BACKGROUND OF THE INVENTION
[0001] The present invention relates to additives and compositions useful as lubricants
and functional fluids with good extreme pressure and antiwear properties.
[0002] Dithiocarbamate compounds are known and useful as lubricant additives. U.S. Patent
4,758,362, Butke, July 19, 1988, discloses carbamate additives for low phosphorus
or phosphorus free lubricating compositions. The additive has the formula

where X is O or S and Z one of several listed groups. These additives are said to
impart improved extreme pressure and anti-wear properties to lubricant compositions.
The compositions can contain other additives and chemistries.
[0003] Likewise, phosphonic acid salts are known as lubricant additives. U.S. Patent 3,185,728,
Schallenberg et al., May 25, 1965, discloses amine salts of hydrocarbyl thiophosphonic
acids, represented by, e.g., the formula

where R is a hydrocarbyl radical and R' is an aliphatic hydrocarbyl radical containing
preferably 5-22 carbon atoms. R is usually an olefinic radical containing 12 to 100
carbon atoms. The amines involved in the formation of the salts can be Primene™ 81-R
(a mixture of branched chain t-alkylamines said to contain 11-14 carbon atoms). The
salts are useful as ashless detergents for lubricating oils and dispersants for fuels.
[0004] U.S. Patent 4,804,456, Forester, Feb. 14, 1989, discloses a petrochemical or hydrocarbon
to which is added 0.5 to 10,000 ppm of an amine salt of polyalkenylthiophosphonic
acid, to control fouling during processing at elevated temperatures. Alkenyl polymers
are reacted with P₂S₅ at 100-320°C in the presence of elemental sulfur. The product
is then steam hydrolyzed at 100-260°C. The preferred material is polyisobutenylthiophosphonic
acid wherein the polyisobutenyl moiety of the acid has a molecular weight of about
1300. Amines/fatty amines may be used to form the amine addition salts.
[0005] Moreover, surfactants of various types have found use in lubricating applications.
U.S. Patent 4,959,168, Schroeck, September 25, 1990, discloses sulfurized mixtures
which include at least one partial fatty acid ester of a polyhydric alcohol and at
least one other listed material. The ester can be glycerol monooleate. Other additives
can also be present. In one example, a composition is described which includes a C₁₁₋₁₄
t-alkylamine salt of the reaction product of P₂O₅ with hydroxypropyl O,O-di(4-methyl-2-pentyl)
phosphorodithioate and a borated reaction product of an ethylenepolyamine with polyisobutenyl
succinic anhydride, a fatty amide, and a sulfurized isobutylene.
SUMMARY OF THE INVENTION
[0006] The present invention provides a composition which exhibits good antiwear performance.
The invention includes a composition of matter comprising:
(a) an oil of lubricating viscosity;
(b) a compound of the structure
R₁R₂N - C(X)S - Q
where R₁ and R₂ are independently hydrogen or hydrocarbyl groups; X is an oxygen or
sulfur atom; and Q is an alkyl group or an alkyl group containing at least one substituent
selected from the group consisting of activating groups, hydrocarbyl groups, hetero
groups, or -SC(X)-NR₁R₂ groups, groups R₁, R₂, and Q containing in total at least
4 carbon atoms; and
(c) A sulfur-containing phosphonic acid or a salt thereof.
A preferred embodiment of the composition further comprises (d) a surfactant.
DETAILED DESCRIPTION OF THE INVENTION
[0007] The present invention provides a composition which can serve as a functional fluid
such as a power transmission fluid and, in particular, a tractor hydraulic fluid,
with improved properties. Specifically, the compositions exhibit improved anti-wear
performance, good rust inhibition, good water tolerance, and good oxidation performance.
Certain formulations, in particular, are capable of passing the JDQ-95 spiral bevel
test, a test standard for tractor hydraulic fluids, established by John Deere & Company
Engineering Standards Department, John Deere Rd., Moline, IL 61265. Other applications
in which the present composition or equivalents thereof can be advantageously used
include crankcase lubricating oils for spark-ignited and compression-ignited internal
combustion engines, including automibile and truck engines, two-cycle engines, aviation
piston engines, and marine and railroad diesel engines. They can also be used in gas
engines and stationary power engines and turbines. Automatic or manual transmission
fluids, transaxle lubricants, gear lubricants, including open and enclosed gear lubricants,
tractor lubricants, metal-working lubricants, hydraulic fluids, and other lubricating
oil and grease composition can also benefit from the incorporation therein of the
compositions of the present invention. They can also be used as wirerope, walking
cam, way, rock drill, chain and conveyor belt, worm gear, bearing, and rail and flange
lubricants.
[0008] The first and major component of this invention is an oil of lubricating viscosity.
The oils of lubricating viscosity include natural or synthetic lubricating oils and
mixtures thereof. Natural oils include animal oils, mineral lubricating oils, and
solvent or acid treated mineral oils. Synthetic lubricating oils include hydrocarbon
oils (polyalpha-olefins), halo-substituted hydrocarbon oils, alkylene oxide polymers,
esters of dicarboxylic acids and polyols, esters of phosphorus-containing acids, polymeric
tetrahydrofurans and silicon-based oils. Preferably, the oil of lubricating viscosity
is a hydrotreated mineral oil or a synthetic lubricating oil, such as a polyolefin.
Examples of useful oils of lubricating viscosity include XHVI basestocks, such as
100N isomerized wax basestock (0.01% sulfur/ 141 VI), 120N isomerized wax basestock
(0.01% sulfur/ 149 VI), 170N isomerized wax basestock (0.01% sulfur/ 142 VI), and
250N isomerized wax basestock (0.01% sulfur/ 146 VI); refined basestocks, such as
250N solvent refined paraffinic mineral oil (0.16% sulfur/89 VI), 200N solvent refined
naphthenic mineral oil (0.2% sulfur/ 60 VI), 100N solvent refined/ hydrotreated paraffinic
mineral oil (0.01% sulfur/98 VI), 240N solvent refined/ hydrotreated paraffinic mineral
oil (0.01% sulfur/ 98 VI), 80N solvent refined/ hydrotreated paraffinic mineral oil
(0.08% sulfur/ 127 VI), and 150N solvent refined/ hydrotreated paraffinic mineral
oil (0.17% sulfur/ 127 VI). For further description of oils of lubricating viscosity,
attention is directed to U.S. Patent 4,582,618 (column 2, line 37 through column 3,
line 63, inclusive).
[0009] In one embodiment, the oil of lubricating viscosity is a polyalpha-olefin (PAO).
Typically, the polyalpha-olefins are derived from monomers having from about 4 to
about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms. Examples
of useful PAOs include those derived from decene. These PAOs may have a viscosity
from about 3 to about 150, or from about 4 to about 100, or from about 4 to about
8 cSt at 100°C. Examples of PAOs include 4 cSt polyolefins, 6 cSt polyolefins, 40
cSt polyolefins and 100 cSt polyalphaolefins.
[0010] In one embodiment, the lubricating composition contains an oil of lubricating viscosity
which has an iodine value of less than about 9, determined according to ASTM D-460.
In one embodiment, the oil of lubricating viscosity has a iodine value less than about
8, or less than about 6, or less than about 4.
[0011] In one embodiment, the oils of lubricating viscosity are selected to provide lubricating
compositions with a kinematic viscosity of at least about 3.5 cSt, or at least about
4.0 cSt at 100°C. In one embodiment, the lubricating compositions have an SAE gear
viscosity grade of at least about SAE 75W. The lubricating composition may also have
a so-called multigrade rating such as SAE 75W-80, 75W-90, 75W-140, 80W-90, 80W-140,
85W-90, or 85W-140. Multigrade lubricants may include a viscosity improver which is
formulated with the oil of lubricating viscosity to provide the above lubricant grades.
Useful viscosity improvers include but are not limited to polyolefins, such as ethylene-propylene
copolymers, or polybutylene rubbers, including hydrogenated rubbers, such as styrene-butadiene
or styrene-isoprene rubbers; or polyacrylates, including polymethacrylates. In one
embodiment, the viscosity improver is a polyolefin or polymethacrylate. Viscosity
improvers available commercially include Acryloid™ viscosity improvers available from
Rohm & Haas; Shellvis™ rubbers available from Shell Chemical; Trilene™ polymers, such
as Trilene™ CP-40, available commercially from Uniroyal Chemical Co., and Lubrizol
3100 series and 8400 series polymers, such as Lubrizol® 3174 available from The Lubrizol
Corporation.
[0012] In one embodiment, the oil of lubricating viscosity includes at least one ester of
a dicarboxylic acid. Typically the esters containing from about 4 to about 30, preferably
from about 6 to about 24, or from about 7 to about 18 carbon atoms in each ester group.
Here, as well as elsewhere, in the specification and claims, the range and ratio limits
may be combined. Examples of dicarboxylic acids include glutaric, adipic, pimelic,
suberic, azelaic and sebacic. Example of ester groups include hexyl, octyl, decyl,
and dodecyl ester groups. The ester groups include linear as well as branched ester
groups such as iso arrangements of the ester group. A particularly useful ester of
a dicarboxylic acid is diisodecyl azelate. The lubricating oil in the invention will
normally comprise the major amount of the composition. Thus it will normally be at
least 50% by weight of the composition, preferably about 83 to about 98%, and most
preferably about 88 to about 96%. As an alternative embodiment, however, the present
invention can provide an additive concentrate in which the oil can be 0 to about 20%
by weight, preferably about 1 to about 10%, and the other components, described in
greater detail below, are proportionately increased.
[0013] The second component (b) of the present composition is a compound of the structure
R₁R₂N - C(X)S - Q where R₁ and R₂ are independently hydrogen or hydrdocarbyl groups;
X is an oxygen or sulfur atom; and Q is an alkyl group or an alkyl group containing
at least one substituent selected from the group consisting of hydrocarbyl groups,
hetero groups (that is, a group attached through a heteroatom such as O, N, or S),
additional -SC(X)-NR₁R₂ groups, or, preferably, activating groups. Groups R₁, R₂,
and Q should contain in total at least 4, preferably at least 6, and more preferably
at least 8 carbon atoms. In a preferred embodiment, Q is (CR₃R₄)
aY, wherein R₃ and R₄ are independently hydrogen or hydrocarbyl groups, a is 1 or 2,
and Y is the hydrocarbyl group, hetero group, -SC(X)-NR₁R₂ group, or activating group.
[0014] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used
in its ordinary sense, which is well-known to those skilled in the art. Specifically,
it refers to a group having a carbon atom directly attached to the remainder of the
molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups
include:
(1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic
(e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted
aromatic substituents, as well as cyclic substituents wherein the ring is completed
through another portion of the molecule (e.g., two substituents together form an alicyclic
radical);
(2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon
groups which, in the context of this invention, do not alter the predominantly hydrocarbon
substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto,
alkylmercapto, nitro, nitroso, and sulfoxy);
(3) heteroatom-containing substituents, that is, substituents which, while having
a predominantly hydrocarbon character, in the context of this invention, contain other
than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms include
sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and
imidazolyl. In general, no more than two, preferably no more than one, non-hydrocarbon
substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically,
there will be no non-hydrocarbon substituents in the hydrocarbyl group.
[0015] When a in the above formula is 2, Y is preferably an activating group. In describing
Y 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 the method by which the material of this component
is normally prepared, by reaction of an activated olefin with CS₂ and an amine.) The
activating group Y 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 or salts corresponding to
the aforementioned esters. Y can also be an amide group, that is, based on the condensation
of an acid group, preferably a carboxylic acid group, with an amine. In that case
the - (CR₃R₄)
aY group could be suitably derived from acrylamide. Y can also be an ether group, -OR₅;
a carbonyl group, that is, an aldehyde or a ketone group; a cyano group, -CN, or an
aryl group. In a preferred embodiment Y is an ester group of the structure, -COOR₅,
where R₅ is a hydrocarbyl group. R₅ can preferably comprise 1 to 18 carbon atoms,
preferably 1 to 6 carbon atoms. Most preferably R₅ is methyl so that the activating
group is -COOCH₃. R₅ can be a hydrocarbyl group derived from a mono- or a polyalcohol;
in the latter instance, the polyfunctional R₅ alcohol can be reacted with a plurality
of R₁R₂N-C(X)S-(CR₃R₄)
aCOO- groups.
[0016] When a is 1, Y need not be an activating group, because the molecule is generally
prepared by methods, described below, which do not involve nucleophilic addition to
an activated double bond.
[0017] Groups R₃ and R₄ are preferably independently hydrogen or methyl or ethyl groups.
When a is 2, at least one of R₃ and R₄ is normally hydrogen so that this component
will be R₁R₂N-C(S)S-CR₃R₄CR₃HCOOR₅. Preferably most or all of the R₃ and R₄ groups
are hydrogen so that this component of the composition will be R₁R₂N-C(S)S-CH₂CH(CH₃)COOCH₃
or preferably R₁R₂N-C(S)S-CH₂CH₂COOCH₃. (These materials can be seen as derivable
from methyl methacrylate and methyl acrylate, respectively.) These and other materials
containing appropriate activating groups are disclosed in greater detail in PCT publication
WO87/05622, equivalent to U.S. Patent 4,758,362.
[0018] The substituents R₁ and R₂ on the nitrogen atom are likewise hydrogen or hydrocarbyl
groups, but at least one should preferably be a hydrocarbyl group. It is generally
believed that at least one such hydrocarbyl group is desired in order to provide suitable
oil-solubility to the molecule. However, R₁ and R₂ can both be hydrogen, provided
the other groups in the molecule provide sufficient oil solubility. In practice this
means that one of the groups R₃ or R₄ could be a hydrocarbyl group of at least 4 carbon
atoms. R₁ or R₂ are preferably alkyl groups of 1-18 carbon atoms, preferably alkyl
groups of 1-8 carbon atoms. In a particularly preferred embodiment, both R₁ and R₂
are butyl groups. Thus a particularly preferred embodiment of this component of the
composition has the formula

Materials of this type can be prepared by a process more fully described in PCT
publication WO87/05622. The materials are derived from an amine such as those described
in detail below, 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 temperature to insure complete reaction. After a reaction time of typically 3-5
hours, the volatile materials are removed under reduced pressure and the residue is
filtered to yield the final product.
[0019] The relative amounts of the reactants used to prepare the compounds of this component
are not particularly critical. The charge ratios to the reactor can vary where economics
and the amount of the product desired are controlling factors. Thus, the 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. As a preferred embodiment, the charge
ratios of these reactants will be 1:1:1.
[0020] In the case where a is 1, the activating group Y 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.
[0021] It is preferred that the amount of component (b) in the composition of the present
invention will be 0.1 to 10 percent by weight; more preferably 0.5 to 5% by weight.
The amount of this component will be proportionately increased if the composition
takes the form of a concentrate.
[0022] The third major component (c) of the composition of the present invention is a salt
of a sulfur-containing phosphonic acid. The sulfur-containing phosphonic acid can
be a monothio- or di- or tri-thiophosphonic acid, in which the sulfur replaces one
or more of the oxygen atoms in the phosphonic acid group, e.g.,

and isomers thereof.
[0023] Alternatively, and preferably, the sulfur can be contained elsewhere in the phosphonic
acid molecule, for instance, principally within or associated with the R group, i.e.
the hydrocarbyl group. In this preferred embodiment materials of the structure (II)
will not be present in readily detectable amounts, although small amounts may nevertheless
be present. The sulfur-containing materials may be speculated to have substantially
the structure of a sulfurized and possibly crosslinked olefin, such as

where the bond emanating from the sulfur atom indicates the possibility of any of
a number of structures, including mercapto groups, thioalkoxy groups, or bridging
groups. The x indicates that there may be a single sulfur atom or a chain of two or
more sulfur atoms.
[0024] In the above structures R or R' indicates a hydrocarbyl group, preferably an alkyl
group containing, for R, 8 to 24 carbon atoms, more preferably 16 to 18 carbon atoms,
although materials with longer hydrocarbyl chains can be used. Thus polymeric chains,
such as polyalkenes prepared from olefins of 2-30 carbon atoms, for instance, polyisobutylene,
with number average molecular weight of 900 or 1000 to 2000, are also permitted. (R',
in the structure written, would in each case contain 2 fewer carbon atoms than R.)
It is to be understood that an alkyl group containing 16-18 carbon atoms generally
means a mixture of alkyl groups, the average chain length being 16-18. Most often
this will comprise a mixture of C₁₆ and C₁₈ alkyl groups, although minor amounts of
shorter and longer-chain alkyl groups can also be present.
[0025] Component (c) is a salt, which indicates that a positively charged ion is associated
with the above anions. This can be a metal ion, derived from the neutralization of
the phosphonic acid with a metal-containing base. However, since the composition is
in one embodiment a largely ashless or metal-free composition, it is preferred that
the positively charged ion is an ion derived from an organic base such as an amine.
Suitable amines include monoamines and polyamines. The amines can be aliphatic, cycloaliphatic,
aromatic, or heterocyclic, including mixtures thereof, and can be saturated or unsaturated.
The amines can also generally contain non-hydrocarbon substituents or groups. Such
non-hydrocarbon substituents or groups include lower alkoxy, lower alkylmercapto,
nitro, interrupting groups such as -O- and -S- (e.g., as in such groups as -CH₂CH₂-X-CH₂CH₂-
where X is -O- or -S-). In general, the amines can be characterized by the formula
NR⁷R⁸R⁹ wherein R⁷, R⁸, and R⁹ are each independently hydrogen or hydrocarbon, amino-substituted
hydrocarbon, hydroxy-substituted hydrocarbon, alkoxy-substituted hydrocarbon, amino,
carbamyl, thiocarbamyl, guanyl, or acylimidoyl groups, provided that not all of R⁷,
R⁸, and R⁹ are hydrogen. In a preferred embodiment R⁷ is an aliphatic hydrocarbyl
group having 6-22 carbon atoms, while R⁸ and R⁹ are each independently hydrogen or
C₁₋₄ aliphatic hydrocarbyl groups, where hydrocarbyl is defined as above.
[0026] With the exception of the branched polyalkylenepolyamines, the polyoxy-alkylenepolyamines,
and the high molecular weight hydrocarbyl-substituted amines described more fully
hereafter, the amines ordinarily contain less than about 40 carbon atoms in total
and usually not more than about 20 carbon atoms in total.
[0027] Aliphatic monoamines include mono-aliphatic, di-aliphatic, and tri-aliphatic substituted
amines wherein the aliphatic group can be saturated or unsaturated and straight or
branched chain. Thus, they are primary, secondary, or tertiary aliphatic amines. Specific
examples of such monoamines include ethylamine, diethylamine, triethylamine, n-butylamine,
di-n-butylamine, tri-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine,
laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, and
octadecylamine.
[0028] Cycloaliphatic monoamines are those monoamines wherein there is one cycloaliphatic
substituent attached directly to the amino nitrogen. Examples of cycloaliphatic monoamines
include cyclohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentenylamines,
N-ethyl-cyclohexylarnine, dicyclohexylamines, and the like. Heterocyclic monoamines
are monoamines in which the amine nitrogen forms a part of the cyclic ring structure.
Examples include piperidine, pyrrolidine, and morpholine.
[0029] Aromatic amines include those monoamines wherein a carbon atom of the aromatic ring
structure is attached directly to the amino nitrogen. The aromatic ring will usually
be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused
aromatic rings, especially those derived from naphthalene. Examples of aromatic monoamines
include aniline, di-(paramethylphenyl)amine, naphthylamine, and N,N-di(butyl)aniline.
Examples of aliphatic-substituted, cycloaliphatic-substituted, and heterocyclic-substituted
aromatic monoamines are para-ethoxyaniline, para-dodecylaniline, cyclohexyl-substituted
naphthylamine, and thienyl-substituted aniline.
[0030] The amine which forms the salt in the present invention can also be a polyamine.
The polyamine can be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples
of the polyamines include alkylenepolyamines, hydroxy-containing polyamines, arylpolyamines,
and heterocyclic polyamines.
[0031] Alkylene polyamines are represented by the formula

wherein n has an average value from 1 or 2 to 10, 7, or 5, and the "Alkylene" group
has from 1 or 2 to 10, 6, or 4 carbon atoms. Each R₆ is independently hydrogen, or
an aliphatic or hydroxy-substituted aliphatic group of up to 30 carbon atoms.
[0032] Such alkylenepolyamines include methylenepolyamines, ethylenepolyamines, propylenepolyamines,
butylenepolyamines, and pentylenepolyamines. The higher homologues and related heterocyclic
amines such as piperazines and N-aminoalkyl-substituted piperazines are also included.
Specific examples of such polyamines are ethylenediamine, diethylenetriamine (DETA),
triethylenetetramine (TETA), tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine,
tripropylenetetramine, tetraethylenepentamine, hexaethyleneheptamine, and pentaethylenehexamine.
[0033] Higher homologues obtained by condensing two or more of the above-noted alkylene
amines are similarly useful as are mixtures of two or more of the aforedescribed polyamines.
[0034] Ethylenepolyamines are described in detail under the heading Ethylene Amines in Kirk
Othmer's "Encyclopedia of Chemical Technology," 2d Edition, Vol. 7, pages 22-37, Interscience
Publishers, New York (1965). Ethylenepolyamine mixtures are also useful. Other useful
types of polyamine mixtures are those resulting from stripping of the above-described
polyamine mixtures to leave as residue what is often termed "polyamine bottoms."
[0035] A highly preferred class of amines in the present application is the alkyl primary
amine, preferably branched primary amines, such as in particular C₈₋₁₈ tertiary alkyl
primary amines. Preferably the alkyl group contains 11-14 or 12-14 carbon atoms. One
such material is sold under the trade name Primene™ 81R, available from Rohm and Haas
Company, which is believed to be a mixture of C₁₂₋₁₄ tertiary alkyl primary amines.
Other related materials include Primene™ JMT, which is a mixture of C₁₈₋₂₂ tertiary
alkyl primary amines. Tertiary aliphatic primary amines and methods for their preparation
are known in the art and are described in U.S. Patent 2,945,749.
[0036] The materials comprising component (c) of the present invention can be prepared by
reacting an olefinic material with phosphorus pentasulfide followed by treatment with
water (or, conveniently, steam) and reaction of the product with a basic material
such as an amine, to form the salt. Olefins or olefinic materials are well-known substances,
which include ethylene and other olefins having 3 to 40, preferably 4 to 24, carbon
atoms. The olefins are preferably alpha-olefins (sometimes referred to as mono-1-olefins
or terminal olefins) or isomerized alpha-olefins. Examples of alpha-olefins include
1-octene, 1-nonene, 1-decene, 1-ridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene,
and 1-tetracosene. Commercially available alpha-olefin fractions that can be used
include the C₁₅₋₁₈ alpha-olefins, C₁₂₋₁₆ alpha-olefins, C₁₄₋₁₆ alpha-olefins, C₁₄₋₁₈
alpha olefins, C₁₆₋₁₈ alpha-olefins, C₁₆₋₂₀ alpha-olefins, C₁₈₋₂₄ alpha olefins, and
C₂₂₋₂₈ alpha-olefins. Olefins can also be polyolefins including diolefins such as
1,3-butadiene and isoprene.
[0037] For purposes of illustration, a mixture of C₁₆₋₁₈ olefins (1000 parts by weight,
4.26 equivalents) can be heated to 145 to 170°C, preferably 150-160°C. Phosphorus
pentasulfide, P₂S₅ (472.3 parts, 4.26 equivalents) is added in increments over a period
of 1.5 to 4.5 hours, preferably about 3 hours. The resulting mixture is further heated
to 150-180°C, preferably 160-170°C, and maintained at temperature for an additional
3 to 12 hours, preferably 3-5 hours. The reaction product is purified by filtration
through a filter aid (FAX-5™) while the mixture is still warm (130 - 155°C, preferably
140-150°C). Without intending to be bound by the following interpretation, the resulting
sulfur- and phosphorus-containing intermediate is speculated to have a variety of
structures which can be approximately designated by:

where, as above, the bonds emanating from the sulfur atoms represent a variety of
possible structures such as mercapto groups, thioalkoxy groups, or bridging groups,
and the x indicates that there may be a single sulfur atom or a chain of two or more
sulfur atoms. Component (V) is optionally mixed with diluent oil (30%), then heated
to 170-190°C and hydrolyzed by treatment with steam. The steam treatment is continued
for 6 to 12 hours, until the acid neutralization number to bromophenol blue indicator
(NNA
bpb) is about 100. The structure of the hydrolyzed material is not precisely known but
is speculated to be a mixture of materials having a general structure which can be
designated as

Intermediate (VI) is purged with nitrogen at temperature for about 1 hour, then cooled
to 110-120°C, at which time a suitable amine (such as Primene™ 81R, 893 parts, 4.68
equivalents) is added dropwise over a period of 1-4 hours. The mixture is thereafter
maintained at 110-160°C, preferably 130-140°C for a suitable time, e.g. an additional
1-6 hours (preferably about 3 hours) to permit complete reaction. The product is isolated
by filtration through Fax-5™ filter aid while hot, yielding a product speculated to
comprise at least in part materials having structures which can be designated by

and other isomers and related structures. Structures which retain phosphorus-sulfur
bonds may also be present.
Example A.
[0038] A 5L, 4-necked flask equipped with stirrer, thermowell, solids addition funnel, and
water-cooled condenser with exit to two 50% aqueous sodium hydroxide traps and a NaOCl
final trap with aspirator vacuum source is charged with 1848 g (7.86 moles) of a C₁₆₋₁₈
alpha olefin mixture. The olefin mixture is heated to 155°C, after which time P₂S₅
(888 g, 4.0 moles) is added in increments over about 1 hour. The mixture exhibits
a mild exotherm to 175°C. The mixture is stirred at 170°C for four hours, then filtered
at 100°C through FAX-5™.
[0039] The above isolated product, 1059 g (1.6 moles) is returned to a similar flask to
which is added 450 g of SSO-99 diluent oil. The material is heated to 190-200°C and
steam is added via a subsurface tube for a period of 6-8 hours. The material is analyzed
by NNA
bpb and found to have a value of 99, indicating substantially complete reaction. The
material is stirred for an additional 1 hour at 190°C to remove residual water. The
material is then cooled to 100°C and decanted.
[0040] A 2L, 4-necked flask equipped with a stirrer, addition funnel, nitrogen purge, and
water-cooled condenser is charged with 600 g (1.06 moles) of the above steam-blown
intermediate. The material is heated to 85°C and 201.4 g (1.06 moles) of Primene™
81R is added dropwise through an addition funnel over a period of about 1 hour. A
mild exotherm is noted (to 105°C). An additional 20 g of Primene™ 81R is added at
100 - 135°C followed by stirring for 1 hour. The product is isolated by filtration.
Example B.
[0041] A 12L, 4-necked flask equipped with a stirrer, thermowell, two Claisen adapters,
a powder addition funnel, and two vents attached to two 50% aqueous sodium hydroxide
traps and a NaOCl final trap is charged with 2745 g (11.7 moles) C₁₆₋₁₈ α-olefins.
The material is heated to 155°C, whereupon 1296.5 g P₂S₅ (11.7 equivalents) is added
in 40 g increments over a 1.5 hour period. An exotherm to 165°C is controlled by rate
of addition of the P₂S₅. After complete addition, the mixture is stirred for 2.5 hours
at 170°C, whereupon 1742 g diluent oil is added in one portion. Stirring of the mixture
is continued at 170°C for 1 hour, and thereafter allowed to cool overnight. The mixture
is heated to 180°C and steam is slowly blown into the mixture over a 4.5 hour period
at which time the material is analyzed to have a NNA
bpb of about 100, indicating complete reaction. The material is cooled under a nitrogen
purge to 135°C. Primene™ 81R, 2009 g (10.57 equivalents) is added via an addition
funnel over a 1.5 hour period, followed by stirring for 0.5 hours. The mixture is
vacuum stripped at 135°C at 4 kPa (30 mm Hg) to remove traces of water, then filtered
through a filter aid to yield the product.
Example C.
[0042] The steam blown intermediate from Example A, 1455 g, is reacted with an equimolar
amount of oleylamine by adding the oleylamine dropwise at 100°C over a period of about
3-4 hour, followed by heating with stirring at 145°C for 4-5 hours. A few drops of
an antifoam agent are included in the mixture.
Example D.
[0043] The steam blown intermediate from Example A, 293g, is reacted with an equimolar amount
of succinimide dispersant (1500 g, including 43% diluent oil) by adding the steam
blown product in one portion to the succinimide dispersant. The succinimide dispersant
is the reaction product of polyisobutylene substituted succinic anhydride (polyisobutylene
number average molecular weight about 1000) with polyethyleneamines (comprising about
20% diethylenetriamine and 80% amine bottoms), the product containing about 1.5% nitrogen
and a carbonyl:nitrogen ratio of about 1:1.1. The mixture is heated to 100°C for 3
hours and 130°C for 2 hours.
Example E.
[0044] The steam blown intermediate from Example A, 500 g, is reacted with 20.4 g of tetraethylenepentamine
(TEPA), by heating the intermediate to 100°C and adding the TEPA dropwise over 1/2
hour, followed by stirring for 2 hours and heating to 140°C, and filtration through
a filter aid.
Example F.
[0045] The steam-blown intermediate from Example A, 800 g, is reacted with 1179 g of a succinimide
dispersant similar to that of Example D (containing 60% chemical and 40% diluent oil;
having a carbonyl:nitrogen ratio of 1:2 and 2.5% nitrogen in the composition), by
a route comparable to that of Example E.
Example G.
[0046] Example A is substantially repeated except in place of the C₁₆₋₁₈ olefins a polypropylene
containing residual unsaturation (equivalent weight 386) 1500 g is reacted with 431
g P₂S₅. The initial reaction temperature is 150-200°C; reaction time is 1.5 hours
(at 200°C), followed by heating and stirring at 220-250°C over 5 hours. The isolated
intermediate is treated with steam, as in Example A, for 6 hours. The resulting material
is reacted with mixed tertiary alkyl (C₁₁₋₁₄) aliphatic primary amine to form the
salt. The final product contains about 25% diluent oil.
Example H.
[0047] Example A is substantially repeated using polyisobutylene having residual unsaturation,
equivalent weight 1000. The polyisobutylene, 3000 g, is reacted with 333 g P₂S₅. The
resulting mixture has a milky appearence which clarifies upon heating to 260°C. The
isolated intermediate is treated with steam for 9 hours, isolated, and reacted with
the amine of Example G.
Example I.
[0048] A portion of steam-treated intermediate prepared as in Example H, 504 g, is reacted
with 7.2 g tetraethylenepentamine, using essentially the procedure of Example E.
Example J.
[0049] A sample of steam-treated polyisobutylene-P₂S₅ product, 625 g, is placed with 200
g toluene in a 2 L flask equipped with a stirrer, a cold water condenser, caustic
traps, a powder funnel, and a nitrogen inlet. To this mixture is added 14.6 g zinc
oxide, at room temperature. The mixture is heated slowly to 135°C (under a nitrogen
flow) and maintained at temperature for 2.5 hours, collecting water and toluene. After
cooling to room temperature, 10 mL water, 100 mL acetic acid, and 1 mL toluene are
added ad the mixture heated at reflux at 95° for 2 hours. The product is vacuum stripped
(135°C, 20 mm Hg, 1/2 hour), then filtered using filter aid. The filtrate is the product.
Example K.
[0050] Example J is substantially repeated except that in place of the zinc oxide 30 g 50%
aqueous sodium hydroxide is added. The mixture is reacted at 125°C for 1 hour (collecting
water) and thereafter 145°C for 1 hour (collecting toluene). An intermediate is isolated
by vacuum stripping; to this intermediate is added an additional 5 g 50% sodium hydroxide,
followed by treatment at 145°C for 1 hour, vacuum stripping at 145°C for 1/2 hour,
and isolation of the product.
[0051] It is preferred that the amount of component (c) in the composition of the present
invention will be 0.05 to 8 percent by weight; more preferably 0.1 to 3 percent by
weight. The amount of this component will be proportionately increased if the composition
takes the form of a concentrate.
[0052] A fourth component of the composition of the present invention, which is a preferred
component, is (d) a surfactant. Surfactants (sometimes more narrowly referred to as
dispersants) are well-known materials, which can be generally classified as anionic,
cationic, zwitterionic, or non-ionic. Anionic surfactants include substances containing
a long lipophilic tail bonded to a water-soluble (hydrophilic) group, wherein the
hydrophilic group contains an anionic moiety derived from a carboxylic acid, sulfonic
acid, or phenol, by neutralizing with an alkali metal or an amine. The lipophilic
tail is preferably an alkyl group, typically having about 8 to about 21 carbon atoms.
[0053] Typical anionic surfactants include carboxylic acid salts such as fatty acid salts
having the formula R₁COOZ wherein R₁ is a straight chain, saturated or unsaturated,
hydrocarbon radical of about 8 to about 21 carbon atoms and Z is a base-forming radical
such as Li⁺, Na⁺, K⁺, or NH₄⁺ which makes the detergent-like surfactant soluble in
water or increases its affinity to water. Alternatively Z may be a divalent or polyvalent
metal, in which case the appropriate number of acid groups are normally present in
order to provide the neutral salt. Multivalent metal ions can be derived from metals
including Mg, Ca, Sr, Ba, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Pb, and others. Typical
fatty acid salts include sodium stearate, sodium palmitate, ammonium oleate, and triethanolammonium
palmitate. Additional carboxylic acid salts useful as anionic surfactants include
salts, and especially sodium and potassium salts, of coconut oil fatty acids and tall
oil acids as well as other carboxylic acids salt compounds including amine salts such
as triethanolamine salts, acylated polypeptides, and salts of N-lauryl sarcosine such
as N-dodecanoyl-N-methylglycine sodium salt.
[0054] Other anionic surfactants include aryl and alkaryl sulfonates such as linear and
branched alkylbenzene sulfonates, sodium tetrapropylene benzene sulfonate, sodium
dodecylbenzene sulfonate, toluene-, xylene-, and cumene sulfonates, lignin sulfonates,
petroleum sulfonates, paraffin sulfonates, secondary n-alkanesulfonates, α-olefin
sulfonates, alkylnaphthalene sulfonates, N-acyl-N-alkyltaurates, sulfosuccinate esters,
isethionates, alkyl sulfates having the formula R₁OSO₃Z wherein R₁ and Z are defined
above, such as lithium dodecyl sulfate, sodium dodecyl sulfate, potassium dodecyl
sulfate, and sodium tetradecyl sulfate, alkyl sulfonates having the formula R₁SO₃Z
wherein R₁ and Z are as defined above, such as sodium lauryl sulfonate, sulfated and
sulfonated amides and amines, sulfated and sulfonated esters such as lauric monoglyceride
sodium sulfate, sodium sulfoethyl oleate, and sodium lauryl sulfoacetate, sulfuric
acid ester salts such as sulfated linear primary alcohols, sulfated polyoxyethylenated
straight chain alcohols and sulfated triglyceride oils, phosphoric and polyphosphoric
acid esters, perfluorinated carboxylic acids, and polymeric anionic surfactants such
as alginic acids.
[0055] Also included are polymeric anionic surfactants such as salts of polymers of alkyl
acrylates and/or alkyl methacrylates and acrylic and/or methacrylic acid, and salts
of partial esters of maleic anhydride-styrene copolymers.
[0056] Another group of materials which can be classified as anionic surfactants are those
materials known as overbased or superbased materials. These are basic metal salts,
preferably alkali or alkaline earth metal salts, of acidic organic compounds (carboxylic
acids, sulfonic acids, phosphonic acids, phenols, and so on). Overbased materials
are generally single phase homogeneous Newtonian systems characterized by a metal
content in excess of that which would be present for neutralization according to the
stoichiometry of the metal and the particular acidic organic compound reacted with
the metal. The overbased materials are prepared by reacting an acidic material (typically
an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture
comprising an acidic organic compound, a reaction medium comprising at least one inert,
organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic
material, a stoichiometric excess of a metal base, and a promoter such as a phenol
or alcohol.
[0057] The acidic organic material will normally have a sufficient number of carbon atoms
to provide a degree of solubility in oil and to provide a measure of surfactant activity
to the product. The amount of excess metal is commonly expressed in terms of metal
ratio. The term "metal ratio" is the ratio of the total equivalents of the metal to
the equivalents of the acidic organic compound: a neutral metal salt has a metal ratio
of one; a salt having 4.5 times as much metal as present in a normal salt will have
metal excess of 3.5 equivalents, or a ratio of 4.5.
[0058] Overbased materials are commonly used as lubricant additives and are well known to
those skilled in the art. While they are useful for some applications, the scope of
their utility may be different from that of other surfactants. Patents describing
techniques for making basic salts of sulfonic acids, carboxylic acids, and mixtures
of any two or more of these include U.S. Patents 2,501,731; 2,616,905; 2,616,911;
2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284;
and 3,629,109. Overbased materials are not generally preferred for use in the present
invention, however, because one advantage of the present invention is that it provides
a useful fluid even in the absence of overbased materials, i.e., in the absence of
relatively large amounts of metal salts. The present materials likewise provide a
material with good antiwear properties even in the absence of typical zinc compounds
such as zinc dialkyldithiophosphates. Accordingly, to fully exploit the advantages
of the present invention, overbased materials would not be employed as the surfactant,
nor would zinc compounds be added. Thus these materials will, in one embodiment, be
present, if at all, in amounts of less than about 3% by weight, more preferably less
than 1%. In another embodiment the composition of the present invention will be substantially
free from (e.g., less than 3% or 1%) dispersants of the type used in crankcase lubricants
(e.g., polyalkenylsuccinimide types or Mannich dispersant types), olefin copolymer
viscosity index improvers, or halogenated olefins or halogenated waxes.
[0059] Cationic surfactants are similar to anionic surfactants except that the surface-active
portion of the molecule has a positive charge. Examples of cationic surfactants include
salts of long-chain amines such as primary amines derived from animal and vegetable
fatty acids and tall oil and synthetic C₁₂-C₁₈ primary, secondary, or tertiary amines;
diamines and their salts, quaternary ammonium salts including tetraalkylammonium salts
and imidazolinium salts derived from e.g. tallow or hydrogenated tallow, or N-benzyl-N-alkyldimethylammonium
halides; polyoxyethylenated long-chain amines; quaternized polyoxyethylenated long-chain
amines; and amine oxides such as N-alkyldimethylamine oxides (which may be considered
zwitterionic) such as cetyl dimethylamine oxide or stearyl dimethylamine oxide.
[0060] Zwitterionic surfactants include amino acids such as β-N-alkylaminopropionic acids,
N-alkyl-β-iminodipropionic acids, imidazoline carboxylates, N-alkylbetaines, sulfobetaines,
and sultaines.
[0061] Nonionic surfactants, which are preferred for the present invention, are similar
materials in which the polar functionality is not provided by an anionic or cation
group, but by a neutral polar group such as typically an alcohol, amine, ether, ester,
ketone, or amide function. Typical nonionic surfactants include polyoxyethylenated
alkylphenols such as polyoxyethylenated p-nonylphenol, p-octylphenol, or p-dodecylphenol,
polyoxyethylenated straight-chain alcohols derived from coconut oil, tallow, or synthetic
materials including oleyl derivatives; polyoxyethylenated polyoxypropylene glycols
(block copolymers of ethylene oxide and propylene oxide), typically having molecular
weights of 1000 to 30,000; polyethylene glycol; polyoxyethylenated mercaptans; long-chain
carboxylic acid esters including glyceryl and polyglyceryl esters of natural fatty
acids, propylene glycol esters, sorbitol esters, polyoxyethylenated sorbitol esters,
polyoxyethylene glycol esters, and polyoxyethylenated fatty acids; alkanolamine "condensates"
e.g. the condensates made by reaction of methyl or triglyceride esters of fatty acids
with equimolar or twice equimolar amounts of alkanolamine; tertiary acetylenic glycols;
polyoxyethylenated silicones, prepared by reaction of a reactive silicone intermediate
with a capped alkylene or polyalkylene oxide such as propylene oxide or mixed ethylene
oxide/propylene oxide copolymer; N-alkylpyrrolidinones, and alkylpolyglycosides (long
chain acetals of polysaccharides). Many of these and other ionic and non-ionic surfactants
are discussed in Rosen, "Surfactants and Interfacial Phenomena," John Wiley & Sons,
pp. 7-31, 1989.
[0062] Further nonionic surfactants more specifically include ethoxylated coco amide, oleic
acid, t-dodecyl mercaptan, modified polyester dispersants, ester, amide, or mixed
ester-amide dispersants based on polyisobutenyl succinic anhydride, dispersants based
on polyisobutyl phenol, ABA type block copolymer nonionic dispersants, acrylic graft
copolymers, octylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol, ethoxylated
amines, borated olefin epoxides, alkyl aryl ethers, alkyl aryl polyethers, amine polyglycol
condensates, modified polyethoxy adducts, modified terminated alkyl aryl ethers, modified
polyethoxylated straight chain alcohols, terminated ethoxylates of linear primary
alcohols, high molecular weight tertiary amines such as 1-hydroxyethyl-2-alkyl imidazolines,
oxazolines, perfluoralkyl sulfonates, sorbitan fatty acid esters, polyethylene glycol
esters, aliphatic and aromatic phosphate esters. Also included are the reaction products
of hydrocarbyl-substituted succinic acylating agents and amines. These reaction products
and methods for preparing them are described in U.S. Patents 4,234,435; 4,952,328;
4,938,881; and 4,957,649.
[0063] Other nonionic surfactants include functionalized polysiloxanes. These materials
contain functional groups such as amino, amido, imino, sulfonyl, sulfoxyl, cyano,
hydroxy, hydrocarbyloxy, mercapto, carbonyl (including aldehydes and ketones), carboxy,
epoxy, acetoxy, phosphate, phosphonyl, and haloalkyl groups. These polysiloxanes can
be linear or branched and generally have molecular weight above 800, i.e. up to 10,000
or 20,000. The functionality can be randomly distributed on the polymer chain or present
in blocks. The functionality can be present as alkyl or alkaryl groups as well as
groups such as -(C₂H₄O)
a-(C₃H₆O)
b-R where a and b are independently numbers from 0 to about 100 provided that at least
one of a or b is at least 1, and R is H, acetoxy, or a hydrocarbyl group. Other suitable
substituent groups can include C₃H₆X, where X is OH, SH, or NH₂. Examples of such
materials include SILWET™ surfactants from Union Carbide and Tegopren™ silicone surfactants
from Goldschmidt Chemical Corp., Hopewell, VA.
[0064] Preferred nonionic surfactants include esters of polyols, in particular, partial
esters of glycerol where the acid moiety of the ester is a fatty acid of 8 to 24 carbon
atoms, preferably about 18 carbon atoms. Particularly preferred are surfactants which
comprise in large part glycerol monooleate.
[0065] It is preferred that the amount of the surfactant (d) in the composition of the present
invention will be 0.05 to 8 percent by weight; more preferably 0.1 to 3% by weight.
The amount will be proportionately increased if the present invention is used as a
concentrate.
[0066] Whether the present invention is used as a concentrate or as a fully formulated material,
the relative amounts of (b), (c), and (d) employed will preferably be within the relative
weight ratios of b:c:d = 1-10:0.2-3:0.3-3, and more preferably within the relative
weight ratios of b:c:d: = 1-3:0.2-1:0.3-1.
[0067] Other additives can also be used in compositions of the present invention in conventional
amounts, including the additives listed below. Antioxidants, corrosion inhibitors,
extreme pressure and anti-wear agents include but are not limited to chlorinated aliphatic
hydrocarbons, boron-containing compounds including borate esters, and molybdenum compounds.
Other additives are viscosity improvers, which include but are not limited to polyisobutenes,
polymethacrylate esters, polyacrylate esters, diene polymers, polyalkylstyrenes, alkenylaryl
conjugated diene copolymers polyolefins and multifunctional viscosity improvers. Also
included are pour point depressants, which are often included in the lubricating oils
described herein. See for example, page 8 of "Lubricant Additives" by C. V. Smalheer
and R. Kennedy Smith (Lesius-Hiles Company Publishers, Cleveland, Ohio, 1967). Anti-foam
agents can be used to reduce or prevent the formation of stable foam, and include
silicones or organic polymers. A particularly suitable antifoam agent is poly(dimethylsiloxane),
which is preferably present in an amount of 0.0004 to 0.4 weight percent, preferably
0.001 to 0.1 weight percent, in a fully formulated composition. Examples of these
and additional anti-foam compositions are described in "Foam Control Agents," by Henry
T. Kerner (Noyes Data Corporation, 1976), pages 125-162. Sulfurized organic materials
can also be present. Materials which may be sulfurized to form the sulfurized organic
compositions include oils, fatty acids or esters, olefins or polyolefins made thereof,
terpenes, or Diels-Alder adducts. Sulfurized olefins can be produced by reacting sulfur
monochloride with a low carbon atom olefin, treating the resulting product with an
alkali metal sulfide in the presence of free sulfur, and reacting that product with
an inorganic base, as described by reference to U.S. Patent 3,471,404. Alternatively,
organic polysulfides can be prepared by reacting, optionally under superatmospheric
pressure, an olefin with a mixture of sulfur and hydrogen sulfide in the presence
or absence of a catalyst, such as an alkyl amine catalyst, followed by removal of
low boiling materials. For suitable olefins, sulfurized olefins, and methods of preparing
the same, reference is made to U.S. Patents 4,119,549, 4,199,550, 4,191,659, and 4,344,854.
[0068] Another additive which can be present is a dimercaptothiadiazole or a derivative
thereof, which can be used as a copper corrosion inhibitor. These materials are prepared
by reaction of CS₂ with hydrazine. Dimercaptothiadiazoles consist of a five-membered
ring having the structure

The carbon atoms are substituted by sulfur-containing groups, in particular -S-H (as
shown), -S-R, or -S-S-R groups, where R is hydrocarbyl group. Substitution by -S-R
groups can be obtained by condensation of (VIII) with an alcohol or by addition of
above material to an activated olefin such as an alkyl acrylate; substitution by -S-S-R
can be obtained by reaction with an alkyl mercaptan.
[0069] These and other additives are described in greater detail in U.S. Patent 4,582,618
(column 14, line 52 through column 17, line 16, inclusive).
EXAMPLES
[0070] Examples 1-27. Compositions are prepared by mixing the following components in the
amounts indicated in Table I:
Oil: A: A mixture of mineral oils from Sun Oil Company, comprising 70% Sun™ 70 neutral
oil and 30% Sun™ 60 neutral oil. (The oil composition used also contains maleic anhydride-styrene
viscosity improver and pour point depressant in an amount of 3.29 percent by weight.)
This and the other oil compositions listed may contain small amount of other oils
normally introduced along with the other ingredients as diluents.
B: A mixture of sunflower oil and 2-ethylhexyl adipate ester (BASF Glisso-fluid A-9™)
C: Mineral oil, Sun™ 70 neutral, without additives.
Dithiocarbamate esters:
[0071]
G: The material of formula (I) prepared from methyl acrylate
H: Methylene-bis(di-n-butyldithiocarbamate)
J: A material akin to formula (I) prepared from the reaction of diethylamine, carbon
disulfide, and methyl acrylate
K: A material akin to (J), prepared using butyl acrylate
L: A material akin to (J), prepared from dipropylamine as the amine
M: A material akin to (J), prepared from di-2-ethylhexylamine as the amine.
N. A material akin to (J), prepared from hexylamine as the amine and butyl acrylate
as the activated olefin reactant.
S-containing phosphonate:
[0072]
O: The material of Example A
P: Material akin to Example A but prepared as the acid, i.e., without reaction with
the amine.
Q: Material akin to Example A where the amine is oleyl amine
R: Material akin to Example A where the amine is 2-ethylhexyl amine
S: Material prepared from reacting Primene 81R™ with the reaction product of α-pinene
and phosphorus pentasulfide.
Surfactant:
[0073]
V: Glycerol monooleate
W: Borated C₁₆ α-olefin epoxide
X: Alkyl hydrogen phosphite from oleyl alcohol
Y: 1-hydroxyethyl-2-heptadecenyl imidazoline
Z: ethoxylated fatty (tallow) amine (Ethomeen T12™)
AA: Calcium carbonate-overbased fatty acid carboxylate
AB: Reaction product of C₁₈₋₂₄ alkenyl succinic anhydride with diethanolamine
AC: Calcium carbonate-overbased alkyl salicylate
AD: Oleylamide
[0074]
Table I
Ex. |
Oil: |
DTC ester: |
Phosphonate |
Surfactant |
|
typea |
% |
type |
% |
type |
% |
type |
% |
1 |
A |
95.2 |
G |
3.0 |
O |
0.83 |
V |
1.0 |
2 |
A |
95.3 |
G |
2.0 |
O |
1.24 |
V |
1.5 |
3 |
A |
96.1 |
G |
2.0 |
O |
0.41 |
V |
1.5 |
4 |
A |
97.1 |
G |
2.0 |
O |
0.41 |
V |
0.5 |
5 |
A |
96.3 |
G |
2.0 |
O |
1.24 |
V |
0.5 |
6 |
A |
95.1 |
G |
4.0 |
O |
0.41 |
V |
0.5 |
7 |
A |
94.3 |
G |
4.0 |
O |
1.24 |
V |
0.5 |
8 |
A |
94.1 |
G |
4.0 |
O |
0.41 |
V |
1.5 |
9 |
A |
93.3 |
G |
4.0 |
O |
1.24 |
V |
1.5 |
10 |
A |
96.0 |
H |
2.2 |
O |
0.83 |
V |
1.0 |
11 |
A |
93.8 |
G |
3.0 |
P |
2.17 |
V |
1.0 |
12 |
Ab |
94.9 |
G |
3.0 |
Q |
1.08 |
V |
1.0 |
13 |
A |
95.0 |
G |
3.0 |
R |
1.05 |
V |
1.0 |
14 |
A |
95.7 |
J |
2.43 |
O |
0.83 |
V |
1.0 |
15 |
A |
97.1 |
G |
2.0 |
O |
0.41 |
W |
0.5 |
16 |
A |
97.1 |
G |
2.0 |
O |
0.41 |
X |
0.5 |
17 |
A |
97.1 |
G |
2.0 |
O |
0.41 |
Y |
0.5 |
18 |
A |
97.1 |
G |
2.0 |
O |
0.41 |
Z |
0.5 |
19 |
A |
97.1 |
G |
2.0 |
O |
0.41 |
AA |
0.21 |
20 |
A |
96.6 |
G |
1.5 |
O |
0.83 |
AB |
1.06 |
21 |
A |
96.5 |
G |
1.5 |
O |
0.83 |
AC |
1.2 |
22 |
A |
96.7 |
H |
1.5 |
O |
0.83 |
V + |
0.95 |
|
|
|
|
|
|
|
AD |
0.05 |
23 |
A |
96.9 |
G |
1.5 |
S |
0.56 |
V |
1.0 |
24 |
B |
88.9 |
K |
0.1 |
O |
8.0 |
V |
3.0 |
25 |
B |
88.5 |
L |
0.5 |
O |
3.0 |
V |
8.0 |
26 |
C |
94.9 |
M |
5.0 |
O |
0.1 |
-- |
0 |
27 |
C |
89.8 |
N |
10 |
P |
0.05 |
V |
0.1 |
a: The oil, except in Examples 12 and 24-27, also contains 0.02% dimercaptothiadiazole
condensate and 0.2% silicone foam inhibitor. |
b: Contains 0.05% dimercaptothiadiazole condensate. |
[0075] Each of the documents referred to above is incorporated herein by reference. Except
in the Examples, or where otherwise explicitly indicated, all numerical quantities
in this description specifying amounts of materials, reaction conditions, molecular
weights, number of carbon atoms, and the like, are to be understood as modified by
the word "about." Unless otherwise indicated, each chemical or composition referred
to herein should be interpreted as being a commercial grade material which may contain
the isomers, by-products, derivatives, and other such materials which are normally
understood to be present in the commercial grade. However, the amount of each chemical
component is presented exclusive of any solvent or diluent oil which may be customarily
present in the commercial material, unless otherwise indicated. As used herein, the
expression "consisting essentially of" permits the inclusion of substances which do
not materially affect the basic and novel characteristics of the composition under
consideration.