalent
weight of substituent groups.
The carboxylic acylating agents are known in the art and have been described
in detail, for example, in the following U.S. Patents 3,215,707 (Rense); 3,219,666
(Norman et al); 3,231,587 (Rense); 3,912,764 (Palmer); 4,110,349 (Cohen); and
4,234,435 (Meinhardt et al); and U.K. 1,440,219. The disclosures of these patents
are hereby incorporated by reference. These patents are incorporated herein by
reference for their disclosure of carboxylic acylating agents and methods for making
the same.
The above-described carboxylic acylating agents are reacted with amines to
form the acylated amines. The amines may be monoamines or polyamines. Useful
amines include those amines disclosed in U.S. Patent 4,234,435 at Col. 21, line 4 to
Col. 27, line 50, these passages being incorporated herein by reference. The amines
may be any of the above described amines.
In one embodiment, the amine may be a hydroxyamine. Typically, the
hydroxyamines are primary, secondary or tertiary alkanol amines or mixtures thereof.
Such amines can be represented by the formulae: H2--NR'~H,
HR'I--N--R'~H, and (R',)2--N--R'--OH, wherein each R'l is independently a
hydrocarbyl group having from one to about eight carbon atoms or
hydroxyhydrocarbyl group having from one to about eight carbon atoms, or from one
to about four, and R' is a divalent hydrocarbyl group of about two to about 18 carbon
atoms, or from two to about four. The group -R'-OH in such formulae represents
the hydroxyhydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group.Typically, R' is an acyclic straught or branched alkylene group such as an ethylene,
1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. group. Where two R'l groups are
present in the same molecule they can be joined by a direct carbon-to-carbon bond
or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, ~, 7- or
8-membered Ang structure. Examples of such heterocyclic amines include
N-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperAdines, -oxazolidines,
-thiazolidines and the like. Typically, however, each R', is independently a methyl,
ethyl, propyl, butyl, pentyl or hexyl group. Examples of these alkanolamines include
.
`` 21~23~
S mon~, di-, and triethanolamine, diethylethanolamine, ethylethanolamine,
butyldiethanolamine, etc.
The hydroxyamines may also be an ether N-(hydroxyhydrocarbyl)amine.
These are hydroxypoly(hydrocarbyloxy) analogs of the above-described
hydroxyamines (these analogs also include hydroxyl-substituted oxyallylene analogs).
Such N-(hydroxyhydrocarbyl) amines can be conveniently prepared by reaction of
epoxides with aforedescribed amines and may be represented by the formulae~
H2N--~R'O)I- H, HR',- N--~R'O)~ - H, and ~R',)2 - NtR'O)~ - H, wherein x
is a number from about 2 to about 15 and Rl and R' are as described above. R'l may
also be a hydroxypoly(hydrocarbyloxy) group.
In another embodiment, the amine is a hydroxyamine which may be
represented by the formula
~R260)~a (R260)~H
R2s ( N--R27 ) Y N~R26O)~H
wherein R7 is a hydrocarbyl group containing from about 6 to about 30 carbon atoms;
R8 is an alkylene group having from about two to about twelve carbon atoms,
preferably an ethylene or propylene group; Rg is an alkylene group containing up to
about 5 carbon atoms; y is zero or one; and each z is independently a number from
zero to about 10, with the proviso that at least one z is zero.
Useful hydroxyhydrocarbyl amines where y in the above forrnula is zero
include 2-hydroxyethylhexylamine; 2-hydroxyethyloctylamine;
2-hydroxyethylpentadecylamine;2-hydroxyethyloleylamine;2-hydroxyethylsoyamine;
bis(2-hydroxyethyl)hexylamine; bis(2-hydroxyethyl)oleylamine; and rluxtures thereof.
Also included are th 'e comparable members wherein in the above formula at least one
z is at least 2, as for example, 2-hydroxyethoxyethyl, hexylarnine.
In one embodiment, the amine may be a hydroxyhydrocarbyl amine, where
referring to the above formula, y equals zero. These hydroxyhydrocarbyl amines are
available from the Akzo Chemical Division of Akzona, Inc., Chicago, Illinois, under
the general trade designations "Ethomeen" and "Propomeen". Specific examples of
such products include: Ethomeen C/15 which is an ethylene oxide condensate of a
.- . . . . .
~1~7~38
2 6
coconut fatty acid containing about 5 moles of ethylene oxide; Ethomeen C/20 andC/25 which are ethylene oxide condensation products from coconut fatty acid
containing about 10 and 15 moles of ethylene oxide, respectively; Bthomeen O/12
which is an ethylene oxide condensation product of oleyl amine containing about 2
moles of ethylene oxide per mole of amine; Ethomeen S/15 and S/20 which are
ethylene oxide condensation products with stearyl amine containing about 5 and 10
moles of ethylene oxide per mole of amine, respectively; Ethomeen TJ12, T/15 andT/25 which are ethylene oxide condensation products of tallow amine containing
about 2, 5 and 15 moles of ethylene oxide per mole of amine, respectively; and Pro-
pomeen O/12 whicll is the condensation product of one mole of oleyl amine with 2moles propylene oxide.
The acylated amine rnay also be derived from a polyamine. The polyamines
include alkoxylated diamines, fatty polyamine diamines, alkylenepolyamines, hydroxy
containing polyamines, condensed polyarnines, arylpolyamines, and heterocyclic
polyamines. Commercially available examples of alkoxylated diamines include those
amines where y in the above formula is one. Examples of these amines include
Ethoduomeen T/13 and T/20 which are ethylene oxide condensation products of
N-tallowtrimethylenediamine containing 3 and 10 moles of ethylene oxide per moleof diarnine, respectiYely.
In another embodiment, the polyamine is a fatty diamine. The fatty diamines
include mono- or diaLkyl, symmetrical or asymmetrical ethylenediamines,
propanediamines (1,2, or 1,3), and polyamine analogs of the above. Suitable
commercial fattypolyaminesareDuomeen C (N coco 1,3-diaminopropane), Duomeen
S (N-soya-1,3-diaminopropane~, Duomeen T (N-tallow-1,3~iaminopropane), and
Duomeen O (N-oleyl-1,3-diaminopropane). "Duomeens" are commercially available
from Armak Chemical Co., Chicago, Illinois.
In another embodiment, the amine is an alkylenepolyamine.
Alkylenepolyamines are represented by the formula HR28N-(Alkylene N)"-(R28)2,
wherein each R28 is independently hydrogen; or an aliphatic or hydroxy-substituted
aliphatic group of up to about 30 carbon atoms; n is a number from 1 to about lû,
or from about 2 to about 7, or from about 2 to about 5; and the "All~lene" group has
from 1 to about 10 carbon atoms, or from about 2 to about 6, or from about 2 to
about 4. In another embodiment, R28 is defined the same as R'l above. Such
214723~
27
21kylenepolyamines include methylenepolyamines, ethylenepolyamines, -~
butylenepolyamines, propylenepolyamines, pentylenepolyarnines, etc. The higher
homologs and related heterocyclic arnines, such as piperazines and N-amino
alkyl-substituted piperazines, are also included. Specific examples of such
polyamines are ethylenediamine, triethylenetetramine, tris-(2-aminoethyl)amine,
propylenediamine, trimethylenediamine, tripropylenetetramine, triethylenetetraamine,
tetraethylenepentamine,hexaethyleneheptamine, pentaethylenehexamine, etc. Higherhomologs obtained by condensing two or more of the above-noted alkyleneamines are
similarly useful as are mixtures of two or more of the aforedescribed polyamines.
In one embodiment, the polyamine is an ethylenepolyamine. Such polyamines
are described in detail under the heading Ethylene Amines in Kirk Othmer's "Ency-
clopedia of Chemical Technology~, 2d Edition, Vol. 7, pages 22-37, Interscience
Publishers, New York (1965). Ethylenepolyamines are often a complex mixture of
polyaL~cylenepolyam~nes including cyclic condensation products. Other useful types
of polyamine mixtures are those resulting from stripping of the above-described
polyarnine mixtures to leave, as residue, what is often termed "polyamine bottomsn.
In general, alkylenepolyamine bottoms can be characterized as having less than 2%,
usually less than 1% (by weight) material boiling below about 200C. A typical
sample of such ethylenepolyanine bottoms obtained from the Dow Chemical
Company of Freeport, Texas designated "E-100" has a specific gravity at 15.6C of
1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40C of 121
centistokes. Gas chromatography analysis of such a sample contains about 0.93%
"Light Ends" (most probably diethylenetriamine), 0.72% tirethylenetetraamine,
21.74% tetraethylenepentaamine and 76.61% pentaethylenehexamine and higher ~i
analogs. These alkylenepolyamine bottoms include cyclic condensation products such
as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the
like. These alkylenepolyamine bottoms may be reacted solely with the acylating
agent or they may be used with other amines, polyamines, or mixtures thereof.
Another useful polyamine is a condensation reaction between at least one
hydroxy compound with at least one polyamine reactant containing at least one
primary or secondary amino group. The hydroxy compounds are preferably
polyhydric alcohols and amines. The polyhydric alcohols are described below. In
one embodiment, the hydroxy compounds are polyhydric amines. Polyhydric amines
-`" 21~7238 ~
~ ~.
28
include any of the above-described monoamines reacted with an alkylene oxide (e.g.,
ethylene oxide, propylene oxide, butylene oxide, etc.) having from two to about 20
carbon atoms, or from two to about four. E~carnples of polyhydric amines include tri-
(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane, 2-amin~2-methyl-1,3-
propanediol, N,N,N~ ,N'-tetrakis (2-hydroxypropyl) ethylenediamine, andN,N,N' ,N'-
tetrakis (2-hydro~yethyl) ethylenediamine, preferably tris(hydroxymethyl)
aminomethane (I~
Polyamines which may react with the polyhydric alcohol or amine to form the
condensation products or condensed amines, are described above. Preferred poly-
amines include triethylenetetrarnine ~IETA), tetraethylenepentamine ~I~EiPA), penta-
ethylenehexamine (PEHA), and mixtures of polyamines such as the above-described
"amine bottomsn. The condensation reaction of the polyamine reactant with the
hydroxy compound is conducted at an elevated temperature, usually from about 60C
to about 265C, or from about 220C to about 250C in the presence of an acid cata-
lyst.
The amine condensates and methods of making the same are described in PCI
publication WO86/05501 and U.S. Patent 5,230,714 (Steckel) which are incorporated
by reterence for its disclosure ts the csndensates and methods of making. A
particularly useful amine condensate is prepared from HPA Taft Amines (amine bot^
toms available commercially from Union Carbide Co. with typically 34.1 % by weight
nitrogen and a nitrogen distribution of 12.3% by weight primary amine, 14.4% by
weight secondary amine and 7.4% by weight tertiary amine), and tris(hydroxy-
methyl)aminomethane ~I~IAM).
In another embodiment, the polyamines are polyoxyalkylene polyamines, e.g.
polyoxyalkylene diamines and polyoxyalkylene triamines, having average molecularweights ranging from about 200 to about 4000, or from about 400 to about ~000.
The preferred polyoxyalkylene polyamines include the polyoxyethylene and
polyoxypropylene diamines and the polyoxypropylene triamines. The
polyoxyalkylene polyamines are commercially available and may be obtained, for
example, from the Jefferson Chemical Company, Inc. under ~e trade name
"Jeffamiaes D-230, D-400, D-1000, D-2000, T-403, etc.". U.S. Patents 3,804,763
and 3,948,800 are expressly incorporated herein by reference for their disclosure of
such polyoxyallylene polyamines and acylated products made therefrom.
` . :
21~7238
29
S In anotherembodiment, thepolyamines arehydroxy~ontaining polyamines.
Hydroxy-containing polyamine analogs of hydroxy monoamines, par~cularly alkoxyl-ated alkylenepolyamines, e.g., N,N(diethanol)ethylene diamines can also be used.Such polyamines can be made by reacting the above-described alkylene amines withone or more of the above-described alkylene oxides. Similar alkylene oxide-aLlcanol
amine reaction products may also be used such as the products made by reacting the
above described primary, secondary or tertiary aLtcanol amines with ethylene, propyl-
ene or higher epoxides in a 1.1 to 1.2 molar ratio. Reactant ratios and temperatures
for carrying out such reactions are known to those skilled in the art. Specific
examples of hydroxy-containing polyamines include N-(2-hydroxyethyl)
ethylenediamine, N,N'-bis(2-hydroxyethyl)-ethylenediamine, 1-(2-hydroxyethyl)-
piperazine, mono(hydroxypropyl)-substituted tetraethylenepentamine,
N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtained by
condensation of the above illustrated hydroxy~ontaining polyamines through aminogroups or through hydroxy groups are likewise useful. Condensation through aminogroups results in a higher amine accompanied by removal of arnmonia while
condensation through the hydroxy groups results in products containing ether linkages
accompanied by removal of water. Mixtures of two or more of any of the above
described polyamines are also useful.
In another embodiment, the polyamine is a heterocyclic polyamine. The
heterocyclic polyamines include aziridines, azetidines, azolidines, tetra- and dihydro-
pyridines, pyrroles, indoles, piperidines, imidazoles, di- and tetrahydroimidazoles,
piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmor-pholines, N-aminoaLkylthiomoTpholines, N-aminoalkylpiperazines, N,N'-di-
aminoalkylpiperazines, azepines, azocines, azonines, azecines and tetra-, di- and per-
hydro derivatives of each of the above and mixtures of two or more of these hetsrocy-
clic amines. Preferred heterocyclic amines are the saturated 5- and ~membered
heterocyclic amines containing only nitrogen, oxygen and/or sulfur in the hetero ring,
especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines,
and the lilce. Piperidine, aminoalkyl substituted piperidines, piperazine, aminoallyl
substituted piperazines, morpholine, aminoalkyl substituted morpholines, pyrrolidine,
and aminoalkyl-substituted pyrrolidines, are especially preferred. Usually the
aminoalkyl substituents are substituted on a nitrogen atom forming part of the hetero
21~7238
3 0
ring. Specific examples of such heterocyclic amines include
N-aminopropylmorpholine, N-aminoethylpiperazine, and
N,N'-diaminoethylpiperazine. Hydroxy heterocyclic polyamines are also useful.
Examples include N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine,
parahydroxyaniline, N-hydroxyethylpiperazine, and the like.
Hydrazine and hydrocarbyl substituted-hydrazine may also be used to form the
acylated nikogen dispersants. At least one of the nitrogen atoms in the hydrazine
must contain a hydrogen directly bonded thereto. Preferably there are at least two
hydrogens bonded directly to hydrazine nikrogen and, more preferably, both
hydrogens are on the same nitrogen. Specific examples of substituted hydrazines are
methylhydrazine,N,~-dimethyl-hydrazine,N,N'-dimethylhydrazine,phenylhydrazine,
N-phenyl-N'-ethyl'nydrazine, N-(para-tolyl)-N'-(n-butyl)-hydrazine, N-(para-
nitrophenyl)-hydrazine, N-(para-nitrophenyl)-N-methyl-hydrazine, N,N'-di(para-
chlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine, and the like.
Acylated amines and methods for preparing the sarne are described in U.S.
Patents 3,219,666; 4,234,435; 4,952,328; 4,938,881; 4,957,649; and 4,904,401.
The disclosures of acylated nitrogen dispersants and other dispersants contained in
those patents is hereby inco~)orated by reference.
In another embodiment, the dispersant may also be a carboxylic ester. The
carboxylic ester is prepared by reacting at least one or more of the above carboxylic
acylating agents, prefe~rably a hydrocarbyl substituted carboxylic acylating agent,
with at least one organic hydroxy compound and optionally an amine. In another
embodiment, the carboxylic ester dispersant is prepared by reacting the acylating
agent with at least one of the above~escribed hydroxyamines.
The organic hydroxy compound includes compounds of the general formula
R"(OH)m wherein R" is a monovalent or polyvalent organic group joined to the -OHgroups through a carbon bond, and m is an integer from 1 to about 10 wherein thehydrocarbyl group contains at least about 8 aliphatic carbon atoms. The hydroxy
compounds may be aliphatic compounds, such as monohydric and polyhydric
alcohols, or aromatic compounds, such as phenols and naphthols. The aromatic
hydroxy compounds from which the esters may be derived are illustrated by the
following specific examples: phenol, beta-naphthol, alpha-naphthol, cresol,
resorcinol, catechol, p,p'-dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol, etc.
- --` 2147238 ~ ~
31
The alcohols from which the esters may be derived generally contain up to
about 40 carbon atoms, or from 2 to about 30, or from 2 to about 10. They may bemonohydric alcohols, such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol,
etc. The hydroxy compounds may also be polyhydric alcohols, such as aLkylene
polyols. In one embodiment, the polyhydric alcohols contain from 2 to about 40
carbon atoms, from 2 to about 20; and from 2 to about 10 hydroxyl groups, or from
2 to about 6. Polyhydric alcohols include ethylene glycols, including di-, tri- and
tetraethylene glycols; propylene glycols, including di-, tri- and tetrapropylene glycols;
glycerol; butanediol; hexanediol; sorbitol; arabitol; mannitol; trimethylolpropane;
sucrose; fructose; glucose; cyclohexanediol; erythritol; and pentaerythritols, including
lS di- and tripentaerythritol.
The polyhydric alcohols may be esterified with monocarboxylic acids having
from 2 to about 30 carbon atoms, or from about 8 to about 18, provided that at least
one hydroxyl group remains unesterified. Examples of monocarboxylic acids include
acetic, propionic, butyric and above described fatty acids. Specific examples of these
esterified polyhydric alcohols include sorbitol oleate, including mono- and dioleate,
sorbitol stearate, including mono- and distearate, glycerol oleate, including glycerol
mono-, di- and trioleate and erythritol octanoate.
The carboxylic ester dispersants may be prepared by any of several hlown
methods. The method which is preferred because of convenience and the superior
properties of the esters it produces, involves the reaction of the carboxylic acylatinsg
agents described above with one or more alcohol or phenol in ratios from about 0.5
esquivalent to about 4 equivalents of hydroxy compound per equivalent of acylating
agent. The esterification is usually carried out at temperatures above about 100C,
or between 150C and 300C. The water formed as a by-procuct is removed by
distillation as the esterification proceeds. The preparation of useful carboxylic ester
dispersant is described in U.S. Patents 3,522,179 and 4,234,43S, and their disclosures
are incorporated by reference.
The carboxylic ester dispersants may be further reacted with at least one of
the above described amines asld preferably at least one of the above described
polyamines, such as a polyethylenepolyamine or a heterocyclic arnine, such as
aminopropylmopholine. The amine is added in an amount sufficient to neuhalize any
nonesterified carboxyl groups. In one embodiment, the carboxylic ester dispersants
. . . .
:, : ,-
~14723~
.`
32
S are prepared by reacting from about 1 to about 2 equivalents, or from about 1.0 to
1.8 equivalents of hydroxy compounds, and up to about 0.3 equivalent, or from about
0.02 to about 0.2S equivalent of polyamine per equivalent of acylating agent. The
carboxylic acid acylating agent may be reacted simultaneously with both the hydroxy
compound and the amine. There is generally at least about 0.01 equivalent of thealcohol and at least 0.01 equivalent of the amine although the total arnount of
equivalents of the combination should be at least about 0.5 equivalent per equivalent
of acylating agent. These carboxylic ester dispersant compositions are known in the
art, and the preparation of a number of these derivatives is described in, for example,
U.S. Patents 3,957,854 and 4,234,435 which have been incorporated by reference
lS previously. :
In another embodiment, the dispersant may also be a hydrocarbyl-substituted
amine. These hydrocarbyl-substituted amines are well known to those skilled in the
art. These amines are disclosed in U.S. Patents 3,275,554; 3,438,757; 3,454,555;3,565,804; 3,755,433; and 3,822,289. These patents are hereby incorporated by
2Q reference for their disclosure of hydrocarbyl amines and methods of making the same.
Typically, hydrocarbyl substituted amines are prepared by reacting olefins and olefin
polymers, including the above polyalkenes and halogenated derivatives thereof, with
amines (mono- or polyamines). The amines may be any of the amines described
above, preferrably-an alkylenepolyamine. E-xamples of hydrocarbyl substituted
amines include poly(propylene)amine; N,N~imethyl-N-poly(ethyl-
ene/propylene)amine, (50:50 mole ratio of monomers); polybutene amine; N,N-
di(hydroxyethyl)-N-polybutene amine; N-(2-hydroxypropyl)-N-polybutene amine; N-
polybutene-aniline; N-polybutenemorpholine; N-poly(butene)ethylenediamine; N-
poly(propylene)trimethylenediamine; N-poly(butene)diethylenetriamine; N',N'- ~ -~
poly(butene)tetraethylenepentamine; N,N-dimethyl-N'-poly(propylene)~1,3-
propylenediamine and the like.
In another embodiment, the dispersant may also be a Mannich dispersant.
Mannich dispersants are generally formed by the reaction of at least one of the above
described aldehydes, such as formaldehyde and paraformaldehyde, at least one of the
above described amines and at least one aLkyl substituted hydroxyaromatic compound.
Tlle reaction may occur from room temperature to about 225C, or from about 50
to about 200C, or from about 75C to about 150C. The amounts of the reagents
21~7~38
, ~
is such that the molar ratio of hydroxyaromatic compound to formaldehyde to amine
is in the range from about (1:1:1) to about (1:3:3).
The first reagent is an alkyl substituted hydroxyaromatic compound. This
term includes the above described phenols, alythough the phenol need not be
hindered. The hydroxyaromatic compounds are those substituted with at least one,and preferably not more than two, aliphatic or alicyclic groups having from about 6
up to about 400, or from about 30 up to about 300, or from about 5Q up to about
200 carbon atoms. These groups may be derived from one or more of the above
described olefins or polyalkenes. In one embodiment, the hydroxyaromatic compound
is a phenol substituted with an aliphatic or alicyclic hydrocarbon-based group having
an Mn of about 420 to about 10,000.
The third reagent is any amine described above. Preferably the amine is one
or more of the above described polyamines, such as the polyaLkylenepolyamines.
Mannnich dispersants are described in the follo~,ving patents: U.S. Patent 3,980,569;
U.S. Patent 3,877,899; and U.S. Patent 4,454,059 (herein incorporated by reference
for their disclosure to Mannich dispersants).
In another embodiment, the dispersant is a borated dispersant. The borated
dispersants are prepared by reacting one or more of the above disperants with at least
one boron compound. The boron compounds include boron oxide, boron oxide
hydrate, boron trioxide, boron acids, such as boronic acid (i.e., allyl-B(OH)2 or
aryl-B(OH)~), including methylboronic acid, phenyl-boronic acid, cyclohexyl boronic
acid, p-heptylphenyl boronic acid and dodecyl boronic acid, boric acid (i.e., H3BO3),
tetraboric acid ~i.e., H2B4O7), metaboric acid (i.e., HBO2), boron anhydrides, boron
amides and various esters of such boron acids.
In one embodiment, the boron compounds include mono-, di-, and tri-organic
esters of boric acid and alcohols or phenols. Examples of the alcohols include
methanol, ethanol, propanol, butanol, l-octanol, benzyl alcohol, ethylene glycol,
glycerol, and Cellosolve. Lower alcohols, having less than about 8 carbon atoms,and glycols, such as 1,2-glycols and 1,3-glycols, are especially useful. Methods for
preparing the esters are known and disclosed in the art (such as "Chemical Reviews,"
pp. 959-1064, Vol. 56).
Typically, the borated dispersant contains from about 0.1% up to about 5 %,
or from about 0.5% up to about 4%, or from 0.7% up to about 3% by weight boron.
; . . - .
: . :
21~723~
S In one embodiment, the borated dispersant is a borated acylated amine, such as a
borated succinin~ide dispersant. Borated dispersants are described in 3,000,916;3,087,936; 3,254,025; 3,282,955; 3,313,727; 3,491,025; 3,533,945; 3,666,662 and
4,925,983. These references are incoIporated by reference for their disclosure of
borated dispersants.
- The following examples relate to dispersants useful in the present invention.
Exarnple B-l
(a) An acylated nitrogen composition is prepared by reacting 3880 grams
of the polyisobutenyl succinic anhydride, 376 grams of a mixture of
triethylenetetramine and diethylene triamine (75:25 weight ratio), and 2785 grams of
mineral oil in toluene at 150 C. The product is vacuum stripped 'LO remove toluene.
(b) A mixture of 62 grarns (1 atomic proportion of boron) of boric acid and
1645 grams (2.35 atomic proportions of nitrogen) of the acylated nitrogen composition
obtained from B-l(a) is heated at l50 C in nitrogen atmosphere for 6 hours. The
mixture is then filtered and the filtrate is found to have a nitrogen content of 1.94%
and a boron content of 0.33%.
Example B-2
A mixture of 372 grarns (6 atomic proportions of boron) of boric acid and 3111
grams (6 atomic proportions of nitrogen) of a acylated nitrogen composition, obtained
by reacting 1 equivalent of a polybutenyl (Mn=850) succinic anhydlide, having anacid number of 113 (corresponding to an equivalent weight of 500), with 2
equivalents of a commercial ethylene arnine mixture having an average composition
corresponding to that of tetraethylene-pentamine, is heated at l50 C for 3 hours and
then filtered. The filtrate is found to have a boron content of 1.64% and a nitrogen
content of 2.56%.
Example B-3
Boric acid (124 grams, 2 atomic proportions of boron) is added to the acylated
nitrogen composition (556 grams, 1 atomic proportion of nitrogen) of EJ~ample B-2.
The resulting mixture is heated at l50 C for 3.5 hours and filtered at that
temperature. The filtrate is found to have a boron compound of 3.23% and a
nitrogen content of 2.3%.
~. ~ .
-`" 21ll7,'~38
S Example B~
(a) A reaction vessel is charged with 1000 parts of a polybutenyl (Mn=1000
substituted succinic anhydride having a total acid number of 108 with a mixture of
275 grams of oil and 139 parts of a commercial mixture of polyamines corresponding
to 85% E-100 amine bottoms and 15% diethylenetriamine. The reaction mixture is
heated to 150 to 160 C and held for four hours. The reaction is blown with nitrogen
to remove water.
(b) A reaction vessel is charged with 1405 parts of the product of Example B-
4~a), 229 parts of boric acid, and 398 parts of diluent oil. The mixture is heated to
100 to 150 C and the temperature maintained until water is removed. The final
product contains 2.3 % nitrogen, 1.9 % boron, 33 % 100 neutral mineral oil and a total
base number of 60.
In another embodiment, the dispersant or detergent (B) is an overbased metal
salt and is present in an amount from about 0.5% to about 4%, or from about 0.7%to about 3%, or from about 0.9% to about 2% by weight of the lubricating
composition. Overbased metal salts are characterized by having a metal content in
excess of that which would be present according to the stoichiometry of the metal and
the acidic organic compound. The amount of excess metal is commonly expressed
in metal ratio. The term "metal ratio" is the ratio of the total equivalents of the metal
to the equivalents of the acidic organic compound. A salt having a metal ratio of 4.5
will have 3.5 equivalents of excess metal. The overbased salts generally have a me~al
ratio from about 1.5 up to about 40, or from about 2 up to about 30, or from about
3 up to about 25. In one embodiment, the metal ratio is greater than about 7, orgreater than about 10, or greater than about 15.
The overbased materials are prepared by reacting an acidic material, typically
carbon dioxide, with a mixture comprising an acidic organic compound, a reactionmedium comprising at least one inert, organic solvent for the acidic organic
compound, a stoichiometric excess of a basic metal compound, and a promoter.
Generally, the basic metal compounds are oxidss, hydroxides, chlorides, carbonates,
and phosphorus acids (phosphonic or phosphoric acid) salts, and sulfur acid (sulfuric
or sulfonic) salts. The metals of the basic metal compounds are generally aLl~ali,
alkaline earth, and transition metals. Examples of the metals of the basic metalcompound include sodium, potassium, lithium, magnesium, calcium, barium,
~ 2147238 -
.
titanium, manganese, cobalt, nickel, copper, zinc, and preferably sodium, potassium,
calcium, and magnesium.
The acidic organic compounds useful in making the overbased compositions
of the present inveneion include carboxylic acylating agents, sulfonic acids,
phosphorus containing acids, phenols, or mixtures of two or more thereof.
Preferably, the acidic organic compounds are carboxylic acylating agents, or sulfonic
acids. In one embodiment, the acidic organic compounds is one or more of the above
described carboxylic acyalting agent, such as a hydrocarbyl substituted carboxylic
acylating agents, such as the hydrocarbyl substituted succinic anhydrides.
In another embodiment, the carboxylic acylating agent is an
alkylalkyleneglycol-acetic acid, or alkylpolyethyleneglycol-acetic acid. Some specific
examples of these compounds include: iso-stearylpentaethyleneglycol-acetic acid;iso-stearyl-O-(CH2CH2O)5CH2CO2Na; lauryl-O-(CH2CH2O)2 5-CH2CO2H;
lauryl-O-(CH2CH20)3,3CH2CO2H; oleyl-O-(CH2C-H20)4-CH2C02H; ~: ,;
lauryl-O-(CH2CH2O)4 5CH2CO2H; lauryl-O-(CH2CH2O)-~OCH2CO2H;
lauryl-O-(CH2CH2O)~6CH2CO2H; octyl-phenyl-O-(CH2CH2O)8CH2cO2H;
octyl-phenyl-O-(CH2CH2O),9CH2CO2H; 2-octyl~ecanyl-~(CH2CH2O)6CH2CO2H.
These acids are available commercially from Sandoz Chernical Co. under the
tradename of Sandopan acids. ~-
In another embodiment, the carboxylic acylating agents are aromatic
carboxylic acids. A group of useful aromatic carboxylic acids are those of the
formula
(R2s)~--Ar-((~ XH)b -
(XH)
wherein R28 is an aliphatic hydrocarbyl group having from about 4 to about 400
carbon atoms, a is a number in the range of zero to about 4, Ar is an aromatic group,
such as those discussed above, each X is independently sulfur or oxygen, preferably ~ -
oxygen, b is a number in the range from one to abou~ four, c is a number in the
range of zero to about four, usually one or two, with the proviso that the sum of a,
b and c does not exceed the number of valences of Ar. In one embodiment, R2" and
2~7238
a are such that there is an average of at least about eight aliphatic carbon atoms
provided by the R28 groups.
The R28 group is a hydrocarbyl group that is directly bonded to the aromatic
group Ar. R28 typically contains from about 6 to about 80, or from about 7 to about
30, or from about 8 to about 25, or from about 8 to about 15 carbon atoms.
Examples of R28 groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl,
S-chlorohexyl, 4-ethoxypentyl, 3-cyclohexyloctyl, 2,3,5-trimethylheptyl, propylene
tetramer, triisobutenyl and substituents derived from one of the above describedolefins or polyalkenes.
Within this group of aromatic acids, a useful class of carboxylic acids are
lS those of the formula
(R28)~ {~(COOH)b
OH)o
wherein R28 is defined above, a is a number in the range of from zero to about 4, or
from 1 to about 3; b is a number in the range of 1 to about 4, or from 1 to about 2,
c is a number in the range of zero to about 4, or from 1 to about 2, and or 1; with
the proviso that the sum of a, b and c does not exceed 6. In one embodiment, R28and a are such that the acid molecules contain at least an average of about 12 aliphatic
carbon atoms in the aliphatic hydrocarbon substituents per acid molecule. Typically,
b and c are each one and the carboxylic acid is a salicylic acid.
In one embodiment, the salicylic acids are hydrocarbyl substituted salicylic
acids, wherein each hydrocarbyl substituent contains an average of at least about 8
carbon atoms per substituent and 1 to 3 substituents per molecule. In one
embodiment, the hydrocarbyl substituent is derived from one or more above-described
polyalkenes.
The above aromatic carboxylic acids are well known or can be prepared
according to procedures known in the art. Carboxylic acids of the type illustrated by
these formulae and processes for preparing their neutral and basic metal salts are well
known and disclosed, for example, in U.S. Patents 2,197,832; 2,197,835; 2,252,662;
2,252,664; 2,714,092; 3,410,798; and 3,S95,791.
2147238
38
In another embodiment, the acidic organic compound is a sulfonic acid. The
sulfonic acids include sulfonic and thiosulfonic acids, preferably sulfonic acids. The
sulfonic acids include the mono- or polynuclear aromatic or cycloaliphatic
compounds. The oil-soluble sulfonic acids may be represented for the most part ~y
one of the following formulae: R29-T-(SO3).H and R30-(SO3)bH, wherein T is a cyclic
nucleus such as benzene, naphthalene, anthracene, diphenylene oxide, diphenylenesulfide, and petroleum naphthenes; R29 is an aliphatic group such as alkyl, alkenyl,
alkoxy, alkoxyalkyl, etc.; (R29)+T contains a total of at least about 15 carbon atoms;
and R30 is an aliphatic hydrocarbyl group containing at least about 15 carbon atoms.
Examples of R30 are alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specificexamples of R30 are groups derived from petrolatum, saturated and unsaturated
paraffin wax, and one or more of the above-described polyalkenes. The groups T,
R29, and R30 in the above Formulae can also contain other inorganic or organic
substituents in addition to those enumerated above such as, for exarnple, hydroxy,
mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide, etc. In the above
Forrnulae, a and b are at least 1.
A preferr~d group of sulfonic acids are mono, di-, and tri-alkylated benæne
and naphthalene sulfonic acids including their hydrogenated forms. Illustrative of
synthetically produced alkylated benæne and naphthalene sulfonic acids are thosecontaining alkyl substituents having from about 8 to about 30 carbon atoms, or from
about 12 to about 30 carbon atoms, and or to about 24 carbon atoms. Specific
examples of sulfonic acids are mahogany sulfonic acids; bright stock sulfonic acids;
sulfonic acids derived from lubricating oil fractions having a Saybolt viscosity from
about 100 seconds at 100F to about 200 seconds at 210F; petrolatum sulfonic acids;
mono- and polywax-substituted sulfonic acids; alkylbenzene sulfonic acids (where the
alkyl group has at least 8 carbons), dilaurylbeta-naphthyl sul~onic acids, and alkaryl
sulfonic acids, such as dodecylbenzene "bottoms" sulfonic acids.
Dodecylbenzene "bottoms" sulfonic acids are the material leftover after the
removal of dodecylbenzene sulfonic acids that are used for household detergents. The
"bottoms" may be straight-chain or branched~hain alkylates with a straight-chaindialkylate preferred. The production of sulfonates from detergent manufactured
by-products by reaction with, e.g., S03, iS well known to those skilled in the art
See, for example, the article "Sulfonates" in Kirk-Othmer "Encyclopedia of Chemical
.
-`~ 21~7238
Technology", Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley &
Sons, N.Y. (1969).
In another embodiment, the acidic organic compound is a phosphorus
containing acid. The phosphorus containing acids are one or more of the above
described phosphorus containing acids. In one embodiment, the phosphorus -
containing acid is the reaction product of one or more of the above polyaLkenes and
a phosphorus sulfide. Useful phosphorus sulfide sources include phosphorus
pentasulfide, phosphorus sesquisulfide, phosphorus heptasulfide and the lilce. The
reaction of the polyalkene and the phosphorus sulfide generally may occur by simply
mixing the two at a ~mperature above 80C, or from about 100C to about 300C.
Generally, the products have a phosphorus content from about 0.05% to about 105~,
or from about 0.1% to about 5%. The relative proportions of the phosphorizing
agent to the olefin polymer is generally from 0.1 part to 50 parts of the phosphoAzing
agent per 100 parts of the olefin polymer. The phosphorus containing acids are
described in U.S. Patent 3,232,883, issued to LeSuer. This reference is herein
incorporated by reference for its disclosure to the phosphorus containing acids and
methods for preparing the same.
In another embodiment, the acidic organic compound is a phenol. The
phenols may be represented by the formula (R28),-Ar~OH)b, wherein R28 is definedabove; Ar is an aromatic group as described above; 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, which is
defined above. In one embodiment, a and b are each independently numbers in the
range from one to about four, or from one to about two. In one embodiment, R28 and
a are such that there is an average of at least about eight aliphatic carbon atoms
provided by the R28 groups for each phenol compound.
Promoters are often used in preparing the overbased metal salts. The
promoters, that is, the materials which facilitate the incor~oration of the excess metal
into the overbased material, are also quite diverse and well known in the art. A s
particularly comprehensive discussion of suitable promoters is found in U.S. Patents
2,777,874, 2,69S,910, 2,616,904, 3,384,586 and 3,492,231. These patents are
incorporated by reference for their disclosure of promoters. In one embodiment,
promoters include the alcoholic and phenolic promoters. The alcoholic promoters
r~ 2 1 ll 7 3 ~
.
S include the alkanols of one to about 12 carbon atoms, such as methanol, ethanol,
amyl alcohol, octanol, isopropanol, and mixtures of these and the like. Phenolicpromoters include a variety of hydroxy-substituted ben~enes and naphthalenes. A
particularly usefi~l class of phenols are the allylated phenols of the type listed in U.S.
Patent 2,777,874, e.g., heptylphenols, octylphenols, and nonylphenols. Mixtures of
various promoters are sometimes used.
Acidic mateAals, which are reacted with the mixture of acidic organic
compound, promoter, metal compound and reactive medium, are also disclosed in the
above cited patents, for example, U.S. Patent 2,616,904. Those disclosures are
incorporated by reference for their disclosure of such acidic materials. Included
within the known group of useful acidic mateAals are liquid acids, such as formic
acid, acetic acid, nitric acid, boric acid, sulfuric acid, hydrochloric acid, hydrobromic
acid, carbamic acid, substituted carbamic acids, etc. Acetic acid is a very useful
acidic material although inorganic acidic compounds such as HCl, S2~ S03, C02,
H2S, N2O3, etc., are ordinarily employed as the acidic materials. Particularly useful
acidic materials are carbon dioxide and acetic acid.
The methods for preparing the overbased materials, as well as overbased
materials, are la own in the prior art and are disclosed, for example, in the following
U.S. Patent Nos.: 2,616,904; 2,616,905; 2,616,906; 3,242,080; 3,250,710;
3,2S6,186;3,274,135;3,492,231;and4,230,586. Thesepatentsdiscloseprocesses,
materials, which can be overbased, suitable metal bases, promoters, and acidic
materials, as well as a variety of specific overbased products useful in producing the
overbased systems of this invention and are, accordingly, incorporated herein byreference for these disclosures.
The temperature at which the acidic material ls contacted with the remainder
of the reaction mass depends to a large measure upon the promoting agent used.
With a phenolic promoter, the temperature usually ranges from about 80C to about
300C, and preferably from about 100C to about 200C. When an alcohol or
mercaptan is used as the promoting agent, the temperature usually will not exceed the
reflux temperature of the reaction mixture and preferably will not exceed about
100C.
In one embodiment, the overbased metal salts are borated overbased metal
salts. The borated overbased metals salts are prepared by reacting one or more of the
,~, .,. , . . ~
,~ 2~4~23~
above overbased metals salts with one or more of the above descAbed boron
compounds. The borated overbased metal salts generally contains from about 0.1 %up to about 15%, or from about 0.5% up to about 10%, or from about 1% up to
about 8% by weight of the boron. ~3orated overbased compositions, lubricating
compositions containing the same and methods of preparing borated overbased
compositions are found in U.S. Patent 4,744,920, issued to Fischer et al; U.S. Patent
4,792,410 issued to Schwind et al and PCT Publication W088/03144. The
disclosures relating to the above are hereby incorporated by reference.
The following exarnples relate to borated overbased metal salts and methods
of making the same. Unless the context indicates otherwise, here as well as
elsewhere in the specification and claims, parts and percentages are by weight,
temperature is in d~grees Celsius and pressure is atmospheric pressure.
~xample B-5
~a) A mixture of 853 grams of methyl alcohol, 410 grams of blend oil, 54
grams of sodium hydroxide, and a neutralizing amount of additional sodium
hydroxide is prepared. The amount of the latter addition of sodium hydroxide is
dependent upon the acid number of the subsequently added sulfonic acid. The
temperature of the mixture is adjuste~ to 49 C. 1070 grams of a mixture of straight
chain dialkyl benæne sulfonic acid (Mw=430) and blend oil (42% by weight active
content) are added while maintaining the temperature at 49-57 C. 145 grams of
polyisobutenyl (number average Mn=950)-substituted succinic anhydride are added.838 grams of sodium hydroxide are added. The temperature is adjusted to 71-C.
The reaction mixture is blown with 460 grams of carbon dioxide. The mL~cture is
flash stripped to 149-C, and filtered to clarity to provide the desired product. The
product is an overbased sodium sulfonate having a base number (bromophenol blue)of 440, a metal content of 19.45% by weight, a metal ratio of 20, a sulfate ash
content of 58% by weight, and a sulfur content of 1.35% by weight.
(b) A mixture of 1000 grams of the product from Example B-5(a) above,
0.13 gram of an antifoaming agent (kerosene solution of Dow Corning 200 Fluid
having a viscosity of 1000 cSt at 25 C), and 133 grams of blend oil is heated to 74-
79 C with stirring. 486 grams of boric acid are added. The reaction mixture is
heated to 121 C to liberate water of reaction and 40-50% by weight of the CO
contained in the product from Example l(a). The reaction mixture is heated to 154-
2147~3~
42
150 C and maintained at that temperature until the free and total water contents are
reduced to 0.3~ by weight or less and approximately 1-2% by weight, respectively.
The reaction product is cooled to room temperature and filtered. The filtrate has
6.1% boron, 14.4% sodium, and 35% 100 neutral mineral oil.
Example B-6
(a) A mixture of 1000 grams of a primarily branched chain monoalkyl
benzene sulfonic acid (Mw=500), 771 grams of o-xylene, and 75.2 grams of
polyisobutenyl (number average Mn=950) succinic anhydride is prepared and the
temperature is adjusted to 46'C. 87.3 grams of magnesium oxide are added. 35.8
grams of acetic acid are added. 31.4 grams of methyl alcohol and 59 grams of water
are added. The reaction mixture is blown with 77.3 grams of carbon dioxide at a
temperature of 49-54 C. 87.3 grams of magnesium oxide, 31.4 grams of methyl
alcohol and 59 grams of water are added, and the reaction mixture is blown with 77.3
grams of carbon dioxide at 49-54 C. The foregoing steps of magnesium oxide,
methyl alcohol and water addition, followed by carbon dioxide blowing are repeated
once. O-xylene, methyl alcohol and water are removed from the reaction mixture
using atmospheric and vacuum flash stripping. The reaction mixture is cooled andfiltered to clarity. The product is an overbased magnesium sulfonate having a base -
number (bromophenol blue) of 400, a metal content of 9.39~ by weight, a metal ratio
14.7, a sulfate ash content of 46.0%, and a sulfur content of 1.6% by weight. ;~
(b) A mixture of 1000 grams of the product from ExampleB-6(a) and 181
grams of diluent oil is heated to 79 C. Boric acid (300 grams) is added and the
reaction mixture is heated to 124 C over a period of 8 hours. The reaction mixture
is maintained at 121-127 C for 2-3 hours. A nitrogen sparge is started and the
reaction mixture is heated to 149 C to remove water until the water content is 3%
by weight or less. The reaction mixture is filtered to provide the desired product.
The product contains 7.63% magnesium and 4.35% boron.
Example B-7
(a) A reaction vessel is charged wi~ 281 parts (0.5 equivalent) of a
polybutenyl-substituted succinic anhydride derived from a polybutene (Mn=1000),
281 parts of xylene, 26 parts of tetrapropenyl substituted phenol and 250 parts of 100
neutral mineral oil. The mixture is heated to 80C and 272 parts (3.4 equivalents)
of an aqueous sodium hydroxide solution are added to the reaction mLxture. The
~;
~`` 21~7238
43
mixture is biown with nitrogen at 1 scfh (standard cu. ftlhr) and the reaction
temperature is increased to 148C. The reaction mixture is then blown with carbon
dioxide at 1 scfh for one hour and 25 minutes while 150 parts of water is collected.
The reaction mLxture is cooled to 80C where 272 parts (3.4 equivalents) of the
above sodium hydroxide solution is added to the reaction mixture and the mixture is
blown with nitrogen at 1 scfh. The reaction temperature is increased to 140C where
the reaction mixture is blown with carbon dioxide at 1 scfh for 1 hour and 25 minutes
while 150 parts of water is collected. The reaction temperature is decreased to 100C
and 272 parts (3.4 equivalents) of the above sodium hydroxide solution is added while
blowing the mixture with nitrogen at 1 scfh. The reaction temperature is increased
to 148C and the reaction mixture is blown with carbon dioxide at 1 scfh for 1 hour
and 40 minutes while 160 parts of water is collected. The reaction mixture is cooled
to 90C and where 250 parts of 100 neutral mineral oil are added to the reactionmixture. The reaclion mixture is vacuum stripped at 70C and the residue is filtered
through diatomaceous earth. The filtrate contains 50.0% sodium sulfate ash
(theoretical 53.8%) by ASTM D-874, total base number of 408, a specific gravity of
1.18 and 37.1 % oil.
(b) A reaction vessel is charged with 700 parts of the product of Example
B-7(a). The reaction mixture is heated to 75C where 340 parts (5.5 equivalents) of
boric acid is added over 30 r~unutes. Th~ reaction mixture is heated to 110C over
45 minutes and the reaction temperature is maintained for 2 hours. A 100 neutralmineral oil (80 parts) is added to the reaction mixture. The reaction mixture is blown
with nitrogen at 1 scfh at 160C for 30 minutes while 95 parts of water is collected.
Xylene (20Q parts) is added to the reaction mixture and the reaction temperature is
maintained at 13~140C for 3 hours. The reaction mixture is vacuum stripped at
150C and 20 millimeters of mercury. The residue is filtered through diatomaceous
earth. The filtrate contains 5.84% boron (theoretical 6.43) and 33.1% oil. The
residue has a total base number of 309.
As previously indicated, the combination of the antioxidant (A) and the
dispersant or detergent (B) are useful as additives for lubricants in which they can
function to control oxidation and subsequent viscosity increase. They may be em-ployed in a variety of lubricants based on diverse oils of lubricating viscosity,
including natural and synthetic lubricating oils and mixtures thereof. These lubricants
k
r~ 2 1 4 7 2 3 8
44
S include crankcase lubricating oils for spark-ignited and compression-ignited internal
combustion engines, including automobile and truck engines, two~ycle engines,
aviation piston engines, marine and railroad diesel engines, and the like. They can
also be used in gas engines, stationary power engines and turbines and the like.Automatic or manual transmiss;on fluids, transaxle lubricants, gear lubricants,
including open and enclosed gear lubricants, tractor lubricants, metal-working lubri-
cants, hydraulic fluids and other lubricating oil and grease compositions can also
benefit from the incorporation therein of the compositions of the present invention.
They may also be used as wirerope, walking cam, way, rock drill, chain and
conveyor belt, worm gear, bearing, and rail and flange lubricants.
The combination of the antioxidant (A) and the dispersant or detergent (B)
may be used in lubAcants or in concentrates. The concentrate may contain the above
combination alone or with other components used in preparing fully formulated
lubricants. The concentrate also contains a substantially inert organic diluent, which
includes kerosene, mineral distillates, or one or more of the oils of lubricating
viscositydiscussedbelow. Inoneembodiment, theconcentratescont~infromO.01%,
or from about 0.1%, or from about 1% up to about 70% or up to about 80%, even
up to about 90% by weight of the combination.
The combination of the antioxidant (A) or the dispersant or detergent (B) may
be present in a final product, blend, or concentrate in any amount effective to act as
antioxidation agents in lubricating compositions. Generally, the antioxidant (A) is
present in an amount of at least about 2% by weight. The total arnount of antioxidant
(A) is equal to the sum of the amounts of all antioxidants in the lubricant. In one
embodiment, the antioxidant is present in an amount from about 2.5 % to about 10%,
or from about 3% to about 8% by weight of the lubdcating composition. The
dispersant or detergent (B) is generally present in an amount from about 0.01% to
about 4%, or from about to 0.1% to aobut 3%, or from about 0.5% to about 2.5%
by weight of the lubricating composition.
The lubricating compositions and methods of this invention employ one or
more of the above described oils of lubricating viscosity. Additionally the lubricants
may contain (C) at least one additive selected from the group consisting of (i) at least
one sulfur containing antiwear or extreme pressure agent, (ii) at least one phosphorus
: '
:~ ~
. .:. - . . ~ .
. - - - -
~1~7~)3~
or boron antiwear or extreme pressure agent, and (iii) mixtures thereof, provided that
when (A) is a dithiocarbamate, then (C) is different from (A).
(C~ Sulfur Com~unds
The combination of an antioxidant (A) and a dispersant or detergent (B) may
be used in lubdcating compositions together with a sulfur compound (C)(i). The
sulfur compounds include sulfudzed organic compounds and dithiocarbamate
containing compounds. In one embodiment, the sulfur compound is present in an
amount from about 0.5% up to about 10%, or from about 1% up to about 8%, or
from about 2% up to about 7% by weight of the lubricating composition. The sulfur
compounds (C)(i) include mono- or polysulfide compositions, or mixtures thereof.The sulfur compounds are generally characterized as having sulfide linkages
containing an average from 1 up to about 10, or from about 2 up to about 8, or from
about 3 up to about 4 sulfur atoms. In one embodiment, the organic polysulfides may
be a mixture of di-, tri- or tetrasulfide materials, preferably having a majority of
trisulfide being preferred. Materials having at least 70% trisulfide are preferred, with
materials contzuning greater than 80% trisulfide more preferred.
Materials which may be sulfurized to form (C)(i) include oils, unsaturated
fatty acids, such as those described above, unsaturated fatty esters, olefins or poly-
olefins, terpenes, or Diels-Alder adducts. Oils which may be sulfurized are natural
or synthetic oils, including mineral oils, lard oil, carbo~cylic acid esters derived from
aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate
and oleyl oleate) s~erm whale oil and synthetic sperm whale oil substitutes and
synthetic unsaturated esters or glycerides.
The unsaturated fatty esters include fatty oils, that is, naturally occurring orsynthetic esters of glycerol and one or more of the above fatty acids. Examples of
fatty esters include animal fats, such as Neat's-foot oil, lard oil, depot fat, beef
tallow, vegetable oils including cottonseed oil, corn oil, safflower oil, sesame oil,
soybean oil, and sunflower seed oil. The unsaturated fatty esters also may be
prepared by esterifying alcohols and polyols with a fatty acid. The alcohols include
the above described mono- and polyhydric alcohols, such as methanol, ethanol,
propanol, butanol, ethylene glycol, neopentyl glycol, and glycerol.
The olefins, which may be sulfurized, contain at least one olefinic double
bond, which is defined as a non-aromatic double bond. In its broadest sense, the
::
21~7238
46
S olefin may be defined by the formula R-'R-2C=CR'3R-4, wherein each of R-', R 2,
R-3, and R-4 is hydrogen, or an organic group. In general, the R- groups in the above
formula which are not hydrogen may be represented by -(CH~)n-A, wherein n is a
number from 0 to about 10 and A is represented by -C(R-5)3, -COOR 5, -CoN(R-5)2,-CooN(R-5)4, -COOM, -CN, -X, -YR-5 or -Ar, wherein: each R-5 is independently
hydrogen, or a hydrocarbyl group, with the proviso that any two R-5 groups may be
connected to form a ring of up to about 12 carbon atoms is formed; M is one
equivalent of a metal cation (preferably Group I or II, e.g., sodium, potassium,barium, calcium); X is halogen (e.g., chloro, bromo, or iodo); Y is oxygen or
divalent sulfur; Ar is an aromatic group of up to about 12 carbon atoms.
The olefinic compound is usually one in which each R group which is not
hydrogen is independently alkyl, aLlcenyl or aryl group. In one embodiment, R-3 and
R-4 are hydrogen and R ' and R-2 are aL~yl or aryl, especially alkyl having 1 up to
about 30, or up to about 16, or up to about 8, or even up to about 4 carbon atoms.
Olefins having from 2 up to about 30, or from about 3 up to about 16 (most oftenless than about 9) carbon atoms are particularly useful. Olefins having two to about
5 or to about 4 carbon atoms are particularly use~ful. Isobutene, propylene and their
dimers, trimers and tetramers, and mixtures thereof are especially preferred olefins.
Of these compounds, isobutylene and diisobutylene are particularly desirable. In one
embodiment, the organic polysulfides may be a mixture of di-, tri- or tetrasulfide
materials, preferably having a majority of trisulfide being preferred. Materials having
at least 70% trisulfide are preferred, with materials containing greater than 80trisulfide morepreferred.
The sulfurized olefins may be produced by reacting sulfur monochloride with
an olefin, and then treating the resulting product with an alkali metal sulfide in the
presence of free sulfur. The resulting product is then treated with an inorganic base
The sulfurized olefin may also be prepared by the reacting, under superatmospheric
pressure, the olefin with a mixture of sulfur and hydrogen sulfide in the presence, or
absence, of a catalyst, followed by removal of low boiling materials. The olefins
which may be sulfurized, the sulfurized olefin, and methods of preparing the same
are described in U.S. Patents 4,119,549, 4,199,550, 4,191,659, and 4,344,854. The
disclosure of these patents is hereby incorporated by reference for its description of
the sulfurized olefins and preparation of the same.
21~7~38
S In another embodiment, the organic polysulfide comprise sulfunzed olefins
prepared by the sulfochlorination of olefins containing four or more carbon atoms and
further treatment with inorganic higher polysulfides according to U.S. Patent
2,708,199. The sulfurized olefins may be produced by (1) reacting sulfur
monochloride with a stoichiometric excess of a lower olefin, e.g. containing two to
about seven carbon atoms, (2) treating the resulting product with an aLkali metal
sulfide in the presence of free sulfur in a mole ratio of no less than 2:1 in analcohol-water solveht, and (3) reacting that product with an inorganic base. This
procedure is descri~ed in U.S. Patent 3,471,404, and the disclosure of U.S. Patent
3,471,404 is hereby incorporated by reference for its discussion of this procedure for
preparing sulfurized olefins and the sulfurized olefins thus produced. Generally, the
olefin reactant contains from about 2 to 5 carbon atoms and examples include
ethylene, propylene, butylene, isobutylene, amylene, etc.
The following example relates to an organic polysulfide.
Example S-l
Sulfur (526 parts, 16.4 moles) is charged to a jacketed, high-pressure reactor
which is fitted with an agitator and internal cooling coils. Refrigerated brine is
circulated through the coils to cool the reactor prior to the introduction of the gaseous
. . -. -
reactants. After sealing the reactor, evacuadng to about 2 torr and cooling, 920 parts
~16.4 moles) of isobutene and 279 parts (8.2 moles) of hydrogen sulfide are charged
to the reactor. The reactor is heated using steam in the extemal jacket, to a
temperature of about 182 C over about 1.5 hours. A maximum pressure of 1350
psig is reached at about 168 C during this heat-up. Prior to reaching the peak
reaction temperature, the pressure starts to decrease and con~nues to decrease steadily
as the gaseous reactants are consumed. After about 10 hours at a reaction
temperature of about 182- C, the pressure is 310-340 psig and the rate of pressure
change is about 5-10 psig per hour. The unreacted hydrogen sulfide and isobuteneare vented to a reco~rery system. After the pressure in the reactor has decreased to
atmospheric, the sulfurized mixture is recovered as a liquid.
The mixture is blown with nitrogen at about lOO C to remove low boiling
materials including unreacted isobutene, mercaptans and monosulfides. The residue
after nitrogen blowing is agitated with 5% Super Filtrol and filtered, using a
,,i, ~ . . .
2147238
.
48
diatomaceous earth filter ~ud. The filtrate is the desired sulfurized composition which
contains 42.5 % sulfur. -
In another embodiment, (C) is a sulfurized terpene compound. The term
"terpene compound" as used in the specification and claims is intended to include the
various isomeAc terpene hydrocarbons having the empirical forrnula CIoHl6, suc~ as
contained in turpentine, pine oil and dipentenes, and the various synthetic and
naturally occumng oxygen~ontaining derivatives. Pine-oil derivatives, which are
commercially available from Hercules Incorporated, include alpha-terpineol (a high
purity tertiary terpene alcohol); and Terpineol 318 Prime (a mixture containing about
6065% weightalpha-terpineoland 15-20~6 weightbeta-terpinesl); Yarmor302;
Herco pine oil; Yarmor 302W; Yarmor F; and Yarmor 60.
In another embodiment, (C) is a sulfurized Diels Alder adduct. The sulfurized
Diels Alder adduct is prepared by reacting a sulfur source, such as elemental sulfur,
sulfur halides and organic polysulfides, including dialkyl polysulfides. A Diels-Alder
reaction involves the reaction of at least one conjugated diene with at least one
ethylenically or acetylenically unsaturated compound, these latter compounds being
known as dienophiles. Piperylene, isoprene, methylisoprene, chloroprene, and
1,3-butadiene are arnong the preferred dienes for use in preparing the Diels-Alder
adducts. Other dienes include linear 1,3-conjugated dienes, cyclic dienes, such as
cyclopentadienes, fulvenes, 1,3-cyclohexadienes, 1,3,5-cy~loheptatrienes,
cyclooctatetraene, etc.
Dienophiles. used in preparing the Diels-Alder ~dducts, include nitroaLkenes;
alpha, beta-ethylenically unsaturated carboxylic esters, acids or arnides; ethylenically
unsaturated aldehydes and vinyl ketones. The unsaturated car~oxylic esters, acids and
amides are described above. Specific exarnples of dienophiles include l-nitrobutene-
1, alkylacrylates, acrylamide, dibutylacrylamide, methacrylamide, crotonaldehyde;
crotonic acid, dimethyldivinyl ketone, methylvinyl ketone, propiolaldehyde,
methylethynyl ketone, propiolic acid, propargylaldehyde, cyclopentenedione, 3-cyano-
coumaran, etc. The sulfurized Diels-Alder adducts are readily prepared by heating
a mixture of a sulfur source, preferably sulfur and at least one of the Diels-Alder
adducts of the types discussed hereinabove at a temperature within the range of from
about 110C to just below the decomposi~ion temperature of the Diels-Alder adducts.
Temperatures within the range of about 110 to about 200C will normally be used.
~ 21~7238
4 9
Generally, the molar ratio of sulfur source to Diels-Alder adduct is in a range of from
about 0.75 up to about 4 or from about 1 up to about 3 or up to about 2.5. The
Diels-Alder adducts are a well-known, art-recognized class of compounds preparedfrom dienes by Diels-Alder reaction. An example of a useful sulfurized Diels-Alder
adduct is a sulfurized reaction product of butadiene and butyl-acrylate. Sulfurized
Diels Alder adducts are described in U.S. Patents 3,498,915, 4,582,618, and Re
27331 These patents are hereby incorporated by reference for their disclosures of
sulfurized Diels Alder adducts and methods of making the same.
In another embodiment, the sulfur compound (C)(i) is a dithiocarbamate
containing compound. The dithiocarbamate-containing compounds include
dithiocarbamate esters, dithiocarbamate amides, dithiocarbamic ethers, a sulfur
coupled dithiocarbamates, and alkylene-coupled dithiocarbamates. These are
described above. When the antioxidant (A) is a dithiocarbamte then (C) is different
from (A).
(C~ Phosphorus or Boron Agents
In one embodiment, the combination of the antioxidant (A) and the dispersant
or detergent (B) are used in lubricating compositions in combination with at least one
phosphorus or boron containing antiweartextreme pressure agent (C)(ii). In this
embodiment, (C)(ii) is present in an amount sufficient to impart antiwear, antiweld,
andtor extreme pressure properties to the lubricants and functional fluids. The
phosphorus or boron containing agents (C)(ii) are typically present in the lubricants
and functional fluids at a level of up to about 20% by weight, preferably up to about
loæ by weight, based on the total weight of the lubricant, functional fluid, or grease.
Typically, the phosphorus or boron containing antiwear/extreme pressure agent ispresent in the lubricants and functional fluids at a level from about 0.01% up to about
10%, or from about 0.05% or up to about 4%, or from about 0.08% up to about 3%
or from 0.1% to about 2% by weight.
Exarnples of phosphorus or boron containing antiwear/extreme pressure agents
(C)(ii) include a phosphoric acid ester or salt thereof; a phosphite; a phosphorus~
containing carboxylic ester, ether, or amide; a borated dispersant; an alkali metal or
a mixed alkali metal, aLI~aline earth metal borate; a borated overbased metal salt; and
a borate ester. The phosphorus acids include the phosphoric, phosphonic, phosphinic
and thiophosphoric acids including dithiophosphoAc acid as well as the
2147~38
, .
monothiophosphoric acid, thiophosphinic and thiophosphonic acids. The phosphoruscontaining carboxylic esters, acids, ethers, or amides, the borated dispersants and the
boIated overbased metal salts have been descAbed above. When the antioxidant (A)is a metal thiophosphate, then (C) is different than (A).
In one embodiment, (C)(ii) is a phosphorus acid ester is prepared by reacting
one or more phosphorus acid or anhydride with an alcohol containing from 1 up toabout 30, or from about 2 up to about 24, or from about 3 up to about 12 carbon
atoms. The phosphorus acids or anhydrides and the alcohols are described above.
Examples of useful phosphorus acid esters include the phosphoric acid di- and tri-
esters prepared by reacting a phosphoric acid or anhydride with cresol alcohols. An
example is tricresylphosphate.
In one embodiment, (C)(ii) may be a phosphorus ester prepared by reacting
one or more dithiophosphoric acid with an epoxide or a glycol. This reaction product
may be used alone, or further reacted with a phosphorus acid, anhydride, or iower
ester. The epoxide is generally an aliphatic epoxide or a styrene oxide. Examples
of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octeneoxide, dode ene oxide, styrene oxide, etc. Propylene oxide is preferred. The glycols
may be aliphatic glycols, having from 1 to about 12, or from about 2 to about 6, or
about 2 or 3 carbon atoms, or aromatic glycols. Glycols include ethylene glycol,propylene glycol, catechol, resorcinol, and the like. The dithiophosphoric acids,
glycols, epoxides, inorganic phosphorus reagents and methods of reacting the same
are described in U.S. patent 3,197,405 and U.S. patent 3,544,465 which are
incorporated herein by reference for their disdosure to these.
The following Examples P-l and P-2 exemplify the preparation of useful
phosphorus acid esters.
Example P-l
Phosphorus pentoxide (64 grams) is added at 58C over a period of 45
minutes to 514 grams of hydroxypropyl O,O-di(4-methyl-2pentyl)phosphorodithioate(prepared by reacting di(4-methyl-2pentyl)-phosphorodithioic acid with 1.3 moles of
propylene oxide at 25C). The mixture is heated at 75C for 2.5 hours, mixed with
a diatomaceous earth and filtered at 70C. The filtrate contains 11.8% by weightphosphorus, 15.2% by weight sulfur, and an acid number of 87 (bromophenol blue).
: :
21~7238
51
S Bxample P-2 ~ ;~
A mixture of 667 grams of phosphorus pentoxide and the reaction product of
3514 grams of diisopropyl phosphorodithioic acid with 986 grams of propylene oxide
at SO C is heated at 85 C for 3 hours and filtered. The filtrate contains 15.3~o by
weight phosphorus, 19.6% by weight sulfur, and an acid number of 126
(bromophenol blue).
Acidic phosphoric acid esters may be reacted with an amine compound or -
metallic base to form an amine or metal salt. The salts may be formed separately and
then the salt of the phosphorus acid ester may be added to the lubricating
composition. Alternatively, the salts may also be formed in situ when the acidicphosphorus acid ester is blended with other components ~o form a fully formulated
lubricating composition.
. ,
The amine salts of the phosphorus acid esters may be formed from ammonia
or one or more of the above described amines, including monoamines and
polyamines. In one embodiment, the amine is one or more of the above described
tertiary aliphatic primary arnines.
The metal salts of the phosphorus acid esters are prepared by the reaction of
a metal base with the phosphorus acid ester. The m~tal base may be any metal
compound capable of forming a metal salt. Examples of metal bases include metal
oxides, hydroxides, carbonates, sulfates, borates, or the like. The metals of the metal
base include Group IA, IIA, IB through VIIB, and VIII metals (CAS version of thePeriodic Table of the Elements). These metals include the aLkali metals, alkaline
earth metals and transition metals. In one embodiment, the metal is a Group IIA
metal, such as calcium or magnesium, a Group IB metal, such as copper, a Group
IIB metal, such as zinc, or a Group VIIB metal, such as manganese. Preferably the
metal is magnesium, calcium, copper or zinc. Examples of metal compounds which
may be reacted with the phosphorus acid include zinc hydroxide, zinc 07cide, copper
hydroxide, copper oxide, etc.
In one embodiment, (C)(ii) is a metal thiophosphate, preferably a metal
dithiophosphate. The metal thiophosphate is prepared by means known to those in
the art. Examples of metal dithiophosphates include zinc isopropyl, methylamyl
dithiophosphate, zinc isopropyl isooctyl dithiophosphate, barium di(nonyl) dithio-
phosphate, zinc di(cyclohexyl~ dithiophosphate, copper di(isobutyl) dithiophosphate,
~47~38 ~:
calcium di(hexyl) di~iophosphate, zinc isobutyl isoarnyl dithiophosphate, and inc
isopropyl secondary-butyl dithiophosphate.
The following Examples P-3 to P-6 exemplify the preparation of useful
phosphorus acid ester salts.
ExampleP-3
A reaction vessel is charged with 217 grams of the filtrate from Example P-l.
A commercial aliphatic primary arnine (66 grams), having an average molecular
weight of 191 in which the aliphatic radical is a mixture of tertiary alkyl radicals
containing from 11 to 14 carbon atom, is added over a peAod of 20 minutes at 25-60C. The resulting product has a phosphorus content of 10.2% by weight, a
nitrogen content of 1.5% by weight, and an acid number of 26.3.
Example P-4
The filtrate of Example P-2 (1752 grams) is mixed at 25-82 C with 764 grams
of the aliphatic primary amine used in of Example P-3. The resulting product has9.95% phosphorus, 2.72% nitrogen, and 12.6% sulfur.
Example P-5
Phosphorus pentoxide (852 grams) is added to 2340 grams of iso octyl alcohol
over a period of 3 hours. The temperature increases from room temperature but ismaintained below 65C. After the addition is complete the reaction mixture is heated
to 90C and the temperature is maintained for 3 hours. Matomaceous earth is added
to the mixture, and the mixture is filtered. The filtrate has 12.4% phosphorus, a 192
acid neutralization number (bromophenol blue) and a 290 acid neutralization number
(phenolphthalein).
The above filtrate is mixed with 200 grams of toluene, 130 grams of mineral -
oil, 1 gram of acetic acid, 10 grams of water and 45 grams of zinc oxide. The
mixture is heated to 6~70C under a pressure of 30 mm Hg. The resulting product
mixture is filtered using a diatomaceous earth. The filtrate has 8.58% zinc and
7.03 g6 phosphorus.
Example P-6
Phosphorus pentoxide (208 grams) is added to the product prepared by
reacting 280 grams of propylene oxide with 1184 grams of O,O'-di-isobutylphos-
phorodithioic acid at 3~60C. The addition is made at a temperature of 50-60 C and
the resulting mixture is then heated to 80C and held at that temperature for 2 hours.
- ' ~ ':~
: ~;
~. . .
2147238
The commercial aliphatic primary amine identified in Example P-3 (384 grams) is
added to thie mixture, while the temperature is maintained in the range of 30-60C.
The reaction mixture is filtered through diatomaceous earth. The filtrate has 9.31%
phosphorus,11.37%sulfur,2.50%nitrogen,andabasenumber-of6.9(brornophenol
blue indicator).
In another embodiment, (C)(ii) is a metal salt of (a) at least one
dithiophosphoric acid and (b) at least one aliphatic or alicyclic carboxylic acid. The
dithiophosphoric acids are described above. The carboxylic acid may be a
monocarboxylic or polycarboxylic acid, usually containing from 1 to about 3, or just
one carboxylic acid group. The preferred carboxylic acids are those having the
formula R3,COOH, wherein R31 is a hydrocarbyl group, preferably free from
acetylenic unsaturation. Generally, R3, contains from about 2 up to about 40, or from
about 3 up to about 24, or from about 4 up to about 12 carbon atoms. In one
embodiment, R3, contains from about 4, or from about 6 up to about 12, or up to
about 8 carbon atoms. In one embodiment, R3, is an alkyl group. Suitable acids
include the butanoic, pentanoic, hexanoic, octanoic, nonanoic, decanoic, dodecanoic,
octodecanoic and eicosanoic acids, as well as olefinic acids such as oleic, linoleic,
and linolenic acids, and linoleic dimer acid. A preferred carboxylic acid is 2-
ethylhexanoic acid.
The metal salts may be prepared by merely blending a metal salt of a
dithiophoshoric acid with a metal salt of a carboxylic acid in the desired ratio. The
ratio of equivalents of dithiophosphoric acid to carboxylic acid is from about 0.5 up
to about 400 to 1. The ratio may be from 0.5 up to about 200, or up to about 100,
or up to about 50, or up to about 20 to 1. In one embodiment, the ratio is from 0.5
up to about 4.5 to 1, or from about 2.5 up to about 4.25 to 1. For this purpose, the
equivalent weight of a dithiophosphoric acid is its molecular weight divided by the
number of -PSS~I groups therein, and the equivalent weight of a carboxylic acid is
its molecular weight divided by the number of carboxy groups therein.
A second and preferred method for preparing the metal salts useful in this
invention is to prepare a mixture of the acids in the desired ratio, such as those
described above for the metal salts of the individual metal salts, and to react the acid
mixture with one of the above described metal compounds. When this method of
preparation is used, it is frequently possible to prepare a salt containing an excess of
21~7~38 - ~
.
54
metal with respect to the number of equivalents of acid present; thus the metal salts
may contain as many as 2 equivalents and especially up to about 1.5 equivalents of
metal per equivalent of acid may be prepared. The equivalent of a metal for thispurpose is its atomic weight divlded by its valence. The temperature at which the
metal salts are prepared is generally between about 30C and about 150C, preferably
up to about 125C. U.S. Patents 4,308,154 and 4,417,990 describe procedures for
preparing these metal salts and disclose a number of examples of such metal sa!ts.
These patents are hereby incorporated by reference for those disclosures.
In another embodiment, (C)(ii) may be an aromatic phosphite as described
above. In ano~ier embodiment, (C)(ii) may be an aliphatic phosphite. The phosphite
may be a di- or trihydrocarbyl phosphite. Generally, each hydrocarbyl group has
from l up to about 24, or from about 2 up to about 18, or from 3 up to about 8
carbon atoms. Examples of specific hydrocarbyl groups include propyl, butyl, hexyl,
heptyl, octyl, oleyl, linoleyl, stearyl, and mixtures of two or more of thereof. In one
embodiment, eaeh hydrocarbyl group is independently propyl, butyl, pentyl, hexyl,
heptyl, or oleyl. Phosphites and their preparation are known and many phosphitesare available commercially. Particularly useful phosphites are dibutyl phosphite, and
trioleyl phosphite.
In another embodiment, (C)(ii) is an alkali or an alkali metal and alkaline e~h
metal borate. These metal borates are generally a hydrated particulate metal borate
which are known in the art. Alkali metal borates include mixed aLkali and alkaline
metal borates. These metal borates are available commercially. Representative
patents disclosing suitable alkali and alkali metal and alkaline earth metal borates and
their methods of manufacture include U.S. 3,997,454; 3,819,521; 3,853,772;
3,907,601; 3,997,454; and 4,089,790. These patents are incorporated by referencefor their disclosures of the metal borates and methods of their manufacture.
In another embodiment, (C)(ii) is a borated fatty amine. The borated amines
are prepared by reacting one or more of the above boron compounds with a fatty
amine, e.g., an amine having from about four up to about eighteen carbon atoms.
The borated fatty amines are prepared by reacting the amine with the boron
compound at about 50C to about 300C, preferably about 100C to about 250C,
~ . ~
:.. :........... , :. ' .'
s~
~: - : , - . . ,
.
2 ~ '1 7 2 3 8
~ -
and at a ratio of 3:1 to 1:3 equivalents of amine to equivalents of boron
compound.
The borated fatty epoxides are generally the reaction product of one or more
of the above boron compounds with at least one epoxide. The epoxide is generallyan aliphatic epoxide having at least 8, preferably at least about 10, more preferably
at least about 12 up to about 24, preferably up to about 20 carbon atoms. Examples
of useful aliphatic epoxides include heptyl oxide, octyl oxide, stearyl oxide, oleyl
oxide and the like. Mi~ctures of epoxides may also be used, for instance commercial
mixtures of epoxides having from about 14 to about 16 carbon atoms and from about
14 to about 18 carbon atoms. The borated fatty epoxides are generally known and
are disclosed in U.S. Patent 4,584,115. This patent is incorporated by reference for
its disclosure of borated fatty epoxides and methods for preparing the same.
In one embodiment, (C)(ii) is a borate ester. The borate esters may be
prepared by reacting of one or more of the above boron compounds with one or more
of the above identified alcohols. Typically, the alcohols contain from about 6 up to
about 30, or from about 8 to about 24 carbon atoms. The methods of making such
borate esters are known to those in the art. ~;-
In another embodiment, borate ester is a borated phospholipid. The borated
phospholipids are prepared by reacting a combination of a phospholipid and a boron
compound, Optionally, the combination may include an amine, an acylated nitrogencompound, a carboxylic ester, a Mannich reaction product, or a basic or neutral metal
salt of an organic acid compound. These additional components are described above.
Phospholipids, sometimes referred to as phosphatides and phospholipins, may be
natural or synthetic. Naturally deAved phospholipids include those derived from fish, ~ -
fish oil, shellfish, bovine brain, chicken egg, sunflowers, soybean, corn, and cotton-
seeds. Phospholipids may be derived from microorganisms, including blue-green
algae, green algae, and bacteria.
The reactions usually occurs at a temperature from about 60C up to about
200 C, or from about 90C, or up to about 150C. The reaction is typically
accomplished in abont 0.5 up to about 10 hours. The boron compound and phosph~ ~-
lipid are reacted at an atomic proportion ratio of boron to phosphorus of 1-6:1 or 2- ; ~
2147238
5 6
4:1, or 3:1. When the combination includes additional components, the boron
compound is reacted with the mixture of the phospholipid and one or more optional
ingredients in an amount of one atomic proportion of boron to an equivalent of the
mixture of a phospholipid and an optional ingredient in a ra~o from about one, or
about two up to about six, to about four to one. The equivalents of the mixture are
based on the combined equivalents of phospholipid based on phosphorus and
equivalents of the optional ingredients.
The antioxidant (A) and the dispersant or detergent (B) may be used in
lubricating compositions together with other additives such as auxiliary extremepressure agents, corrosion and oxidation inhibiting agnets and metal deactivators.
Auxiliary extreme pressure agents and corrosion- and oxidation-inhibiting agentswhich may be included in the lubricants of the invention are exemplified by chlori
nated aliphatic hydrocarbons, such as chlorinated wax; phosphosulfurized hydrocar
bons, such as the reaction product of a phosphorus sulfide with turpentine or methyl
oleate; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium
diheptylphenyl dithiocarbamate. The metal deactivators include
dimercaptothiadiazoles, such as the reaction products of octyl mercaptan and
dimercaptothiadiazole as well as the reaction product of hepylphenol, fonnaldehyde
and dimercaptothiadiazole. Many of the above-mentioned extreme pressure agents
and corrosion- and oxidation-inhibitors also serve as antiwear agents.
Pour point depressants are an additive often included in the lubricating oils de-
scribed herein. Examples of useful pour point depressants are polymethacrylates;polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and
aromatic compounds; vinyl carboxylate polymers; and polymers of dialkylfumarates,
vinyl esters of fatty acids and alkyl vinyl ethers. Pour point depressants useful for
the purposes of this invention, techniques for their preparation and their uses are
described in U.S. Patents 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498;2,666,746; 2,721,877; 2,721,878; and 3,250,715 which are hereby incorporated by
reference for their relevant disclosures.
Antifoarn agents are used to reduce or prevent the formation of stable foam.
Typical antifoam agents include silicones or organic polymers. Additional antifoam
. .
- 21~723~
57
compositions are descAbed in "Foam Control Agents", by Henry T. Kerner (Noyes
Data Corporation, 1976), pages 125-162.
The following examples relate to lubricating compositions of the present
invention containing the antioxidant (A) and the dispersant or detergent (B). ~ -
Example I~l
Alubricantispreparedbyincorporating3.5% of dinonyldiphenylamine, 1.2%
of the product of Example B-4, 0.1% oleylamide, 1.7% of the product of Example
P-3, 4.6% of the product of Example S-l, 0.05% of a reaction product of C9
mercaptan and dimercaptodithiodiazole, 0.1% of a reaction product of heptylphenol,
formaldehyde and dimercaptothiadiazole, 0.1% of a copolymer of methylacrylate and
2-ethylhexylacrylate, 30 ppm of Dow Corning 200 fluid, 0.04% by weight of
monoisopropanolamine, and 2% by weight of a polybu~ene ha~ing a number average
molecular weight of 2000, and 1.8!~i by weight of a 4 cSt PAO into a 75W-90
synthetic base fluid having a kinematic viscosity of 17.7 cSt.
Example L,2
A lubricant is prepared by incorporating 3.5 % of dinonyldiphenylamine, 1.1%
of the product of Example B~, 0.03 % of a substituted imidiazoline from oleylamine,
0.1% oleylamide, 1.7% of the product of Example P-3, 4.6% of the product of
Example S-l, 0.05% of a reaction product of C9 mercaptan and
dimercaptodithiodiazole, 0.1% of a reaction product of heptylphenol, formaldehyde
and dimercaptothiadiazole, 0.03 % of TOLAD 370 available from Petrolite Chemical,
0.1% of a copolymer of methylacrylate and 2-ethylhexylacrylate, 30 ppm of Dow
Corning 200 fluid, and 1.7% by weight of a 4 cSt PAO into a 75w-90 synthetic base ` ~;
fluid.
Example L,3
A 75W-90 lubricant is prepared by incorporating 3.5 % of
dinonyldiphenylamine, 1.2% of the product of Example ~4, 0.03% of a substituted
imidiazoline from oleylamine, 0.1% oleylamide, 1.7% of the product of Example
P-3, 4.6% of the product of Example S 1, 0.1% of a reaction product of C
mercaptan and dimercaptodithiodiazole, 0.1% of a reaction product of heptylphenol,
formaldehyde and dimercaptothiadiazole, 0.03% of TOLAD 370 available from
~ ~ '
-- 2147~38
58
Petrolite Chemical, 0.1 % of a copolymer of methylacrylate and 2-ethylhexylacrylate,
0.5 % by weight of a maleic anhydride-styrene copolymer esterified with C~,8 and C4
alcohols and post-treated with aminopropylmorpholine, 30 ppm of Dow Corning 200
fluid, 2.01% of diisodecylazelate, and 32% polybutene having a number average
molecular weight of 2000 into 54.0% by weight of a 4 cSt PAO.
Example IA
A 75W-90 lubricating composition is prepared by incorporating 3.5% of
dinonyldiphenylamine, 1.4% of the product of Example B-6(b), 4.1 % of the product
of Example S-l, 1.6% of the product of Exa nple P-3, 0.8% of a reaction product of
dimercaptothiadiazole and a carboxylic ester dispersant prepared by reacting a
polybutenyl (Mn=950) substituted succinic anhydride with penteaerythrithol and
polyethylenepolyamines, 0.3% triphenylphosphite, 0.3% glycerol monooleate, 0.1 %by weight of a polymer of vinyl acetate, ethylacrylate and 2~thylhexylacrylate, 1.9 %
of diisodecylazelate, 30 parts per million Dow Corning 200 fluid, 18% by weight a
methacrylate polymer having a Mn=14000 and Mw=25000, 1% by weight of a
methacrylate polymer having a Mn=31000 and Mw=55000 into 46.9% XHVI lOON
isomerized wax basestock (0.01% sulfur/ 141 VI) and 20.1% by weight of a 6 cSt
PAO.
Example L,5
A lubricating composition is prepared as described in Example L-l except an
SAE lOW30 base fluid is used in place of the SAE 75W-90 fluid.
Example I~6
A lubAcant is prepared as described in Exarnple L-3 except 3% of di-t-
butylphenol is used in place of 3.5% of dinonyldiphenylamine.
Example L.7
A lubricant is prepared as described in Example L-4 except 1.6% of
methylenebis(di-n-butyldithiocarbarnate)and 1.5% of 2,6-di-t-butyl-4-hepthylphenol
are used in place of dinonyldiphenylamine.
Example I,8
A lubricant is prepared as described in Example L-4 except 1.5% of the
product of Example B-7(a) is used in place of the product of Example B-6(b).
- 214723~
59
Examples L-9 through L-14 are further examples of 75W-90 lubricating
compositions using a 75W-90 syntheitic base fluid into which is incorporated theadditives described in the following table.
L-9 L-10 L-ll L-12 L-13 L-14 :
¦ Dinonyldiphenylamine 1 3.5 3.5
¦ Triphenyl phosphite 0.5 0.2 0.3 0.7
¦ Methylenebis(di-n-butyl- 1 3.0
I dithiocarbamate)
¦ Sulfur coupled tetrapropenyl 2.5 `
I ..
¦ N-phenyl-l-naphthylamine 3.1
I .
¦ Product of Ex ~ 4 1.2 1.1 1.1 0.9
¦ Product of Ex B-6(a) _
l .
¦ Product of Ex B-6(b) 1.5
¦ Product of Ex S-l 3.5 4.1 4.0 3.7 -~
Product of Ex P-3 _ 1.3 0.8 1.2
¦ Reaction product of _ 0.8
polybutenyl (Mn=850)
succinic anhydride and
tet~aethylene pentan~ine l ~
The lubricants containing the antioxidant and the dispersant or detergent show
25improved oxidation stability as measured by extended (e.g. 300 hours) L-60 Thermal
Oxidation Stability Test. The method and apparatus are defined by CRC L-60
Thermal Stability test. Viscosity increase of the lubricants due to oxidation isminimized. Viscosity increase change is often below 100%. Further the viscosity
increase is minimized while maintaining favorable carbon/varnish ratings.
30While the invention has been explained in relation to its preferred embodi-
ments, it is to be understood that various modifications thereof will become apparent
2147238
S to those skilled in the art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover such modifications
as fall within the scope of the appended claims.
