U.S. patent application number 09/993063 was filed with the patent office on 2003-05-15 for lubricating compositions and concentrates containing an antiwear amount of a thiadiazole.
This patent application is currently assigned to The Lubrizol Corporation. Invention is credited to Galic Raguz, Mary, O'Connor, Brian M..
Application Number | 20030092585 09/993063 |
Document ID | / |
Family ID | 25539052 |
Filed Date | 2003-05-15 |
United States Patent
Application |
20030092585 |
Kind Code |
A1 |
O'Connor, Brian M. ; et
al. |
May 15, 2003 |
Lubricating compositions and concentrates containing an antiwear
amount of a thiadiazole
Abstract
This invention relates to lubricating compositions comprising a
major amount of an oil of lubricating viscosity and at least about
0.4% by weight of at least one amine free thiadiazole, wherein the
lubricating composition is free of organic polysulfides and
contains less than about 2% by weight of at least one dispersant.
The invention also relates to concentrates and methods of using the
lubricating compositions to control micro pitting. The lubricants
provide improved performance for both macro and micro pitting,
especially micro pitting.
Inventors: |
O'Connor, Brian M.; (South
Euclid, OH) ; Galic Raguz, Mary; (Mentor,
OH) |
Correspondence
Address: |
THE LUBRIZOL CORPORATION
Patent Dept. - Patent Administrator-022B
29400 Lakeland Boulevard
Wickliffe
OH
44092-2298
US
|
Assignee: |
The Lubrizol Corporation
Wickliffe
OH
|
Family ID: |
25539052 |
Appl. No.: |
09/993063 |
Filed: |
November 13, 2001 |
Current U.S.
Class: |
508/273 ;
508/283; 508/454 |
Current CPC
Class: |
C10M 2209/107 20130101;
C10N 2030/06 20130101; C10N 2040/044 20200501; C10M 2215/223
20130101; C10M 141/10 20130101; C10M 2219/046 20130101; C10M 135/36
20130101; C10M 2215/224 20130101; C10M 161/00 20130101; C10N
2010/04 20130101; C10M 2209/084 20130101; C10M 2215/26 20130101;
C10N 2030/43 20200501; C10M 2219/106 20130101; C10M 2229/02
20130101; C10N 2010/02 20130101; C10M 2223/047 20130101; C10M
2217/043 20130101; C10M 2223/043 20130101; C10M 167/00 20130101;
C10M 2215/28 20130101; C10N 2060/06 20130101; C10M 141/08 20130101;
C10N 2040/04 20130101; C10M 2223/045 20130101; C10N 2020/02
20130101; C10M 163/00 20130101; C10M 2215/064 20130101; C10M
2215/08 20130101; C10N 2020/013 20200501; C10N 2020/067
20200501 |
Class at
Publication: |
508/273 ;
508/283; 508/454 |
International
Class: |
C10M 135/36; C10M
133/46 |
Claims
1. A lubricating composition comprising a major amount of an oil of
lubricating viscosity and at least about 0.4% by weight of at least
one amine free thiadiazole, wherein the lubricating composition is
free of organic polysulfides and contains less than about 2% by
weight of at least one dispersant.
2. The composition of claim 1 wherein the mercaptothiadiazole is at
least one hydrocarbyl or bis-hydrocarbyl substituted thio or di
thiothiadiazole.
3. The composition of claim 1 further comprising less that about
1.5% by weight of at least one dispersant.
4. The composition of claim 1 further comprising at least one
anti-foam agent.
5. The composition of claim 1 further comprising at least one
imidazoline or reaction product of at least one fatty carboxylic
acid and at least one polyamine.
6. The composition of claim 1 further comprising at least one
phosphorus antiwear agent.
7. A lubricating composition comprising a major amount of an oil of
lubricating viscosity and at least about 0.4% by weight of an amine
free thiadiazole, at least one phosphorus antiwear agent, less than
about 2% by weight of at least one dispersant, wherein the
lubricating composition is free of polysulfide compounds.
8. The composition of claim 7 further comprising at least one
imidazoline or reaction product of at least one fatty carboxylic
acid and at least one polyamine.
9. The composition of claim 7 further comprising at least one
antifoam agent.
10. An industrial gear oil composition comprising a major amount of
an oil of lubricating viscosity and at least about 0.4% of at least
one amine-free thiadiazole and at least one phosphorus antiwear
agent, wherein the lubricant is free of polysulfide compounds.
11. The composition of claim 10 wherein the composition further
comprises less that about 2% by weight of at least one
dispersant.
12. The composition of claim 10 wherein the composition further
comprises at least one imidazoline or reaction product of at least
one fatty carboxylic acid and at least one polyamine.
13. An industrial gear oil composition comprising a major amount of
an oil of lubricating viscosity and at least about 0.4% by weight
of at least one amine-free thiadiazole, less than about 2% by
weight of at least one dispersant, and at least one phosphorus
antiwear agent, wherein the industrial gear oil composition is free
of polysulfide compounds.
14. The composition of claim 13 further comprising at least one
imidazoline or reaction product of at least one fatty carboxylic
acid and at least one polyamine.
15. An manual transmission composition comprising a major amount of
an oil of lubricating viscosity and at least about 0.4% of at least
one amine-free thiadiazole, wherein the lubricant is free of
organic polysulfides and contains less than about 2% by weight of
at least one dispersant.
16. The composition of claim 15 further comprising at least one
phosphorus antiwear agent.
17. The composition of claim 15 further comprising at least one
imidazoline or reaction product of at least one fatty carboxylic
acid and at least one polyamine.
18. The composition of claim 15 further comprising at least one
overbased metal salt of an acidic organic compound.
19. The composition of claim 15 further comprising at least one
antioxidant.
20. The composition of claim 15 further comprising at least one
antifoam agent.
21. A manual transmission composition comprising a major amount of
an oil of lubricating viscosity and at least 0.4% by weight of at
least one amine free thiadiazole, at least one phosphorus antiwear
agent, less than about 2% by weight of at least one dispersant,
wherein the manual transmission composition is free of organic
polysulfides.
22. The composition of claim 21 further comprising at least one
antifoam agent or at least one imidazoline or reaction product of
at least one fatty carboxylic acid and at least one polyamine.
Description
FIELD OF THE INVENTION
[0001] This invention relates to lubricating compositions and
concentrates that contains an amine free thiadiazole. The
thiadiazole is present to provide improved surface fatigue
properties. The lubricants are typically manual transmission fluids
and industrial gear oils.
BACKGROUND OF THE INVENTION
[0002] Surface fatigue, commonly referred to as pitting or
spalling, is a wear mode which results in the loss of material as a
result of repeated stress cycles acting on the surface. For years,
science has sought to control the large scale wear of equipment
with the use of lubricant additives. Additives with active sulfur
and phosphorus have been used to control wear. The wear was
typically revealed on the surfaces of equipment. Tests were devised
to determine the extent of wear protection provided by additives.
These test include the 4 ball wear test, the FZG gear test,
etc.
[0003] There are two major sub-groups under surface fatigue known
as micro- and macropitting. As their names imply the type of
pitting is related to the size of the pit. Macropits are usually
able to be seen with the naked eye as irregular shaped cavities in
the surface of the tooth. Damage beginning on the order of 0.5 to
1.0 mm in diameter is considered to be a macropit.
[0004] Macropitting is a fatigue phenomenon that can initiate
either at or near the surface of a gear tooth. The crack usually
propagates for a short distance at a shallow angle to the surface
before turning or branching back to the surface. Eventually, the
material will dislodge from the surface forming a pit, an irregular
shaped cavity in the surface of the material. With gears, the
origin of the crack is more likely surface initiated because the
lubricant film thickness is low resulting in a high amount of
asperity or metal-to-metal contact. For high-speed gears with
smooth surface finishes, the film thickness is larger and
sub-surface initiated crack formation may predominate. In these
cases an inclusion or small void in the material is a source for
stress concentration.
[0005] Micropitting is a fatigue phenomenon that occurs in Hertzian
contacts that operate in elastohydrodynamic or boundary lubrication
regimes and have combined rolling and sliding. Besides operating
conditions, such as load, speed, sliding, temperature and specific
film thickness, the chemical composition of a lubricant strongly
influences micropitting. Damage can start during the first 10.sup.5
to 10.sup.6 stress cycles with generation of numerous surface
cracks. The cracks grow at a shallow angle to the surface forming
micropits that are about 10-20 .mu.m deep by about 25-100 .mu.m
long and 10-20 .mu.m wide. The micropits appear as a dull, matte
surface to the observer.
[0006] Micropitting is the preferred name for this mode of damage,
but it has also been referred to as grey staining, grey flecking,
frosting and peeling. Although micropitting generally occurs with
heavily loaded, carburized gears, it also occurs with nitrided,
induction hardened and through-hardened gears. Micropitting may
arrest after running-in. If micropitting continues to progress,
however, it may result in reduced gear tooth accuracy, increased
dynamic loads and noise. Eventually, it can progress to
macropitting and gear failure.
[0007] It is desirable to have a lubricant which provide improved
wear protection, especially improved protection from
micropitting.
SUMMARY OF THE INVENTION
[0008] This invention relates to lubricating compositions
comprising a major amount of an oil of lubricating viscosity and at
least about 0.4% of at least one amine free thiadiazole, wherein
the lubricant is free of organic polysulfides and contains less
than about 2% by weight of at least one dispersant. The invention
also relates to concentrates and methods of using the lubricating
compositions to control surface fatigue. The lubricants provide
improved performance for surface fatigue.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0009] The term "hydrocarbyl" includes hydrocarbon as well as
substantially hydrocarbon groups. Substantially hydrocarbon
describes groups which contain heteroatom substituents which do not
alter the predominantly hydrocarbon nature of the group. Examples
of hydrocarbyl groups include the following:
[0010] (1) hydrocarbon substituents, i.e., aliphatic (e.g., alkyl
or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, aromatic-, aliphatic- and alicyclic-substituted
aromatic substituents and the like as well as cyclic substituents
wherein the ring is completed through another portion of the
molecule (that is, for example, any two indicated substituents may
together form an alicyclic radical);
[0011] (2) substituted hydrocarbon substituents, i.e., those
substituents containing non-hydrocarbon groups which, in the
context of this invention, do not alter the predominantly
hydrocarbon nature of the substituent; those skilled in the art
will be aware of such groups (e.g., halo (especially chloro and
fluoro), hydroxy, mercapto, nitro, nitroso, sulfoxy, etc.);
[0012] (3) heteroatom substituents, i.e., substituents which will,
while having a predominantly hydrocarbon character within the
context of this invention, contain an atom other than carbon
present in a ring or chain otherwise composed of carbon atoms
(e.g., alkoxy or alkylthio). Suitable heteroatoms will be apparent
to those of ordinary skill in the art and include, for example,
sulfur, oxygen, nitrogen and such substituents as, e.g., pyridyl,
furyl, thienyl, imidazolyl, etc.
[0013] In general, no more than about 2, or no more than one,
hetero substituent will be present for every ten carbon atoms in
the hydrocarbyl group. Typically, there will be no such hetero atom
substituents in the hydrocarbyl group. Therefore, the hydrocarbyl
group is purely hydrocarbon.
[0014] The term "organinc polysulifde" refers to organic compounds
which contain sulfide linkages of two or more sulfur atoms. The
sulfide linkages usually extend between two or more unsaturated
compounds, such as olefins. These organic polysulfides have been
referred to as polysulfurized olefins which are illustrated by the
reaction of olefins with sulfur, sulfur compounds or a combination
thereof to form a reaction product that contains an average of more
than one sulfur atom per olefins. These products are generally
referred to as polysulfurized olefins or polysulfides. An example
of these products is the reaction product of isobutylene, sulfur
and hydrogen sulfide under pressure.
[0015] In the specification and claims, the term "lubricating
composition" refers to the combination of an oil of lubricating
viscosity and additives. The percentages by weight are based on the
total amount of the additive and the oil of lubricating viscosity.
If not specifically stated, the oil of lubricating viscosity makes
up the balance of the lubricating composition.
[0016] As described herein, the lubricating compositions contain
less than about 2% by weight of at least one dispersant. When
dispersant levels exceed about 2% by weight, the lubricating
compositions are more susceptible to foaming. The foaming destroys
the lubricants ability to form a protective layer over the surface
of the equipment, such as the gears and pinions of a manual
transmission or industrial gear assembly. In one embodiment, the
dispersant is present in an amount less than about 1.5%, or less
than about 1% by weight. In another embodiment, the lubricating
compositions is free of one or all of the dispersants described
below. In another embodiment the lubricating composition is free of
dispersants.
[0017] As described above, the lubricating compositions contain at
least about 0.4% of at least one amine free thiadiazole. These
thiadiazoles are typically oil soluble or oil dispersible. The term
"amine free" refers to thiadiazole derivatives which are not
prepared using amines. Amine-free thiadiazole are those that are
not amine salts or amine coupled thiadiazoles when added to the
lubricating oil. The present amine free thiadiazoles derivatives
are not prepared using an amine. In one embodiment, the lubricating
compositions contain at least about 0.6%, or at least about 0.8% or
at least about 0.9% by weight of at least one thiadiazole compound.
In one embodiment, the lubricating composition contains up to about
8%, or up to about 5%, or up to about 3% by weight of at least one
thiadiazole compound. In another embodiment, thiadiazole provides
the only sulfur from additives to the lubricating composition. It
should be noted that the oils of lubricating viscosity may contain
sulfur inherently.
[0018] The present invention involves derivatives of thiadiazoles.
Thiadiazoles, which are cyclic compounds in which the ring contains
2 nitrogen, 2 carbon, and 1 sulfur atoms. They are discussed by W.
R. Sherman, "The Thiadiazoles," in Heterocyclic Compounds, Volume
7, R. C. Elderfield Editor, John Wiley & Sons, Inc. New York,
Pages 541-626, 1961. The synthesis and properties of many
thiadiazoles are described in this reference. Examples of
thiadiazoles include 2,5-substituted-1,3,4-thiadia- zole;
3,5-substituted-1,2,4-thiadiazole; 3,4-substituted-1,
2,5-thiadiazole; and 4,5-substituted-1,2,3-thiadiazole. The
compound which is most readily available and particularly useful
for purposes of the present invention, is 2,5-substituted- 1,3,4-
thiadiazole, of which an example is
2-5-dimercapto-1,3,4-thiadiazole, sometimes referred to herein as
"DMTD." It should be understood, however, that the term DMTD, as
used herein, can encompass any of the dimercaptothiadiazoles or
mixtures of two or more dimercaptothiadiazoles. A convenient
preparation of 2,5-dimercapto-1,3,4-thiadiazole is the reaction of
1 mole of hydrazine or a salt of hydrazine with 2 moles of carbon
disulfide in an alkaline medium. The product can be recovered by
acidification of the reaction mixture.
[0019] The thiadiazole derivatives include a) mono or di
substituted hydrocarbylthio or hydrocarbyldithio substituted
thiadiazoles; b) carboxylic esters of DMTD; c) condensation
products of halogenated aliphatic monocarboxylic acids with DMTD;
d) reaction products of unsaturated cyclic hydrocarbons and
unsaturated ketones with DMTD; e) reaction products of an aldehyde,
and an alcohol or aromatic hydroxy compound, and DMTD; f) reaction
products of an aldehyde, a mercaptan and DMTD; and g) mixtures of
two or more thereof. Compositions a-g are described in U.S. Pat.
No. 4,612,129 and patent references cited therein. This patent is
hereby incorporated by reference.
[0020] In one embodiment, the thiadiazole derivatives include mono
or disubstituted thiadiazoles having a hydrocarbylthio group, a
hydrocarbyldithio group, or mixture of these groups. Examples of
these thiadiazoles include hydrocarbylthio, mercaptothiadiazole;
bis-(hydrocarbylthio) thiadiazole; hydrocarbyldithio,
mercaptothiadiazole; and bis-(hyd rocarbyidithio) thiadiazole. It
is understood that the hydrocarbyl groups on the thiadiazole may be
the same or different. The hydrocarbyl groups may be aliphatic or
aromatic, including alkyl, cyclic, alicyclic, aralkyl, aryl and
alkaryl. In one embodiment, the hydrocarbyl groups independently
contain from 1 to about 30, or from about 2 to about 24, or from
about 4 to about 12 carbon atoms. Here and elsewhere in the
specification and claims, the range or ratio limits may be
combined. Examples of specific hydrocarbyl groups may be an alkyl
group such as methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl,
nonyl, decyl or dodecyl groups undecyl, dodecyl, cetyl goups, and
isomers thereof.
[0021] The 1,3,4-thiadiazole compounds, or mixtures thereof,
contemplated for use in the present invention can be readily
obtained from commercial sources, such as the Amoco Petroleum
Additives Company, or can be synthesized from hydrazine and carbon
disulfide in a well-known manner. Particularly useful thiadiazoles
include compositions commercially available from the Amoco
Petroleum Additives Company under the trade names "Amoco-153" and
"Amoco-158". A 2,5-bis-(hydrocarbyidithio)-1,3,4-th- iadiazole and
its monosubstituted equivalent 2-hydrocarbylthio-5-mercapto-
1,3,4-thiadiazole are commercially available as a mixture of the
two compounds in a ratio of about 85 percent bis-hydrocarbyl to 15
percent monohydrocarbyl from the Ethyl Corporation as Hitec 4313.
U.S. Pat. Nos. 2,719,125; 2,719,126; 2,765,289; 2,749,311;
2,760,933; 2,850,453; 2,910,439; 3,087,937; 3,663,561; 3,862,798;
and 3,840,549 may be referred to for detailed procedures on the
preparation of the 1,3,4-thiadiazole compounds contemplated for use
in lubricating compositions of the present invention. These patents
are incorporated by reference herein.
[0022] A process for preparing such derivatives is described in
U.S. Pat. No. 2,191,125 as comprising the reaction of DMTD with a
suitable sulfenyl chloride or by reacting the dimercapto
diathiazole with chlorine and reacting the resulting disulfenyl
chloride with a primary or tertiary mercaptan. Suitable sulfenyl
chlorides useful in the first procedure can be obtained by
chlorinating a mercaptan (RSH or R.sup.1 SH) with chlorine in
carbon tetrachloride. In a second procedure, DMTD is chlorinated to
form the desired bissulfenyl chloride which is then reacted with at
least one mercaptan (RSH and/or R.sup.1 SH). The disclosures of
U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,937 are hereby
incorporated by reference for their description of derivatives of
DMTD useful in the compositions of the invention. U.S. Pat. No.
3,087,932 describes a one-step process for preparing
2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazole. The procedure
involves the reaction of either DMTD or its alkali metal or
ammonium salt and a mercaptan in the presence of hydrogen peroxide
and a solvent.
[0023] Oil-soluble or oil-dispersible reaction products of DMTD can
be prepared also by the reaction of the DMTD with a mercaptan and
formic acid. Compositions prepared in this manner are described in
U.S. Pat. No. 2,749,311. Any mercaptan can be employed in the
reaction, such as aliphatic and aromatic mono- or poly-mercaptan
containing from 1 to about 30, or from about 2 to about 18, carbon
atoms. The disclosures of U.S. Pat. Nos. 3,087,932 and 2,749,311
are hereby incorporated by reference for their description of DMTD
derivatives which can be utilized as components of the composition
of this invention. It will be understood by those skilled in the
art that the reactions outlined above produce some amounts of the
monohydrocarbyldithio-thiadiazole as well as the bis-hydrocarbyl
compounds. The ratio of the two can be adjusted by varying the
amounts of the reactants.
[0024] The preparation of
2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole- s is described in
U.S. Pat. No. 3,663,561, which is hereby incorporated by reference.
The compositions are prepared by the oxidative coupling of
equimolecular portions of a hydrocarbyl mercaptan and DMTD or its
alkali metal mercaptide. The mono-mercaptans used in the
preparation of the compounds are represented by the formula R.sup.1
SH, wherein R.sup.1 is a hydrocarbyl group containing from 1 to
about 28 carbon atoms. A peroxy compound, hypohalide or air, or
mixtures thereof can be utilized to promote the oxidative coupling.
Specific examples of the mono-mercaptan include methyl mercaptan,
isopropyl mercaptan, hexyl mercaptan, decyl mercaptan, and long
chain alkyl mercaptans, for example, mercaptans derived from the
polyalkenes described herein, such as propene polymers and
isobutylene polymers especially polyisobutylenes, having 3 to about
70 propene or isobutylene units per molecule. The disclosure of
U.S. Pat. No. 3,663,561 is hereby incorporated by reference for its
identification of DMTD derivatives, which are useful as components
in the compositions of this invention.
[0025] Carboxylic esters of DMTD (b) are described in U.S. Pat. No.
2,760,933. These esters are prepared by reacting DMTD with an
organic acid halide (chloride) and a molar ratio of 1:2 at a
temperature of from about 25 to about 130E C. Suitable solvents,
such as benzene or dioxane, can be utilized to facilitate the
reaction. The reaction product is washed with dilute aqueous alkali
to remove hydrogen chloride and any unreacted carboxylic acid. The
disclosure of U.S. Pat. No. 2,760,933 is hereby incorporated by
reference for its description of various DMTD derivatives which can
be utilized in the compositions of the present invention.
[0026] Condensation products of alpha-halogenated aliphatic
monocarboxylic acids with DMTD (c) are described in U.S. Pat. No.
2,836,564. Examples of alpha-halogenated aliphatic fatty acids
which can be used include alpha-bromo or alpha-chloro carboxylic
acids containing form about 6 to about 30, or from about 8 to about
24 carbon atoms. Specific examples include alpha-bromo-lauric acid,
alpha-chloro-lauric acid, alpha-chloro-stearic acid, etc. The
disclosure of U.S. Pat. No. 2,836,564 is hereby incorporated by
reference for its disclosure of derivatives of DMTD which can be
utilized in the compositions of the present invention.
[0027] Oil-soluble reaction products of unsaturated cyclic
hydrocarbons and unsaturated ketones (d) are described in U.S. Pat
Nos. 2,764,547 and 2,799,652, respectively, and a disclosure of
these references also are hereby incorporated by reference for
their description of materials. Examples of unsaturated cyclic
hydrocarbons described in the '547 patent include styrene,
alpha-methyl styrene, pinene, dipentene, cyclopentadiene, etc. The
unsaturated ketones, described in U.S. Pat. No. 2,799,652, include
aliphatic, aromatic or heterocyclic unsaturated ketones containing
from about 4 to about 40 carbon atoms and from 1 to 6 double bonds.
Examples include mesityl oxide, phorone, isophorone, benzal
acetophenone, furfural acetone, difurfuryl acetone, etc.
[0028] U.S. Pat. No. 2,850,453 describes products which are
obtained by reacting DMTD, an aldehyde and an alcohol or an
aromatic hydroxy compound (e) in a molar ratio of from 1:2:1 to
1:6:5. The aldehyde employed can be an aliphatic aldehyde
containing from 1 to about 20 carbon atoms or an aromatic or
heterocyclic aldehyde containing from about 5 to about 30 carbon
atoms. Examples of suitable aldehydes include formaldehyde,
acetaidehyde, benzaldehyde, etc. The reaction can be conducted in
the presence or absence of suitable solvents by (a) mixing all of
the reactants together and heating, (b) by first reacting an
aldehyde with the alcohol or the aromatic hydroxy compound, and
then reacting the resultant intermediate with the thiadiazole, or
(c) by reacting the aldehyde with thiadiazole first and the
resulting intermediate with the hydroxy compound. The disclosure of
U.S. Pat. No. 2,850,453 is hereby incorporated by reference.
[0029] U.S. Pat. No. 2,703,784 describes products obtained by
reacting DMTD with an aldehyde and a mercaptan (f). The aldehydes
are similar to those disclosed in U.S. Pat. No. 2,850,453. The
disclosure of this patent also is incorporated by reference. The
mercaptans may be one or more of those described herein. In one
embodiment, the mercaptans are aliphatic or aromatic mono- or
poly-mercaptans containing from about 1 to about 30, or from about
2 to about 24 carbon atoms. Examples of suitable mercaptans include
ethyl mercaptan, butyl mercaptan, octyl mercaptan, etc.
[0030] U.S. Pat. No. 3,663,561 describes thiadiazole derivatives
which are prepared by the oxidative coupling of equimolecular
portions of a hydrocarbyl mercaptan and DMTD or its alkali metal
mercaptide. The mono-mercaptans used in the preparation of the
compounds include those described herein and may be represented by
the formula R'SH, wherein R' is a hydrocarbyl group containing from
1 to about 280 carbon atoms. A peroxy compound (such as the
peroxides described herein) hypohalide or air, or mixtures thereof
can be utilized to promote the oxidative coupling. Specific
examples of the mono-mercaptan include methyl mercaptan, isopropyl
mercaptan, hexyl mercaptan, decyl mercaptan, and long chain alkyl
mercaptans, for example, mercaptans derived from propene polymers
and isobutylene polymers especially polyisobutylenes, having 3 to
about 70 propene or isobutylene units per molecule. The disclosure
of U.S. Pat. No. 3,663,561 is hereby incorporated by reference.
[0031] Dispersants
[0032] The lubricating compositions may also contain at least one
dispersant. In one embodiment, the dispersants are selected from
(a) acylated nitrogen dispersants, (b) hydrocarbyl substituted
amines, (c) carboxylic ester dispersants, (d) Mannich dispersants,
and (e) mixtures thereof. The dispersant are generally present in
an amount from about 0.1% to about 2%, or from about 0.2% to about
1.75%, or from about 0.3% to about 1.4% by weight. In one
embodiment, the dispersants are present in an amount of less than
2%, or less than 1.5%, or less than 1% by weight.
[0033] The acylated nitrogen dispersants include reaction products
of one or more carboxylic acylating agents such as the
hydrocarbyl-substituted carboxylic acylating agents and an amine.
In one embodiment, the hydrocarbyl groups are derived from one or
more of polyalkenes. The polyalkene includes homopolymers and
interpolymers of olefins having from 2 to about 40, or from 3 to
about 24, or from 4 to about 12 carbon atoms. The olefins may be
monoolefins, such as ethylene, propylene, 1-butene, isobutene, an
alpha-olefin, or polyolefinic monomers, including diolefinic
monomers, such 1,3-butadiene and isoprene. The alpha-olefins
generally have from about 4 to about 30, or from about 8 to about
18 carbon atoms. These olefins are sometimes referred to as
monoolefins or terminal olefins. The "-olefins and isomerized
"-olefins include 1-octene, 1-nonene, 1-decene, 1-dodecene,
1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,
1-heneicosene, 1-docosene, 1-tetracosene, etc. Commercially
available "-olefin fractions that can be used include the
C.sub.15-18 olefins, C.sub.12-16-olefins, C.sub.14-16-olefins,
C.sub.14-18olefins, C.sub.16-18-olefins, C.sub.16-20-olefins,
C.sub.18-24-olefins, C.sub.22-28 -olefins, etc. The polyalkenes are
prepared by conventional procedures. The polyalkenes are described
in U.S. Pat. Nos. 3,219,666 and 4,234,435, the disclosures of which
is hereby incorporated by reference. Examples of polyalkenes
includes polypropylenes, polybutylenes, polyisoprene and
polybutadienes. In one embodiment, the polyalkene is a homopolymer,
such as a polybutene. One example of a useful polybutene is a
polymer where about 50% of the polymer is derived from isobutylene.
Useful polybutenes include those having an Mw of about 4,000 to
about 8,000, or 6,000 to about 7,000.
[0034] In one embodiment, the polyalkene is derived from one or
more dienes. The dienes include 1,3 pentadiene, isoprene,
methylisoprene, 1,4-hexadiene, 1,5-hepatadiene, 1-6-octadiene,
5-ethylidene-2-norbornene, 5-methylene-2-norbornene, linear
1,3-conjugated dienes (e.g. 1,3-butadiene,
2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene) and cyclic dienes
(e.g. cyclopentadiene, dicyclopentadiene, fulvene,
1,3-cyclohexadiene, 1,3,5-cycloheptatriene, and cyclooctatetraene).
The polyalkene may be a homopolymer of a diene, or a co- or
terpolymer of a diene with either another diene or one or more of
the above monoolefins. The polyalkene may be hydrogenated. A
commercially available polyalkene derived from at least one diene
is LIR-290, a hydrogenated polyisoprene (Mw=25,000), available
commercially from Kuraray Co, Ltd.
[0035] The polyalkene is generally, characterized as containing
from at least about 8 carbon atoms up to about 300, or from about
30 up to about 200, or from about 35 up to about 100 carbon atoms.
In one embodiment, the polyalkene is characterized by an Mn (number
average molecular weight) greater than about 400, or greater than
about 500. Generally, the polyalkene is characterized by an Mn from
about 500 up to about 5000, or from about 700 up to about 2500, or
from about 800 up to about 2000, or from about 900 up to about
1500. In another embodiment, the polyalkene has a Mn up to about
1300, or up to about 1200.
[0036] Number average molecular weight, as well as weight average
molecular weight and the entire molecular weight distribution of
the polymers, are provided by gel permeation chromatography (GPC).
For purpose of this invention a series of fractionated
polyisobutene, is used as the calibration standard in the GPC. The
techniques for determining Mn and Mw values of polymers are well
known and are described in numerous books and articles. For
example, methods for the determination of Mn and molecular weight
distribution of polymers is described in W. W. Yan, J. J. Kirkland
and D. D. Bly, "Modern Size Exclusion Liquid Chromatographs", J.
Wiley & Sons, Inc., 1979.
[0037] In another embodiment, the polyalkenes have a Mn from about
1300 up to about 5000, or from about 1500 up to about 4500, or from
about 1700 up to about 3000. The polyalkenes also generally have a
Mw/Mn from about 1.5 to about 4, or from about 1.8 to about 3.6, or
from about 2.5 to about 3.2. The hydrocarbyl substituted carboxylic
acylating agents are described in U.S. Pat. No. 4,234,435, the
disclosure of which is hereby incorporated by reference.
[0038] In another embodiment, the acylating agents are prepared by
reacting one or more of polyalkene with an excess of maleic
anhydride to provide substituted succinic acylating agents wherein
the number of succinic groups for each equivalent weight of
substituent group, i.e., polyalkenyl group, is at least 1.3. The
maximum number will generally not exceed 4.5. A suitable range is
from about 1.4 to 3.5 and or from about 1.4 to about 2.5 succinic
groups per equivalent weight of substituent groups.
[0039] The above-described carboxylic acylating agents are reacted
with one or more amines to form the acylated nitrogen dispersants.
The amines may be mono or polyamines, or mixture of mono and
polyamines. The amines may be primary amines, secondary amines or
tertiary amines. Useful amines include those amines disclosed in
U.S. Pat. No. 4,234,435 at Col. 21, line 4 to Col. 27, line 50,
these passages being incorporated herein by reference.
[0040] The monoamines generally contain from 1 up to about 24
carbon atoms, or up to about 12, or up to about 6 carbon atoms.
Examples of monoamines include methylamine, ethylamine,
propylamine, butylamine, octylamine, and dodecylamine,
dimethylamine, diethylamine, dipropylamine, dibutylamine, methyl
butylamine, ethyl hexylamine, trimethylamine, tributylamine, methyl
diethylamine, ethyl dibutylamine, etc.
[0041] In one embodiment, the amine may be a fatty (C.sub.4-30)
amine which include n-hexylamine, n-octylamine, n-decylamine,
n-dodecylamine, n-tetradecylamine, n-hexadecylamine,
n-octadecylamine, oleylamine, etc. Also useful fatty amines include
commercially available fatty amines such as "Armeen" amines
(products available from Armak Chemicals, Chicago, Ill.), such as
Armak's Armeen-C, Armeen-O, Armeen-OL, Armeen-T, Armeen-HT, Armeen
S and Armeen SD, wherein the letter designation relates to the
fatty group, such as cocoa, oleyl, tallow, or soya groups.
[0042] Other useful amines include primary ether amines, such as
those represented by the formula, R"(ORN).sub.XNH.sub.2, wherein RN
is a divalent alkylene group having about 2 to about 6 carbon
atoms, x is a number from one to about 150 (or one), and R" is a
hydrocarbyl group of about 5 to about 150 carbon atoms. An example
of an ether amine is available under the name SURFAM.RTM. amines
produced and marketed by Mars Chemical Company, Atlanta, Ga. Useful
etheramines are exemplified by those identified as SURFAM P14B
(decyloxypropylamine), SURFAM P16A (linear C.sub.16), SURFAM P17B
(tridecyloxypropylamine). The carbon chain lengths (i.e., C.sub.14,
etc.) of the SURFAMS described above and used hereinafter are
approximate and include the oxygen ether linkage.
[0043] 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: H.sub.2)N)R')OH, H(R'.sub.1)N)R')OH, and
(R'.sub.1).sub.2)N)R')OH, wherein each R'.sub.1 is independently a
hydrocarbyl group having from one to about eight carbon atoms or
hydroxyhydrocarbyl group having from one to about eight carbon
atoms, or from one to about four, and R' is a divalent hydrocarbyl
group offrom about two to about 18 carbon atoms, or from two to
about four. The group --R'--OH in such formulae represents the
hydroxyhydrocarbyl group. R' can be an acyclic, alicyclic or
aromatic group. Typically, R' is an acyclic straight or branched
alkylene group, such as an ethylene, propylene, 1,2-butylene,
1,2-octadecylene, etc. group. Where two R'1 groups are present in
the same molecule they can be joined by a direct carbon-to-carbon
bond or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to
form a 5-, 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'.sub.1 is independently a
methyl, ethyl, propyl, butyl, pentyl or hexyl group. Examples of
these alkanolamines include mono-, di-, and triethanolamine,
diethylethanolamine, ethylethanolamine, butyldiethanolamine,
etc.
[0044] The hydroxyamines may also be an ether
N-(hydroxyhydrocarbyl)amine. These are hydroxypoly(hydrocarbyloxy)
analogs of the above-described hydroxyamines (these analogs also
include hydroxyl-substituted oxyalkylene analogs). Such
N-(hydroxyhydrocarbyl) amines can be conveniently prepared by
reaction of one or more of the above epoxides with afore described
amines and may be represented by the formulae:
H.sub.2N)(R'O).sub.x)H, H(R'.sub.1))N)(R'O).sub.x)H, and
(R'.sub.1).sub.2)N)(R'O)x)H, wherein x is a number from about 2 to
about 15 and R.sub.1 and R' are as described above. R'.sub.1 may
also be a hydroxypoly(hydrocarbyloxy) group.
[0045] The amines may be hydroxyamines, such as those represented
by the formula R.sub.1--( N ( ( R.sub.2O)zH ) --R.sub.3).sub.a--N (
(R.sub.2O).sub.zH ) --(R.sub.2O).sub.zH , wherein R.sub.1 is a
hydrocarbyl group generally containing from about 6 to about 30
carbon atoms; R.sub.2 and each R.sub.3 is independently an alkylene
group containing up to about 5 carbon atoms, or an ethylene or
propylene group; a is zero or one; and each z is independently a
number from zero to about 10, with the proviso that at least one z
is at least one. These hydroxyamines can be prepared by techniques
well known in the art and many such hydroxyamines are commercially
available. The hydroxy amines include mixtures of amines such as
obtained by the hydrolysis of fatty oils (e.g., tallow oils, sperm
oils, coconut oils, etc.). Specific examples of fatty amines,
containing from about 6 to about 30 carbon atoms, include saturated
as well as unsaturated aliphatic amines, such as octyl amine, decyl
amine, lauryl amine, stearyl amine, oleyl amine, dodecyl amine, and
octadecyl amine.
[0046] Useful hydroxyamines wherein a in the above formula is zero
include 2-hydroxyethyl, hexylamine; 2-hydroxyethyloctylamine;
2-hydroxyethyl, pentadecylamine; 2-hydroxyethyl, oleylamine;
2-hydroxyethyl,soyamine; bis(2-hydroxyethyl) hexylamine;
bis(2-hydroxyethyl)oleylamine; and mixtures thereof. Also included
are the comparable members wherein in the above formula at least
one of z is at least 2, as for example, 2-hydroxyethoxyethyl,
hexylamine.
[0047] A number of hydroxyamines wherein a in the above formula is
zero are available from the Armak Chemical Division of Akzona,
Inc., Chicago, Ill., under the general trade designations
"Ethomeen" and "Propomeen". Specific examples of such products
include: Ethomeen C/15 which is an ethylene oxide condensate of a
coco alkyl amine containing about 5 moles of ethylene oxide;
Ethomeen C/20 and C/25 which are ethylene oxide condensation
products from coco alkyl amine containing about 10 and 15 moles of
ethylene oxide, respectively; Ethomeen 0/12 which is an ethylene
oxide condensation product of oleylamine containing about 2 moles
of ethylene oxide per mole of amine; Ethomeen S/15 and S/20 which
are ethylene oxide condensation products with stearyl amine
containing about 5 and 10 moles of ethylene oxide per mole of
amine, respectively; Ethomeen T/12, T/15 and T/25 which are
ethylene oxide condensation products of tallow amine containing
about 2, 5 and 15 moles of ethylene oxide per mole of amine,
respectively; and Propomeen 0/12 which is the condensation product
of one mole of oleylamine with 2 moles propylene oxide.
[0048] Commercially available examples of alkoxylated amines where
a in the above formula is one include Ethoduomeen T/13 and T/20
which are ethylene oxide condensation products of N-tallow
trimethylenediamine containing 3 and 10 moles of ethylene oxide per
mole of diamine, respectively.
[0049] The amine may also be a polyamine. The polyamines include
alkoxylated diamines, fatty diamines, alkylenepolyamines, hydroxy
containing polyamines, condensed polyamines and heterocyclic
polyamines. Commercially available examples of alkoxylated diamines
include those amines where a in the above formula is one. Examples
of these amines include Ethoduomeen T/13 and T/20 which are
ethylene oxide condensation products of N-tallowtrimethylenediamine
containing 3 and 10 moles of ethylene oxide per mole of diamine,
respectively.
[0050] In another embodiment, the polyamine is a fatty diamine. The
fatty diamines include mono- or dialkyl, symmetrical or
asymmetrical ethylenediamines, propanediamines (1,2, or 1,3), and
polyamine analogs of the above. Suitable commercial fatty
polyamines are Duomeen C (N-coco-1,3-diaminopropane), Duomeen S
(N-soya-1,3-diaminopropane), Duomeen T (N-tallow-1,
3-diaminopropane), and Duomeen O (N-oleyl-1,3-diaminopropane).
"Duomeens" are commercially available from Armak Chemical Co.,
Chicago, Ill.
[0051] In another embodiment, the amine is an alkylenepolyamine.
Alkylenepolyamines are represented by the formula
HR.sub.1N-(Alkylene-N).- sub.n-(R.sub.1).sub.2, wherein each
R.sub.1 is independently hydrogen; or an aliphatic or
hydroxy-substituted aliphatic group of up to about 30 carbon atoms;
n is a number from 1 to about 10, or from about 2 to about 7, or
from about 2 to about 5; and the "Alkylene" group has from 1 to
about 10 carbon atoms, or from about 2 to about 6, or from about 2
to about 4. In another embodiment, R.sub.1 is defined the same as
R'.sub.1 above. Such alkylenepolyamines include
methylenepolyamines, ethylenepolyamines, butylenepolyamines,
propylenepolyamines, pentylenepolyamines, etc. The higher homologs
and related heterocyclic amines, such as piperazines and N-amino
alkyl-substituted piperazines, are also included. Specific examples
of such polyamines are ethylenediamine, triethylenetetramine,
tris-(2-aminoethyl)amine, propylenediamine, trimethylenediamine,
tripropylenetetramine, triethylenetetraamine,
tetraethylenepentamine, hexaethyleneheptamine,
pentaethylenehexamine, etc. Higher homologs obtained by condensing
two or more of the above-noted alkyleneamines are similarly useful
as are mixtures of two or more of the afore described
polyamines.
[0052] In one embodiment, the polyamine is an ethylenepolyamine.
Such polyamines 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). Ethylenepolyamines are often a complex mixture of
polyalkylenepolyamines including cyclic condensation products.
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". In general,
alkylenepolyamine bottoms can be characterized as having less than
2%, usually less than 1% (by weight) material boiling below about
200 C.
[0053] A typical sample of such ethylenepolyamine bottoms obtained
from the Dow Chemical Company of Freeport, Tex. designated "E-100"
has a specific gravity at 15.6 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 contains about 0.93%
"Light Ends" (most probably diethylenetriamine), 0.72%
triethylenetetraamine, 21.74% tetraethylenepentamine and 76.61%
pentaethylenehexamine and higher analogs. These alkylenepolyamine
bottoms include cyclic condensation products, such as piperazine,
and higher analogs of diethylenetriamine, triethylenetetramine and
the like. These alkylenepolyamine bottoms may be reacted solely
with the acylating agent or they may be used with other amines,
polyamines, or mixtures thereof.
[0054] Another useful polyamine is a condensation reaction between
at least one hydroxy compound with at least one polyamine reactant
containing at least one primary or secondary amino group. The
hydroxy compounds areor polyhydric alcohols or polyhydric amines.
The polyhydric alcohols are described below. In one embodiment, the
hydroxy compounds are polyhydric amines. Polyhydric amines include
any of the above-described monoamines reacted with an alkylene
oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.)
having from two to about 20, or from two to about eight carbon
atoms. Examples of polyhydric amines include
tri-(hydroxypropyl)amine, tris-(hydroxymethyl)amino methane,
2-amino-2-methyl-1 ,3-propanediol, N,N, N',N'-tetrakis
(2-hydroxypropyl) ethylenediamine, and N,N,N',N'-tetrakis
(2-hydroxyethyl) ethylenediamine, or tris(hydroxymethyl)
aminomethane (THAM).
[0055] Polyamines which may react with the polyhydric alcohol or
amine to form the condensation products or condensed amines, are
described above. Useful polyamines include triethylenetetramine
(TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine
(PEHA), and mixtures of polyamines such as the above-described
"amine bottoms". The condensation reaction of the polyamine
reactant with the hydroxy compound is conducted at an elevated
temperature, usually from about 60 C. to about 265 C, or from about
220.degree. C. to about 250 C in the presence of an acid
catalyst.
[0056] The amine condensates and methods of making the same are
described in PCT publication WO 86/05501 and U.S. Pat. No.
5,230,714 (Steckel) which are incorporated by reference for its
disclosure to the condensates and methods of making. A particularly
useful amine condensate is prepared from HPA Taft Amines (amine
bottoms available commercially from Union Carbide Co. with
typically 34.1% by weight nitrogen and a nitrogen distribution of
12.3% by weight primary amine, 14.4% by weight secondary amine and
7.4% by weight tertiary amine), and tris(hydroxymethyl)aminomet-
hane (THAM).
[0057] In another embodiment, the polyamines are polyoxyalkylene
polyamines, e.g. polyoxyalkylene diamines and polyoxyalkylene
triamines, having average molecular weights ranging from about 200
to about 4000, or from about 400 to about 2000. Useful
polyoxyalkylene polyamines include the polyoxyethylene and
polyoxypropylene diamines and the polyoxypropylene triamines. The
polyoxyalkylene polyamines are commercially available and may be
obtained, for example, from the Jefferson Chemical Company, Inc.
under the trade name "Jeffamines D-230, D-400, D-1000, D-2000,
T-403, etc.". U.S. Pat. Nos. 3,804,763 and 3,948,800 are expressly
incorporated herein by reference for their disclosure of such
polyoxyalkylene polyamines and acylated products made
therefrom.
[0058] In another embodiment, the polyamines are hydroxy-containing
polyamines. Hydroxy-containing polyamine analogs of hydroxy
monoamines, particularly alkoxylated alkylenepolyamines, e.g.,
N,N(diethanol)ethylene diamines may also be used. Such polyamines
can be made by reacting one or more above-described alkylene amines
with one or more of the above-described alkylene oxides. Similar
alkylene oxide-alkanol amine reaction products may also be used
such as the products made by reacting the above described primary,
secondary or tertiary alkanol amines with ethylene, propylene or
higher epoxides in a 1.1 to 1.2 molar ratio. Reactant ratios and
temperatures for carrying out such reactions are known to those
skilled in the art. Specific examples of hydroxy-containing
polyamines include N-(2-hydroxyethyl) ethylenediamine,
N,N'-bis(2-hydroxyethyl)-ethylenediamine, 1-(2-hydroxyethyl)
piperazine, mono(hydroxypropyl)-substituted tetraethylenepentamine,
N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs
obtained by condensation of the above illustrated
hydroxy-containing polyamines through amino groups or through
hydroxy groups are likewise useful. Condensation through amino
groups results in a higher amine accompanied by removal of ammonia
while condensation through the hydroxy groups results in products
containing ether linkages accompanied by removal of water. Mixtures
of two or more of any of the above described polyamines are also
useful.
[0059] In another embodiment, the amine is a heterocyclic amine.
The heterocyclic polyamines include aziridines, azetidines,
azolidines, tetra- and dihydropyridines, pyrroles, indoles,
piperidines, imidazoles, di- and tetrahydroimidazoles, piperazines,
isoindoles, purines, morpholines, thiomorpholines,
N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,
N-aminoalkylpiperazines, N,N'-diaminoalkylpiperazines, azepines,
azocines, azonines, azecines and tetra-, di- and perhydro
derivatives of each of the above and mixtures of two or more of
these heterocyclic amines. Useful heterocyclic amines are the
saturated 5- and 6-membered heterocyclic amines containing only
nitrogen, oxygen and/or sulfur in the hetero ring, especially the
piperidines, piperazines, thiomorpholines, morpholines,
pyrrolidines, and the like. Piperidine, aminoalkyl substituted
piperidines, piperazine, aminoalkyl substituted piperazines,
morpholine, aminoalkyl substituted morpholines, pyrrolidine, and
aminoalkyl-substituted pyrrolidines, are especially useful. Usually
the aminoalkyl substituents are substituted on a nitrogen atom
forming part of the hetero ring. Specific examples of such
heterocyclic amines include N-aminopropylmorpholine,
N-aminoethylpiperazine, and N,N'-diaminoethylpiperazine. Hydroxy
heterocyclic amines are also useful. Examples include
N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine,
parahydroxyaniline, N-hydroxyethylpiperazine, and the like.
[0060] Acylated nitrogen dispersants and methods for preparing the
same are described in U.S. Pat. Nos. 3,219,666; 4,234,435;
4,952,328; 4,938,881; 4,957,649; and 4,904,401. The disclosures of
acylated nitrogen dispersants and other dispersants contained in
those patents is hereby incorporated by reference.
[0061] The dispersant may also be a hydrocarbyl-substituted amines.
These hydrocarbyl-substituted amines are well known to those
skilled in the art. These amines are disclosed in U.S. Pat. Nos.
3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; and
3,822,289. These patents are hereby incorporated by reference for
their disclosure of hydrocarbyl amines and methods of making the
same.
[0062] Typically, hydrocarbyl substituted amines are prepared by
reacting olefins and olefin polymers (polyalkenes) with amines
(mono- or polyamines). The polyalkene may be any of the polyalkenes
described above. The amines may be any of the amines described
above. Examples of hydrocarbyl substituted amines include
poly(propylene)amine; N,N-dimethyl-N-poly
(ethylene/propylene)amine, (50:50 mole ratio of monomers);
polybutene amine; N,N-di(hydroxyethyl)-N-polybutene amine;
N-(2-hydroxypropyl)-N-polybutene amine; N-polybutene-aniline;
N-polybutenemorpholine; -poly(butene) ethylenediamine;
-poly(propylene)trimethylenediamine; -poly(butene)
diethylenetriamine; N',N'-poly(butene)tetraethylenepentamine;
N,N-dimethyl-N'-poly (propylene)-1,3-propylenediamine and the
like.
[0063] In another embodiment, the dispersant may also be a
carboxylic ester dispersant. The carboxylic ester dispersant is
prepared by reacting at least one of the above
hydrocarbyl-substituted carboxylic acylating agents with at least
one organic hydroxy compound and optionally an amine. In another
embodiment, the carboxylic ester dispersant is prepared by reacting
the acylating agent with at least one of the above-described
hydroxyamines.
[0064] The organic hydroxy compound includes compounds of the
general formula R"(OH).sub.m wherein R" is a monovalent or
polyvalent organic group joined to the --OH groups through a carbon
bond, and m is an integer of from 1 to about 10 wherein the
hydrocarbyl group contains at least about 8 aliphatic carbon atoms.
The hydroxy compounds may be aliphatic compounds, such as
monohydric and polyhydric alcohols, or aromatic compounds, such as
phenols and naphthols. The aromatic hydroxy compounds from which
the esters may be derived are illustrated by the following specific
examples: phenol, beta-naphthol, alpha-naphthol, cresol,
resorcinol, catechol, p,p'-dihydroxybiphenyl, 2-chlorophenol,
2,4-dibutylphenol, etc.
[0065] The alcohols from which the esters may be derived generally
contain up to about 40 aliphatic carbon atoms, or from 2 to about
30, or from 2 to about 10. They may be monohydric alcohols such as
methanol, ethanol, isooctanol, dodecanol, cyclohexanol, etc. In one
embodiment, the hydroxy compounds are polyhydric alcohols, such as
alkylene polyols. In one embodiment, the polyhydric alcohols
contain from 2 to about 40 carbon atoms, or from 2 to about 20; and
or from 2 to about 10 hydroxyl groups, or from 2 to about 6.
Polyhydric alcohols include ethylene glycols, including di-, tri-
and tetraethylene glycols; propylene glycols, including di-, tri-
and tetrapropylene glycols; glycerol; butane diol; hexane diol;
sorbitol; arabitol; mannitol; sucrose; fructose; glucose;
cyclohexane diol; erythritol; and pentaerythritols, including di-
and tripentaerythritol. Particularly useful polyhydric alcohols
include diethylene glycol, triethylene glycol, glycerol, sorbitol,
pentaerythritol and dipentaerythritol.
[0066] The polyhydric alcohols may be esterified with
monocarboxylic acids having from 2 to about 30 carbon atoms, or
from about 8 to about 18, provided that at least one hydroxyl group
remains unesterified. Examples of monocarboxylic acids include
acetic, propionic, butyric and fatty carboxylic acids. The fatty
monocarboxylic acids are described above. Specific examples of
these esterified polyhydric alcohols include sorbitol oleate,
including mono- and dioleate, sorbitol stearate, including mono-
and distearate, glycerol oleate, including glycerol mono-, di- and
trioleate and erythritol octanoate.
[0067] The carboxylic ester dispersants may be prepared by any of
several known methods. The method which is particularly useful
because of convenience and the superior properties of the esters it
produces, involves the reaction of the carboxylic acylating agents
described above with one or more alcohols or phenols in ratios from
about 0.5 equivalent to about 4 equivalents of hydroxy compound per
equivalent of acylating agent. The esterification is usually
carried out at a temperature above about 100.degree. C., or between
150.degree. C. and 300.degree. C. The water formed as a by-product
is removed by distillation as the esterification proceeds. The
preparation of useful carboxylic ester dispersant is described in
U.S. Pat. Nos. 3,522,179 and 4,234,435, and their disclosures are
incorporated by reference.
[0068] The carboxylic ester dispersants may be further reacted with
at least one of the above described amines, including at least one
of the above described polyamines. The amine is added in an amount
sufficient to neutralize any nonesterified carboxyl groups. In one
embodiment, the nitrogen-containing carboxylic ester dispersants
are prepared by reacting about 1.0 to 2.0 equivalents, or about 1.0
to 1.8 equivalents of hydroxy compounds, and up to about 0.3
equivalent, or about 0.02 to about 0.25 equivalent of polyamine per
equivalent of acylating agent.
[0069] In another embodiment, the carboxylic acid acylating agent
may be reacted simultaneously with both the alcohol and the amine.
There is generally at least about 0.01 equivalent of the alcohol
and at least 0.01 equivalent of the amine although the total amount
of equivalents of the combination should be at least about 0.5
equivalent per equivalent of acylating agent. These
nitrogen-containing carboxylic ester dispersant compositions are
known in the art, and the preparation of a number of these
derivatives is described in, for example, U.S. Pat. Nos. 3,957,854
and 4,234,435, which have been incorporated by reference
previously.
[0070] In another embodiment, the dispersant may also be derived
from a Mannich dispersant. Mannich dispersants are generally formed
by the reaction of at least one aldehyde, at least one of the above
described amine and at least one alkyl substituted hydroxyaromatic
compound. The reaction may occur from room temperature to
225.degree. C., or from 50.degree. C. to about 200.degree. C., or
from about 75.degree. C. to about 150.degree. C., with the amounts
of the reagents being such that the molar ratio of hydroxyaromatic
compound to formaldehyde to amine is in the range from about
(1:1:1) to about (1:3:3).
[0071] The first reagent is an alkyl substituted hydroxyaromatic
compound. This term includes phenols (which are particularly
useful), carbon-, oxygen-, sulfur- and nitrogen-bridged phenols and
the like as well as phenols directly linked through covalent bonds
(e.g. 4,4'-bis(hydroxy)biphenyl), hydroxy compounds derived from
fused-ring hydrocarbon (e.g., naphthols and the like); and
polyhydroxy compounds such as catechol, resorcinol and
hydroquinone. Mixtures of one or more hydroxyaromatic compounds can
be used as the first reagent.
[0072] The hydroxyaromatic compounds are those substituted with at
least one, and or not more than two, aliphatic or alicyclic groups
having at least about 6 (usually at least about 30, or from at
least 50) carbon atoms and up to about 400 carbon atoms, or up to
about 300, or up to about 200. These groups may be derived from the
above described polyalkenes. In one embodiment, the hydroxy
aromatic compound is a phenol substituted with an aliphatic or
alicyclic hydrocarbon-based group having an Mn of about 420 to
about 10,000.
[0073] The second reagent is a hydrocarbon-based aldehyde, such as
a lower aliphatic aldehyde. Suitable aldehydes include
formaldehyde, benzaldehyde, acetaldehyde, the butyraldehydes,
hydroxybutyraldehydes and heptanals, as well as aldehyde precursors
which react as aldehydes under the conditions of the reaction such
as paraformaldehyde, paraldehyde, formalin and methal. Formaldehyde
and its precursors (e.g., paraformaldehyde, trioxane) are
particularly useful. Mixtures of aldehydes may be used as the
second reagent.
[0074] The third reagent is any amine described above. In one
embodiment, the amine is a polyamine as described above. Mannich
dispersants are described in the following patents: U.S. Pat. No.
3,980,569; U.S. Pat. No. 3,877,899; and U.S. Pat. No. 4,454,059
(herein incorporated by reference for their disclosure to Mannich
dispersants).
[0075] In one embodiment, the dispersant is a borated dispersant.
The borated dispersant are prepared by reacting one or more of the
above dispersant is a borating agent. Borating agents include boron
oxide, boron oxide hydrate, boron trioxide, boron trifluoride,
boron tribromide, boron trichloride, boron acid such as boric acid,
tetraboric acid and metaboric acid, boron hydrides, boron amides
and various esters of boron acids. The boron esters include lower
alkyl (1-7 carbon atoms) esters of boric acid. A particularly
useful boron compound is boric acid.
[0076] The following example relate to borated dispersants.
EXAMPLE D-1
[0077] A mixture of 372 grams (6 equivalents of boron) of boric
acid and 3111 grams (6 equivalents of nitrogen) of an acylated
nitrogen composition, obtained by reacting 1 equivalent of a
polybutenyl (Mn=850) succinic anhydride, having an acid number of
113 (corresponding to an equivalent weight of 500), with 2
equivalents of a commercial ethylene amine mixture having an
average composition corresponding to that of
tetraethylenepentamine, is heated at 150 C for 3 hours a then
filtered. The filtrate is found to have a boron content of 1.64%
and a nitrogen content of 2.56%.
EXAMPLE D-2
[0078] (a) A reaction vessel is charged with 1000 parts of a
polybutenyl (Mn=1000) substituted succinic anhydride, having a
total acid number of 108, with a mixture of 275 grams of oil and
139 parts of a commercial mixture of polyamines corresponding to
85% E-100 amine bottoms and 15% diethylenetriamine. The reaction
mixture is heated to 150 to 160 C and the reaction temperature is
maintained for four hours. The reaction is blown with nitrogen to
remove water.
[0079] (b) A reaction vessel is charged with 1405 parts of the
product of Example D-2a, 229 parts of boric acid, and 398 parts of
diluent oil. The mixture is heated to 100 to 150 C and the
temperature maintained until water distillate ceases. The final
product contains 2.3% nitrogen, 1.9% boron, 33% 100 neutral mineral
oil and a total base number of 60.
[0080] Phosphorus Antiwear Agents
[0081] The lubricating compositions of the present invention may
also include at least one phosphorus antiwear/extreme pressure
agent. Generally the phosphorus antiwear/extreme pressure agent is
present in an amount from about 0.01% to about 3%, or from about
0.1% to about 1.25%, or from about 0.2% to about 1% by weight.
[0082] Examples of phosphorus containing antiwear/extreme pressure
agents include a metal thiophosphate; a phosphoric acid ester or
salt thereof; a phosphorus-containing carboxylic acid, ester,
ether, or amide; and a phosphite. The phosphorus acids include the
phosphoric, phosphonic, phosphinic and thiophosphoric acids
including dithiophosphoric acid as well as the monothiophosphoric
acid, thiophosphinic and thiophosphonic acids.
[0083] In one embodiment, the phosphorus containing
antiwear/extreme pressure agent is a phosphorus acid ester prepared
by reacting one or more phosphorus acid or anhydride with an
alcohol containing from one, or about 3 carbon atoms. The alcohol
generally contains up to about 30, or up to about 24, or up to
about 12 carbon atoms. The phosphorus acid or anhydride is
generally an inorganic phosphorus reagent, such as phosphorus
pentoxide, phosphorus trioxide, phosphorus tetroxide, phosphorus
acid, phosphorus halide, lower phosphorus esters, or a phosphorus
sulfide, including phosphorus pentasulfide, and the like. Examples
of phosphorus acids or anhydrides include phosphorus pentoxide,
phosphorus pentasulfide and phosphorus trichloride. Lower
phosphorus acid esters independently 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. Alcohols used to prepare
the phosphorus acid esters generally have from 1 to 30, or from
about 2 to 24, or from about 4 to 18 carbon atoms. Examples include
butyl, amyl, 2-ethylhexyl, hexyl, octyl, oleyl, and cresol
alcohols. Examples of commercially available alcohols include Alfol
810 (a mixture of primarily straight chain, primary alcohols having
from 8 to 10 carbon atoms); Alfol 1218 (a mixture of synthetic,
primary, straight-chain alcohols containing 12 to 18 carbon atoms);
Alfol 20+ alcohols (mixtures of C.sub.18-C.sub.28 primary alcohols
having mostly C.sub.20 alcohols as determined by GLC
(gas-liquid-chromatography)); and Alfol 22+ alcohols
(C.sub.18-C.sub.28 primary alcohols containing primarily C.sub.22
alcohols). Alfol alcohols are available from Continental Oil
Company.
[0084] Another example of a commercially available alcohol mixtures
are Adol 60 (about 75% by weight of a straight chain C.sub.22
primary alcohol, about 15% of a C.sub.20 primary alcohol and about
8% of C.sub.18 and C.sub.24 alcohols) and Adol 320 (oleyl alcohol).
The Adol alcohols are marketed by Ashland Chemical.
[0085] A variety of mixtures of monohydric fatty alcohols derived
from naturally occurring triglycerides and ranging in chain length
of from about C.sub.8 to C.sub.18 are available from Procter &
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
C.sub.10 alcohol, 66.0% of C12 alcohol, 26.0% of C.sub.14 alcohol
and 6.5% of C.sub.16 alcohol.
[0086] Another group of commercially available mixtures include the
"Neodol" products available from Shell Chemical Co. For example,
Neodol 23 is a mixture of C.sub.12 and C.sub.13 alcohols; Neodol 25
is a mixture of C.sub.12 and C.sub.15 alcohols; and Neodol 45 is a
mixture of C14 to C.sub.15 linear alcohols. Neodol 91 is a mixture
of C.sub.9, C.sub.10 and C.sub.11 alcohols.
[0087] Fatty vicinal diols also are useful and these include those
available from Ashland Oil under the general trade designation Adol
114 and Adol 158. The former is derived from a straight chain alpha
olefin fraction of C.sub.11-C.sub.14, and the latter is derived
from a C15-C18 fraction.
[0088] Examples of useful phosphorus acid esters include the
phosphoric acid esters prepared by reacting a phosphoric acid or
anhydride with cresol alcohols. An example of these phosphorus acid
esters is tricresylphosphate.
[0089] In another embodiment, the phosphorus antiwear/extreme
pressure agent is a thiophosphorus acid ester or salt thereof. The
thiophosphorus acid ester may be prepared by reacting a phosphorus
sulfide, such as those described above, with an alcohol, such as
those described above. The thiophosphorus acid esters may be mono-
or dithiophosphorus acid esters. Thiophosphorus acid esters are
also referred to generally as thiophosphoric acids.
[0090] In one embodiment, the phosphorus acid ester is a
monothiophosphoric acid ester or a monothiophosphate.
Monothiophosphates may be prepared by the reaction of a sulfur
source with a dihydrocarbyl phosphite. The sulfur source may for
instance be elemental sulfur. The sulfur source may also be a
monosulfide, 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. Pat. No.
4,755,311 and PCT Publication WO 87/07638, which are incorporated
herein by reference for their disclosure of monothiophosphates,
sulfur sources, and the process for making monothiophosphates.
Monothiophosphates may also be formed in the lubricant blend by
adding a dihydrocarbyl phosphite to a lubricating composition
containing a sulfur source, such as a sulfurized olefin. The
phosphite may react with the sulfur source under blending
conditions (i.e., temperatures from about 30 C to about 100 C or
higher) to form the monothiophosphate.
[0091] In another embodiment, the phosphorus antiwear/extreme
pressure agent is a dithiophosphoric acid or phosphorodithioic
acid. The dithiophosphoric acid may be represented by the formula
(RO).sub.2PSSH wherein each R is independently a hydrocarbyl group
containing from about 3 to about 30 carbon atoms. R generally
contains up to about 18, or to about 12, or to about 8 carbon
atoms. Examples R include isopropyl, isobutyl, n-butyl, sec-butyl,
the various amyl, n-hexyl, methylisobutyl carbinyl, heptyl,
2-ethylhexyl, isooctyl, nonyl, behenyl, decyl, dodecyl, and
tridecyl groups. Illustrative lower alkylphenyl R groups include
butylphenyl, amylphenyl, heptylphenyl, etc. Examples of mixtures of
R groups include: 1-butyl and 1-octyl; 1-pentyl and
2-ethyl-1-hexyl; isobutyl and n-hexyl; isobutyl and isoamyl;
2-propyl and 2-methyl-4-pentyl; isopropyl and sec-butyl; and
isopropyl and isooctyl.
[0092] In one embodiment, the dithiophosphoric acid may be reacted
with an epoxide or a glycol. This reaction product may be used
alone, or further 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 particularly useful. The
glycols may be aliphatic glycols having from 1 to about 12, or
about 2 to about 6, or 2 or 3 carbon atoms, or aromatic glycols.
Glycols include ethylene glycol, propylene glycol, catechol,
resorcinol, and the like. The dithiophosphoric acids, glycols,
epoxides, inorganic phosphorus reagents and methods of reacting the
same are described in U.S. Pat. No. 3,197,405 and U.S. Pat. No.
3,544,465 which are incorporated herein by reference for their
disclosure to these.
[0093] The following Examples P-1 and P-2 exemplify the preparation
of useful phosphorus acid esters.
EXAMPLE P-1
[0094] Phosphorus pentoxide (64 grams) is added at 58 C. over a
period of 45 minutes to 514 grams of hydroxypropyl
O,O-di(4-methyl-2-pentyl) phosphorodithioate (prepared by reacting
di(4-methyl-2-pentyl)-phosphorod- ithioic acid with 1.3 moles of
propylene oxide at 25 C). The mixture is heated at 75.degree. C.
for 2.5 hours, mixed with a diatomaceous earth and filtered at
70.degree. C. The filtrate contains 11.8% by weight phosphorus,
15.2% by weight sulfur, and an acid number of 87 (bromophenol
blue).
EXAMPLE P-2
[0095] A mixture of 667 grams of phosphorus pentoxide and the
reaction product of 3514 grams of diisopropyl phosphorodithioic
acid with 986 grams of propylene oxide at 50.degree. C. is heated
at 85.degree. C. for 3 hours and filtered. The filtrate contains
15.3% by weight phosphorus, 19.6% by weight sulfur, and an acid
number of 126 (bromophenol blue).
[0096] Acidic phosphoric acid esters may be reacted with ammonia,
an amine compound or a metallic base to form an ammonium or metal
salt. The salts may be formed separately and then the salts of the
phosphorus acid ester may be added to the lubricating composition.
Alternately, the salts may also be formed in situ when the acidic
phosphorus acid ester is blended with other components to form a
fully formulated lubricating composition.
[0097] The amine salts of the phosphorus acid esters may be formed
from ammonia, or an amine, including the above described monoamines
and polyamines. The metal salts of the phosphorus acid esters are
prepared by the reaction of a metal base with the phosphorus acid
ester. The metal base may be any metal compound capable of forming
a metal salt. Examples of metal bases include metal oxides,
hydroxides, carbonates, sulfates, borates, or the like. The metals
of the metal base include Group IA, IIA, IB through VIIB, and VIII
metals (CAS version of the Periodic Table of the Elements). These
metals include the alkali metals, alkaline earth metals and
transition metals. In one embodiment, the metal is a Group IIA
metal, such as calcium or magnesium, Group IIB metal, such as zinc,
or a Group VIIB metal, such as manganese. In one embodiment, the
metal is magnesium, calcium, manganese or zinc. Examples of metal
compounds which may be reacted with the phosphorus acid include
zinc hydroxide, zinc oxide, copper hydroxide, copper oxide,
etc.
[0098] In one embodiment, phosphorus containing antiwear/extreme
pressure agent is a metal thiophosphate, or a metal
dithiophosphate. The metal thiophosphate is prepared by means known
to those in the art. Examples of metal dithiophosphates include
zinc isopropyl, methylamyl dithiophosphate, zinc isopropyl isooctyl
dithiophosphate, barium di(nonyl) dithiophosphate, zinc
di(cyclohexyl) dithiophosphate, zinc di(isobutyl) dithiophosphate,
calcium di(hexyl) dithiophosphate, zinc isobutyl isoamyl
dithiophosphate, and zinc isopropyl secondary-butyl
dithiophosphate.
[0099] The following Examples P-3 to P-6 exemplify the preparation
of useful phosphorus acid ester salts.
EXAMPLE P-3
[0100] A reaction vessel is charged with 217 grams of the filtrate
from Example P-1. A commercial aliphatic primary amine (66 grams),
having an average molecular weight of 191 in which the aliphatic
radical is a mixture of tertiary alkyl radicals containing from 11
to 14 carbon atom, is added over a period of 20 minutes at
25-60.degree. C. The resulting product has a phosphorus content of
10.2% by weight, a nitrogen content of 1.5% by weight, and an acid
number of 26.3.
EXAMPLE P-4
[0101] Following the procedures of Examples P-1 and P-3, 1320 parts
of the product described in P-1 was reacted with 584 parts of the
amine of P-3. The final product has 8.4% phosphorus and 10%
sulfur.
EXAMPLE P-5
[0102] The filtrate of Example P-2 (1752 grams) is mixed at
25-82.degree. C. with 764 grams of the aliphatic primary amine used
in of Example P-3. The resulting product has 9.9% phosphorus, 2.7%
nitrogen, and 12.6% sulfur.
EXAMPLE P-6
[0103] Phosphorus pentoxide (852 grams) is added to 2340 grams of
iso-octyl alcohol over a period of 3 hours. The temperature
increases from room temperature but is maintained below 65.degree.
C. After the addition is complete the reaction mixture is heated to
90 C and the temperature is maintained for 3 hours. Diatomaceous
earth is added to the mixture, and the mixture is filtered. The
filtrate has 12.4% phosphorus, a 192 acid neutralization number
(bromophenol blue) and a 290 acid neutralization number
(phenolphthalein).
[0104] The above filtrate is mixed with 200 grams of toluene, 130
grams of mineral oil, 1 gram of acetic acid, 10 grams of water and
45 grams of zinc oxide. The mixture is heated to 60-70.degree. C.
under a pressure of 30 mm Hg. The resulting product mixture is
filtered using a diatomaceous earth. The filtrate has 8.6% zinc and
7.0% phosphorus.
EXAMPLE P-7
[0105] Alfol 8-10 (2628 parts, 18 moles) is heated to a temperature
of about 45.degree. C. whereupon 852 parts (6 moles) of phosphorus
pentoxide are added over a period of 45 minutes while maintaining
the reaction temperature between about 45-65.degree. C. The mixture
is stirred an additional 0.5 hour at this temperature, and is
there- after heated at 70 C for about 2-3 hours. Primene 81-R (2362
parts, 12.6 moles) is added dropwise to the reaction mixture while
maintaining the temperature between about 30-50.degree. C. When all
of the amine has been added, the reaction mixture is filtered
through a filter aid, and the filtrate is the desired amine salt
containing 7.4% phosphorus (theory, 7.1%).
EXAMPLE P-8
[0106] Phosphorus pentoxide (208 grams) is added to the product
prepared by reacting 280 grams of propylene oxide with 1184 grams
of O,O-di-isobutyl phosphorodithioic acid at 30-60.degree. C. The
addition is made at a temperature of 50-60EC and the resulting
mixture is then heated to 80.degree. C. and held at that
temperature for 2 hours. The commercial aliphatic primary amine
identified in Example B-3 (384 grams) is added to the mixture,
while the temperature is maintained in the range of 30-60.degree.
C. The reaction mixture is filtered through diatomaceous earth. The
filtrate has 9.3% phosphorus, 11.4% sulfur, 2.5% nitrogen, and a
base number of 6.9 (bromophenol blue indicator).
[0107] In another embodiment, the phosphorus antiwear/extreme
pressure agent is a metal salt of (a) at least one dithiophosphoric
acid and (b) at least one aliphatic or alicyclic carboxylic acid.
The dithiophosphoric acids are described above. The carboxylic acid
may be a monocarboxylic or polycarboxylic acid, usually containing
from 1 to about 3, or just one carboxylic acid group. Useful
carboxylic acids are those having the formula RCOOH, wherein R is
an aliphatic or alicyclic hydrocarbyl group preferably free from
acetylenic unsaturation. R generally contains from about 2, or from
about 4 carbon atoms. R generally contains up to about 40, or up to
about 24, or to up about 12 carbon atoms. In one embodiment, R
contains from about 4, or from about 6 up to about 12, or up to
about 8 carbon atoms. In one embodiment, R is an alkyl group.
Suitable acids include the butanoic, pentanoic, hexanoic, octanoic,
nonanoic, decanoic, dodecanoic, octadecanoic and eicosanoic acids,
as well as olefinic acids such as oleic, linoleic, and linolenic
acids and linoleic acid dimer. A particularly useful carboxylic
acid is 2-ethylhexanoic acid.
[0108] The metal salts may be prepared by merely blending a metal
salt of a dithiophosphoric acid with a metal salt of a carboxylic
acid in the desired ratio. The ratio of equivalents of
dithiophosphoric acid to carboxylic acid is from about 0.5 up to
about 400 to 1. The ratio may be from 0.5 up to about 200, or up to
about 100, or up to about 50, or up to about 20 to 1. In one
embodiment, the ratio is from 0.5 up to about 4.5 to one, or from
about 2.5 up to about 4.25 to one. For this purpose, the equivalent
weight of a dithiophosphoric acid is its molecular weight divided
by the number of --PSSH groups therein, and the equivalent weight
of a carboxylic acid is its molecular weight divided by the number
of carboxy groups therein.
[0109] A second method for preparing the metal salts useful in this
invention is to prepare a mixture of the acids in the desired
ratio, such as those described above for the metal salts of the
individual metal salts, and to react the acid mixture with one of
the above described metal compounds. When this method of
preparation is used, it is frequently possible to prepare a salt
containing an excess of metal with respect to the number of
equivalents of acid present; thus the metal salts may contain as
many as 2 equivalents and especially up to about 1.5 equivalents of
metal per equivalent of acid may be prepared. The equivalent of a
metal for this purpose is its atomic weight divided by its valence.
The temperature at which the metal salts are prepared is generally
between about 30.degree. C. and about 150.degree. C., or up to
about 125.degree. C. U.S. Pat. Nos. 4,308,154 and 4,417,990
describe procedures for preparing these metal salts and disclose a
number of examples of such metal salts. These patents are hereby
incorporated by reference for those disclosures.
[0110] In one embodiment, the phosphorus containing
antiwear/extreme pressure agent is a phosphorus containing amide.
The phosphorus containing amides are prepared by the reaction of
one of the above described phosphorus acids, or a dithiophosphoric
acid, with an unsaturated amide. Examples of unsaturated amides
include acrylamide, N,N-methylene bis(acrylamide), methacrylamide,
crotonamide, and the like. In one embodiment, the dithiocarbamate
containing composition is derived from the reaction product of a
diamylamine or dibutylamine with carbon disulfide which forms a
dithiocarbamic acid or a salt which is ultimately reacted with a
acrylamide. The reaction product of the phosphorus acid and the
unsaturated amide may be further reacted with a linking or a
coupling compound, such as formaldehyde or paraformaldehyde. The
phosphorus containing amides are known in the art and are disclosed
in U.S. Pat. Nos. 4,670,169, 4,770,807, and 4,876,374, which are
incorporated by reference for their disclosures of phosphorus
amides and their preparation.
[0111] In one embodiment, the phosphorus antiwear/extreme pressure
agent is a phosphorus containing carboxylic ester. The phosphorus
containing carboxylic esters are prepared by reaction of one of the
above-described phosphorus acids, preferably a dithiophosphoric
acid, and one of the unsaturated carboxylic acids or esters
described herein. If the carboxylic acid is used, the ester may
then be formed by subsequent reaction of the phosphoric
acid-unsaturated carboxylic acid adduct with an alcohol, such as
those described herein.
[0112] In one embodiment, the phosphorus containing
antiwear/extreme pressure agent is a reaction product of a
phosphorus acid, preferably a dithiophosphoric acid, and a vinyl
ethers. The vinyl ether is represented by the formula
R.sub.1--CH.dbd.CH--OR.sub.2 wherein R.sub.1 is independently
hydrogen or a hydrocarbyl group having from 1 up to about 30, or up
to about 24, or up to about 12 carbon atoms. R.sub.2 is a
hydrocarbyl group defined the same as R.sub.1. Examples of vinyl
ethers include methyl vinyl ether, propyl vinyl ether, 2-ethylhexyl
vinyl ether and the like.
[0113] In one embodiment, the phosphorus antiwear/extreme pressure
agent is a phosphorus containing carboxylic ester contain at least
one phosphite. The phosphite may be a di- or trihydrocarbyl
phosphite. In one embodiment, each hydrocarbyl group independently
contains 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, alkenyl, or aryl.
When the hydrocarbyl group is an aryl group, then it contains at
least about 6 carbon atoms; or 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, or butyl, oleyl or phenyl
and or butyl or oleyl. One method of preparing phosphites includes
reacting a lower (C.sub.1-8) Phosphites and their preparation are
known and many phosphites are available commercially. Particularly
useful phosphites are dibutyl hydrogen phosphite, dioleyl hydrogen
phosphite, di(C.sub.1418) hydrogen phosphite, and triphenyl
phosphite.
[0114] Fatty Imidazoline or Fatty Acid-polyamine Reaction
Product
[0115] The lubricating compositions also may include at least one
fatty imidazoline or at least one reaction product of at least one
fatty carboxylic acid and at least one polyamine. In one
embodiment, the fatty imidazoline or reaction product of a fatty
carboxylic acid of and at least one polyamine is present in an
amount to provide from about 0.01% to about 0.7%, or from about
0.02% to about 0.4%, or from about 0.03% to about 0.2% by weight to
the final lubricant.
[0116] The fatty imidazoline has fatty substituents containing from
about 8 to about 30, or from about 12 to about 24 carbon atoms. The
substituent may be saturated or unsaturated. Saturated substituents
are particularly useful. In one aspect, the fatty imidazoline may
be prepared by reacting a fatty carboxylic acid with a
polyalkylenepolyamine, such as those discussed above.
[0117] The fatty carboxylic acids are generally mixtures of
straight and branched chain fatty carboxylic acids containing about
8 to about 30 carbon atoms, or from about 12 to about 24, or from
about 16 to about 18. Carboxylic acids include the polycarboxylic
acids or carboxylic acids or anhydrides having from 2 to about 4
carbonyl groups, preferably 2. The polycarboxylic acids include
succinic acids and anhydrides and Diels-Alder reaction products of
unsaturated monocarboxylic acids with unsaturated carboxylic acids
(such as acrylic, methacrylic, maleic, fumaric, crotonic and
itaconic acids). In one embodiment, the fatty carboxylic acids are
fatty monocarboxylic acids, having from about 8 to about 30, or
from about 12 to about 24 carbon atoms. Specific examples include
such as octanoic, oleic, stearic, linoleic, dodecanoic, and tall
oil acids. Stearic acid is particularly useful.
[0118] One or more fatty carboxylic acid is reacted with at least
one polyamine. The polyamines may be aliphatic, cycloaliphatic,
heterocyclic or aromatic. Examples of the polyamines include
alkylene polyamines and heterocyclic polyamines. Specific examples
are described above.
[0119] A useful reaction product of a carboxylic acid and polyamine
is made by reacting the above-described alkylene polyamines with a
mixture of fatty acids having from 5 to about 30 mole percent
straight chain acid and about 70 to 95 mole percent branch chain
fatty acids. Among the commercially available mixtures are those
known commonly 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. Pat. Nos. 2,812,342; and 3,260,671.
These patents are hereby incorporated by reference for their
disclosure of these reaction products and methods of making the
same.
[0120] 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 acid/alkylene polyamine products have been
described extensively in the art. See, for example, U.S. Pat. Nos.
3,110,673; 3,251,853; 3,326,801; 3,337,459; 3,405,064; 3,429,674;
3,468,639; and 3,857,791. These patents are hereby incorporated by
reference for their disclosures of fatty acid/ polyamine
condensates for their use in lubricating oil formulations.
[0121] In another embodiment, the reaction product of a fatty
carboxylic acid and a polyamine are further reacted with an
epoxide. Epoxides are generally lower aliphatic epoxides, having
from 1 to about 7 carbon atoms, or from 1 to about 5 carbon atoms,
or from 2 to about 4 carbon atoms. Examples of these epoxides
include ethylene oxide, propylene oxide, butylene oxide,
cyclohexene oxide and octylene oxide. The epoxides generally react
in an amount from about 0.5% to about 5% by weight of lower epoxide
based on the total weight of the reaction product. The reaction
generally occurs at a temperature above about 100 C The reaction
product of a fatty acid, polyamine and epoxide is described in U.S.
Pat. No. 3,240,575 which is hereby incorporated by reference for
its teachings to carboxylic acids, polyamines, epoxides and
reaction products and methods of making the reaction products.
[0122] The following examples illustrate the reaction product of a
fatty carboxylic acidof and at least one polyamine of the present
invention.
EXAMPLE I-1
[0123] To 1133 parts of commercial diethylenetriamine heated at 1
10-150.degree. C. is slowly added 6820 parts of isostearic acid
over a period of two hours. The mixture is held at 150.degree. C.
for one hour and then heated to 180.degree. C. over an additional
hour. Finally, the mixture is heated to 205.degree. C. over 0.5
hour; through this heating, the mixture is blown with nitrogen to
remove volatiles. The mixture is held at 205-230.degree. C. for a
total of 11.5 hours and then stripped at 230.degree. C./20 torr to
provide the desired acylated polyamine as a residue containing 6.2%
nitrogen.
EXAMPLE I-2
[0124] To 205 parts of commercial tetraethylenepentamine heated to
about 75 C there is added 1000 parts of isostearic acid while
purging with nitrogen, and the temperature of the mixture is
maintained at about 75E-110 C. The mixture then is heated to
220.degree. C. and held at this temperature until the acid number
of the mixture is less than 10. After cooling to about 150.degree.
C., the mixture is filtered, and the filtrate is the desired
acylated polyamine having a nitrogen content of about 5.9%.
EXAMPLE I-3
[0125] A mixture (565 parts by weight) of an alkylene amine mixture
consisting of triethylenetetramine and diethylenetriamine in weight
ratio of 3:1 is added at 20E-80.degree. C. to a mixture of
equivalent amounts of a naphthenic acid having an acid number of
180 (1270 parts) and oleic acid (1110 parts; the total quantity of
the two acids used is such as to provide one equivalent for each
two equivalents of the amine mixture used). The reaction is
exothermic. The mixture is blown with nitrogen while it is being
heated to 240.degree. C. in 4.5 hours and thereafter heated at this
temperature for 2 hours. Water is collected as the distillate. To
the above residue ethylene oxide (140 parts) is added at
170E-180.degree. C. within a period of 2 hours while nitrogen is
bubbled through the reaction mixture. The reaction mixture is then
blown with nitrogen for 15 minutes and diluted with 940 parts of
xylene to a solution containing 25% of xylene. The resulting
solution has a nitrogen content of 5.4% and a base number of 82 at
pH of 4, the latter being indicative of free amino groups.
[0126] Antifoam Agents
[0127] In one embodiment, the lubricating compositions contain at
least one antifoam agent. Antifoam agents are well-known in the art
as silicone or fluorosilicone compositions. Such antifoam agents
are available from Dow Corning Chemical Corporation and Union
Carbide Corporation. Useful antifoam product is Dow FS-1265, Dow
Corning DC-200 ,Union Carbide UC-L45 and polyacrylate antifoamer
available from Monsanto Polymer Products Co. of Nitro, W. Va. known
as PC-1 244. Also, a siloxane polyether copolymer antifoamer
available from OSI Specialties, Inc. of Farmington Hills, Mich. and
may also be included. One such material is sold as
SILWET-L-7220.
[0128] Polyacrylates or acrylic polymers are also known antifoam
agents are disclosed in U.S. Pat. No. 3,166,508 and UK patent
publication GB 2,234,978. These references are hereby incorporated
by reference. Polyacrylates are commercially available from several
manufactures and the types used as antifoamants are typically
polymers and copolymers comprising one or more of ethyl acrylate
and 2-ethylhexyl acrylate, along with other monomers, such as
vinylacetate, as is known to those skilled in the art. A useful
antifoam agent is a copolymer of ethyl acrylate and 2-ethylhexyl
acrylate sold by Monsanto as PC-1244 defoamer was used as the
polyacrylate. The antifoam agents are included in the compositions
of this invention at a level from about 100 to 2000, or from about
150 to 1500, or from about 200 to 1000 parts per million with the
active ingredient being on an oil-free basis.
[0129] Antioxidant
[0130] In another embodiment, the lubricant may also contain one or
more antioxidants. In one embodiment, the antioxidant is present in
an amount from about 0.001% to about 5%, or from about 0.01% to
about 2%, or from about 0.05% to about 1% by weight of the
lubricating composition. The antioxidants may be present in a total
amount generally from about 1.5% up to about 10%, or about 1.8% up
to about 8%, or from about 1.9% up to about 6% by weight. In
another embodiment, the lubricating composition contains at least
about 1% by weight of an amine antioxidant, a dithiocarbamate
antioxidant, or mixture thereof. In one embodiment, the antioxidant
is an amine antioxidant, or a dithiocarbamate antioxidant. In one
embodiment, the antioxidants are ashless, i.e., free of metal. In
another embodiment, the antioxidant is other than a polyphenol.
[0131] Amine antioxidants include alkylated aromatic amines and
heterocyclic amines. The alkylated aromatic amines include
compounds represented by the formula Ar.sup.1-NR.sub.1-Ar.sup.2,
wherein Ar.sup.1 and Ar.sup.2 are independently mononuclear or
polynuclear, substituted or unsubstituted aromatic groups; and
R.sub.1 is hydrogen, halogen, OH, NH.sub.2, SH, NO.sub.2 or a
hydrocarbyl group having from 1 to about 50 carbon atoms. The
aromatic group as represented by "Ar", as well as elsewhere in
other formulae in this specification and in the appended claims,
may be mononuclear or polynuclear. Examples of mononuclear Ar
moieties include benzene moieties, such as 1,2,4-benzenetriyl;
1,2,3-benezenetriyl; 3-methyl-1,2,4-benzenetriyl;
2-methyl-5-ethyl-1,3,4-- benzenetriyl;
3-propoxy-1,2,4,5-benzenetetrayl; 3-chloro-1,2,4-benzenetriy- l;
1,2,3,5-benzenetetrayl; 3-cyclohexyl-1,2,4-benzenetriyl; and
3-azocyclopentyl- 1,2,5-benzenetriyl, and pyridine moieties, such
as 3,4,5-azabenzene; and 6-methyl-3,4,5-azabenzene. The polynuclear
groups may be those where an aromatic nucleus is fused at two
points to another aromatic nucleus, such as naphthyl and
anthracenyl groups. Specific examples of fused ring aromatic
moieties Ar include: 1,4,8-naphthylene; 1,5,8-naphthylene;
3,6-dimethyl-4,5,8(1 -azonaphthalene); 7-methyl-9-methoxy-1,2,5,
9-anthracenetetrayl; 3,10-phenathrylene; and
9-methoxy-benz(a)phenanthrene-5,6,8,12-yl. The polynuclear group
may be those where at least two nuclei (either mononuclear or
polynuclear) are linked through bridging linkages. These bridging
linkages may be chosen from the group consisting of alkylene
linkages, ether linkages, keto linkages, sulfide linkages, and
polysulfide linkages of 2 to about 6 sulfur atoms. Specific
examples of Ar when it is linked polynuclear aromatic moiety
include: 3,3',4,4',5-bibenzenetetrayl; di(3,4-phenylene) ether;
2,3-phenylene-2,6-naphthylenemethane; and 3-methyl,9H-fluorene-1,2-
,4,5,8-yl; 2,2-di(3,4-phenylene)propane; sulfur-coupled
3-methyl-1,2,4-benzatriyl (having 1 to about 10 thiomethylphenylene
groups); and amino-coupled 3-methyl-1,2,4-benzatriyl (having 1 to
about 10 aminomethylphenylene groups). Typically Ar is a benzene
nucleus, lower alkylene bridged benzene nucleus, or a naphthalene
nucleus.
[0132] In another embodiment, the alkylated aromatic amine is
represented by the formula R.sub.2--Ar--NH--Ar--R.sub.3, wherein
R.sub.2 and R.sub.3 are independently hydrogen or hydrocarbyl
groups having from 1 to about 50, or from about 4 to about 20
carbon atoms. Examples of aromatic amines include
p,p'-dioctyldiphenylamine; octylphenyl-beta-naphthylamine;
octylphenyl-"-naphthylamine, phenyl-"-naphthylamine;
phenyl-beta-naphthylamine; p-octylphenyl-"-naphthylamine and
4-octylphenyl- 1 -octyl-beta-naphthylamine and
di(nonylphenyl)amine, with di(nonylphenyl)amine preferred. U.S.
Pat. Nos. 2,558,285; 3,601,632; 3,368,975; and 3,505,225 disclose
diarylamines useful as antioxidants. These patents are incorporated
herein by reference.
[0133] In another embodiment, the antioxidant may be a
phenothiazine. Phenothiazines include phenothiazine, substituted
phenothiazine, or derivatives so as those described in U.S. Pat.
Nos. 4,785,095, and 5,883,057 and the disclosures of the patent are
hereby incorporated by reference for its teachings of such methods
and compounds. In one embodiment, a dialkyldiphenylamine is treated
with sulfur at an elevated temperature such as in the range of
145.degree. C. to 205.degree. C. for a sufficient time to complete
the reaction. A catalyst, such as iodine, may be utilized to
establish the sulfur bridge.
[0134] Phenothiazine and its various derivatives may be converted
to the above compounds by contacting the phenothiazine compound
containing the free NH group with a thioalcohol of the formula
R.sub.5SR.sub.4OH where R.sub.4 is an alkylene, alkenylene or an
aralkylene group, or mixtures thereof, R.sub.5 is selected from the
group consisting of higher alkyl groups, or an alkenyl, aryl,
alkaryl or aralkyl group and mixtures thereof; each R.sub.6 is
independently alkyl, alkenyl, aryl, alkyl, arylalkyl, halogen,
hydroxyl, alkoxy, alkylthio, arylthio, or fused aromatic rings, or
mixtures thereof; a and b are each independently 0 or greater. In
one embodiment, R.sub.4 contains from about 2 to about 8, or two or
three carbon atoms. R.sub.5 typically contains from about 3 to
about 30, or from about 4 to about 15 carbon atoms. R.sub.6
contains from 1 to about 50, or from about 4 to about 30, or from 6
to about 20 carbon atoms. The thioalcohol may be obtained by the
reaction of a mercaptan (e.g. a C.sub.4-30 mercaptan), such as
hexanethiol, octanethiol and dodecanethiol, with an alkylene oxide,
such as ethylene or propylene oxide under basic conditions.
Alternatively, the thioalcohol may be obtained by reacting a
terminal olefin, such as those described herein, with
mercaptoethanol under free radical conditions. In another
embodiment, the phonothiazone derivatives are prepared by the
reaction with the thioalcohols described above are oxidized with an
oxidizing agent, such as hydrogen peroxide, in a solvent such as
glacial acetic acid or ethanol under an inert gas blanket. The
partial oxidation takes place conveniently at from about 20.degree.
C. to about 15.degree. C.
[0135] In another embodiment, the antioxidant (A) is at least one
phenol antioxidant. The phenol antioxidants include metal and metal
free hindered phenols. Alkylene coupled derivatives of hindered
phenols and phenol sulfides or sulfur coupled phenols may also be
used. Hindered phenols are defined as those containing a sterically
hindered hydroxyl group, and these include those derivatives of
dihydroxy aryl compounds wherein the hydroxyl groups are in the o-
or p-position to each other. The phenols may have one or more alkyl
groups. In one embodiment, alkyl groups are derived from one or
more of the above polyalkenes. The alkyl groups may be derived from
polymers of ethylene, propylene, 1-butene and isobutene, propylene
tetramers or trimers are particularly useful. Examples of R.sub.2
groups include hexyl, heptyl, octyl, decyl, dodecyl, tripropenyl,
tetrapropenyl, etc. Examples of R.sub.1, R.sub.2 and R.sub.3 groups
include propyl, isopropyl, butyl, sec-butyl, tert-butyl, heptyl,
octyl, and nonyl. In another embodiment, each R.sub.1 and R.sub.3
are tertiary groups, such as tert-butyl or tert-amyl groups. The
phenolic compounds may be prepared by various techniques, and in
one embodiment, such phenols are prepared in stepwise manner by
first preparing the para-substituted alkylphenol, and thereafter
alkylating the para-substituted phenol in the 2- and/or 6-position
as desired. When it is desired to prepare coupled phenols, the
second step alkylation is conducted under conditions which result
in the alkylation of only one of the positions ortho to the
hydroxyl group. Examples of useful phenolic materials include:
2-t-butyl-4-heptylphenol; 2-t-butyl-4-octylphenol;
2-t-butyl-4-dodecylphenol; 2,6-di-t-butyl-4-butylphenol;
2,6-di-t-butyl-4-heptylphenol; 2,6-di-t-butyl-4-dodecylphenol;
2,6-di-t-butyl-tetrapropenylphenol;
2-methyl-6-di-t-butyl-4-heptylphenol;
2,6-di-t-butyl-tripropenylphenol; 2,4-dimethyl-6-t-butylphenol;
2,6-t-butyl-4-ethylphenol; 4-t-butyl catechol;
2,4-di-t-butyl-p-cresol; 2,6-di-t-butyl-4-methylphenol; and
2-methyl-6-di-t-butyl-4-dodecylphenol. Examples of the ortho
coupled phenols include: 2,2'-bis(6-t-butyl-4-hepty- lphenol);
2,2'-bis(6-t-butyl-4-octylphenol); 2,6-bis-(1'-methylcyclohexyl)-
-4-methylphenol; and 2,2'-bis (6-t-butyl-4-dodecylphenol).
[0136] Alkylene-coupled phenolic compounds may be prepared from the
phenols by reaction of the phenolic compound with an aldehyde,
typically those containing from one to about eight carbon atoms,
such as formaldehyde or acetaldehyde, aldehyde precursors, such as
paraformaldehyde or trioxane, or a ketone, such as acetone. The
alkylene-coupled phenols may be obtained by reacting from 0.3 to
about 2 moles a phenol with 1 equivalent of an aldehyde or ketone.
Procedures for coupling of phenolic compounds with aldehydes and
ketones are known to those in the art. Examples of phenolic
compounds include 2,2'-methylenebis(6-t-butyl-4-heptylphenol);
2,2'-methylenebis(6-t-butyl-- 4-octylphenol);
2,2'-methylenebis(4-dodecyl-6-t-butylphenol);
2,2'-methylenebis(4-octyl-6-t-butylphenol); 2,2'-methylenebis
(4-octylphenol); 2,2'-methylenebis(4-dodecylphenol);
2,2'-methylenebis(4-heptylphenol);
2,2'-methylenebis(6-t-butyl-4-dodecylp- henol);
2,2'-methylenebis(6-t-butyl-4-tetrapropenylphenol); and
2,2'-methylenebis (6-t-butyl-4-butyl phenol).
[0137] In another embodiment, the antioxidant is a metal-free (or
ashless) alkylphenol sulfide or sulfur coupled phenols. The
alkylphenols from which the sulfides are prepared also may comprise
phenols of the type discussed above and represented by Formula III
wherein R.sub.3 is hydrogen. For example, the alkylphenols which
can be converted to alkylphenol sulfides include:
2-t-butyl-4-heptylphenol; 2-t-butyl-4-octylphenol; and 2-t-
butyl-4-dodecylphenol; 2-t-butyl-4-tetrapropenylphenol. The term
"alkylphenol sulfides" is meant to include di-(alkylphenol)
monosulfides, disulfides, and polysulfides, as well as other
products obtained by the reaction of the alkylphenol with sulfur
monochloride, sulfur dichloride or elemental sulfur. One mole of
phenol typically is reacted with about 0.5-1.5 moles, or higher, of
sulfur compound. For example, the alkylphenol sulfides are readily
obtained by mixing, one mole of an alkylphenol and 0.5-2.0 moles of
sulfur dichloride. The reaction mixture is usually maintained at
about 100 C. for about 2-5 hours, after which time the resulting
sulfide is dried and filtered. When elemental sulfur is used,
temperatures from about 150-250.degree. C. or higher are typically
used. It is also desirable that the drying operation be conducted
under nitrogen or a similar inert gas. A particularly useful
alkylphenol sulfide is thio-bis(tetrapropenylphenate).
[0138] Suitable basic alkylphenol sulfides are disclosed, for
example, in U.S. Pat. Nos. 3,372,116; 3,410,798; and 4,021,419,
which are hereby incorporated by reference. These sulfur-containing
phenolic compositions described in U.S. Pat. No. 4,021,419 are
obtained by sulfurizing a substituted phenol with sulfur or a
sulfur halide and thereafter reacting the sulfurized phenol with
formaldehyde or an aldehyde precursor, e.g., paraformaldehyde or
trioxane. Alternatively the substituted phenol may be first reacted
with formaldehyde or paraformaldehyde and thereafter reacted with
sulfur or a sulfur halide to produce the desired alkylphenol
sulfide.
[0139] Oil of Lubricating Viscosity
[0140] The lubricant and concentrate include an oil of lubricating
viscosity. The oil of lubricating viscosity is generally present in
a major amount (i.e. an amount greater than about 50% by weight).
In one embodiment, 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 oils of
lubricating viscosity include natural or synthetic lubricating oils
and mixtures thereof. Natural oils include animal oils, vegetable
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. Unrefined, refined, and rerefined oils, either
natural or synthetic, may be used in the compositions of the
present invention. A description of oils of lubricating viscosity
occurs in U.S. Pat. No. 4,582,618 (column 2, line 37 through column
3, line 63, inclusive), herein incorporated by reference for its
disclosure to oils of lubricating viscosity.
[0141] In one embodiment, the oil of lubricating viscosity is a
polyalpha-oletin (PAO). Typically, the polyalpha-olefins are
derived from monomers having from about 3 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.degree. C.
Examples of PAOs include 4 cSt polyolefins, 6 cSt polyolefins, 40
cSt polyolefins and 100 cSt polyalphaolefins.
[0142] In one embodiment, the oil of lubricating viscosity are
selected to provide lubricating compositions with a kinematic
viscosity of at least about 3.5 cSt, or at least about 4.0 cSt at
100.degree. 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-90, 75W-1 40, 80W-90, 80W-1 40,
85W-90, or 85W-1 40.
[0143] In one embodiment, the oil of lubricating viscosity is a
mineral oil. The mineral oils have an iodine number of less than 9
and/or at least about 45% of the saturates present as aliphatic
saturates. Iodine value is determined according to ASTM D-460. In
one embodiment, the mineral oil has a iodine value less than about
8, or less than about 6, or less than about 4. The saturates level
are determined by mass spectrometer. By mass spectroscopy, Group I
stocks have about 70% saturates, Group II stocks have about 95% to
about 98% saturates and Group IlIl stocks have about 98%-100%
saturates. Group II stocks have greater than 50% of their saturates
present as cycloparaffinic compounds. The saturates of the mineral
oils used in the present invention typically have at least about
45%, or at least about 50%, or at least about 60% aliphatic
saturates. These aliphatic saturates are often referred to as
paraffinic saturates. The cyclic saturates are generally referred
to as cycloparaffinic saturates. Cyclic saturates compose the
balance of the saturates in the mineral oils. The inventors have
discovered that mineral oils having a higher proportion of
aliphatic saturates have better oxidation properties and low
temperature properties.
[0144] As use herein the term "mineral oil" refers to oils of
lubricating viscosity which are derived from petroleum crude. The
petroleum crudes may be subjected to processing such as
hydroprocessing, hydrocracking, and isomerizing. Hydroprocessing
includes processes such as sequential isocracking, isodewaxing and
hydrofinishing. These mineral oils are those referred to as Group
IlIl basestock or base oils. In one embodiment, the mineral oil has
less than 0.3% or less than 0.1% sulfur. In another embodiment, the
oils of lubricating viscosity generally have a viscosity index of
120 or more.
[0145] Examples of useful oils of lubricating viscosity include HVI
and XHVI basestocks, such isomerized wax base oils and UCBO
(Unconventional Base Oils) base oils. Specific examples of these
base oils include 1OON 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),
10ON 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 15ON solvent
refined/ hydrotreated paraffinic mineral oil (0.17% sulfur/127 VI).
Further examples of the mineral oils include those Group IlIl
basestocks made by Texaco such as the TEXHVI stocks which include
TEXHVI-100N (95% saturates, 125 viscosity index and 0.02% sulfur);
TEXHVI-70N (97.8% saturates, 123 viscosity index and 0.02% sulfur);
Texaco "MOTIVA" TEXHVI 90N-1OON (100% saturates, 125 viscosity
index and 0.01% sulfur); and "MOTIVA" TEXHVI 75N (100% saturates,
125 viscosity index and 0.0% sulfur). Examples of useful Group III
basestocks made by Chevron include UCBO 200N (100% saturates, 142
viscosity index and 0.005% sulfur); UCBO 1OON (100% saturates, 129
viscosity index, and 0.004% sulfur).
[0146] Polymers
[0147] In one embodiment, the multigrade lubricant will have at
least one polymer present. The polymer generally is present in an
amount from about 3% to about 40%, or from about 5% to about 35%,
or from about 10% to about 30% by weight of the lubricating
composition. The polymers include a polyalkene or derivative
thereof, an ethylene-"-olefin copolymer, an ethylene-propylene
polymer, an "-olefin-unsaturated carboxylic reagent copolymer, a
polyacrylate, a polymethacrylate, a hydrogenated interpolymer of an
alkenylarene and a conjugated diene, and mixtures thereof. Here,
and elsewhere in the specification and claims, any member of a
genus (or list) may be excluded from claims.
[0148] In one embodiment, the polymer is characterized by an Mw
(weight average molecular weight) of less than about 50,000, or
less than about 45,000, or less than about 40,000. In one
embodiment, the polymer has an Mw of less than about 25,000, or
less than about 10,000, or less than about 7,000. Typically the
polymer has an Mw of at least about 1,000, or at least about 2,000,
or at least about 3,000. In one embodiment, the polymer is
characterized by an Mn (number average molecular weight) of up to
about 6000, or up to about 5000. Generally, the polymer is
characterized by having an Mn from about 800 to about 6000, or from
about 900 to about 5000, or from about 1000 to 4000. In another
embodiment, the polymers have a Mn from about 1300 to about 5000,
or from about 1500 to about 4500, or from about 1700 to about 3000.
The polymers also generally have a Mw/Mn from about 1.5 to about 8,
or from about 1.8 to about 6.5, or from about 2 to about 5.5.
[0149] In one embodiment, the polymer may be a sheared polymer of
higher molecular weight, e.g. greater than 50,000. In this
embodiment, a higher molecular weight polymer is sheared to the
desired molecular weight. The shearing may be done in any suitable
apparatus, such as an extruder, an injector, an FZG apparatus,
etc.
[0150] The abbreviation Mw and Mn is the conventional symbol
representing weight average and number average molecular weight,
respectively. Gel permeation chromatography (GPC) is a method which
provides both molecular weights as well as the entire molecular
weight distribution of the polymers. For purpose of this invention
a series of fractionated polymers of isobutene, polyisobutene, is
used as the calibration standard in the GPC. The techniques for
determining n and w values of polymers are well known and are
described in numerous books and articles. For example, methods for
the determination of n and molecular weight distribution of
polymers is described in W. W. Yan, J. J. Kirkland and D. D. Bly,
"Modern Size Exclusion Liquid Chromatographs," J. Wiley & Sons,
Inc., 1979.
[0151] In one embodiment, the polymer is one of the polyalkenes
described herein. In another embodiment, the polymer is a
derivative of a polyalkene. The derivatives are typically prepared
by reacting one or more of the above polyalkenes or a halogenated
derivative thereof with an unsaturated reagent. The halogenated
polyalkenes are prepared by reacting a polyalkene with a halogen
gas, such as chlorine. The preparation of these materials is known
to those in the art. The unsaturated reagents include unsaturated
amines, ethers, and unsaturated carboxylic reagents, such as
unsaturated acids, esters, and anhydrides. Examples of unsaturated
amines include unsaturated amides, unsaturated imides, and nitrogen
containing acrylate and methacrylate esters. Specific examples of
unsaturated amines include acrylamide, N,NN-methylene
bis(acrylamide), methacrylamide, crotonamide, N-(3,6-diazaheptyl)
maleimide, N-(3-dimethylaminopropyl) maleimide,
N-(2-methoxyethoxyethyl) maleimide, N-vinyl pyrrolidinone, 2- or
4-vinyl pyridine, dimethylaminoethyl methacrylate and the like.
[0152] In one embodiment, the unsaturated carboxylic reagent is an
acid, anhydride, ester, or mixtures thereof. If an ester is
desired, it can be prepared by reacting an unsaturated carboxylic
acid or anhydride with a polyalkene or halogenated derivative
thereof and subsequently reacting the reaction product with an
alcohol to form the ester. The unsaturated carboxylic reagents
include acrylic acid, methacrylic acid, cinnamic acid, crotonic
acid, 2-phenylpropenoic acid, maleic acid, maleic anhydride,
fumaric acid, mesaconic acid, itaconic acid and citraconic acid
maleic, fumaric, acrylic, methacrylic, itaconic, and citraconic
acids, esters, and anhydrides (where possible). The esters may be
represented by one of the formulae:
(R.sub.1).sub.2C.dbd.C(R.sub.1)C(O)OR- .sub.2, or
R.sub.2O--(O)C--HC.dbd.CH--C(O)OR.sub.2, wherein each R.sub.1 and
R.sub.2 are independently hydrogen or a hydrocarbyl group having 1
to about 30, or to about 12, or to about 8 carbon atoms, R.sub.1 is
hydrogen or an alkyl group having from 1 to about 6 carbon atoms.
In one embodiment, R.sub.1 ispreferably hydrogen or a methyl group.
In another embodiment, R.sub.2 is an alkyl or hydroxyalkyl group
having from about 1 to about 30, or from 2 to about 24, or from
about 3 to about 18 carbon atoms. R.sub.2 may be derived from one
or more alcohols described below. Unsaturated carboxylic esters
include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate,
2-hydroxyethyl acrylate, ethyl methacrylate, 2-hydroxyethyl
methacrylate, 2-hydroxypropyl methacrylate, 2-2-hydroxypropyl
acrylate, ethyl maleate, butyl maleate and 2-ethylhexyl maleate.
The above list includes mono- as well as diesters of maleic,
fumaric, and itaconic acids and anhydrides.
[0153] The polyalkene derivatives are prepared by means known to
those in the art. These materials have been referred to as
hydrocarbyl substituted carboxylic acylating agents, and are
discussed below. U. S. Pat. Nos. 3,219,666 and 4,234,435 describe
the polyalkene derivatives and methods of making the same and are
incorporated for such descriptions.
[0154] In another embodiment, the polymer is an ethylene-"-olefin
copolymer. Typically, the copolymer is a random copolymer. The
copolymer generally has from about 30% to about 80%, or from about
50% to about 75% by mole of ethylene. The "-olefins include butene,
pentene, hexene or one more of the described above described
"-olefins. In one embodiment, the "-olefin contains from about 3 to
about 20, or from about 4 to about 12 carbon atoms. In one
embodiment, the ethylene-"-olefin copolymers have an Mw from about
10,000 up to about 40,000, or from about 15,000 up to about 35,000,
or from about 20,000 up to about 30,000. In another embodiment, the
ethylene-"-olefin copolymers have an n from about 800 to about
6000, or from about 1500 to about 5000, or from about 2000 to about
4500. Examples of ethylene "-olefins copolymers include
ethylene-butene copolymers and ethylene-octene copolymers. Examples
of commercially available copolymers include Lucant HC 600 and
Lucant HC 2000 (Mw=25,000), available from Mitsui Petrochemical
Co.,Ltd.
[0155] In another embodiment, the polymer is an ethylene propylene
polymer. These polymers include ethylene propylene copolymers and
ethylene propylene terpolymers. When the ethylene propylene polymer
is an ethylene propylene copolymer (EPM, also called EPR polymers),
it may be formed by copolymerization of ethylene and propylene
under known conditions, such as Ziegler-Natta reaction conditions.
In one embodiment, ethylene propylene copolymers contain units
derived from ethylene in an amount from about 40% to about 70%, or
from about 50% to about 60%, or about 55% by mole, the remainder
being derived from propylene. The molecular weight distribution may
be characterized by a polydispersity (Mw/Mn) from about 1 to about
8, or from about 1.2 to about 4.
[0156] In another embodiment, the ethylene propylene polymer is a
terpolymer of ethylene, propylene and a diene monomer. In one
embodiment, the diene is a conjugated diene. The dienes are
disclosed herein. The terpolymers are produced under similar
conditions as those of the ethylene propylene copolymers. Useful
terpolymers contain units derived form ethylene in amount from
about 10% to about 80%, or from about 25% to about 85%, or about
35% to about 60% by mole, and units derived from propylene in
amount from about 15% to about 70%, or from about 30% to about 60%
by mole, and units derived from diene third monomer in amount from
about 0.5% to about 20%, or from about 1% to about 10%, or about 2%
to about 8% by mole. The following table contains examples of
ethylene propylene terpolymers.
1 Example Ethylene Propylene Diene A 42%* 53% 5% 1,5 heptadiene B
48% 48% 4% dicyclopentadiene C 45% 45% 10%
5-ethylidene-2-norbornene D 48% 48% 4% 1,6 octadiene E 48% 48% 4%,
4 cyclohexadiene F 50% 45% 4% 5-methylene-2-norbornene *Percentages
are by mole
[0157] In one embodiment, the ethylene propylene polymer is a
terpolymer of ethylene, propylene and dicyclopentadiene or
ethylidene norbornene, available commercially as Trilene elastomers
from the Uniroyal Corporation. A useful ethylene propylene
terpolymer is Trilene CP-40. The ethylene propylene polymers are
prepared by means know to those in the art. U.S. Pat. No. 3,691,078
describes ethylene propylene polymers and methods of preparing
them, and is incorporated by reference for such disclosures.
[0158] In another embodiment, the polymer is a copolymer of an
"-olefin and an unsaturated reagent. The "-olefins may be any of
those discussed above, and include propylene, 1-butene, 2-methyl
propene, 2-methyl-1-octene, and 1-decene. The unsaturated reagents
are described above. The unsaturated carboxylic reagents include
acrylates, methacrylates, maleates and fumarates. The
"-olefin-unsaturated carboxylic reagent polymers are prepared by
means known to those in the art. Examples of "-olefin-unsaturated
carboxylic reagent copolymers include
poly(octene-co-ethylacrylate), poly(decene-co-butylmethacrylate),
poly(hexene-co-maleic anhydride), poly(octene-co-methyl fumarate)
and the like.
[0159] In another embodiment, the polymer is a polyacrylate or
polymethacrylate. The polyacrylates and polymethacrylates include
homopolymers and interpolymers of one or more of the above
described acrylic or methacrylic acids or esters. The polyacrylates
and polymethacrylates include the Acryloid 1019 polymers, available
from Rohm and Haas Company, Garbacryl 6335 available from Societe
Francaise d'Organo-Sythese (SFOS), LZ 7720C available from The
Lubrizol Corporation, and Viscoplex 0-101 polymers, available from
Rohm Darmstadt.
[0160] In another embodiment, the polymer is a hydrogenated
interpolymer of an vinyl substituted aromatic compound and a
conjugated diene. The interpolymers include diblock, triblock and
random block interpolymers. The vinyl substituted aromatic
compounds generally have from about 8 to about 20, or from about 8
to about 18, or from about 8 to about 12 carbon atoms. Examples of
vinyl substituted aromatics include styrene, "-methylstyrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene,
p-t-butylstyrene, with styrene being preferred. The conjugated
dienes are described above. Isoprene and 1,3-butadiene are
preferred conjugated dienes.
[0161] The vinyl substituted aromatic content of these copolymers
is in the range from about 20% to about 70%, or from about 40% to
about 60% by weight. Thus, the conjugated diene content is in the
range from about 30% to about 80%, or from about 40% to about 60%
by weight. These interpolymers are prepared by conventional methods
well known in the art. Such copolymers usually are prepared by
anionic polymerization using, for example, an alkali metal
hydrocarbon (e.g., sec-butyllithium) as a polymerization catalyst.
Examples of suitable hydrogenated copolymers of a vinyl substituted
aromatic compound and a conjugated diene include Shellvis-40, and
Shellvis-50, both hydrogenated styrene-isoprene block copolymers,
manufactured by Shell Chemicals.
[0162] Fluidizing Agent
[0163] The lubricating compositions may additionally contain at
least one fluidizing agent. Generally, the fluidizing agent is
present in an amount up to about 30% by weight. Typically the
fluidizing agent is present in an amount from about 3% to about
30%, or from about 5% to about 28%, from about 10% to about 27%, or
from about 15% to about 25% by weight of the lubricating
composition. The amount of fluidizing agent equals the total amount
of fluidizing agents in the lubricating compositions.
[0164] In one embodiment, the fluidizing agent is at least one
member selected from the group consisting of an alkylated aromatic
hydrocarbon, a naphthenic oil, a poly"-olefin having a kinematic
viscosity from about 3 to about 20 cSt at 1 00.degree. C., a
carboxylic acid esters, and mixtures of two or more thereof. The
alkylated aromatic hydrocarbons typically include mono- or di- (or
mono-) substituted benzenes wherein the substituents are
hydrocarbon-based groups having from about 8 to about 30, or from
about 10 to about 14 carbon atoms. An example is Alkylate A- 215 (a
237 molecular weight alkylated benzene) and Alkylate A-230 (a 230
molecular weight alkylated benzene) available from Monsanto.
[0165] The naphthenic oils are those derived from naphthenic crudes
such as found in the Louisiana area. The viscosity of such
naphthenic oils at 40.degree. C. generally is less than 4
centistokes and more generally within the range of from about 3.0
to about 3.8 centistokes. At 100.degree. C. the viscosity of the
desirable naphthenic crudes is within the range of about 0.8 to
about 1.6 centistokes.
[0166] The poly"-olefins (PAOs) are described above. Examples of
useful PAOs include those derived from one or more of the above
olefins, such as the "-olefins. These PAOs may have a viscosity
from about 2 to about 30, or from about 3 to about 20, or from
about 3 to about 8 cSt at 100EC. Examples of PAOs include 4 cSt
poly"-olefins, 6 cSt poly"-olefins, and 8 cSt poly"-olefins. A
particularly useful PAO is derived from decene.
[0167] The carboxylic ester fluidizing agents are reaction products
of dicarboxylic esters with alcohols having from about 1 to about
30, or from about 2 to about 18, or from about 3 to about 12 carbon
atoms. The alcohols are described below and include methyl, ethyl,
propyl, butyl, hexyl, heptyl, octyl, decyl and dodecyl alcohols.
The dicarboxylic acids generally contain from about 4 to about 18,
or from about 4 to about 12, or from about 4 to about 8 carbon
atoms. Examples of dicarboxylic acids include phthalic acid,
succinic acid, alkyl (C.sub.1-24 )succinic acids, azelaic acid,
adipic acid, and malonic acid. Particularly useful esters are
dicarboxylic esters of C.sub.1-12 alcohols, such as esters of
propyl, butyl, pentyl, hexyl, and octyl alcohols and azelaic acid.
In one embodiment, the lubricating compositions contain less than
about 20%, or less than about 15% by weight of carboxylic ester
fluidizing agent.
[0168] The above-described mineral oil may be used with
commercially available gear and transmission concentrates such as
those sold by Exxon, Lubrizol, Ethyl and Mobil corporations. In
this embodiment, those commercial concentrates are diluted with the
basestocks to form the transmission and gear formulations.
[0169] The combinations may be used in lubricants or in
concentrates. The concentrate may contain the above combinations
and/or other components used in preparing fully formulated
lubricants. The concentrate also contains a substantially inert
organic diluent, which includes kerosene, mineral distillates, or
one or more of the oils of lubricating viscosity discussed herein.
The combinations are present in a final product, blend, or
concentrate in any amount effective to act as an antiwear,
antiweld, and/or extreme pressure agents in lubricating
compositions.
[0170] In one embodiment, the lubricating composition is free of
sulfurized olefins and fatty acids or esters. In another
embodiment, the lubricating composition is free of overbased metal.
In another embodiment, the lubricating composition is free of zinc
dithiophosphates. In another embodiment, the lubricating
composition is free of added lead compounds, such as lead
napthanates, dithiophosphates and dithiocarbamates. In another
embodiment, the lubricating composition is free of succinimides
derived from olefins or polyolefins and ammonia or a mono-amine. In
another embodiment, the lubricating composition is free of
detergents or overbased metal salts of acidic organic
compounds.
[0171] Other Additives
[0172] The invention also contemplates the use of other additives
together with the above combinations. Such additives include, for
example, detergents and dispersants, corrosion- and
oxidation-inhibiting agents, pour point depressing agents, extreme
pressure agents, antiwear agents, color stabilizers and anti-foam
agents.
[0173] The detergents are exemplified by oil-soluble neutral and
basic salts (i.e. overbased salts) of alkali or alkaline earth
metals with sulfonic acids, carboxylic acids, phenols or organic
phosphorus acids, such as those described above. The oil-soluble
neutral or basic salts of alkali or alkaline earth metal salts may
also be reacted with a boron compound. Examples of useful overbased
and borated overbased metal salts include sodium, calcium and
magnesium overbased and borated overbased sulfonates and
carboxylates, including the above hydrocarbyl substituted
carboxylic acylating agents.
[0174] Auxiliary extreme pressure agents and corrosion- and
oxidation-inhibiting agents which may be included in the lubricants
of the invention are exemplified by chlorinated aliphatic
hydrocarbons such as chlorinated waxes; sulfurized alkylphenols;
phosphosulfurized hydrocarbons, such as the reaction product of a
phosphorus sulfide with turpentine or methyl oleate; metal
thiocarbamates, such as zinc dioctyldithiocarbamate, and barium
diheptylphenyl dithiocarbamate; and ashless dithiocarbamates such
as reaction products of a dithiocarbamic acid and an unsaturated
acid, ester, anhydride, amide, ether, or imide. Many of the
above-mentioned extreme pressure agents and corrosion- and
oxidation-inhibitors also serve as antiwear agents.
[0175] Pour point depressants are an additive often included in the
lubricating oils described herein. Examples of useful pour point
depressants are polymethacrylates; polyacrylates; polyacrylamides;
condensation products of haloparaffin waxes and aromatic compounds;
vinyl carboxylate polymers; and polymers of dialkylfumarates, vinyl
esters of fatty acids and alkyl vinyl ethers. Pour point
depressants useful for the purposes of this invention, techniques
for their preparation and their uses are described in U.S. Pat.
Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498;
2,666,746; 2,721,877; 2,721,878; and 3,250,715, which are hereby
incorporated by reference for their relevant disclosures.
[0176] It is understood that any of the above described additives
that are taught as potential ingredients may be restricted from the
lubricating compositions.
[0177] The following examples relate to lubricating compositions
containing thiadiazole.
EXAMPLE 1
[0178] An industrial gear oil is prepared by blending 0.95 parts of
2, 5- bis (tert nonyldithio) 1,3,4-thiadiazole into an industrial
gear basestock.
EXAMPLE 2
[0179] An industrial gear oil is prepared by blending 1.2 parts of
2-mercapto, 5-tert nonyldithio- 1,3,4 thiadiazole and 0.02 parts of
as 50% solution of an ester copolymer made from ethyl acrylate and
2-ethylhexyl acrylate (100:40) into an industrial gear oil base
stock.
EXAMPLE 3
[0180] An industrial gear oil is prepared by blending 1.2 parts of
the thiadiazole from Example 1, 0.02 parts of the ester copolymer
of Example 1, and 0.4 parts of the product of Example P-3.
EXAMPLE 4
[0181] An industrial gear oil is prepared as described in Example
3, except 1.2 parts of the product of Example P-8 replaces the
product of Example P-3.
EXAMPLE 5
[0182] An industrial gear oil is prepared as described in Example 2
except that 0.05 parts of the product of Example 1-2 is included in
the industrial gear oil.
EXAMPLE 6
[0183] An industrial gear oil is prepared as described in Example 4
except that 0.05 parts of the product of Example 1-2 in included in
the industrial gear oil.
EXAMPLE 7
[0184] An industrial gear oil is prepared as described in Example 6
except that 0.02 parts of tolyltriazole is also included.
EXAMPLE 8
[0185] An industrial gear oil is prepared as described in Example 7
except that 0.05 parts of a 40% oil solution of a dispersant (the
reaction product of a polyisobutenyl succinic anhydride (Mn 850)
and polyethylene polyamines and having a TBN of 70) and 0.01 parts
of Pluradyne FL1 1 (ethylene oxide-propylene oxide copolymer
available from BASF).
EXAMPLE 9
[0186] A manual transmission fluid is prepared by blending 1.1
parts of 2,5- bis (tert nonyldithio) 1,3,4-thiadiazole into a
manual transmission basestock.
EXAMPLE 10
[0187] A manual transmission fluid is prepared by blending 1.5
parts of 2-mercapto, 5- tert nonyldithio- 1,3,4 thiadiazole and
0.01 parts of a kerosene solution of Dow Corning 200 Fluid
(kinematic viscoisty of 30,000 cSt) into a manual transmission base
stock.
EXAMPLE 9A
[0188] A manual transmission fluid is prepared by blending 1.5
parts of 2, 5- bis (tert nonyidithio) 1,3,4-thiadiazole and 0.5
parts of the product of Example P-8 into a manual transmission
basestock.
EXAMPLE 10B
[0189] A manual transmission fluid is prepared as described in
Example 9 except that 0.01 parts of a kerosene solution of Dow
Corning 200 Fluid (kinematic viscoisty of 30,000 cSt) is also
included into a manual transmission fluid.
EXAMPLE 11
[0190] A manual transmission fluid is prepared as described in
Example 10 except that 0.5% of dinonyidiphenyl amine is also
included in the manual transmission fluid.
EXAMPLE 12
[0191] A manual transmission fluid is prepared as described in
Example 11 except that 1.5 parts of a 42% oil solution of overbased
calcium substitutetd benzenesulfonate (300 TBN, 12% calcium, and
40.8% sulfated ash) is also included.
EXAMPLE 13
[0192] A manual transmission fluid is prepared as described in
Example 12 except that 1 part of a 50% oil solution of a dispersant
(the reaction product of a polyisobutenyl succinic anhydride (Mn
1500) and polyethylene polyamines and having a TBN of 27) is also
included.
[0193] 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.
* * * * *