Note: Descriptions are shown in the official language in which they were submitted.
- CA 022130~0 1997-08-1~
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2758R
Title: COMPOSITIONS CONTAINING THIOCARBONATES AND
ACYLATED-NITROGEN CONTAINING COMPOUNDS
Technical Field
Thisinventionrelatestocompositionscontainingthiocarbonates
and acylated nitrogen-containing compounds. These compositions are useful
in formulating lubricants and functional fluids characterized by enhanced
antiwear properties.
Background of the Invention
Engine lubricating oils require the presence of additives to
protect the engine from wear. For almost 40 years, the principal antiwear
additive for engine lubricating oils has been zinc dialkyl dithiophosphate
(ZDDP). However, ZDDP is typically used in the lubricating oil at a sufficient
concentration to provide a phosphorus content of 0.12% by weight or higher
in order to pass required industry standard tests for antiwear. Since
phosphates may result in the deactivation of emission control catalysts used
in automotive exhaust systems, a reduction in the amount of phosphorus-
containing additives (e.g., ZDDP) in the oil would be desirable. The problem
sought to be overcome is to provide for a reduction in the amount of
phosphorus-containing additive in the lubricating oil and yet provide the
lubricating oil with desired antiwear properties. The present invention
provides a solution to this problem by providing compositions that can
function as either a partial or complete replacement for ZDDP.
CA 022130~0 1997-08-1~
U.S. Patent 2,020,021 discloses the use of thiocarbonates
represented by the formulae RO-C(S)-SR1 and RS-C(S)-SRl as lubricant
additives for improving the extreme pressure characteristics of lubricants.
U.S. Patents 2,110,281 and 2,206,245 disclose the use of
5xanthic acid esters represented by the formula RO-C(S)-SR as additives for
lubricants used on bearing surfaces which are subjected to high pressures
and high rubbing velocities during use.
U.S. Patent 5,026,492 discloses the use of alkyl alkoxy alkyl
xanthates represented by the formula R1-O-R2-O-C(S)-S-R3 in combination
10with metal thiophosphates as antiwear additives for lubricating oil
compositions.
The use of ashless dispersants in lubricants is disclosed in
numerous patents, including U.S. Patents 3,172,892; 3,219,666;
3,272,746; 3,310,492; 3,341,542; 3,444,170; 3,455,831; 3,455,832;
153,576,743; 3,630,904; 3,632,511; 3,804,763; and 4,234,435.
The use of metal salts of phosphorodithioic acids as additives
for lubricants is disclosed in U.S. Patents 4,263,150; 4,289,635; 4,308,-
154; 4,322,479; and 4,417,990. Amine salts of such acids are disclosed
as being useful as additives for grease compositions in U.S. Patent
205,256,321.
The use of disulfides represented by the formula (RzYC = S)2S2,
wherein Y is O, S or N, and z is 1 when Y is O or S and 2 when Y is N, as
lubricant additives is disclosed in U.S. Patents 2,681,316; 2,691,632; and
2,694,682.
25U.S. Patent 2,307,307 discloses the use of compounds
represented by the formula (RXC=S)2Sn, wherein X is O or S, and n is
greater than 2, as lubricant additives.
The use of compounds represented by the formula (ROC = S)S2
in lubricants for use on bearing surfaces is disclosed in U.S. Patents
2,110,281 and 2,206,245. U.S. Patent 2,431,010 discloses the use of
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compounds represented by the formula ~ROC=S)Sn, wherein n is 2-4, as
soluble cutting oil additives.
The use of thiuram sulfides as lubricant additives is disclosed
in U.S. Patents 2,081,886; 2,201,258; 3,249,542; 3,352,781; 4,207,196;
and 4,501,678.
U.S. Patent 5,034,141 discloses that improved antiwear results
can be obtained by combining a thiodixanthogen (e.g., octylthiodixanthogen)
with a metal thiophosphate (e.g., ZDDP). U.S. Patent 5,034,142 discloses
the addition of a metal alkoxyalkylxanthate (e.g., nickel ethoxyethylxan-
thate), a dixanthogen (e.g., diethoxyethyl dixanthogen) and a metal
thiophosphate (e.g., ZDDP) to a lubricant to improve antiwear.
European patent application 0 609 623 A1 discloses an engine
oil composition containing a metal-containing detergent, zinc
dithiophosphate, a boron-containing ashless dispersant, aliphatic amide
compound, and either a dithiocarbamate compound or an ester derived from
a fatty acid and boric acid. Among the dithiocarbamates that are disclosed
are sulfides and disulfides.
U.S. Patent 3,409,635 discloses a process for making cyclic
compounds represented by the formula
R' R2
Rl _C--~--R2
O~ ,S
S
wherein R1 and R2 are hydrogen or methyl. The reference indicates that the
cyclic xanthates are useful as fungicides, and the epithiranes yield polymers
which aid in the vulcanization of rubber.
U.S. Patent 3,448,120 discloses a process for making alkylene
dithiocarbonates.
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U.S. Patent4,51 1 ,464discloses 1 ,3-oxathiolane-2-thiones and
1 ,3-dithiolane-2-thiones as collectors for concentrating sulfide mineral ores
using froth flotation.
U.S. Patent 4,758,362 discloses the addition of a
thiocarbamate to a low phosphorus or phosphorus free lubricating oil
composition to provide a composition with enhanced extreme-pressure and
antiwear properties.
S~..,...~c.r.~ of the Invention
This invention relates to a composition, comprising:
(A) a thiocarbonate represented by the formula
R1--X--C--S--(CRZR3)nT (A-l~
wherein in Formula (A-l): R~, R2 and R3 are independently hydrogen or
hydrocarbyl groups; X is O or S; n is zero, 1 or 2; and T is a hydrocarbyl
group, a hetero group, a hydroxyhydrocarbyl group, or an activating group;
with the proviso that when n is zero, T can be a metal, and when n is 2,
each R2 and R3 can be the same or different; and
(B) an acylated nitrogen-containing compound having a
substituent of at least about 10 carbon atoms.
In one embodiment, the inventive composition further comprises
(C) a phosphorus compound. In one embodiment, the inventive composition
further comprises (D) an organic sulfide. In one embodiment, the inventive
composition further comprises (E) a heterocyclic compound. In one
embodiment, the inventive composition further comprises (F) a
thiocarbamate. In one embodiment, the invention relates to a process
comprising mixing the foregoing components (A) and (B) with an oil of
lubricating viscosity, and, optionally, one or more of the foregoing
components (C), (D), (E) and/or (F).
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The inventive compositions are useful in formulating lubricating
compositions and functional fluids characterized by enhanced antiwear
properties. In one embodiment, these lubricating compositions and
functional fluids are characterized by reduced phosphorus levels when
compared to those in the prior art, and yet have sufficient antiwear
properties to pass industry standard tests for antiwear. In one embodiment,
the inventive lubricating compositions are characterized by enhanced
extreme pressure properties. In one embodiment, the inventive lubricating
compositions are characterized by good seal compatibility. The inventive
lubricating compositions are especially suitable for use in lubricating oil
compositions for internal combustion engines.
Descri"lion of the ~lef~r,ed Embodiments
As used in this specification and in the appended claims, the
terms "hydrocarbyl" and "hydrocarbon based" denote a group having a
carbon atom directly attached to the remainder of the molecule and having
a hydrocarbon or predominantly hydrocarbon character within the context
of this invention. Such groups include the following:
(1) Hydrocarbon groups; that is, aliphatic, (e.g., alkyl or
alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic, aliphatic- andalicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic
groups, and the like, as well as cyclic groups wherein the ring is completed
through another portion of the molecule (that is, any two indicated
substituents may together form an alicyclic group). Such groups are known
to those skilled in the art. Examples include methyl, ethyl, octyl, decyl,
octadecyl, cyclohexyl, phenyl, etc.
(2) Substituted hydrocarbon groups; that is, groups
containing non-hydrocarbon substituents which, in the context of this
invention, do not alter the predominantly hydrocarbon character of the
group. Those skilled in the art will be aware of suitable substituents.
Examples include halo, hydroxy, nitro, cyano, alkoxy, acyl, etc.
CA 02213050 1997-08-15
(3) Hetero groups; that is, groups which, while predominant-
ly hydrocarbon in character within the context of this invention, contain
atoms other than carbon in a chain or ring otherwise composed of carbon
atoms. Suitable hetero atoms will be apparent to those skilled in the art and
include, for example, nitrogen, oxygen and sulfur.
In general, no more than about three substituents or hetero
atoms, and preferably no more than one, will be present for each 10 carbon
atoms in the hydrocarbyl group.
Terms such as "alkyl-based," "aryl-based," and the like have
meanings analogous to the above with respect to alkyl groups, aryl groups
and the like.
The term "hydrocarbon-based" has the same meaning and can
be used interchangeably with the term hydrocarbyl when referring to
molecular groups having a carbon atom attached directly to the remainder
of a molecule.
The term "lower" as used herein in conjunction with terms such
as hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is intended to describe
such groups which contain a total of up to 7 carbon atoms.
The term "oil-soluble" refers to a material that is soluble in
mineral oil to the extent of at least about one gram per liter at 25~C.
(A) Thiocarbonates
The thiocarbonates are compounds represented by the formula
2~ R'--X--C--S--(CR2R3)nT (A-l)
wherein in Formula (A~ Rl, R2 and R3 are independently hydrogen or
hydrocarbyl groups; X is 0 or S; n is zero, 1 or 2; and T is a hydrocarbyl
group, a hetero group, a hydroxyhydrocarbyl group, or an activating group;
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with the proviso that when n is zero, T can be a metal, and when n is 2,
each R2 and R3 can be the same or different.
The substituent R' is hydrogen or a hydrocarbyl group, but is
preferably a hydrocarbyl group. It is generally believed that such
hydrocarbyl group is desired in order to provide a measure of oil-solubility to
the molecule. However, R1 can be hydrogen, provided the other R groups
in the molecule provide sufficient oil solubility to the molecule. In practice
this means that at least one R group should be a hydrocarbyl group of at
least about 4 carbon atoms. In one embodiment, R1 is a hydrocarbyl group
(e.g., aliphatic hydrocarbyl groups such as alkyl groups) of 1 to about 50
carbon atoms, and in one embodiment 1 to about 30 carbon atoms, and in
one embodiment 1 to about 18 carbon atoms, and in one embodiment 1 to
about 12 carbon atoms.
In one embodiment, R2 and R3 are independently hydrogen or
methyl or ethyl groups, with hydrogen being preferred.
In describing T as an "activating group," what is meant is a
group which will activate an olefin to which it is attached toward
nucleophilic addition by CS2. (This is reflective of a method by which this
material can be prepared, by reaction of an activated olefin with CS2 and a
mercaptan or an alcohol.) The activating group T can be, for instance, an
ester group, typically but not necessarily a carboxylic ester group of the
structure -COOR. It can also be an ester group based on a non-carbon acid,
such as a sulfonic or sulfinic ester or a phosphonic or phosphinic ester. The
activating group can also be any of the acids corresponding to the
aforementioned esters. T can also be an amide group, that is, based on the
condensation of an acid group, preferably a carboxylic acid group, with an
amine. In that case the -(CR2R3)nT group can be derived from acrylamide.
T can also be an ether group, -OR; a carbonyl group, that is, an aldehyde or
a ketone group; a cyano group, -CN, or an aryl group.
In one embodiment, T is -R, -OR, -R*OR, -COR, -COOR,
-R*COR, -R*COOR, -CONRR, -R*CONRR, -COO(R*O)tR, -R*COO(R*O)tR,
-CN, -R*CN,
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O O O O
Il 11 11 11
-SR, -R*SR, -SOR, -R*SOR,
O O O O
11 ll ll ll
-SR, -R*SR, -S-OR, -R *S-OR
11 11 11 11
O O O O
wherein each R is independently hydrogen or a hydrocarbyl group, and each
R* is independently a hydrocarbylene or hydrocarbylidene group, and t is
number of at least 1. The R groups are hydrogen or hydrocarbyl groups
generally having from 1 to about 30 carbon atoms, and in one embodiment
1 to about 18 carbon atoms, and in one embodiment 1 to about 12 carbon
atoms. Examples include methyl, ethyl, propyl, n-butyl, isobutyl, pentyl,
isopentyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, and the
corresponding hydroxy-substituted hydrocarbyl groups such as
hydroxymethyl, hydroxyethyl, hydroxypropyl, etc. The R * groups are
preferably alkylene or alkylidene groups of 1 to about 8 carbon atoms, and
in one embodiment 1 to about 4 carbon atoms, and in one embodiment 2 or
3 carbon atoms. Alkylene groups such as ethylene and propylene are
especially preferred. t is a number in the range of about 1 to about 30, and
in one embodiment 1 to about 20, and in one embodiment 1 to about 12 and
in one embodiment 1 to about 8.
In one embodiment, the thiocarbonate is a compound
represented by the formula
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R1_X--C--S--R (A-ll)
wherein in Formula ~A-ll), Rl and R are independently hydrogen or
hydrocarbyl groups as discussed above, and X is 0 or S.
In one embodiment, the thiocarbonate is a compo-~nd
represented by the formula
S ' O
Il 11
Rl_X--C--S--R7 C--O(R30)tR4 (A-lll)
wherein in Formula (A-lll): R' and R4 are independently hydrogen or
hydrocarbyl groups; R2 and R3 are independently hydrocarbylene or
hydrocarbylidene groups; X is 0 or S; and t is a number in the range of 1 to
about 12, and in one embodiment 1 to about 8. In one embodiment, R1 and
R4 are independently hydrogen or hydrocarbyl groups of 1 to about 50
carbon atoms, and in one embodiment 1 to about 30 carbon atoms, and in
one embodiment 1 to about 18 carbon atoms. In one embodiment, R2 and
R3 are independently alkylene or alkylidene groups of 1 to about 8 carbon
- atoms, and in one embodiment 1 to about 4 carbon atoms, and in one
embodiment 2 or 3 carbon atoms.
The thiocarbonate compounds (A) can be made by reacting a
mercaptan or an alcohol with a metal base to form a mercaptide or an
alkoxide. The mercaptide or alkoxide is then reacted with CS2, or a source
material for CS2, to form a thiocarbonate salt represented by the formula
S
(R'-X-C-S-)8Ta (A-IV)
wherein in Formula (A-lVl, R~ and X are as defined in Formula (A-l), T is a
metal, and a is the valence of the metal T. T can be a metal selected from
the group consisting of Group IA, IIA or IIB metals, aluminum, tin, iron,
cobalt, lead, molybdenum, manganese, nickel, antimony, bismuth, or a
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-10-
mixture of two or more thereof. Sodium is especially useful. In one
embodiment, the thiocarbonate salt represented by Formula (A-IV) is useful
as component (A) of the invention. In one embodiment, the thiocarbonate
salt is further reacted with an additional reactant to form the structure
represented by Formula (A-l). This additional reactant is, in one
embodiment, an activated olefin, an hydrocarbyl halide (e.g., chloride,
bromide), epoxide, or an olefin in combination with an acid catalyst (e.g.,
HCI) .
The mercaptans that can be used include the hydrocarbyl
mercaptans represented by the formula R1-S-H, wherein R1 is as defined
above in Formula (A-l). In one embodiment, R' is an alkyl, an alkenyl,
cycloalkyl, or cycloalkenyl group. R1 may be an aryl (e.g., phenyl, naphthyl),
alkylaryl, arylalkyl or alkylaryl alkyl group. R1 may also be a haloalkyl,
hydroxyalkyl, or hydroxyalkyl-substituted (e.g., hydroxymethyl,
hydroxyethyl, etc.) aliphatic group. In one embodiment, R' contains from
about 1 to about 30 carbon atoms, or from about 2 to about 24, or from
about 3 to about 18 carbon atoms. Examples include butyl mercaptan, amyl
mercaptan, hexyl mercaptan, octyl mercaptan, 1-octanethiol, 6-
hydroxymethyloctanethiol, nonyl mercaptan, decyl mercaptan, 10-amino-
dodecanethiol, dodecyl mercaptan, t-dodecyl mercaptan, 1 O-hydroxymethyl-
tetradecanethiol, and tetradecyl mercaptan.
The alcohols that can be used include isopropyl, methyl propyl,
n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, hexyl, isooctyl, decyl, dodecyl,
tetradecyl, 2-pentenyl, dodeceny!, aromatic alcohols such as the phenols,
etc. Higher synthetic monohydric alcohols of the type formed by Oxo
process (e.g., 2-ethylhexyl), the Aldol condensation, or by organo- aluminum
catalyzed oligomerization of alpha-olefins (especially ethylene), followed by
oxidation and hydrolysis, also are useful. Examples of useful monohydric
alcohols and alcohol mixtures include the commercially available "Alfol"
alcohols marketed by Continental Oil Corporation. Alfol 810 is a mixture of
alcohols containing primarily straight chain, primary alcohols having from 8
to 10 carbon atoms. Alfol 12 is a mixture of alcohols containing mostly C12
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fatty alcohols. Alfol 1218 is a mixture of synthetic, primary, straight-chain
alcohols containing primarily 12 to 18 carbon atoms. The Alfol 20 +
alcohols are mixtures of Cl8-C28 primary alcohols having mostly, on an
alcohol basis, C20 alcohols as determined by GLC (gas-liquid-chromato-
graphy). The Alfol 22+ alcohols are Cl8-C28 primary alcohols containing
primarily, on an alcohol basis, C 2 alcohols. These Alfol alcohols can contain
a fairly large percentage (up to 40% by weight) of paraffinic compounds
which can be removed before the reaction if desired.
Another example of a commercially available alcohol mixture is
Adol 60 which comprises about 75% by weight of a straight chain C22
primary alcohol, about 15% of a C20 primary alcohol and about 8% of C18
and C24 alcohols. Adol 320 comprises predominantly oleyl alcohol. The
Adol alcohols are marketed by Ashland Chemical.
A variety of mixtures of monohydric fatty alcohols derived from
naturally occurring triglycerides and ranging in chain length of from C8 to C18
are available from Proctor & Gamble Company. These mixtures contain
various amounts of fatty alcohols containing mainly 12, 14, 16, or 18
carbon atoms. For example, CO-1214 is a fatty alcohol mixture containing
0.5% of C10 alcohol, 66.0% of C12 alcohol, 26.0% of C14 alcohol and 6.5%
of C16 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 C13 alcohols; Neodol 25 is a mixture of C12 and
C15 alcohols; and Neodol 45 is a mixture of C14 to C15 linear alcohols.
Neodol 91 is a mixture of Cg, C10 and C11 alcohols.
Fatty vicinal diols also are useful and these include those
available from Ashland Oil under the general trade designation Adol 1 14 and
Adol 158. The former is derived from a straight chain alpha olefin fraction
of C11-C14, and the latter is derived from a C15-C18 fraction.
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The metal in the metal base can be a metal selected from the
group consisting of Group IA, IIA or IIB metals, aluminum, tin, iron, cobalt,
lead, molybdenum, manganese, nickel, antimony, bismuth, or a mixture of
two or more thereof. The metal base can be a nitrate, nitrite, halide,
carboxylate, phosphate, phosphite, sulfate, sulfite, carbonate, borate,
hydroxide or oxide. Sodium hydroxide is a preferred metal base.
The relative amounts of the reactants used to prepare the
thiocarbonate salts are not particularly critical. The charge ratios to the
reactor can vary over a wide range where economics and the amount of the
product desired are controlling factors. Thus, in one embodiment, the
charge ratio of the mercaptan or alcohol to the CS2 reactant to metal base
may vary from about 5:1:1 to about 1:6:1 to about 1:1:5. In one
embodiment, the charge ratio of these reactants is about 1:1:1.
The activated olefins, hydrocarbyl halides, epoxides and olefins
that can be used as the additional reactant include compounds generally
containing from 1 carbon atom in the case of hydrocarbyl halides, or 2
carbon atoms in the case of activated olefins, epoxides or olefins, up to
about 30 carbon atoms, and in one embodiment up to about 18 carbon
atoms, and in one embodiment up to about 12 carbon atoms. These include
hydrocarbon compounds and hydroxy-substituted hydrocarbon compounds.
The activated olefins that can be used include ethylenically-
unsaturated carboxylic acids, or alpha-chloro or alpha-bromo carboxylic
acids, or derivatives thereof. These include acrylic acid, methacrylic acid,
methylacrylate, ethylacrylate, 2-ethylhexylacrylate, 2-hydroxyethylacrylate,
ethylmethacrylate, 2-hydroxyethylmethacrylate, 2-hydroxy-
propylmethacrylate, 2-hydroxypropylacrylate, acrylamide, acrylonitrile,
ethylsulfonylethene, methylsulfinylethene, and the like. Also, alpha-
chloroacetic acid and alpha-bromoacetic acid and derivatives thereof can be
used.
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The hydrocarbyl halides can be alkyl halides. These include the
methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, isopentyl, heptyl, octyl, 2-
ethylhexyl, nonyl, decyl and dodecyl chlorides and bromides, as well as the
corresponding hydroxy-substituted hydrocarbyl chlorides and bromides such
as the hydroxymethyl, hydroxyethyl and hydroxylpropyl chlorides and
bromides.
The epoxides include: ethylene oxide; propylene oxide; 1,2-
epoxyhexane; 1 ,2-epoxyhexadecane; 1 ,2-epoxybutane; 3,4-epoxyheptane;
1,2-epoxy-cyclohexane; 4,5-epoxydecane; 1,2-epoxydodecane; 1,2-
epoxytetradecane; 1 ,2-epoxy-5-oxy-heptane; 1 ,2-epoxy-6-propyltridecane;
oxetanes; 9,1 0-epoxystearic acid esters; styrene oxides; para-chlorostyrene
oxide; and mixtures of two or more of these.
Also included are the epoxidized fatty acid esters. Typical fatty
acid esters include C1 20 alkyl esters of C8.24 unsaturated fatty acids such as
palmitoleic, oleic, ricinoleic, petroselic, linoleic, linolenic, oleostearic, licanic,
etc. Specific examples of the fatty acid esters which can be epoxidized
include lauryl tallate, methyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate,
lauryl ricinoleate, oleyl linoleate, oleyl stearate and alkyl glycerides. Also
useful are the saturated fatty acid esters prepared from mixed unsaturated
fatty acid esters such as are obtained from animal fats and vegetable oils
including tall oil, linseed oil, olive oil, castor oil, soybean oil, peanut oil, rape
seed oil, fish oil, sperm oil, etc.
The olefins that can be used include aliphatic compounds,
alicylic compounds, aliphatic- and alicyclic-substituted aromatic compounds,
and the like. These include ethene, propene, butene, isobutene, pentene,
hexene, styrene, and the like.
The relative amounts of the reactants used to prepare the
thiocarbonate compounds (A) is not particularly critical. The charge ratios
to the reactor can vary over a wide range where economics and the amount
of the product desired are controlling factors. Thus, the charge ratio of the
thiocarbonate salt to additional reactant (e.g., activated olefin, hydrocarbyl
-
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-14-
halide, epoxide or olefin) may vary from about 5:1 to about 1:5. In one
embodiment, the charge ratio of these reactants is about 1:1.
A number of methods for preparing trithiocarbonates are
disclosed in the article by H.C. Godt Jr., et al. entitled "The Synthesis of
Organic Trithiocarbonates", Journal of Organic Chemistry, Vol. 26, October
1961, pp. 4047-4051, which is incorporated herein by reference. Briefly,
this article discloses a number of methods for preparing trithiocarbonates.
One method involves reacting an aryl- or alkylthiol in the presence of a base
(e.g., NaOH) with an alkyl or aryl chlorodithioformate. Another method
involves reacting an alkylthiol with carbon disulfide in the presence of
potassium hydroxide to form a potassium alkyl trithiocarbonate, then
reacting the latter with an alkyl or aralkyl bromide to form the desired
trithiocarbonate. Another method involves reacting thiophosgene with an
aryl thiol in the presence of a base to form diaryl trithiocarbonates. Another
method involves reacting m-nitro phenyldiazonium chloride with potassium
ethyl trithiocarbonate to form m-nitro phenyl trithiocarbonate.
The following examples illustrate the preparation of the
thiocarbonate compounds (A) that are useful with the invention. In the
following examples, as well as throughout the specification and in the
claims, unless otherwise indicated, all parts and percentages are by weight,
all temperatures are in degrees Celsius, and all pressures are atmospheric.
Examr~le A-1
t-Dodecyl mercaptan (606 grams), a 50% aqueous solution of
sodium hydroxide (240 grams) and toluene (250 grams) are charged to a
reactor and heated at 110-130~C until the water is removed. Carbon
disulfide (251 grams) is added. The temperature of the mixture is
maintained below 50~C using an ice bath during the carbon disulfide
addition. The mixture is heated to 1 1 0~C to remove water. The mixture is
cooled to 50~C. Propylene oxide (191.4 grams) is added. A 38% by
weight aqueous solution of hydrochloric acid (330 grams) is added dropwise.
The resulting organic layer is decanted, filtered and stripped at 110~C and
CA 022130~0 1997-08-1~
20 mm Hg to provide the desired product which is in the form of a brown
liquid .
Examole A-2
t-Dodecyl mercaptan (912 grams), a 50% aqueous solution of
sodium hydroxide (362 grams) and toluene (900 grams) are charged to a
reactor and heated at 1 20~C with a nitrogen purge until 240 grams of water
are removed. Carbon disulfide (377 grams) is added. The temperature of
the mixture is maintained at 50~C using an ice bath during the carbon
disulfide addition. The mixture is stripped at 110~C and 20 mm Hg. The
mixture is cooled to room temperature and filtered through diatomaceous
earth to provide the desired product which is in the form of a red viscous
liquid .
Exa~.~Ple A-3
1-Butanol (222 grams), and a 50% aqueous sodium hydroxide
1 5 solution (240 grams) are charged to a reactor and heated to 1 00~C until the
water is removed. The reaction mixture is cooled to ~0~C. Carbon disulfide
(251 grams) is added. Acrylic acid (216 grams) is added with the result
being the formation of a gel. Acetone (400 grams) is added to disperse the
gel with the result being the formation of a two-layered mixture. The upper
layer is an orange liquid, and the lower layer is a dark red liquid. The upper
layer is separated from the lower layer, and acetone is stripped from the
upper layer to provide the desired product which is in the form of a gel.
Example A-4
t-Dodecyl mercaptan (808 grams), a 50% aqueous solution of
sodium hydroxide (320 grams) and toluene (200 grams) are charged to a
reactor and heated at 110-130~C until 106 grams of water are removed.
The mixture is cooled to 50~C. Carbon disulfide (334 grams) is added. The
mixture is heated to 1 1 0 ~ C, then allowed to cool. 2-Hydroxyethylacrylate
(464 grams) is added. The mixture is cooled to below 50~C. A 38% by
weight aqueous solution of hydrochloric acid (440 grams) is added
dropwise. Water is separated from the reaction mixture. The mixture is
CA 022130~0 1997-08-1~
filtered and stripped at 110-130~C and 20 mm Hg to provide the desired
product which is in the form of a yellow-brown liquid.
ExamDle A-5
t-Dodecyl mercaptan (404 grams), a ~0% aqueous solution of
sodium hydroxide (160 grams) and toluene (100 grams) are charged to a
reactor and heated to 120~C with a nitrogen purge to remove water. The
mixture is cooled to room temperature. Carbon disulfide (167 grams) is
added. The mixture is heated to 70~C. 2-Hydroxyethylacrylate (232 grams)
is added. The mixture is maintarned at 70~C for one hour. The mixture is
cooled to room temperature. A 38% by weight aqueous solution of
hydrochloric acid (220 grams) is added. One liter of water is added. An
organic layer is formed. The organic layer is drawn off and stripped at 70~C
and 20 mm Hg and filtered through diatomaceous earth to provide the
desired product which is in the form of a liquid.
1 5 ExamPle A-6
t-Dodecyl mercaptan (404 grams), a 60% aqueous solution of
sodium hydroxide (160 grams) and toluene (500 grams) are charged to a
reactor and heated at 1 18-1 30~C to remove water. The mixture is cooled
to ~0~C. Carbon disulfide (168 grams) is added dropwise. The mixture is
heated to 110~C, then allowed to cool. Methylacrylate (172 grams) is
added dropwise. The temperature of the mixture increases exothermically.
A 38% by weight aqueous solution of hydrochloric acid (200 grams) is
added dropwise. Water is separated from the reaction mixture. The mixture
is filtered and stripped at 110-150~C and 20 mm Hg for two hours to
provide the desired product which is in the form of a yellow liquid.
Exsr..,,le A-7
t-Dodecyl merca~ t~,- (404 grams), MoO3 (144 grams) and water
(10 grams) are charged to a reactor. Carbon disuifide (167 grams) is added.
A 50% by weight aqueous solution of sodium hydroxide (trace amount) is
added. The reaction mixture turns purple. The mixture is heated to 60~C
and the desired product, which is in the form of a mixture of blue solid and
a green liquid, is formed.
CA 02213050 1997-08-15
ExamPle A-8
t-Dodecyl mercaptan (404 grams), a 50% aqueous solution of
sodium hydroxide (160 grams) and toluene (200 grams) are charged to a
reactor and heated at 110-150~C until 104 grams of water are removed.
The mixture is cooled to 50~C. Carbon disulfide (168 grams) is added.
Acrylic acid ( 144 grams) is added. The temperature of the mixture increases
exothermically. The formation of a solid green mass is observed. A 37%
by weight aqueous solution of hydrochloric acid (200 grams) is added. An
aqueous layer and an organic layer are formed. The aquous layer is
separated from the organic layer. The organic layer is stripped at 1 1 0~C and
20 mm Hg to provide the desired product which is in the form of an orange
liquid .
Examole A-9
t-Dodecyl mercaptan (2590 grams), a 50% aqueous solution of
sodium hydroxide (515 grams) and toluene 12000 grams) are charged to a
reactor and heated to 100~C to remove water. The mixture is cooled to
room temperature. Carbon disulfide (1070 grams) is added dropwise. The
mixture is heated to 70~C and maintained at that temperature with stirring
for four hours. The mixture is filtered through diatomaceous earth to provide
the desired product which is in the form of a red liquid.
ExamPle A-10
Part A
Hexadecyl mercaptan (2156 grams), a 50% aqueous solution
of sodium hydroxide (735 grams) and toluene (1000 grams) are charged to
~5 a reactor and heated at 1 20~C until 464 grams of water are removed. The
mixture is cooled to 60~C. Carbon disulfide (698 grams) is added. The
mixture is stripped at 1 20~C and 20 mm Hg and filtered through
diatornaceous earth to provide the desired product which is in the form of
a red liquid.
Part B
The product from Part A (350 gramsJ is placed in a reactor and
propylene oxide (57 grams) is added dropwise. The temperature of the
CA 022130~0 1997-08-1~
mixture increases exothermically. The mixture is heated to 70~C and
maintained at that temperature for two hours. The mixture is filtered
through diatomaceous earth to provide the desired product which is in the
form of a liquid.
ExamPle A-11
Hexadecyl mercaptan (201 grams), a 50% aqueous solution of
sodium hydroxide 168 grams) and toluene (100 grams) are charged to a
reactor and heated at 110~C until 42 grams of water are removed. The
mixture is cooled to 60~C. Carbon disulfide 165 grams) is added. The
temperature of the mixture is maintained at 60~C for three hours. The
mixture is stripped at 1 20~C and 20 mm Hg for three hours. The mixture
is filtered through diatomaceous earth to provide the desired product which
is in the form of an orange liquid.
(B) Acvlated Nitrogen-CG..tdi--i..g ComPounds
The second component of the inventive composition is an
acylated nitrogen-containing compound having a substituent of at least
about 10 aliphatic carbon atoms. These compounds typically function as
ashless dispersants in lubricating compositions.
A number of acylated, nitrogen-containing compounds having
a substituent of at least about 10 aliphatic carbon atoms and made by
reacting a carboxylic acid acylating agent with an amino compound are
known to those skilled in the art. In such compositions the acylating agent
is linked to the amino compound through an imido, amido, amidine or salt
linkage. The substituent of at least about 10 aliphatic carbon atoms may be
in either the carboxylic acid acylating agent derived portion of the molecule
or in the amino compound derived portion of the molecule. Preferably,
however, it is in the acylating agent portion. The acylating agent can vary
from formic acid and its acyl derivatives to acylating agents having high
molecular weight aliphatic substituents of up to about 5,000, 10,000 or
20,000 carbon atoms. The amino compounds are characterized by the
presence within their structure of at least one HN < group.
CA 022130~0 1997-08-1~
-19-
ln one embodiment, the acylating agent will be a mono- or
polycarboxylic acid (or reactive equivalent thereof) such as a substituted
succinic or propionic acid and the amino compound is a polyamine or mixture
of polyamines, most typically, a mixture of ethylene polyamines. The amine
also may be a hydroxyalkyl-substituted polyamine. The aliphatic substituent
in such acylating agents typically averages at least about 30 or at least
about 50 and up to about 400 carbon atoms.
Illustrative hydrocarbon based groups containing at least 10
carbon atoms are n-decyl, n-dodecyl, tetrapropylene, n-octadecyl, oleyl,
chlorooctadecyl, triicontanyl, etc. Generally, the hydrocarbon-based
substituents are made from homo- or interpolymers (e.g., copolymers,
terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as
ethylene, propylene, 1-butene, isobutene, butadiene, isoprene, 1-hexene, 1-
octene, etc. Typically, these olefins are 1-monoolefins. The substituent can
also be derived from the halogenated (e.g., chlorinated or brominated)
analogs of such homo- or interpolymers. The substituent can, however, be
made from other sources, such as monomeric high molecular weight alkenes
(e.g., 1-tetracontene) and chlorinated analogs and hydrochlorinated analogs
thereof, aliphatic petroleum fractions, particularly paraffin waxes and
cracked and chlorinated analogs and hydrochlorinated analogs thereof, white
oils, synthetic alkenes such as those produced by the Ziegler-Natta process
(e.g., poly~ethylene) greases) and other sources known to those skilled in the
art. Any unsaturation in the substituent may be reduced or eliminated by
hydrogenation according to procedures known in the art.
Thehydrocarbon-basedsubstituentsaresubstantiallysaturated,
that is, they contain no more than one carbon-to carbon unsaturated bond
for every ten carbon-to-carbon single bonds present. Usually, they contain
no more than one carbon-to-carbon non-aromatic unsaturated bond for every
50 carbon-to-carbon bonds present.
The hydrocarbon-based substituents are also substantially
aliphatic in nature, that is, they contain no more than one non-aliphatic
moiety Icycloalkyl, cycloalkenyl or aromatic) group of 6 or less carbon atoms
CA 022130~0 1997-08-1~
-20-
for every 10 carbon atoms in the substituent. Usually, however, the
substituents contain no more than one such non-aliphatic group for every 50
carbon atoms, and in many cases, they contain no such non-aliphatic groups
at all; that is, the typical substituents are purely aliphatic. Typically, thesepurely aiiphatic substituents are alkyl or alkenyl groups.
Specific examples of the substantially saturated hydrocarbon-
based substituents containing an average of more than 30 carbon atoms are
the following:
a mixture of poly(ethylene/propylene) groups of about 35 to
about 70 carbon atoms
a mixture of the oxidatively or mechanically degraded
poly(ethylene/propylene) groups of about 35 to about 70
carbon atoms
a mixture of poly(propylene/1-hexene) groups of about 80 to
about 150 carbon atoms
a mixture of poly(isobutene) groups having an average of about
50 to about 200 carbon atoms
A useful source of the substituents are poly(isobutene)s obtained by
polymerization of a C4 refinery stream having a butene content of about 35
to about 75 weight percent and isobutene content of about 30 to about 60
weight percent in the presence of a Lewis acid catalyst such as aluminum
trichloride or boron trifluoride. These polybutenes contain predominantly
~greater than 80% of total repeating units) isobutene repeating units of the
configuration
CH3
-CH2-CI -
CH3
In one embodiment, the carboxylic acid acylating agent is a
hydrocarbon substituted succinic acid or anhydride. The substituted
CA 022130~0 1997-08-1~
succinic acid or anhydride consists of hydrocarbon-based substituent groups
and succinic groups wherein the substituent groups are derived from a
polyalkene, said acid or anhydride being characterized by the presence
within its structure of an average of at least about 0.9 succinic group for
each equivalent weight of substituent groups, and in one embodiment about
0.9 to about 2.5 succinic groups for each equivalent weight of substituent
groups. The polyalkene generally has an (Mn) of at least about 700, and in
one embodiment about 700 to about 2000, and in one embodiment about
900 to about 1800. The ratio between the weight average molecular weight
(Mw) and the (Mn) (that is, the Mw/Mn) can range from about 1 to about
10, or about 1.5 to about 5. In one embodiment the polyalkene has an
Mw/Mn value of about 2.5 to about 5. For purposes of this invention, the
number of equivalent weights of substituent groups is deemed to be the
number corresponding to the quotient obtained by dividing the Mn value of
the polyalkene from which the substituent is derived into the total weight of
the substituent groups present in the substituted succinic acid. Thus, if a
substituted succinic acid is characterized by a total weight of substituent
group of 40,000 and the Mn value for the polyalkene from which the
substituent groups are derived is 2000, then that substituted succinic
acylating agent is characterized by a total of 20 (40,000/2000 = 20)
equivalent weights of substituent groups.
In one embodiment the carboxylic acid acylating agent is a
substituted succinic acid or anhydride, said substituted succinic acid or
anhydride consisting of hydrocarbon-based substituent groups and succinic
groups wherein the substituent groups are derived from polybutene in which
at least about 50% of the total units derived from butenes is derived from
isobutylene. The polybutene is characterized by an Mn value of about 1500
to about 2000 and an Mw/Mn value of about 3 to about 4. These acids or
anhydrides are characterized by the presence within their structure of an
average of about 1.5 to about 2.5 succinic groups for each equivalent
weight of substituent groups.
CA 022130~0 1997-08-1~
In one embodiment the carboxylic acid is at least one
substituted succinic acid or anhydride, said substituted succinic acid or
anhydride consisting of substituent groups and succinic groups wherein the
substituent groups are derived from polybutene in which at least about 50%
of the total units derived from butenes is derived from isobutylene. The
polybutene has an Mn value of about 800 to about 1200 and an Mw/Mn
value of about 2 to about 3. The acids or anhydrides are characterized by
the presence within their structure of an average of about 0.9 to about 1.2
succinic groups for each equiva~ent weight of substituent groups.
The amino compound is characterized by the presence within
its structure of at least one HN< group and can be a monoamine or
poiyamine. Mixtures of two or more amino compounds can be used in the
reaction with one or more acylating reagents. In one embodiment, the
amino compound contains at least one primary amino group (i.e., -NH2) and
more preferably the amine is a polyamine, especially a polyamine containing
at least two -NH- groups, either or both of which are primary or secondary
amines. The amines may be aliphatic, cycloaliphatic, aromatic or
heterocyclic amines.
Among the useful amines are the alkylene polyamines, including
the polyalkylene polyamines. The alkylene polyamines include those
conforming to the formula
RN-(U-N)n-R
R R
wherein n is from 1 to about 10; each R is independently a hydrogen atom,
a hydrocarbyl group or a hydroxy-substituted or amine-substituted
hydrocarbyl group having up to about 30 atoms, or two R groups on
different nitrogen atoms can be joined together to form a U group, with the
proviso that at least one R group is a hydrogen atom and U is an alkylene
group of about 2 to about 10 carbon atoms. Preferably, U is ethylene or
propylene. Especially preferred are the alkylene polyamines where each R
CA 022130~0 1997-08-1~
-23-
is hydrogen or an amino-substituted hydrocarbyl group with the ethylene
polyamines and mixtures of ethylene polyamines being the most preferred.
Usually n will have an average value of from about 2 to about 7. Such
alkylene polyamines include methylene polyamine, ethylene polyamines,
propylene polyamines, butylene polyamines, pentylene polyamines, hexylene
polyamines, heptylene polyamines, etc. The higher homologs of such
amines and related amino alkyl-substituted piperazines are also included.
Alkylene polyamines that are useful include ethylene diamine,
triethylene tetramine, propylene diamine, trimethylene diamine,
hexamethylene diamine, decamethylene diamine, octamethylene diamine,
di(heptamethylene) l.ia",i"e, tripropylene tel,~,),i,le, tetraethylene pentamine,
trimethylene diamine, pentaethylene hexamine, di~trimethylene)triamine, N-
(2-aminoethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine, and the like.
Higher homologs as are obtained by condensing two or more of the above-
illustrated alkylene amines are useful, as are mixtures of two or more of any
of the afore-described polyamines.
Ethylene polyamines, such as those mentioned above, are
especially useful for reasons of cost and effectiveness. Such polyamines are
described in detail under the heading "Diamines and Higher Amines" in The
Encyclopedia of Chemical Technology, Second Edition, Kirk and Othmer,
Volume 7, pages 27-39, Interscience Publishers, Division of John Wiley and
Sons, 1965, which is hereby incorporated by reference for the disclosure of
useful polyamines. Such compounds are prepared most conveniently by the
reaction of an alkylene chloride with ammonia or by reaction of an ethylene
imine with a ring-opening reagent such as ammonia, etc. These reactions
result in the production of the somewhat complex mixtures of alkylene
polyamines, including cyclic condensation products such as piperazines.
These mixtures can be used.
Other useful types of polyamine mixtures are those resulting
from stripping of the above-described polyamine mi~tures. In this instance,
lower molecular weight polyamines and volatile contaminants are removed
from an alkylene polyamine mixture to leave as residue what is often termed
CA 022130~0 1997-08-1~
-2~
"polyamine bottoms". In general, alkylene polyamine bottoms can be
characterized as having less than two, usually less than 1% (by weight)
material boiling below about 200~C. In the instance of ethylene polyamine
bottoms, which are readily available and found to be quite useful, the
bottoms contain less than about 2% (by weight) total diethylene triamine
(DETA) or triethylene tetramine (TETAl. A typical sample of such ethylene
polyamine bottoms obtained from the Dow Chemical Company of Freeport,
Texas designated "E-100" showed a specific gravity at 1 5.6~C of 1.0168,
a percent nitrogen by weight of 33.15 and a viscosity at 40~C of 121
centistokes. Gas chromatography analysis of such a sample showed it to
contain about 0.93% "Light Ends" Imost probably DETA), 0.72% TETA,
21.74% tetraethylene pentamine and 76.61% pentaethylene hexamine and
higher (by weight). These alkylene polyamine bottoms include cyclic
condensation products such as piperazine and higher analogs of
diethylenetriamine, triethylenetetramine and the like.
These alkylene polyamine bottoms can be reacted solely with
the acylating agent, in which case the amino reactant consists essentially of
alkylene polyamine bottoms, or they can be used with other amines and
polyamines, or alcohols or mixtures thereof. In these latter cases at least
one amino reactant comprises alkylene polyamine bottoms.
Other polyamines are described in, for example, U.S. Patents
3,219,666 and 4,234,435, and these patents are hereby incorporated by
reference for their disclosures of amines which can be reacted with the
acylating agents described above to form the acylated nitrogen-containing
compounds (B) of this invention.
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:
H2N-R'-OH RN(H)-R'-OH RRN-R'-OH
CA 022130~0 1997-08-1~
.
-25-
wherein each R is independently a hydrocarbyl group of one to about eight
carbon atoms or hydroxyhydrocarbyl group of two to about eight carbon
atoms, preferably one to about four, and R' is a divalent hydrocarbyl group
of about two to about 18 carbon atoms, preferably 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
straight or branched alkylene group such as an ethylene, 1 ,2-propylene, 1,2-
butylene, 1 ,2-octadecylene, etc. group. Where two R groups are present in
the same molecule they can be joined by a direct carbon-to-carbon bond or
through a heteroatom le.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7-
or 8-membered ring structure. Examples of such heterocyclic amines include
N-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines, -
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 mono-, di-, and
triethanol amine, diethylethanolamine, ethylethanolamine,
butyldiethanolamine, etc.
The hydroxyamines can also be an ether N-
(hydroxyhydrocarbyl)-amine. These are hydroxypoly(hydrocarbyloxy)
analogs of the above-described hydroxy amines (these analogs also include
hydroxyl-substituted oxyalkylene analogs). Such N-(hydroxyhydrocarbyl)
amines can be conveniently prepared by reaction of epoxides with afore-
described amines and can be represented by the formulae:
N2N-(R o)x~H RN(H)-(R'O)XH RRN-(R'O)XH
wherein x is a number from about 2 to about 15 and R and R' are as
described above. R may also be a hydroxypoly(hydrocarbyloxy) group.
The acylated nitrogen-containing compounds (B) include amine
salts, amides, imides, amidines, amidic acids, amidic salts and imidazolines
as well as mixtures thereof. To prepare the acylated nitrogen-containing
compounds from the acylating reagents and the amino compounds, one or
CA 022130~0 1997-08-1~
-26-
more acylating reagents and one or more amino compounds are heated,
optionally in the presence of a normally liquid, substantially inert organic
liquid solventtdiluent, at temperatures in the range of about 80~C up to the
decomposition point of either the reactants or the carboxylic derivative but
normally at temperatures in the range of about 100~C up to about 300~C
provided 300~C does not exceed the decomposition point. Temperatures
of about 125~C to about 250~C are normally used. The acylating reagent
and the amino compound are reacted in amounts sufficient to provide from
about one-half equivalent up to about 2 moles of amino compound per
equivalent of acylating reagent.
Many patents have described useful acylated nitrogen-
containing compounds including U.S. Patents 3,172,892; 3,219,666;
3,272,746; 3,310,492; 3,341,542; 3,444,170; 3,455,831; 3,455,832;~
3,576,743; 3,630,904; 3,632,511; 3,804,763; and 4,234,435. A typical
acylated nitrogen-containing compound of this class is that made by reacting
a poly(isobutene)-substituted succinic acid acylating agent ~e.g., anhydride,
acid, ester, etc.) wherein the poly(isobutene) substituent has between about
50 to about 400 carbon atoms with a mixture of ethylenepolyamines having
about 3 to about 7 amino nitrogen atoms per ethylenepolyamine and about
1 to about 6 ethylene units made from condensation of ammonia with
ethylene chloride. The above-noted U.S. patents are hereby incorporated by
reference for their disclosure of acylated amino compounds and their method
of preparation.
Another type of acylated nitrogen compound belonging to this
class is that made by reacting a carboxylic acid acylating agent with a
polyamine, wherein the polyamine is the product made by condensing a
hydroxy material with an amine. These compounds are described in U.S.
Patent 5,053,152 which is incorporated herein by reference for its disclosure
of such compounds.
Another type of acylated nitrogen compound belonging to this
class is that made by reacting the afore-described alkyleneamines with the
afore-described substituted succinic acids or anhydrides and aliphatic
CA 022130~0 1997-08-1~
-27-
monocarboxylic acids having from 2 to about 22 carbon atoms. In these
types of acylated nitrogen compounds, the mole ratio of succinic acid to
monocarboxylic acid ran~es from about 1 :0.1 to about 1: 1. Typical of the
monocarboxylic acid are formic acid, acetic acid, dodecanoic acid, butanoic
acid, oleic acid, stearic acid, the commercial mixture of stearic acid isomers
known as isostearic acid, tall oil acid, etc. Such materials are more fully
described in U.S. Patents 3,216,936 and 3,260,715 which are hereby
incorporated by reference for their disclosures in this regard.
Still another type of acylated nitrogen compound useful in
making the compositions of this invention is the product of the reaction of
a fatty monocarboxylic acid of about 12-30 carbon atoms and the afore-des-
cribed alkyleneamines, typically, ethylene-, propylene- or
trimethylenepolyamines containing 2 to 8 amino groups and mixtures
thereof. The fatty monocarboxylic acids are generally mixtures of straight
and branched chain fatty carboxylic acids containing 12-30 carbon atoms.
A widely used type of acylated nitrogen compound is made by reacting the
afore-described alkylenepolyamines with a mixture of fatty acids having from
5 to about 30 mole percent straight chain acid and about 70 to about 95%
mole branched chain fatty acids. Among the commercially available
mixtures are those known widely in the trade as isostearic acid. These
mixtures are produced as a by-product from the dimerization of unsaturated
fatty acids as described in U.S. Patents 2,812,342 and 3,260,671.
The branched chain fatty acids can also include those in which
the branch is not alkyl in nature, such as found in phenyl and cyclohexyl
stearic acid and the chloro-stearic acids. Branched chain fatty carboxylic
acidlalkylene polyamine products have been described extensively in the art.
See for example, U.S. Patents 3,110,673; 3,251,853; 3,326,801;
3,337,459; 3,405,064; 3,429,674; 3,468,639; 3,857,791. These patents
are hereby incorporated by reference for their disclosure of fatty ac-
id/polyamine condensates for use in lubricating oil formulations.
- -
CA 022130~0 1997-08-1~
The following specific examples illustrate the preparation of
exemplary acylated nitrogen-containing compounds (B) useful with this
invention.
ExamDle B-1
1000 parts by weight of polyisobutylene (Mn = 1700)
substituted succinic anhydride and 1270 parts by weight of diluent oil are
blended together and heated to 110 - C. 59.7 parts by weight of a mixture
of polyethyleneamine bottoms and diethylenetriamine are added over a two-
hour period. The mixture exotherms to 121 -132 ~ C. The mixture is heated
to 149~C with nitrogen blowing. The mixture is maintained at 149-154~C
for one hour with nitrogen blowing. The mixture is then filtered at 149 ~ C.
Diluent oil is added to provide a mixture having an oil content of 55% by
weight.
Examr~le B-2
A blend of 800 parts by weight of polyisobutylene (Mn = 940)
substituted succinic anhydride and 200 parts by weight of diluent oil is
heated to 150 ~ C with a nitrogen sparge. 87.2 parts by weight of
methylpentaerythritol are added over a one-hour period while maintaining the
temperature at 150-160~C. The mixture is heated to 204~C over a period
of eight hours, and maintained at 204-210~ C for six hours. 15.2 parts by
weight of a mixture of polyethyleneamine bottoms and diethylenetriamine
are added over a one-hour period while maintaining the temperature of the
mixture at 204-210~C. 519.5 parts of diluent oil are added to the mixture
while maintaining the temperature at a minimum of 177~C. The mixture is
cooled to 130~C and filtered to provide the desired product.
(C) PhosPhorus Comr~ound.
The phosphorus compound (C) can be a phosphorus acid, ester or
derivative thereof. These include phosphorus acid, phosphorus acid ester,
phosphorus acid salt, or derivative thereof. The phosphorus acids include
the phosphoric, phosphonic, phosphinic and thiophosphoric acids including
dithiophosphoric acid as well as the monothiophosphoric, thiophosphinic and
thiophosphonic acids.
CA 022130~0 1997-08-1~
-29-
The phosphorus compound (C) can be a phosphorus acid ester derived
from a phosphorus acid or anhydride and an alcohol of 1 to about 50 carbon
atoms, and in one embodiment 1 to about 30 carbon atoms. It can be a
phosphite, a monothiophosphate, a dithiophosphate, or a dithiophosphate
disulfide. It can also be a metal, amine or ammonium salt of a phosphorus
acid or phosphorus acid ester. It can be a phosphorus containing amide or
a phosphorus-containing carboxylic ester.
The phosphorus compound can be a phosphate, phosphonate,
phosphinate or phosphine oxide; These compounds can be represented by
the formula
Rl-(O)a
R2-(O)b P = X (C-l)
R3-(O)C--
wherein in Formula (C-l), R~, R2 and R3 are independently hydrogen or
hydrocarbyl groups, X is 0 or S, and a, b and c are independently zero or 1.
The phosphorus compound can be a phosphite, phosphonite,
phosphinite or phosphine. These compounds can be represented by the
formula
Rl-(O)a
R2-(O)b ~ P (C-ll)
R3-(O)C
wherein in Formula (C-ll), R~, R2 and R3 are independently hydrogen or
hydrocarbyl groups, and a, b and c are independently zero or 1.
The total number of carbon atoms in R', R2 and R3 in each of the
above Formulae (C-l) and (C-ll) must be sufficient to render the compound
soluble in the low-viscosity oil used in formulating the inventive
compositions. Generally, the total number of carbon atoms in R', R2 and R3
is at least about 8, and in one embodiment at least about 12, and in one
embodiment at least about 16. There is no limit to the total number of
CA 022130~0 1997-08-1~
-30-
carbon atoms in R', R2 and R3 that is reguired, but a practical upper limit is
about 400 or about 500 carbon atoms. In one embodiment, R1, R2 and R3
in each of the above formulae are independently hydrocarbyl groups of 1 to
about 100 carbon atoms, or 1 to about 50 carbon atoms, or 1 to about 30
carbon atoms, with the proviso that the total number of carbons is at least
about 8. Each R1, R2 and R3 can be the same as the other, although they
may be different. Examples of useful R1, R2 and R3 groups include isopropyl,
n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, isooctyl, decyl, dodecyl,
tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaph-
thyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl, and the
like.
The phosphorus compounds represented by Formulae (C-l) and (C-ll)
can be prepared by reacting a phosphorus acid or anhydride with an alcohol
or mixture of alcohols corresponding to R1, R2 and R3 in Formulae (C-l) and
IC-II). The phosphorus acid or anhydride is generally an inorganic
phosphorus reagent such as phosphorus pentoxide, phosphorus trioxide,
phosphorus tetraoxide, phosphorus acid, phosphorus halide, or lower
phosphorus esters, and the like. Lower phosphorus acid esters contain from
1 to about 7 carbon atoms in each ester group. The phosphorus acid ester
may be a mono, di- or triphosphoric acid ester.
The phosphorus compound (C) can be a compound represented by the
formula
R'(X1)a X3 (C-lll)
~ 11
2 5 P-X4R3
R2(X2)b
wherein in Formula (C-lll): Xl, X2, X3 and X4 are independently oxygen or
sulfur, and X1 and X2 can be NR4; a and b are independently zero or one; R',
R2 R3 and R4 are independently hydrocarbyl groups, and R3 and R4 can be
hydrogen.
CA 022130~0 1997-08-1~
-31 -
Useful phosphorus compounds of the type represented by Formula (C-
Ill) are phosphorus- and sulfur-containing compounds. These include those
compounds wherein at least one X3 or X4 iS sulfur, and in one embodiment
both X3 and X4 are sulfur, at least one X' or X2 is oxygen or sulfur, and in
one embodiment both X' and X2 are oxygen, a and b are each 1, and R3 is
hydrogen. Mixtures of these compounds may be employed in accordance
with this invention.
In Formula (C-lll), R~ and R2 are independently hydrocarbyl groups that
are preferably free from acety~enic unsaturation and usually also from
ethylenic unsaturation and in one embodiment have from about 1 to about
50 carbon atoms, and in one embodiment from about 1 to about 30 carbon
atoms, and in one embodiment from about 1 to about 18 carbon atoms, and
in one embodiment from about 1 to about 8 carbon atoms. Each R' and R2
can be the same as the other, although they may be different and either or
both may be mixtures. Examples of R1 and R2 groups include isopropyl,
n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, isooctyl, decyl, dodecyl,
tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaph-
thyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl, and
mixtures thereof. Particular examples of useful mixtures include, for
example, isopropyl/n-butyl; isopropyl/secondarybutyl; isopropyl/4-methyl-2-
pentyl; isopropyl/2-ethyl-1 -hexyl; isopropyl/isooctyl; isopropyl/decyl; isopro-pyl/dodecyl; and isopropyl/tridecyl.
In Formula (C-lll), R3 and R4 are independently hydrogen or
hydrocarbyl groups (e.g. alkyl) of 1 to about 12 carbon atoms, and in one
embodiment 1 to about 4 carbon atoms. R3 is preferably hydrogen.
Phosphorus compounds corresponding to Formula ~C-III) wherein X3
and X4 are sulfur can be obtained by the reaction of phosphorus pentasulfide
(P2S5) and an alcohol or mixture of alcohols corresponding to R' and R2. The
reaction involves mixing at a temperature of about 20~C to about 200~C,
four moles of alcohol with one mole of phosphorus pentasulfide. Hydrogen
sulfide is liberated in this reaction. The oxygen-containing analogs of these
CA 022130~0 1997-08-1~
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compounds can be prepared by treating the dithioic acid with water or steam
which, in effect, replaces one or both of the sulfur atoms.
In one embodiment, the phosphorus compound (C) is a monothio-
phosphoric acid ester or a monothiophosphate. Monothiophosphates are
prepared by the reaction of a sulfur source and a dihydrocarbyl phosphite.
The sulfur source may be elemental sulfur, a sulfide, such as a sulfur
coupled olefin or a sulfur coupled dithiophosphate. Elemental sulfur is a
useful sulfur source. The preparation of monothiophosphates is disclosed
in U.S. Patent 4,755,311 and PCT Publication W0 87/07638 which are
1 0 incorporated herein by reference for their disclosure of monothiophosphates,
sulfur sources for preparing monothiophosphates and the process for making
monothiophosphates.
Monothiophosphates may also be formed in the lubricant blend or
functional fluid by adding a dihydrocarbyl phosphite to a lubricating oil
1~ composition or functional fluid containing a sulfur source. The phosphite
may react with thè sulfur source under blending conditions (i.e., tempera-
tures from about 30~C to about 100~C or higher) to form the monothio-
phosphate.
Useful phosphorus acid esters include those prepared by reacting a
phosphoric acid or anhydride with cresol alcohols. An example is tricresol
phosphate.
In one embodiment, the phosphorus compound (C) is a dithiophos-
phoric acid or phosphorodithioic acid. The dithiophosphoric acid can be
reacted with an epoxide or a glycol to form an intermediate. The
2~ intermediate is then reacted with a phosphorus acid, anhydride, or lower
ester. The epoxide is generally an aliphatic epoxide or a styrene oxide.
Examples of useful epoxides include ethylene oxide, propylene oxide, butene
oxide, octene oxide, dodecene oxide, styrene oxide, etc. Propylene oxide
is useful. The glycols may be aliphatic glycols having from 1 to about ~ 2,
and in one embodiment about ~ to about 6, and in one embodiment 2 or 3
carbon atoms, or aromatic glycols. Aliphatic glycols include ethylene glycol,
propylene glycol, triethylene glycol and the like. Aromatic glycols include
CA 022130~0 1997-08-1~
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hydroquinone, catechol, resorcinol, and the like. These are described in U.S.
patent 3,1 97,405 which is incorporated herein by reference for its disclosure
of dithiophosphoric acids, glycols, epoxides, inorganic phosphorus reagents
and methods of reacting the same.
In one embodiment the phosphorus compound (C) is a phosphite. The
phosphite can be a di- or trihydrocarbyl phosphite. Each hydrocarbyl group
can have from 1 to about 24 carbon atoms, or from 1 to about 18 carbon
atoms, or from about 2 to about 8 carbon atoms. Each hydrocarbyl group
may be independently alkyl, alkehyl or aryl. When the hydrocarbyl group is
an aryl group, then it contains at least about 6 carbon atoms; and in one
embodiment about 6 to about 18 carbon atoms. Examples of the alkyl or
alkenyl groups include propyl, butyl, hexyl, heptyl, octyl, oleyl, linoleyl,
stearyl, etc. Examples of aryl groups include phenyl, naphthyl, heptylphenol,
etc. In one embodiment each hydrocarbyl group is independently propyl,
butyl, pentyl, hexyl, heptyl, oleyl or phenyl, more preferably butyl, oleyl or
phenyl and more preferably butyl or oleyl. Phosphites and their preparation
are known and many phosphites are available commercially. Useful
phosphites include dibutyl hydrogen phosphite, trioleyl phosphite and
triphenyl phosphite.
In one embodiment, the phosphorus compound (C) is a phosphorus-
containing amide. The phosphorus-containing amides may be prepared by
the reaction of a phosphorus acid (e.g., a dithiophosphoric acid as described
above) with an unsaturated amide. Examples of unsaturated amides include
acrylamide, N,N'-methylenebisacrylamide, methacrylamide, crotonamide, and
the like. The reaction product of the phosphorus acid with the unsaturated
amide may be further reacted with linking or coupling compounds, such as
formaldehyde or paraformaldehyde to form coupled compounds. The
phosphorus-containing amides are known in the art and are disclosed in U.S.
Patents 4,876,374, 4,770,807 and 4,670,169 which are incorporated by
reference for their disclosures of phosphorus amides and their preparation.
In one embodiment, the phosphorus compound (C) is a phosphorus-
containing carboxylic ester. The phosphorus-containing carboxylic esters
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may be prepared by reaction of one of the above-described phosphorus
acids, such as a dithiophosphoric acid, and an unsaturated carboxylic acid
or ester, such as acrylic acid or a vinyl or allyl carboxylic acid or ester. If the
carboxylic acid is used, the ester may then be formed by subsequent reac-
tion with an alcohol.
The vinyl ester of a carboxylic acid may be represented by the formula
RCH=CH-O(O)CR1 wherein R is a hydrogen or hydrocarbyl group having
from 1 to about 30 carbon atoms, preferably hydrogen or a hydrocarbyl
group having 1 to about 12,~more preferably hydrogen, and R1 is a
hydrocarbyl group having 1 to about 30 carbon atoms, preferably 1 to about
12, more preferably 1 to about 8. Examples of vinyl esters include vinyl
acetate, vinyl 2-ethylhexanoate, vinyl butanoate, and vinyl crotonate.
In one embodiment, the unsaturated carboxylic ester is an ester of an
unsaturated carboxylic acid, such as maleic, fumaric, acrylic, methacrylic,
itaconic, citraconic acids and the like. The ester can be represented by the
formula RO-(O)C-HC = CH-C(O)OR wherein each R is independently a
hydrocarbyl group having 1 to about 18 carbon atoms, or 1 to about 12, or
1 to about 8 carbon atoms. Examples of unsaturated carboxylic esters that
are useful include methylacrylate, ethylacrylate, 2-ethylhexylacrylate, 2-
hydroxyethylacrylate, ethylmethacrylate, 2-hydroxyethylmethacrylate, 2-
hydroxypropylmethacrylate, 2-hydroxypropylacrylate, ethylmaleate,
butylmaleate and 2-ethylhexylmaleate. The above list includes mono- as
well as diesters of maleic, fumaric and citraconic acids.
In one embodiment, the phosphorus compound (C) is the reaction
product of a phosphorus acid and a vinyl ether. The vinyl ether is represent-
ed by the formula R-CH2'CH-OR1 wherein R is hydrogen or a hydrocarbyl
group having 1 to about 30, preferably 1 to about 24, more preferably 1 to
about 12 carbon atoms, and Rl is a hydrocarbyl group having 1 to about 30
carbon atoms, preferably 1 to about 24, more preferably 1 to about 12
CA 022130~0 1997-08-1~
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carbon atoms. Examples of vinyl ethers include vinyl methylether, vinyl
propylether, vinyl 2-ethylhexylether and the like.
When the phosphorus compound (C) is acidic, it may be reacted with
an ammonia or a source of ammonia, an amine, or metallic base to form the
corresponding salt. The salts may be formed separately and then added to
the lubricating oil or functional fluid composition. Alternatively, the salts
may be formed when the acidic phosphorus compound (C) is blended with
other components to form the lubricating oil or functional fluid composition.
The phosphorus compound can then form salts with basic materials which
are in the lubricating oil or functional fluid composition such as basic
nitrogen containing compounds (e.g., the above-discussed acylated nitrogen-
containing compounds (8)) and overbased materials.
The metal salts which are useful with this invention include those
salts containing Group IA, IIA or IIB metals, aluminum, lead, tin, iron,
molybdenum, manganese, cobalt, nickel or bismuth. Zinc is an especially
useful metal. These salts can be neutral salts or basic salts. Examples of
useful metal salts of phosphorus-containing acids, and methods for preparing
such salts are found in the prior art such as U.S. Patents 4,263,150,
4,289,635; 4,308,154; 4,322,479; 4,417,990; and 4,466,895, and th
disclosures of these patents are hereby incorporated by reference. These
salts include the Group ll metal phosphorodithioates such as zinc dicyclohex-
ylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphen-
yl)-phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc
salt of a phosphorodithioic acid produced by the reaction of phosphorus
pentasulfide with an equimolar mixture of isopropyl alcohol and n-hexyl
alcohol.
The following examples illustrate the preparation of useful metal salts
of the phosphorus compounds (C).
CA 022130~0 1997-08-1~
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ExamPle C-1
(a) A mixture of 317.33 grams (5.28 moles) of 2-propanol and
359.67 grams (3.52 moles) of 4-methyl-2-pentanol is prepared and heated
to 60~C. Phosphorus pentasulfide (444.54 grams, 2.0 moles) is added to
the alcohol mixture while maintaining the temperature at 60 ~ C. Two moles
of hydrogen sulfide are liberated and trapped with a 50% aqueous sodium
hydroxide trap. The mixture is heated to and maintained at 70~C for two
hours. The mixture is cooled to room temperature and filtered through
diatomaceous earth to yield a liquid green product having an acid number in
the range of 193-203.
(b) 89.1 grams (1.1 mo!es) of ZnO are added to 200 ml of toluene.
566.6 grams (2.0 equivalents based on acid number) of the product from
part (a) are added dropwise to the ZnO/toluene mixture. The resulting
reaction is exothermic. The reaction mixture is stripped to 70 ~ C and 20 mm
Hg to remove water of reaction, toluene and excess aicohol. The residue is
filtered through diatomaceous earth. The filtrate, which is the desired
product, is a yellow viscous liquid.
Examr le C-2
137.6 grams of zinc oxide are mixed with 149.9 grams of diluent oil.
17.7 grams of 2-ethylhexanoic acid are added. 1000 grams of a
phosphorodithioic acid derived from P2S5 and 2-ethylhexanol are then added
to the mixture. The mixture is allowed to neutralize. It is then flash dried
and vacuum stripped. 81.1 grams of triphenyl phosphite are added. The
temperature of the mixture is adjusted to 124-129~C and maintained at that
temperature for three hours. The mixture is cooled to room temperature and
filtered using filter aid to provide the desired product.
When the phosphorus compound (C) is an ammonium salt, the salt is
considered as being derived from ammonia (NH3) or an ammonia yielding
compound such as NH40H. Other ammonia yielding compounds will readily
occur to those skilled in the art.
CA 022130~0 1997-08-1~
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When the phosphorus compound (C) is an amine salt, the salt may be
considered as being derived from amines. Any of the amines discussed
above under the subtitle"(B) Acylated Nitrogen-Containing Compoundsn can
be used.
The following examples illustrate the preparation of amine or
ammonium salts of the phosphorus compounds (C) that can be used with
this invention.
ExamDle C-3
Phosphorus pentoxide (2û8 grams, 1.41 moles) is added at 50- C to
60~C to hydroxypropyl 0,0'-diisobutylphosphorodithioate (prepared by
reacting 280 grams of propylene oxide with 11 84 grams of O,0'-di-
isobutylphosphorodithioic acid at 30~C to 60~C). The reaction mixture is
heated to 80~C and held at that temperature for 2 hours. To the acidic
reaction mixture there is added a stoichiometrically equivalent amount (384
grams) of a commercial aliphatic primary amine at 30~C to 60~C. The
product is filtered. The filtrate has a phosphorus content of 9.31%, a sulfur
content of 11.37%, a nitrogen content of 2.50%, and a base number of 6.9
(bromphenol blue indicator).
Examnle C-4
(a) 0,O-di-(2-ethylhexyl) dithiophosphoric acid (354 grams) having
an acid number of 154 is introduced into a stainless steel "shaker" type
autoclave of 1320 ml capacity having a thermostatically controlled heating
jacket. Propylene oxide is admitted until the pressure rises to 170 psig at
room temperature, and then the autoclave is sealed and shaken for 4 hours
at 50~C to 100~C during which time the pressure rises to a maximum of
550 psig. The pressure decreases as the reaction proceeds. The autoclave
is cooled to room temperature, the excess propylene oxide is vented and the
contents removed. The product (358 grams), a dark liquid having an acid
number of 13.4, is substantially 0,0-di-(2-ethylhexyl)-S-hydroxyisopropyl
dithiophosphate.
CA 022130~0 1997-08-1~
(b) Ammonia is blown into the product of part ~a) until a
substantially neutral product is obtained.
The phosphorus compound (C) can be a phosphorus-containing sulfide
represented by the formula
X1 X2
11
R1O-P-S-(S)n-P-OR3 (C-IV)
R2O/ \OR4
wherein in Formula (C-IV), R1, R2, R3 and R4 are independently hydrocarbyl
groups, Xl and X2 are independently O or S, and n is zero to 3. In one
embodiment Xl and X2 are each S, and n is 1. Rl, R2, R3 and R4 are indepen-
dently hydrocarbyl groups that are preferably free from acetylenic unsatura-
tion and usually also free from ethylenic unsaturation. In one embodiment
R1, R2, R3 and R4 independently have from about 1 to about 50 carbon
1 5 atoms, and in one embodiment from about 1 to about 30 carbon atoms, and
in one embodiment from about 1 to about 18 carbon atoms, and in one
embodiment from about 1 to about 8 carbon atoms. Each Rl, R2, R3 and R4
can be the same as the other, although they may be different and mixtures
may be used. Examples of Rl, R2, R3 and R4 groups include isopropyl, butyl,
n-butyl, isobutyl, amyl, 4-methyl-2-pentyl, octyl, isooctyl, decyl, dodecyl,
tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl, alkylnaph-
thyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl, alkylnaphthylalkyl, and
mixtures thereof.
The compounds represented by Formula (C-IV) can be prepared by
first reacting an alcohol, phenol or aliphatic or aromatic mercaptan with a
sulfide of phosphorus, such as P2S3, P2S6, P4S3, P4S7, P4Slo, and the like, to
form a partially esterified thiophosphorus or thiophosphoric acid, and then
further reacting this product as such or in the form of a metal salt with an
oxidizing agent or with a sulfur halide. Thus, when an alcohol is reacted
CA 022130~0 1997-08-1~
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with phosphorus trisulfide, a dialkylated monothiophosphorus acid is formed
according to the following equation:
4ROH + P2S3~ 2(RO)2PSH + H2S
This alkylated thiophosphorus acid may then be treated with an oxidizing
agent such as hydrogen peroxide or with sulfur dichloride or sulfur
monochloride to form a disulfide, trisulfide, or tetrasulfide, respectively,
according to the following equations:
4(RO)2PSH + ~2 2~RO)2P-S-S-P(OR)2 + 2H2~
2(RO)2PSH + SC12 ~ (RO)2P-S-S-S-P(OR)2 + 2HCI
2(RO)2PSH + S2C12 (RO)2p-s-(s)2-s-p-(oR)2 + 2HCI
Similarly, when the alcohol is reacted with phosphorus pentasulfide, the
corresponding di-substituted dithiophosphoric acid is formed, and this may
likewise be converted into disulfide, trisulfide or tetrasulfide compounds.
Suitable alcohols such as those discussed below may be employed.
Sulfurized alcohols such as sulfurized oleyl alcohol may also be used.
Corresponding reactions take place by starting with mercaptans, phenols or
thiophenols instead of alcohols. Suitable oxidizing agents for converting the
thiophosphorus and thiophosphoric acids to disulfides include iodine,
potassium triodide, ferric chloride, sodium hypochlorite, hydrogen peroxide,
oxygen, etc.
Alcohols that can be used to prepare the phosphorus-containing
sulfides of Formula (C-IVJ include the alcohols discussed above under the
subtitle "(A) Thiocarbonates".
The following examples illustrate the preparation of phosphorus-
containing sulfides (C) represented by Formula (C-IV) that are useful with
this invention.
ExamDle C-5
A phosphorodithioic acid derived from P2S6 and an alcohol
mixture of 40% by weight isopropyl alcohol and 60% by weight 4-methyl-
secondary-amyl alcohol (4518 grams, 14.34 equivalentst is charged to a
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reactor. A 30% aqueous hydrogen peroxide solution (1130 grams, 10.0
moles) is added dropwise at a rate of 7.3 grams per minute. The
temperature of the reaction mixture increases from 24~C to 38~C. A 50%
aqueous sodium hydroxide solution (40 grams, 0.50 equivalents) is added.
The reaction mixture is stirred for 5 minutes, and then allowed to stand.
The mixture separates into two layers. The aqueous layer contains water,
phosphorodithioic acid salt and excess alcohol from the phosphorodithioic
acid. The organic layer contains the desired product. The aqueous layer is
drawn off (1108 grams) and thb remaining organic portion is stripped at
100~C and 20 mm Hg for two hours. The stripped organic product is
filtered using a filter aid to provide the desired product which is a
phosphorus-containing disulfide in the form of a clear yellow liquid (4060
grams).
ExamDle C-6
A phosphorodithioic acid derived from 4-methyl-2-pentanol and
P2S5 (1202 grams, 3.29 equivalents) is charged to a reactor. A 30%
aqueous hydrogen peroxide solution (319 grams, 2.82 moles) is added
dropwise at a rate of 7.3 grams per minute. The temperature of the reaction
mixture increases from 24~C to 38~C. A 50% aqueous sodium hydroxide
solution (12 grams, 0.15 equivalents) is added. The reaction mixture is
stirred for 5 minutes, and then allowed to stand. The mixture separates into
two layers. The aqueous layer contains water, phosphorodithioic acid salt
and excess methylamyl alcohol from the phosphorodithioic acid. The organic
layer contains the desired product. The aqueous layer is drawn off and the
remaining organic portion is stripped at 100~C and 20 mm Hg for two hours.
The stripped organic product is filtered using filter aid to provide the desiredphosphorus-containing disulfide product which is a clear yellow liquid (1016
grams).
-
CA 022130~0 1997-08-1~
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ExamPle C-7
(a) A m;xture of 105.6 grams (1.76 moles) of isoProPYl
alcohol and 269.3 grams (2.64 moles) of 4-methyl-2-pentanol is prepared
and heated to 70~ C. Phosphorus pentasulfide (222 grams, 1 mole) is added
to the alcohol mixture while maintaining the temperature at 70 ~ C. One mole
of hydrogen sulfide is liberated. The mixture is maintained at 70~C for an
additional four hours. The mixture is filtered through diatomaceous earth to
yield a green liquid product having an acid number in the range of 179-189.
(b) 44.6 grams (1.09 equivalents) of ZnO are added to
diluent oil to form a slurry. One equivalent (based upon the measured acid
number) of the phosphorodithioic acid prepared in (a) are added dropwise to
the ZnO slurry. The reaction is exothermic. The reaction mixture is stripped
to 100~ C and 20 mm Hg to remove water of reaction and excess alcohol.
The residue is filtered through diatomaceous earth. The filtrate, which is a
viscous liquid, is diluted with diluent oil to provide a final product having a
9.5% by weight phosphorus content.
(c) A mixture of the product of part (a) of this example ( 184
grams) and part (b) (130 grams) is placed in a reactor. A 30% aqueous
hydrogen peroxide solution (80 grams) is added dropwise. After the
hydrogen peroxide addition is complete, the reaction mixture is stripped at
70~C and 20 mm Hg. The reaction mixture is filtered through diatomaceous
earth to provide the desired product which is in the form of a yellow liquid.
(D) Organic Sulfide.
The organic sulfides (D) that are useful with this invention are
compounds represented by the formula
X' X2
D 11
Tl-C-S-(S)n-C-T2 (D-l)
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wherein in Formula (D-l), T1 and T2 are independently R, OR, SR or NRR
wherein each R is independently a hydrocarbyl group, X1 and X2 are
independently O or S, and n is zero to 3. In one embodiment, X' and X2 are
each S. In one embodiment, n is 1 to 3, and in one embodiment, n is 1.
Thus, compounds represented by the formula
Il 11
T1-C-S-S-C-T2 (D-ll)
wherein in Formula (D-ll), T' and T2 are as defined above can be used. In
one embodiment, each R is a hydrocarbyl group of 1 to about 50 carbon
atoms, and in one embodiment 1 to about 40 carbon atoms, and in one
embodiment 1 to about 30 carbon atoms, and in one embodiment 1 to about
20 carbon atoms. In one embodiment, each R is independently methyl,
ethyl, propyl, isopropyl, n-butyl, isobutyl, amyl, ~methyl-2-pentyl, isooctyl,
decyl, dodecyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl,
alkylphenyl, alkylnaphthyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl or
alkylnaphthylalkyl.
In one embodiment, the organic sulfide is a compound
represented by the formula:
O O
Il 11
R-C-S-(S)n-C-R (D-lll)
wherein in Formula (D-lll), R and n are as defined above, with compounds
wherein n is 1 being especially useful.
In one embodiment, the organic sulfide is a compound
represented by the formula
- - -
CA 022130~0 1997-08-1~
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S S
Il 11
RO-C-S-(S)n-C-OR (D-IV)
wherein in Formula ID-IV), R and n are as defined above, with compounds
wherein n is 1 being useful.
In one embodiment, the organic sulfide is a compound
represented by the formula
Il 11
RS-C-S-(S)n-C-SR (D-V)
wherein in Formula (D-V), R and n are as defined above, with compounds
wherein n is 1 being especially useful.
In one embodiment, the organic sulfide is a compound
represented by the formula
S S
Il 11
RRN-C-S-(S)n-C-NRR (D-VI)
wherein in Formula (D-VI), R and n are as defined above, with compounds
wherein n is 1 being especially useful.
These compounds are known and can be prepared by
conventional techniques. For example, an appropriate mercaptan, alcohol
or amine can first be reacted with an alkali metal reagent (e.g., NaOH, KOH)
and carbon disulfide to form the corresponding thiocarbonate or
dithiocarbamate. The thiocarbonate or dithiocarbamate is then reacted with
an oxidizing agent (e.g., hydrogen peroxide, cobalt maleonitriledithioate,
K2Fe(CN)6, FeCI3, dimethylsulfoxide, dithiobis(thioformate), copper sulfate,
etc.) to form a disulfide, or with sulfur dichloride or sulfur monochloride to
-
CA 022130~0 1997-08-1~
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form a trisulfide or tetrasulfide, respectively. The oxygen-containing analogs
of these compounds wherein X1 and X2 in Formula (D-l) are oxygen can be
prepared by treating the sulfur-containing compounds with water or steam.
Alcohols used to prepare the organic sulfides of Formula (D-l)
can be any of those described above under the subtitle "(C) Phosphorus
CompoundN.
The amines that can be used include those described above
under the subtitle "(B) Acylated Nitrogen-Containing Compounds".
Mercaptans that can be used include those described above
under the subtitle ~(A) ThiocarbonatesN.
The following examples illustrate the preparation of organic
sulfides (D) that are useful with this invention.
ExamPle D-1
Di-n-butylamine (129 grams, 1 equivalent) is charged to a
1 5 reactor. Carbon disulfide (84.0 grams, 1.1 equivalents) is added dropwise
over a period of 2.5 hours. The resulting reaction is exothermic but the
temperature of the reaction mixture is maintained below 50~C using an ice
bath. After the addition of carbon disulfide is complete the mixture is
maintained at room temperature for one hour with stirring. A 50% aqueous
sodium hydroxide solution (80 grams) is added and the resulting mixture is
stirred for one hour. A 30% aqueous hydrogen peroxide solution (200
grams) is added dropwise. The resulting reaction is exothermic but the
temperature of the reaction mixture is maintained below 50~C using an ice
bath. The mixture is transferred to a separatory funnel. Toluene (800
2~ grams) is added to the mixture. The organic layer is separated from the
product and washed with one liter of distilled water. The separated and
washed organic layer is dried over sodium carbonate and filtered through
diatomaceous earth. The mixture is stripped on a rotary evaporator at 77~C
and 20 mm Hg to provide the desired dithiocarbamate disulfide product
which is in the form of a dark orange liquid.
-
CA 022130~0 1997-08-1~
.
-45-
ExamPle D-2
Di-n-butyl amine (1350 grams) is charged to a reactor. Carbon
disulfide ~875 grams) is added dropwise while maintaining the mixture below
50-C. A 50% aqueous sodium hydroxide solution (838 grams) is added
dropwise. A 30% aqueous H2O2 solution (2094 grams) is added dropwise.
The reaction mixture exotherms. An aqueous layer and an organic layer
form. The aqueous layer is separated from the organic layer. Diethyl ether
(1000 grams) is mixed with the aqueous layer to extract organic material
from it. The diethyl ether containing extract is added to the organic layer.
The resulting mixture is stripped at 70~ C and 20 mm Hg, and then filtered
through diatomaceous earth to provide the desired disulfide product which
is in the form of a brown liquid.
ExamPle D-3
A mixture of 1-octanethiol (200 grams), 50% aqueous NaOH
solution (110 grams) and toluene (200 grams) is prepared and heated to
reflux ( 1 20 ~ C) to remove water. The mixture is cooled to room temperature
and carbon disulfide (1 14.5 grams) is added. A 30% aqueous H2O2 solution
(103 grams) is added dropwise while maintaining the temperature below
50~C. Diethyl ether is added and then extracted. The organic layer is
isolated, washed with distilled water, dried and chromotographed using
hexane to provide the desired disulfide product which is in the form of a
yellow liquid.
ExamPle D-4
(a) A mixture of 4000 grams of dodecyl mercaptan, 1600
grams of a 50% aqueous NaOH solution and 2000 grams of toluene is
prepared and heated to 125~C to remove 1100 grams of water. The
reaction mixture is cooled to 40~C and 1672 grams of carbon disulfide are
added. The mixture is heated to 70~C and maintained at that temperature
for ~ hours. The mixture is filtered using diatomaceous earth and stripped
-
CA 022130~0 1997-08-1~
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at 100 ~C and 20 mm Hg to form the desired product which is in the form
of a red liquid.
(b) 200 grams of the product from part (a) and 200 grams
of hexane are placed in a reactor and cooled to 10 ~ C. 130 grams of a 30%
aqueous H2O2 solution are added dropwise while maintaining the
temperature below 45 - C. The mixture is extracted with diethyl ether. The
organic portion is washed with water, dried with Na2CO3, filtered, and
heated under azeotropic conditions to remove water and provide the desired
disulfide product which is in the form of a bright red liquid.
E~ le D-5
1700 grams of methylpentanol and 407 grams of potassium
hydroxide are placed in a reactor. The mixture is heated under reflux
conditions to remove 130-135 grams of water. The mixture is cooled to
50~C, and 627 grams of carbon disulfide are added. 750 grams of a 30%
aqueous H2Oz solution are added dropwise. The mixture exotherms, and an
aqueous layer and an organic layer are formed. The aqueous layer is
separated from the organic layer. The organic layer is stripped at 100 ~ C and
20 mm Hg and filtered to provide the desired disulfide product which is in
the form of an orange liquid.
Example D-6
1100 grams of methylpentyi alcohol and 863 grams of a 50%
aqueous NaOH solution are placed in a reactor and heated to 120~C to
remove 430 grams of water. The mixture is cooled to 50 ~ C and 925 grams
of carbon disulfide are added. 623 grams of a 30% aqueous H2O2 solution
are added dropwise. The resulting reaction is exothermic, and an aqueous
and an organic layer are formed. The aqueous layer is separated. The
organic layer is stripped at 100~ C and 20 mm Hg and filtered to provide the
desired disulfide product.
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ExamDle D-7
A mixture of isopropyl alcohol (132 grams), methyl pentyl
alcohol (330 grams) and a 50% aqueous NaOH solution (435 grams) is
prepared. Water (50 grams) is removed using distillation at 70~C. The
mixture is cooled to room temperature and carbon disulfide (4~5 grams) is
added. A 30% aqueous H202 solution (1352 grams) is added dropwise
while ma;ntaining the temperature below 50~C. Water is removed. The
resulting organic layer is stripped at 70~C and ~0 mm Hg to form a paste-
like composition. The paste-lilce composition is filtered to provide the
desired disulfide product which is in the form of a red liquid.
(E)Heterocvclic Com~ounds
The heterocyclic compounds are compounds represented by the
formula
Xl
1 5 ./1~
X2 X3 (E-l)
G' ~ ~ G4
G2 G3
wherein in Formula (E-l): X~, X2 and X3 are independently O or S, and X2 and
X3 can be NR1 wherein R1 is hydrogen or hydrocarbyl; and G1, G2, G3 and G4
are independently R2, OR2 or R30R2, wherein R2 is hydrogen or hydrocarbyl
and R3 is hydrocarbylene or hydrocarbylidene. In one embodiment, G1 is R2,
OR2 or R30R2, and G2, G3 and G4 are each hydrogen. In one embodiment,
at least one of X1, X2 or X3 is oxygen. In one embodiment, the heterocyclic
compound is a compound represented by one of the following formulas:
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S S S
O~S S J~ SHN ~ S
)J '~J ~
G1 G1 G~
(E-IA) (E-IB) (E-IC)
wherein in each of the above formulas, G1 has the same meaning as in
Formula (A-l).
In one embodiment, each R1 and R2 is, independently, a
hydrocarbyl group of 1 to about 100 carbon atoms, and in one embodiment
1 to about 50 carbon atoms, and in one embodiment 1 to about 40 carbon
atoms, and in one embodiment 1 to about 30 carbon atoms, and in one
embodiment about 4 to about 20 carbon atoms, and in one embodiment
about 8 to about 14 carbon atoms. The hydrocarbyl groups can be
unsubstituted or they can be substituted with one or more halo,
1 5 carbonylalkoxy, alkoxy, thioalkyl, thiol, cyano, hydroxyl or nitro groups. The
hydrocarbyl groups can be alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl,
aryl, alkaryl or aralkyl. Examples include methyl, ethyl, propyl, isopropyl, n-
butyl, isobutyl, amyl, ~methyl-2-pentyl, 2-ethylhexyl, isooctyl, decyl,
dodecyl, tetradecyl, 2-pentenyl, dodecenyl, phenyl, naphthyl, alkylphenyl,
Z0 alkylnaphthyl, phenylalkyl, naphthylalkyl, alkylphenylalkyl or
alkylnaphthyalkyl .
The hydrocarbylene or hydrocarbylidene groups R3 generally
have from 1 to about 20 carbon atoms, and in one embodiment 1 to about
12 carbon atoms, and in one embodiment 1 to about 6 carbon atoms.
These groups can be alkylene, alkylidene, arylene, alkylarylene, arylalkylene,
etc. Examples include methylene, ethylene, propylene, butylene,
isobutylene, pentylene, hexylene, phenylene, methylphenylene,
phenylethylene, etc.
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These compounds can be prepared by reacting CS2, COS, C0z,
or a source material for these reactants, with a compound represented by
the formula.
C C \ (E-ll)
G1 l l G4
G2 G3
wherein in Formula (E-ll), X is 0, S or NR1, and R1, G1, G2, G3 and G4 are the
same as in Formula (E-l), in the presence of a catalyst. The reactants
represented by the Formula (E-ll) can be epoxides, episulfides or aziridines
including 1,2-epoxides, 1,2-episulfides, 1,2-aziridines, internal epoxides,
internal episulfides, and internal aziridines.
Examples of useful epoxides include: ethylene oxide; propylene
oxide; 1,2-epoxyhexane; 1,2-epoxyhexadecane; 1,2-epoxybutane; 3,4-
epoxyheptane; 1,2-epoxy-cyclohexane; 4,5-epoxydecane; 1,2-
epoxydodecane; 1,2-epoxytetradecane; 1,2-epoxy-5-oxy-heptane; 1,2-
epoxy-6-propyltridecane; oxetanes; 9,10-epoxystearic acid esters; styrene
oxides; para-chlorostyrene oxide; and mixtures of two or more of these.
Also included are the epoxidized fatty acid esters. Typical fatty
acid esters include C1 20 alkyl esters of C8 24 unsaturated fatty acids such as
palmitoleic, oleic, ricinoleic, petroselic, linoleic, linolenic, oleostearic, licanic,
etc. Specific examples of the fatty acid esters which can be epoxidized
include lauryl tallate, methyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate,
lauryl ricinoleate, oleyl linoleate, oleyl stearate and alkyl glycerides. Also
useful are the saturated fatty acid esters prepared from mixed unsaturated
fatty acid esters such as are obtained from animal fats and vegetable oils
including tall oil, linseed oil, olive oil, castor oil, soybean oil, peanut oil, rape
seed oil, fish oil, sperm oil, etc.
-
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Examples of useful episulfides include: 1 ,2-epithiohexane; 4,5-
epithiooctane; 1 ,2-epithiodecane, 1 ,2-epithiododecane; 1,2-
epithiotetradecane; and the episulfides derived from fatty acid esters (e.g.,
9,1 0-epithiostearic acid ester) including the fatty acid esters derived from
animal fats and vegetable oils (e.g., tall oil, soybean oil, fish oil, etc.).
Examples of useful aziridines include hexylazacyclopropane,
octylazacyclopropane, decylazacyclopropane, dodecylazacyclopropane,
tetradecylazacyclopropane, and the aziridines derived from fatty acid esters
including the fatty acid esters derived from animal fats and vegetable oils.
Generally, any epoxide, episulfide or aziridine which is stable
under the reaction conditions employed may be used, but the reactivity of
terminal epoxides, episulfides and aziridines make them especially useful.
The higher molecular weight epoxides, episulfides and aziridines (e.g., Cl0.20
epoxides, episulfides and aziridines) are useful for imparting higher levels of
oil solubility to the cyclic organic sulfides.
The catalyst can be an alkali metal halide, alkoxide, alkyl
xanthate, or quaternary ammonium salt. The alkali metals are preferably
lithium, sodium or potassium, with lithium being especially useful. The
halides can be fluoride, chloride, bromide or iodide, with bromide being
especially useful. The alkyl portion of the alkoxides and alkyl xanthates
generally contain from ~ to about 8 carbon atoms. Examples include
methoxide, ethoxide, isopropoxide, t-butoxide, hexoxide, octoxidel methyl
xanthate, ethylxanthate, butyl xanthate, hexylxanthate and octyl xanthate.
Lithium bromide and sodium methoxide are useful catalysts. Tetraalkyl
ammonium halide salts can be used, with tetrabutyl ammonium bromide
being especially useful.
The mole ratio of CS2, COS or C02 to the reactants represented
by Formula (E-ll) is generally in the range of about 0.5 to about 10, and in
one embodiment about 0.5 to about 5, and in one embodiment about 1 to
about 1.2. The weight ratio of CS2, COS or CO2 to alkali metal in the alkali
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metal catalyst is generally from about 0.001 to about 1, and in one
embodiment about 0.01 to about 0.5, and in one embodiment about 0.01
to about 0.1, and in one embodiment about 0.01 to about 0.05.
The heterocyclic compounds are made by charging the
reactants to a reactor, and stirring, generally without heating, since the
reaction is normally exothermic. Once the reaction reaches the temperature
of the exotherm (typically up to about 50~C), the reaction mixture is held at
that temperature to insure complete reaction. After a reaction time of
typically about 1 to about 8 hours, the volatile materials are removed under
reduced pressure and the residue is filtered to yield the final product. The
reaction can be conducted in the presence of a solvent, examples of which
include tetrahydrofuran, diethylether, and the like.
The preparation of heterocyclic compounds within the scope of
Formula (E-l) is disclosed in U.S. Patents 3,409,635 and 3,448, 120. Briefly,
U.S. Patent 3,409,635 discloses making compounds represented by the
formula
R1 R2
R'- C--C--R2
'C '
Il
S
wherein R' and R2 are hydrogen or methyl, by reacting CS2 with a compound
represented by the formula
R1 R2
C--C /
R1 ~ R2
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at a temperature in the range of 0-50~C in the presence of a basic catalyst.
The basic catalyst is a sodium or potassium alkoxide. U.S. Patent
3,448,120 discloses the preparation of alkylene dithiocarbonates
represented by the formula
R--CH--CH2
I
~~c~s
. Il
S
wherein R is hydrogen or a lower alkyl, aryl or cycloalkyl group, by reacting
CS2 with a compound represented by the formula
R--CH--CH2
\O
at a temperature in the range of 10-70~C in the presence of a catalyst
system containing an alkali metal halide (e.g., Lil, Nal, Kl, LiBr, NaBr, LiCI)
and a co-catalyst selected from a sulfonium halide, a xanthate, H2S, an alkali
metal sulfide, a thiocarbonate or an alcohol. These patents are incorporated
herein by reference for their disclosure of processes for making heterocyclic
compounds.
The following examples illustrate the preparation of the
heterocyclic compounds (E) that are useful with this invention.
ExamPle E-l
A mixture of 9.8 gms of LiBr, 382 gms of CS2 and 500 gms of
tetrahydrofuran is placed in a reaction vessel. The reaction vessel is placed
in an ice bath and the reactor contents are cooled. 839 gms of 1,2-
epoxydodecane are added dropwise to the reactor contents over a period of
4 hours. An exotherm is observed. The temperature is maintained at 10-
20~C. After the addition of the 1 ,2-epoxydodecane is complete, the mixture
-
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is heated to room temperature and stripped at 20 mm Hg. The color of the
reaction mixture transforms from colorless to yellow. The mixture is heated
to 50~C over a period of 30 minutes and held at a pressure of 20 mm Hg
absolute for one hour to remove excess CS2 and tetrahydrofuran. The
mixture is cooled to room temperature and filtered through silica gel to
provide 1001 gms of the desired product which is in the form of a yellow
liquid and is a cyclic xanthate.
Example E-2
The following ingredients are placed in a reaction vessel: 50
gms of 1,2-epoxydodecane, 1.2 gms of LiBr, 23 gms of CS2 and 52 gms of
tetrahydrofuran. The reaction vessel is closed and the ingredients are mixed
at room temperature for two days. The mixture is rotary-evaporated at
70~C and 20 mm Hg for one hour. The resulting product is dissolved in a
90:10 weight ratio mixture of hexane and ethyl acetate. The mixture is
chromatographed on silica gel to remove LiBr and unreacted starting
material. The resulting liquid product is stripped at 50~C and 20 mm Hg to
provide 55 gms of the desired product which is in the form of a red-orange
liquid.
ExamPle E-3
The following ingredients are placed in a reaction vessel: 350
gms of epoxidized soybean oil, 266 gms of CS2, 7.5 gms of LiBr, and 200
gms of tetrahydrofuran. The mixture is mixed overnight at room
temperature. The mixture is stripped at 70~C and 20 mm Hg and filtered to
provide 350 gms of the desired product which is in the form of a yellow
liquid.
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Example E-4
The following ingredients are placed in a reaction vessel: 104
gms of CS2, 5 gms of LiBr, and 200 gms of tetrahydrofuran. The reaction
vessel is placed in an ice bath. 223 gms of 2-ethylhexyl glycidyl ether are
added dropwise while maintaining the temperature of the reaction mixture
below 20~C. The reaction mixture is stripped at 50~C and 20 mm Hg and
filtered to provide 288 gms of the desired product which is in the form of a
liquid .
ExamPle E-5
The following ingredients are placed in a reaction vessel: 1267
gms of 1,2-epoxytetradecane, 500 gms of CS2, 20 gms of LiBr, and 400
gms of tetrahydrofuran. An exotherm is observed. The resulting mixture is
mixed overnight. The mixture is stripped at 50~C and 20 mm Hg and
filtered to provide 1724 gms of the desired product which upon cooling is
in the form of a solid.
Example E-6
The following ingredients are placed in a reaction vessel: 800
gms of CS2, 20 gms of LiBr, and 200 gms of tetrahydrofuran. The reaction
vessel is placed in an ice bath and the reactor contents are cooled to 10~C.
1782 gms of 2-ethylhexyl glycidyl ether are added dropwise while
maintaining the temperature of the reaction mixture below 30~C. The
reaction mixture is stripped at 50~C and 20 mm Hg and filtered through
silica gel to provide 2276 gms of the desired product which is in the form
of a yellow liquid.
ExamPle E-7
The following ingredients are placed in a reaction vessel: 382 gms of CS2,
9.8 gms of LiBr, and 500 gms of tetrahydrofuran. The reaction vessel is
placed in an ice bath. 839 gms of 1,2-epoxydodecane are added dropwise
over a period of 4 hours. The reaction mixture is mixed for 8 hours, then is
- -
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stripped at 70~C and 20 mm Hg and filtered through silica gel to provide
1001 gms of the desired product.
(F) Thiocarbamate.
Component ~F) is a thiocarbamate which can be represented by
the formula
R'R2N-C(X)S-(CR3R4)aZ (F-l)
wherein in Formula (F-l), R1, R2, R3 and R4 are independently hydrogen or
hydrocarbyl groups, provided thàt at least one of R' or R2 is a hydrocarbyl
group; X is O or S; a is 1 or 2; and Z is a hydrocarbyl group, a hetero group
(that is, a group attached through a hetero atom such as 0, N, or S), a
hydroxy hydrocarbyl group, an activating group, or a group represented by
the formula -(S)C(X)-NR1R2.
When a is 2, Z is an activating group. In describing Z as an
"activating group," what is meant is a group which will activate an olefin to
which it is attached toward nucleophilic addition by, e.g., CS2 or COS
derived intermediates. (This is reflective of a method by which this material
can be prepared, by reaction of an activated olefin with CS2 or COS and an
amine.) The activating group Z can be, for instance, an ester group,
typically but not necessarily a carboxylic ester group of the structure
-COOR5. It can also be an ester group based on a non-carbon acid, such as
a sulfonic or sulfinic ester or a phosphonic or phosphinic ester. The
activating group can also be any of the acids corresponding to the
aforementioned esters. Z can also be an amide group, that is, based on the
condensation of an acid group, preferably a carboxylic acid group, with an
amine. In that case the -(CR3R4)aZ group can be derived from acrylamide.
Z can also be an ether group, -OR6; a carbonyl group, that is, an aldehyde
or a ketone group; a cyano group, -CN, or an aryl group. In one embodiment
Z is an ester group of the structure, -COOR5, where R5 is a hydrocarbyl
group. R5 can comprise 1 to about 18 carbon atoms, and in one embodi-
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ment 1 to about 6 carbon atoms. In one embodiment R5 is methyl so that
the activating group is-COOCH3.
When a is 1, Z need not be an activating group, because the
moiecule is generally prepared by methods, described below, which do not
involve nucleophilic addition to an activated double bond.
When Z is a hydrocarbyl or a hydroxy hydrocarbyl group, a can
be zero, 1 or 2. These hydrocarbyl groups can have from 1 to about 30
carbon atoms, and in one embodiment 1 to about 18 carbon atoms, and in
one embodiment 1 to about 12 carbon atoms. Examples include methyl,
ethyl, propyl, n-butyl, isobutyl, pentyl, isopentyl, heptyl, octyl, 2-ethylhexyl,
nonyl, decyl, dodecyl, and the corresponding hydroxy-substituted
hydrocarbyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl,
etc.
R3 and R4 can be, independently, hydrogen or methyl or ethyl
groups. When a is 2, at least one of R3 and R4 is normally hydrogen so that
this compound will be R1R2N-C~S)S-CR3HCR3R4COOR5. In one embodiment
the thiocarbamate is R1R2N-C(S)S-CH2CH2COOCH3. (These materials can be
derived from methyl methacrylate and methyl acrylate, respectively.) These
and other materials containing appropriate activating groups are disclosed in
greater detail in U.S. Patent 4,758,362, which is incorporated herein by
reference.
The substituents R' and R2 on the nitrogen atom are likewise
hydrogen or hydrocarbyl groups, but at least one should be a hydrocarbyl
group. It is generally believed that at least one such hydrocarbyl group is
desired in order to provide a measure of oil-solubility to the molecule.
However, R1 and R2 can both be hydrogen, provided the other R groups in
the molecule provide sufficient oil solubility to the molecule. In practice thismeans that at least one of the groups R3 or R4 should be a hydrocarbyl group
of at least 4 carbon atoms. In one embodiment, R1 and R2 can be indepen-
dently hydrocarbyl groups (e.g., aliphatic hydrocarbyl groups such as alkyl
-
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groups) of 1 to about 50 carbon atoms, and in one embodiment 1 to about
30 carbon atoms, and in one embodiment 1 to about 18 carbon atoms, and
in one embodiment 1 to about 12 carbon atoms, and in one embodiment 1
to about 8 carbon atoms.
In one embodiment the thiocarbamate is a compound represent-
ed by the formula
S O
Il 11
RlR2N-C-S-CH2CH2-C-OR5 (F-ll)
wherein in Formula (F-ll) R', R2 and R5 are independently hydrocarbyl (e.g.,
alkyl) groups. These hydrocarbyl groups can have from 1 to about 18
carbon atoms, and in one embodiment 1 to about 12 carbon atoms, and in
one embodiment 1 to about 8 carbon atoms, and in one embodiment 1 to
about 4 carbon atoms. These compounds include S-carbomethoxyethyl-N,N-
dibutyl dithiocarbamate which can be represented by the formula
S O
Il 11
(C4Hg)2N-C-S-CH2CH2C-OCH3 (F-lll)
Materials of this type can be prepared by a process described
in U.S. Patent 4,758,362. Briefly, these materials are prepared by reacting
an amine, carbon disulfide or carbonyl sulfide, or source materials for these
reactants, and a reactant containing an activated, ethylenically-unsaturated
bond or derivatives thereof. These reactants are charged to a reactor and
stirred, generally without heating, since the reaction is normally exothermic.
Once the reaction reaches the temperature of the exotherm (typically 40-
65~C), the reaction mixture is held at the temperature to insure complete
reaction. After a reaction time of typically 3-5 hours, the volatile materials
CA 022130~0 1997-08-1~ .
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are removed under reduced pressure and the residue is filtered to yield the
final product.
The' relative amounts of the reactants used to prepare these
compounds are not critical. The charge ratios to the reactor can vary where
economics and the amount of the product desired are controlling factors.
Thus, the molar charge ratio of the amine to the CS2 or COS reactant to the
ethylenically unsaturated reactant may vary in the ranges 5:1:1 to 1:5:1 to
1:1:5. In one embodiment, the charge ratios of these reactants is 1:1:1.
In the case where a is 1, the activating group Z is separated
from the sulfur atom by a methylene group. Materials of this type can be
prepared by reaction of sodium dithiocarbamate with a chlorine-substituted
material. Such materials are described in greater detail in U.S. Patent
2,897,152, which is incorporated herein by reference.
The following example illustrates the preparation of a thiocar-
bamate (F) that can be used with this invention.
ExamPle F-1
Carbon disulfide (79.8 grams, 1.05 moles) and methyl acrylate
(86 grams, 1.0 mole) are placed in a reactor and stirred at room tempera-
ture. Di-n-butylamine (129 grams, 1.0 mole) is added dropwise to the
mixture. The resulting reaction is exothermic, and the di-n-butylamine
addition is done at a sufficient rate to maintain the temperature at 55~C.
After the addition of di-n-butylamine is complete, the reaction mixture is
maintained at 55~ C for four hours. The mixture is blown with nitrogen at
85~C for one hour to remove unreacted starting material. The reaction
mixture is filtered through filter paper, and the resulting product is a viscousorange liquid.
Lubricating ComPositions and Functional Fluids.
The lubricating compositions and functional fluids of the present
invention are based on diverse oils of lubricating viscosity, including natural
and synthetic lubricating oils and mixtures thereof. The lubricating
-
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compositions may be lubricating oils and greases useful in industrial applica-
tions and in automotive engines, transmissions and axles. These lubricating
compositions are effective in a variety of applications including crankcase
lubricating oils for spark-ignited and compression-ignited internal combustion
engines, including automobile and truck engines, two-cycle engines, aviation
piston engines, marine and low-load diesel engines, and the like. Also,
automatic transmission fluids, farm tractor fluids, transaxle lubricants, gear
lubricants, metalworking lubricants, hydraulic fluids, and other lubricating oiland grease compositions can beriefit from the incorporation of the composi-
tions of this invention. The inventive lubricating compositions are particular-
ly effective as engine lubricating oils having enhanced antiwear properties.
The lubricant compositions of this invention employ an oil of
lubricating viscosity which is generally present in a major amount (i.e. an
amount greater than about 50% by weight). Generally, the oil of lubricating
viscosity is present in an amount greater than about 60%, or greater than
about 70%, or greater than about 80% by weight of the composition.
The natural oils useful in making the inventive lubricants and
functional fluids include animal oils and vegetable oils (e.g., castor oil, lardoil) as well as mineral lubricating oils such as liquid petroleum oils and
solvent treated or acid-treated mineral lubricating oils of the paraffinic,
naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating viscosity
derived from coal or shale are also useful. Synthetic lubricating oils include
hydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,
polybutylenes, polypropylenes, propylene-isobutylene copolymers, etc.);
poly(1-hexenes), poly-(1-octenes), poly(1-decenes), etc. and mixtures
thereof; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,
dinonylbenzenes, di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g.,
biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers
and alkylated diphenyl sulfides and the derivatives, analogs and homologs
thereof and the like.
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Alkylene oxide polymers and interpolymers and derivatives
thereof where the terminal hydroxyl groups have been modified by
esterification, etherification, etc., constitute another class of known
synthetic lubricating oils that can be used. These are exemplified by the oils
prepared through polymerization of ethylene oxide or propylene oxide, the
alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-poly-
isopropylene glycol ether having an average molecular weight of about
1000, diphenyl ether of polyethylene glycol having a molecular weight of
about 500-1000, diethyl ether of polypropylene glycol having a molecular
weight of about 1000-1500, etc.) or mono- and polycarboxylic esters
thereof, for example, the acetic acid esters, mixed C3.8 fatty acid esters, or
the Cl30xo acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils that can be
used comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic
acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid,
suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer,
malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety
of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.)
Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl)
sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl
azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the
2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by
reacting one mole of sebacic acid with two moles of tetraethylene glycol and
two moles of 2-ethylhexanoic acid and the like.
Esters useful as synthetic oils also include those made from C5
to C,2 monocarboxylic acids and polyols and polyol ethers such as neopentyl
glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaery-
thritol, etc.
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Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-,
or polyaryloxy-siloxane oils and silicate oils comprise another useful class of
synthetic lubricants ~e.g., tetraethyl silicate, tetraisopropyl silicate,
tetra-(2-ethylhexyl)silicate, tetra-(4-methylhexyl)silicate, tetra-(p-tert-butyl-
phenyl) silicate, hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl) silox-
anes, poly-(methylphenyl)siloxanes, etc.). Other synthetic lubricating oils
include liquid esters of phosphorus-containing acids (e.g., tricresyl phos-
phate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.),
polymeric tetrahydrofurans and the like.
Unrefined, refined and rerefined oils, either natural or synthetic
(as well as mixtures of two or more of any of these) of the type disclosed
hereinabove can be used in the lubricants of the present invention.
Unrefined oils are those obtained directly from a natural or synthetic source
without further purification treatment. For example, a shale oil obtained
directly from retorting operations, a petroleum oil obtained directly from
primary distillation or ester oil obtained directly from an esterification process
and used without further treatment would be an unrefined oil. Refined oils
are similar to the unrefined oils except they have been further treated in one
or more purification steps to improve one or more properties. Many such
purification techniques are known to those skilled in the art such as solvent
extraction, secondary distillation, acid or base extraction, filtration, percola-
tion, etc. Rerefined oils are obtained by processes similar to those used to
obtain refined oils applied to refined oils which have been already used in
service. Such rerefined oils are also known as reclaimed or reprocessed oils
and often are additionally processed by techniques directed to removal of
spent additives and oil breakdown products.
In one embodiment, component (A) is employed in the lubricant
or functional fluid at a concentration in the range of about 0.001% to about
5% by weight, and in one embodiment about 0.01% to about 3%, and in
one embodiment about 0.02% to about 2% by weight based on the total
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CA 022130~0 1997-08-1~ .
weight of the lubricant or functional fluid. In one embodiment, component
(B) is employed in the lubricant or functional fluid at a concentration in the
range of about 0.01% to about 20% by weight, and in one embodiment
from about 0.1% to about 10%, and in one embodiment from about 0.5%
to about 10% by weight based on the total weight of the lubricant or
functional fluid. In one embodiment, component (C) is employed in the
lubricant or functional fluid at a concentration in the range of up to about
20% by weight, and in one embodiment from about 0.01% to about 10%,
and in one embodiment from about 0.05% to about 5% by weight based on
the total weight of the lubricant or functional fluid. In one embodiment,
component (D) is employed in the lubricant or functional fluid at a concentra-
tion in the range of up to about 10% by weight, and in one embodiment
about 0.01 % to about 5%, and in one embodiment about 0.1 % to about 3%
by weight based on the total weight of the lubricant or functional fluid. In
one embodiment, component (E) is employed in the lubricant or functional
fluid at a concentration in the range of up to about 10% by weight, and in
one embodiment about 0.001% to about 5% by weight, and in one
embodiment about 0.01% to about 3%, and in one embodiment about
0.02% to about 2% by weight based on the total weight of the lubricant or
functional fluid. In one embodiment, component (F) is employed in the
lubricant or functional fluid at a concentration in the range of up to about
10% by weight, and in one embodiment about 0.01% to about 5%, and in
one embodiment about 0.1% to about 3% by weight based on the total
weight of the lubricant or functional fluid.
In one embodiment these lubricating compositions and
functional fluids have a'phosphorus content of up to about 0.12% by
weight, and in one embodiment up to about 0.11% by weight, and in one
embodiment up to about 0.10% by weight, and in one embodiment up to
about 0.09% by weight, and in one embodiment up to about 0.08% by
weight, and in one embodiment up to about 0.05% by weight. In one
CA 022130~0 1997-08-1~
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embodiment the phosphorus content is in the range of about 0.01% to
about 0.12% by weight, and in one embodiment about 0.01% to about
0.10% by weight, and in one embodiment about 0.02% to about 0.09% by
weight and in one embodiment about 0.05% to about 0.09% by weight.
The invention also provides for the use of lubricants and
functional fluids containing other additives in addition to components (A),
(B), (C), (D), and (F). Such additives include, for example, detergents and
dispersants, corrosion-inhibiting agents, antioxidants, viscosity improving
agents, extreme pressure (E.P.r agents, pour point depressants, friction
modifiers, fluidity modifiers, anti-foam agents, etc.
The inventive lubricating compositions and functional fluids can
contain one or more detergents or dispersants of the ash-producing or
ashless type. The ash-producing detergents are exemplified by oil-soluble
neutral and basic salts of alkali or alkaline earth metals with sulfonic acids,
carboxylic acids, or organic phosphorus acids characterized by at least one
direct carbon-to-phosphorus linkage such as those prepared by the treatment
of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000)
with a phosphorizing agent such as phosphorus trichloride, phosphorus
heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur,
white phosphorus and a sulfur halide, or phosphorothioic chloride. The most
commonly used salts of such acids are those of sodium, potassium, lithium,
calcium, magnesium, strontium and barium.
Ashless detergents and dispersants are so called despite the
factthat, depending on its constitution, the dispersant may upon combustion
yield a non-volatile material such as boric oxide or phosphorus pentoxide;
however, it does not ordinarily contain metal and therefore does not yield a
metal-containing ash on combustion. Many types are known in the art, and
any of them are suitable for use in the lubricant compositions and functional
fluids of this invention. The following are illustrative:
CA 022130~0 1997-08-1~
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(1) Reaction products of carboxylic acids (or derivatives
thereof) containing at least about 34 and preferably at least about 54 carbon
atoms with nitrogen containing compounds such as amine, organic hydroxy
compounds such as phenols and alcohols, and/or basic inorganic materials.
Examples of these "carboxylic dispersants" are described in many U.S.
Patents including 3,219,666; 4,234,435; and 4,938,881.
(2) Reaction products of relatively high molecular weight
aliphatic or alicyclic halides with amines, preferably oxyalkylene polyamines.
These may be characterized as ~'amine dispersants" and examples thereof
are described for example, in the following U.S. Patents: 3,275,554;
3,438,757; 3,454,555; and 3,565,804.
(3) Reaction products of alkyl phenols in which the alkyl
group contains at least about 30 carbon atoms with aldehydes (especially
formaldehyde) and amines (especially polyalkylene polyamines), which may
be characterized as "Mannich dispersants." The materials described in the
following U.S. Patents are illustrative: 3,649,229; 3,697,674; 3,725,277;
3,725,480; 3,726,882; and 3,980,569.
(4) Products obtained by post-treating the amine or Mannich
dispersants with such reagents as urea, thiourea, carbon disulfide,
aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic
anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or
the like. Exemplary materials of this kind are described in the following U.S.
Patents: 3,639,242; 3,649,229; 3,649,659; 3,658,836; 3,697,574;
3,702,757; 3,703,536; 3,704,308; and 3,708,422.
(5) Interpolymers of oil-solubilizing monomers such as decyl
methacrylate, vinyl decyl ether and high molecular weight olefins with
monomers containing polar substituents, e.g., aminoalkyl acrylates or
acrylamides and poly-~oxyethylene)-substituted acrylates. These may be
characterized as "polymeric dispersants" and examples thereof are disclosed
CA 022130~0 1997-08-1~
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in the following U.S. Patents: 3,329,658; 3,449,250; 3,519,565;
3,666,730; 3,687,849; and 3,702,300.
The above-noted patents are incorporated by reference herein
for their disclosures of ashless dispersants.
The inventive lubricating compositions and functional fluids can
contain one or more extreme pressure, corrosion inhibitors and/or oxidation
inhibitors in addition to those that would be considered as being within the
scope of the above-discussed components. Extreme pressure agents and
corrosion- and oxidation-inhibiting agents which may be included in the
lubricants and functional fluids of the invention are exemplified by chlori-
nated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and
polysulfides such as benzyl disulfide, bis(chlorobenzyl)disulfide, dibutyl
tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol,
sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons
such as the reaction product of a phosphorus sulfide with turpentine or
methyl oleate; metal thiocarbamates, such as zinc dioctyldithiocarbamate,
and barium heptylphenyldithiocarbamate; dithiocarbamate esters from the
reaction product of dithiocarbamic acid and acrylic, methacrylic, maleic,
fumaric or itaconic esters; dithiocarbamate containing amides prepared from
dithiocarbamic acid and an acrylamide; alkylene-coupled dithiocarbamates;
sulfur-coupled dithiocarbamates. Many of the above-mentioned extreme
pressure agents and oxidation-inhibitors also serve as antiwear agents.
Pour point depressants are a useful type of additive often
included in the lubricating oils and functional fluids described herein. The
use of such pour point depressants in oil-based compositions to improve low
temperature properties of oil-based compositions is well known in the art.
See, for example, page 8 of "Lubricant Additives" by C.V. Smallheer and R.
Kennedy Smith (Lezius Hiles Co. publishers, Cleveland, Ohio, 1967).
Examples of useful pour point depressants are polymethacrylates; polyacryl-
ates; polyacrylamides; condensation products of haloparaffin waxes and
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aromatic compounds; vinyl carboxylate polymers; and terpolymers of
dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers. A specificpour point depressant that can be used is the product made by alkylating
naphthalene with polychlorinated paraffin and C,6-ClB alpha-olefin. 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; 2,65~,479; 1,815,022; 2,191,498; 2,666,746; 2,721,877;
2,721,878; and 3,250,715 which are herein incorporated by reference for
their relevant disclosures.
Anti-foam agents are used to reduce or prevent the formation
of stable foam. Typical anti-foam agents include silicones or organic
polymers. Additional antifoam compositions are described in "Foam Control
Agents," by Henry T. Kerner (Noyes Data Corporation, 1976), pages
125-162.
Each of the foregoing additives, when used, is used at a
functionally effective amount to impart the desired properties to the lubricant
or functional fluid. Thus, for example, if an additive is a dispersant, a
functionally effective amount of this dispersant would be an amount
sufficient to impart the desired dispersancy characteristics to the lubricant
or functional fluid. Similarly, if the additive is an extreme-pressure agent, a
functionally effective amount of the extreme-pressure agent would be a
sufficient amount to improve the extreme-pressure characteristics of the
lubricant or functional fluid. Generally, the concentration of each of these
additives, when used, ranges from about 0.001 % to about 20% by weight,
and in one embodiment about 0.01 % to about 10% by weight based on the
total weight of the lubricant or functional fluid.
The lubricant compositions of the present invention may be in
the form of lubricating oils or greases in which any of the above-described
oils of lubricating viscosity can be employed as a vehicle. Where the
lubricant is to be used in the form of a grease, the lubricating oil generally
CA 022130~0 1997-08-1~
is employed in an amount sufficient to balance the total grease composition
and generally, the grease compositions will contain various quantities of
thickening agents and other additive components of the type described
above to provide desirable properties. Generally, the greases will contain
from about 0.01 to about 20-30% of such additive components.
A wide variety of thickening agents can be used in the
preparation of the greases of this invention. Included among the thickening
agents are alkali and alkaline earth metal soaps of fatty acids and fatty
materials having from about 12 to about 30 carbon atoms. The metals are
typified by sodium, lithium, calcium and barium. Examples of fatty materials
include stearic acid, hydroxy stearic acid, stearin, oleic acid, palmetic acid,
myristic acid, cottonseed oil acids, and hydrogenated fish oils.
Other thickening agents include salt and salt-soap complexes
as calcium stearate-acetate ( U . S. Patent 2, 1 97, 263), barium stearate acetate
(U.S. Patent2,564,561 ),calciumstearate-caprylate-acetatecomplexes~U.S.
Patent 2,999,065), calcium caprylate-acetate (U.S. Patent 2,999,066), and
calcium salts and soaps of low-, intermediate- and high-molecular weight
acids and of nut oil acids.
Useful thickening agents employed in the grease compositions
are essentially hydrophilic in character, but which have been converted into
a hydrophobic condition by the introduction of long chain hydrocarbon
radicals onto the surface of the clay particles prior to their use as a
component of a grease composition, as, for example, by being subjected to
a preliminary treatment with an organic cationic surface-active agent, such
as an onium compound. Typical onium compounds are tetraalkylammonium
chlorides, such as dimethyl dioctadecyl ammonium chloride, dimethyl
dibenzyl ammonium chloride and mixtures thereof. This method of
conversion, being well known to those skilled in the art, and is believed to
require no further discussion. More specifically, the clays which are useful
as starting materials in forming the thickening agents to be employed in the
CA 022130~0 1997-08-1~
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grease compositions, can comprise the naturally occurring chemically
unmodified clays. These clays are crystalline complex silicates, the exact
composition of which is not subject to precise description, since they vary
widely from one natural source to another. These clays can be described as
complex inorganic silicates such as aluminum silicates, magnesium silicates,
barium silicates, and the like, containing, in addition to the silicate iattice,varying amounts of cation-exchangeable groups such as sodium.
Hydrophilic clays which are particularly useful for conversion to desired
thickening agents include montmorillonite clays, such as bentonite,
attapulgite, hectorite, illite, saponite, sepiolite, biotite, vermiculite, zeolite
clays, and the like. The thickening agent is generally employed in an amount
from about 0.5 to about 30% by weight, and in one embodiment from about
3% to about 15% by weight of the total grease composition.
Components (A) and (B), and optional components (C) to (F) of
the inventive compositions as well as one of the other above-discussed
additives or other additives known in the art can be added directly to the
lubricant or functional fluid. In one embodiment, however, they are diluted
with a substantially inert, normally liquid organic diluent such as mineral oil,naphtha, benzene, toluene or xylene to form an additive concentrate which
is then added to the base oil to form the lubricant or functional fluid. These
concentrates usually contain from about 1% to about 99% by weight, and
in one embodiment about 10% to about 90% by weight of components (A)
and (B) and, optionally, one or more of components (C) to (F) as well as one
or more other additives known in the art or described hereinabove. The
remainder of the concentrate is the substantially inert normally liquid diluent.The following Examples 1-37 illustrate lubricating compositions
and functional fluids within the scope of the invention.
CA 022130~0 1997-08-1~
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Example 1
Wt. %
Product of Example A-1 0.5
Product of Example B-1 5.0
Base oil Remainder
ExamPle 2
Wt. %
Product of Example A-2 1.0
Product of Example B-1 4.0
Base oil Remainder
ExamPle 3
Wt. %
Product of Example A-3 1.4
Product of Example B-1 6.0
Base oil Remainder
ExamPle 4
Wt. %
Product of Example A-1 0.7
Product of Example B-2 4.5
Base oil Remainder
ExamPle 5
Wt. %
Product of Example A-2 2.0
Product of Example B-2 6.5
Base oil Remainder
ExamPle 6
Wt. %
Product of Example A-3 0.3
Product of Example B-2 6.5
Base oil Remainder
- - - ~ - - - - -
CA 022130~0 1997-08-1~
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Exam Ple 7
Wt. %
Product of Example A-4 0.5
Product of Example B-1 5.0
Base oil Remainder
ExamPle 8
Wt. %
Product of Example A-5 1.0
Product of Example B-1 4.0
Base oil Remainder
ExamPle 9
Wt. %
Product of Example A-6 1.4
Product of Example B-1 6.0
Base oil Remainder
Example 10
Wt. %
Product of Example A-7 0.7
Product of Example B-1 4.5
Base oil Remainder
ExamPle 1 1
Wt. %
Product of Example A-5 2.0
Product of Example B-2 6.5
Base oil Remainder
ExamPle 12
Wt. %
Product of Example A-7 0.3
Product of Example B-2 6.5
Base oil Remainder
CA 022130~0 1997-08-1~
-71 -
ExamPle 13
Wt. %
Product of Example A-8 0.5
Product of Example B-1 5.0
Base oil Remainder
ExamPle 14
Wt. %
Product of Example A-9 1.0
Product of Example B- 1 4.0
Base oil Remainder
ExamPle 15
Wt. %
Product of Example A-10 1.4
Product of Example B-1 6.0
Base oil Remainder
Example 16
Wt. %
Product of Example A-11 0.7
Product of Example B-1 4.5
Base oil Remainder
ExamPle 17
Wt. %
Product of Example A-9 2.0
Product of Example B-2 6.5
Base oil Remainder
Example 18
Wt. %
Prod uct of Example A- 1 1 0. 3
Product of Example B-2 6.5
Base oil Remainder
-
CA 022130~0 1997-08-1~
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Exa,..l~le 19
Wt. %
Product of Example A-1 2.5
Product of Example B-1 5.0
Product of Example C-1 0.5
Base oil Remainder
ExamDle 20
Wt. %
Product of Example A-2 0.5
Product of Example B-1 4.0
Product of Example C- 1 0.7
Base oil Remainder
ExamDle 21
Wt. %
Product of Example A-3 1.5
Product of Example B-1 5.0
Product of Example C-1 0.5
Base oil Remainder
Exal,.pl~ 22
Wt. %
Product of Example A-1 1.0
Product of Example B-2 5.0
Product of Example C-1 0.3
Base oil Remainder
ExamDle 23
Wt. %
Product of Example A-2 0.3
Product of Example B-2 4.5
Product of Example C-1 0.7
Base oil Remainder
CA 022130~0 1997-08-1~
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ExamPle 24
Wt. %
Product of Example A-3 1.0
Product of Example B-2 5. 5
Product of Example C-1 0.5
Base oil Remainder
Example 25
Wt. %
Product of Example A-1 1.1
Product of Example B-1 6.5
Product of Example C-2 0.5
Base oil Remainder
ExamPle 26
Wt. %
Product of Example A-1 0.9
Product of Example B-1 5.0
Product of Example C-7(a) 0.7
Base oil Remainder
Example 27
Wt. %
Product of Example A-1 0.8
Product of Example B- 1 4. 5
Product of Example C-7(b) . 1.4
Base oil Remainder
ExamPle 28
Wt. %
Product of Example A-1 1.2
Product of Example B-1 6.0
Product of Example C-7(c) 0. 5
Base oil Remainder
CA 022130~0 1997-08-1~
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ExamPle 29
Wt. %
Product of Example A-1 1.2
Product of Example B-1 5.0
Product of Example D-1 0.6
Base oil Remainder
ExamPle 30
Wt. %
Product of Example A-1 0.6
Product of Example B-1 5.0
Product of Example E-1 0.5
Base oil Remainder
ExamPle 31
Wt. %
Product of Example A-1 1.5
Product of Example B-1 4.5
Product of Example F-1 0.5
Base oil Remainder
ExamPle 32
Wt. %
Product of Example A-1 1.5
Product of Example B-1 4.5
Product of Example B-2 3.0
Product of Example D-1 0.5
Base oil Remainder
CA 022130~0 1997-08-1~
ExamPle 33
Wt. %
Product of Example A-1 1.5
Prod uct of Example B- 1 5 . 5
Product of Example B-2 2.5
Product of Example E-1 0.5
Base oil Remainder
Exa~ lc 34
Wt. %
1 0 Product of Example A- 1 1 . 5
Prodùct of Example B-1 4.5
Product of Example B-2 3.5
Product of Example F-1 0.5
Base oil Remainder
1 5 ExamPle 35
Wt. %
Product of Example A-1 0.5
Product of Example B-1 5.5
Product of Example C-1 1.0
Product of Example D-1 0.5
Base oil Remainder
Exam~le 36
Wt. %
Product of Example A-1 1.0
Product of Example B-1 5.5
Product of Example C-1 0.5
Product of Example D-1 0.25
Product of Example E-1 0.25
Base oil Remainder
CA 022130~0 1997-08-1~
-76-
ExamPle 37
Wt. %
Product of Example A-1 0.5
Product of Example B-1 5.0
Product of Example C-1 1.5
Product of Example D-1 0.5
Product of Example E- 1 0. 5
Product of Example F-1 0.5
Base oil Remainder
Examples 38-40 disclosed in Table I are provided for the
purpose of further illustrating lubricating compositions within the scope of
the invention. These compositions are useful as engine lubricating oil
compositions. In Table I all numerical values, except for the concentration
of the silicone antifoam agent are in percent by weight. The concentration
of the silicone antifoam agent is in parts per million, ppm.
CA 022130~0 1997-08-1~
Table I
Examr~le No. 38 39 40
Base oil ~85% 100N + 15% 150N) 80.9 80.9 80.9
Product of Example A-1 0.5 -- --
Product of Example A-5 -- 0.5 --
Prod uct of Example A- 11 -- -- 0.5
Product of Example B-1 4.03 4.03 4.03
Product of Example B-2 1.37 1.37 1.37
Product of Example C-1 0.72 0.72 0.72
Overbased Mg sulfonate, 0.45 0.45 0.45
metal/sulfonate ratio = 14.7,
oil content s 42%
Overbased Ca sulfonate, 0.22 0.22 0.22
metal/sulfonate ratio = 1.2,
oil content = 50%
Overbased Na succinate, 0.2 0.2 0.2
oil content = 49%
Ca overbased sulfur coupled 0.5 0.5 0.5
alkyl phenol,
oil content = 39%
Olefin copolymer Vl improver 0.7 0.7 0.7
Alkylated diphenylamine 0.6 0.6 0.6
Polymethacrylate pour point 0.2 0.2 0.2
depressant
Sulfur monochloride reacted with 0.3 0.3 0.3
alpha olefin mixture followed by
contact with sodium disulfide
Vegetable oil 0.1 0.1 0.1
Diluent oil 8.3 8.3 8.3
Silicone antifoam agent, ppm 18 18 18
Phosphorus content 0.072 0.072 0.072
CA 022130~0 1997-08-1~
-78-
While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various modifications
thereof will become apparent to those skilled in the art upon reading the
specification. 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.
