U.S. patent application number 11/372443 was filed with the patent office on 2007-06-21 for salt of a sulfur-containing, phosphorus-containing compound, and methods thereof.
Invention is credited to David J. DeGonia, Ronald L. Phillips, Roger M. Sheets.
Application Number | 20070142660 11/372443 |
Document ID | / |
Family ID | 37671934 |
Filed Date | 2007-06-21 |
United States Patent
Application |
20070142660 |
Kind Code |
A1 |
DeGonia; David J. ; et
al. |
June 21, 2007 |
Salt of a sulfur-containing, phosphorus-containing compound, and
methods thereof
Abstract
There is disclosed a salt of a sulfur-containing,
phosphorus-containing compound. There is also disclosed a method of
making the salt.
Inventors: |
DeGonia; David J.;
(Midlothian, VA) ; Sheets; Roger M.; (Glen Allen,
VA) ; Phillips; Ronald L.; (Richmond, VA) |
Correspondence
Address: |
NEW MARKET SERVICES CORPORATION;(FORMERLY ETHYL CORPORATION)
330 SOUTH 4TH STREET
RICHMOND
VA
23219
US
|
Family ID: |
37671934 |
Appl. No.: |
11/372443 |
Filed: |
March 9, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60734757 |
Nov 9, 2005 |
|
|
|
Current U.S.
Class: |
558/161 |
Current CPC
Class: |
C10M 2223/049 20130101;
C07F 9/657118 20130101; C10M 2223/043 20130101; C10N 2030/10
20130101; C10N 2030/06 20130101; C10N 2030/08 20130101; F16H 57/04
20130101; C10M 137/105 20130101; C10M 2223/047 20130101; C07F
9/1652 20130101 |
Class at
Publication: |
558/161 |
International
Class: |
C07F 9/02 20060101
C07F009/02 |
Claims
1. An oil-soluble compound of formula (III): ##STR7## wherein
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7,
R.sup.8, and R.sup.9 are independently selected from the group
consisting of hydrogen, cyano, and hydrocarbyl groups comprising
from about 1 to about 30 carbon atoms.
2. The compound of claim 1, wherein R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, and R.sup.8 are hydrogen, R.sup.1 and R.sup.2 are
methyl, and, and R.sup.9 is a tertiary C.sub.12-14 alkyl group.
3. A compound of formula (VI): ##STR8## wherein n is an integer
from 1 to 5; and wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, and R.sup.11
are independently selected from the group consisting of hydrogen,
cyano, and hydrocarbyl groups comprising from about 1 to about 30
carbon atoms.
4. The compound of claim 3, wherein R.sup.1 and R.sup.2 are methyl,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are
hydrogen; R.sup.9 is a tertiary C.sub.12-14 alkyl group; and
R.sup.10 and R.sup.11 are alkyl groups comprising from about 1 to
about 6 carbon atoms
5. A process of preparing a salt of sulfur-containing,
phosphorus-containing compound comprising: providing a
sulfur-containing compound, a nitrogen-containing compound and at
least one compound of formula (I) and (IV): ##STR9## wherein n is
an integer from 1 to 5; and wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.10, and R.sup.11 are independently
selected from the group consisting of hydrogen, cyano, and
hydrocarbyl groups comprising from about 1 to about 30 carbon
atoms.
6. The process of claim 5, wherein in the compound of formula (I),
R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are hydrogen; and R.sup.1
and R.sup.2 are methyl.
7. The process of claim 5, wherein in the compound of formula (IV),
R.sup.1 and R.sup.2 are methyl; R.sup.3, R.sup.4, R.sup.5, and
R.sup.6 are hydrogen; and R.sup.10 and R.sup.11 are alkyl groups
comprising from about 1 to about 6 carbon atoms.
8. The process of claim 5, wherein the sulfur-containing compound
is chosen from elemental sulfur, polysulfide, and sulfurized
olefin.
9. The process of claim 8, wherein the sulfur-containing compound
is elemental sulfur.
10. The process of claim 5, wherein at least an equimolar
equivalent or greater of the sulfur-containing compound is
used.
11. The process of claim 5, wherein the reaction temperature ranges
from about 23.degree. C. to about 90.degree. C.
12. The process of claim 5, wherein the salt of the
sulfur-containing, phosphorus-containing compound is at least one
of a compound of formula (III) and (VI): ##STR10## wherein n is an
integer from 1 to 5; and wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, and
R.sup.11 are independently selected from the group consisting of
hydrogen, cyano, and hydrocarbyl groups comprising from about 1 to
about 30 carbon atoms.
13. The process of claim 12, wherein in the formula (III), R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are hydrogen;
R.sup.1 and R.sup.2 are methyl; and, and R.sup.9 is a tertiary
C.sub.12-14 alkyl group.
14. The process of claim 12, wherein in the formula (VI), R.sup.1
and R.sup.2 are methyl; R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7, and R.sup.8 are hydrogen; R.sup.9 is a tertiary
C.sub.12-14 alkyl group; and R.sup.10 and R.sup.11 are alkyl groups
comprising from about 1 to about 6 carbon atom.
15. The process of claim 5, wherein the nitrogen-containing
compound is an amine.
16. The process of claim 5, wherein the nitrogen-containing
compound is chosen from linear and branched amines.
17. The process of claim 16, wherein the amine is a branched amine
chosen from a mixture of C.sub.8-16 tertiary alkyl primary amines
and a mixture of C.sub.14-24 tertiary alkyl primary amines.
18. The process of claim 16, wherein the nitrogen-containing
compound is a linear amine.
19. The process of claim 5, wherein from about 0.05 to about 2
molar equivalents of the nitrogen-containing compound are used.
20. The process of claim 11, wherein the process takes from about 1
to about 8 hours.
21. A composition comprising a reaction product of a
nitrogen-containing compound, a neopentyl glycol phosphite, and a
sulfur-containing compound.
Description
RELATED APPLICATIONS
[0001] This application claims the benefit of priority of U.S.
Provisional Application No. 60/734,757, filed on Nov. 9, 2005.
FIELD OF THE DISCLOSURE
[0002] The present disclosure relates to a salt of a
sulfur-containing, phosphorus-containing compound, and methods of
making the salt.
BACKGROUND OF THE DISCLOSURE
[0003] The use of phosphorous-containing compounds for use in
lubricant compositions is known. In particular, the
phosphorous-containing compounds generally comprise linear alkyl
chains. However, the problem with these compounds is that they are
known to be thermally unstable at elevated temperatures in a fully
formulated gear lubricant. A thermally unstable compound is more
likely to prematurely decompose in the lubricant composition and
would no longer provide a property, such as antiwear, to the
lubricant composition.
[0004] Lubricant compositions, such as gear oils, typically are
subjected to elevated temperatures and therefore it would be
beneficial to provide a thermally stable compound that would not
prematurely decompose at higher temperatures. A thermally stable
compound would therefore remain in the lubricant composition for an
extended period of time and provide the property, e.g., antiwear,
to the composition over the extended period of time. What is needed
is a compound that has the proper thermal stability to sustain its
antiwear property.
SUMMARY OF THE DISCLOSURE
[0005] In accordance with the disclosure, there is disclosed an
oil-soluble compound of formula (III): ##STR1## wherein R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, and
R.sup.9 are independently selected from the group consisting of
hydrogen, cyano, and hydrocarbyl groups comprising from about 1 to
about 30 carbon atoms.
[0006] There is also disclosed a compound of formula (VI):
##STR2##
[0007] wherein n is an integer from 1 to 5; and
[0008] wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 are
independently selected from the group consisting of hydrogen,
cyano, and hydrocarbyl groups comprising from about 1 to about 30
carbon atoms.
[0009] In another aspect, there is disclosed a process of preparing
a salt of sulfur-containing, phosphorus-containing compound
comprising: providing a sulfur-containing compound, a
nitrogen-containing compound and at least one compound of formula
(I) and (IV): ##STR3## wherein n is an integer from 1 to 5; and
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.10, and R.sup.11 are independently selected from the group
consisting of hydrogen, cyano, and hydrocarbyl groups comprising
from about 1 to about 30 carbon atoms.
[0010] Further, there is also disclosed a composition comprising a
reaction product of a nitrogen-containing compound, a neopentyl
glycol phosphite, and a sulfur-containing compound.
[0011] Additional objects and advantages of the disclosure will be
set forth in part in the description which follows, and/or can be
learned by practice of the disclosure. The objects and advantages
of the disclosure will be realized and attained by means of the
elements and combinations particularly pointed out in the appended
claims.
[0012] It is to be understood that both the foregoing general
description and the following detailed description are exemplary
and explanatory only and are not restrictive of the disclosure, as
claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a graph illustrating the thermal stability of
various phosphorus-containing species.
DESCRIPTION OF THE EMBODIMENTS
[0014] As used herein, the term "hydrocarbyl substituent" or
"hydrocarbyl group" is used in its ordinary sense, which is
well-known to those skilled in the art. Specifically, it refers to
a group having a carbon atom directly attached to the remainder of
the molecule and having predominantly hydrocarbon character.
Examples of hydrocarbyl groups include:
[0015] (1) hydrocarbon substituents, that is, aliphatic (e.g.,
alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)
substituents, and aromatic-, aliphatic-, and alicyclic-substituted
aromatic substituents, as well as cyclic substituents wherein the
ring is completed through another portion of the molecule (e.g.,
two substituents together form an alicyclic radical);
[0016] (2) substituted hydrocarbon substituents, that is,
substituents containing non-hydrocarbon groups which, in the
context of this invention, do not alter the predominantly
hydrocarbon substituent (e.g., halo (especially chloro and fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and
sulfoxy);
[0017] (3) hetero substituents, that is, substituents which, while
having a predominantly hydrocarbon character, in the context of
this invention, contain other than carbon in a ring or chain
otherwise composed of carbon atoms. Heteroatoms include sulfur,
oxygen, nitrogen, and encompass substituents as pyridyl, furyl,
thienyl and imidazolyl. In general, no more than two, for example
no more than one, non-hydrocarbon substituent will be present for
every ten carbon atoms in the hydrocarbyl group; typically, there
will be no non-hydrocarbon substituents in the hydrocarbyl
group.
[0018] As used herein, the term "percent by weight", unless
expressly stated otherwise, means the percentage the recited
component represents to the weight of the entire composition.
[0019] In an aspect, there is provided a compound having at least
one of improved antiwear and thermal stability. The compound can be
a sulfur-containing, phosphorus-containing compound and/or its salt
that can comprise steric hindrance to minimize and/or prevent
decomposition of the compound at high temperatures. The disclosed
compound and/or its salt can exhibit improved thermal stability and
therefore remain in a lubricant composition longer than a
composition that does not include steric hindrance. The steric
hindrance can be present in any form, such as branching of
hydrocarbyl chains, dependant hydrocarbyl chains, etc.
[0020] A phosphorus-containing compound, such as a phosphite or a
phosphate can be used in the process disclosed herein. Methods of
making both phosphites and phosphates are known. For example,
phosphites can be made by reacting either phosphorous acid or
different phosphites with various alcohols. Another synthesis
method includes reacting phosphorus trichloride with an excess of
alcohol. Moreover, cyclic phosphites can be made by
transesterification of phosphites with glycols, which can result in
a mixture of monomeric and polymeric products. See Oswald, Alexis
A., "Synthesis of Cyclic Phosphorous Acid Esters by
Transesterification," Can. J. Chem., 37:1498-1504 (1959); and Said,
Musa A., et al., "Reactivity of Cyclic Arsenites and Phosphites:
X-ray structures of bis(5,5-dimethyl-1,3,2,-diosarsenan-2-yl)ether
and
bis(2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g][1,3,2]dioxarsenocin-6-yl)e-
ther," J. Chem. Soc., 22:2945-51 (1995), the disclosures of which
are hereby incorporated by reference. Methods for making cyclic
hydrogen thiophosphites are also known, such as by reacting a
cyclic chlorophosphite with hydrogen sulfide in the presence of
pyridine. See Zwierzak, A., "Cyclic organophosphorus compounds. I.
Synthesis and infrared spectral studies of cyclic hydrogen
phosphites and thiophosphites, Can. J. Chem., 45:2501-12 (1967),
the disclosure of which is hereby incorporated by reference.
[0021] In an aspect, the phosphite can be a di- or tri-hydrocarbyl
phosphite. Each hydrocarbyl group can have from about 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 can be
independently alkyl, alkenyl, aryl, and mixtures thereof. When the
hydrocarbyl group is an aryl group, then it can contain at least
about 6 carbon atoms; or from about 6 to about 18 carbon atoms.
Non-limiting examples of the alkyl or alkenyl groups include
propyl, butyl, hexyl, heptyl, octyl, oleyl, linoleyl, stearyl, etc.
Non-limiting examples of aryl groups include phenyl, naphthyl,
heptylphenol, etc. In an aspect, each hydrocarbyl group can be
independently methyl, propyl, butyl, pentyl, hexyl, heptyl, oleyl
or phenyl, for example methyl, butyl, oleyl or phenyl, and as a
further example methyl, butyl, oleyl, or phenyl.
[0022] Non-limiting examples of useful phosphites include dibutyl
hydrogen phosphonate, diisobutyl hydrogen phosphonate, dioleyl
hydrogen phosphonate, di(C.sub.14-18) hydrogen phosphonate,
triphenyl phosphite, a dihydrocarbyl phosphite, such as a compound
of formula (I), and a polymeric phosphite, such as a compound of
formula (IV), both shown below. ##STR4##
[0023] wherein n is an integer from about 1 to about 5; and
[0024] wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.10, and R.sup.11 can be independently selected from
the group consisting of hydrogen, cyano, and hydrocarbyl groups
comprising from about 1 to about 30 carbon atoms, for example from
about 1 to about 20 carbon atoms, and as a further example from
about 1 to about 10 carbon atoms. In an aspect, if n is an integer
greater than about 5, it is believed, without being limited to any
particular theory, that the repeating unit will not completely
sulfurize.
[0025] In an aspect, in the compound of formula (I), R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 can be hydrogen; and R.sup.1 and
R.sup.2 can be methyl. This compound is commonly referred to as
neopentyl glycol phosphite (NPGP) and is registered with Chemical
Abstracts Select under the designation CAS # 4090-60-2
(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-one). In an aspect, in the
compound of formula (IV), R.sup.1 and R.sup.2 can be methyl;
R.sup.3, R.sup.4, R.sup.5, and R.sup.6 can be hydrogen; and
R.sup.10 and R.sup.11 can be alkyl groups comprising from about 1
to about 6 carbon atoms. This compound is a polymeric by-product of
the manufacturing process of neopentyl glycol phosphite.
[0026] The phosphorus-containing compound can also be at least one
of a phosphoric acid ester or salt thereof, a reaction product of a
phosphorus acid or anhydride and an unsaturated compound, and
mixtures of two or more thereof.
[0027] A metal dithiophosphate can be prepared by reacting a metal
base with at least one thiophosphorus acids, which can be mono- or
dithiophosphorus acids.
[0028] The phosphorus acid or anhydride can be reacted with an
unsaturated compound, including but not limited to, amides, esters,
acids, anhydrides, and ethers.
[0029] In an aspect, the phosphorus-containing compound, such as a
phosphite, can comprise various functional groups that increase the
steric hindrance of the compound and therefore increase its
resistance to thermal decomposition. In an aspect, the
phosphorus-containing compound can be branched at the position beta
to the oxygen atom in the hydrocarbyl chain. It is believed that
branching at this beta carbon can change, e.g., can improve, the
thermal stability of the phosphorus-containing compound in a
lubricant composition.
[0030] Moreover, the phosphorus-containing compound can be made
using components that would increase the resultant compound's
steric hindrance. For example, the alcohol used to make, for
example, the phosphite can be a beta-branched alcohol. Non-limiting
examples of beta-branched alcohols include isobutanol,
2-ethylhexanol, neopentyl glycol, neopentyl alcohol, pristanol, and
methyl isobutyl carbinol (MIBC).
[0031] The disclosed phosphorus-containing compound can be used as
a starting material to yield a salt of a sulfur-containing,
phosphorus-containing compound. In an aspect, the process for
making a salt of a sulfur-containing, phosphorus-containing
compound can comprise providing a phosphorus-containing compound,
such as those described above, a sulfur-containing compound, and a
nitrogen-containing compound to yield the salt of the
sulfur-containing, phosphorus-containing compound. In another
aspect, there is contemplated a composition comprising a reaction
product of a nitrogen-containing compound; a phosphorus-containing
compound, such as a neopentyl glycol phosphite; and a
sulfur-containing compound. The reaction product can provide
improved antiwear properties as compared to a
non-sulfur-containing, phosphorus-containing compound.
[0032] The sulfur-containing compound can be any compound that
comprises free and/or active sulfur. Non-limiting examples of
sulfur-containing compounds include sulfurized animal or vegetable
fats or oils, sulfurized animal or vegetable fatty acid esters,
fully or partially esterified esters of trivalent or pentavalent
acids of phosphorus, sulfurized olefins, dihydrocarbyl
polysulfides, sulfurized Diels-Alder adducts, sulfurized
dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty
acid esters and monounsaturated olefin, co-sulfurized blends of
fatty acid, fatty acid ester and .alpha.-olefin,
functionally-substituted dihydrocarbyl polysulfides,
thio-aldehydes, thio-ketones and derivatives thereof (e.g., acids,
esters, imines, or lactones), epithio compounds, sulfur-containing
acetal derivatives, co-sulfurized blends of terpene and acyclic
olefins, polysulfide olefin products, and elemental sulfur.
[0033] In an aspect, the sulfur-containing compound can be made by
reacting an olefin, such as isobutene, with sulfur. The product,
e.g., sulfurized isobutylene or sulfurized polyisobutylene,
typically has a sulfur content of 10 to 55%, for example 30 to 50%
by weight. A wide variety of other olefins or unsaturated
hydrocarbons, e.g., isobutene dimer or trimer, can be used to form
such sulfur-containing compounds.
[0034] In another aspect, polysulfides composed of one or more
compounds represented by the formula: R.sup.20--S.sub.x--R.sup.21
where R.sup.20 and R.sup.21 can be hydrocarbyl groups each of which
can contain from about 3 to about 18 carbon atoms and x can be in
the range of from about 2 to about 8, for example in the range of
from about 2 to about 5, and as a further example can be 3. The
hydrocarbyl groups can be of widely varying types such as alkyl,
cycloalkyl, alkenyl, aryl, or aralkyl. Tertiary alkyl polysulfides
such as di-tert-butyl trisulfide, and mixtures comprising
di-tert-butyl trisulfide (e.g., a mixture composed principally or
entirely of the tri, tetra-, and pentasulfides) can be used.
Examples of other useful dihydrocarbyl polysulfides include the
diamyl polysulfides, the dinonyl polysulfides, the didodecyl
polysulfides, and the dibenzyl polysulfides.
[0035] The sulfur-containing compound can be used in at least an
equimolar or greater amount per equivalent of phosphorus-containing
compound. In an aspect, from about 1 to about 1.5 molar equivalents
of the sulfur-containing compound can be used.
[0036] The disclosed process can include the use of solvents. The
solvent can be any inert fluid substance in which at least one of
the reactants is soluble or the product is soluble. Non-limiting
examples include benzene, toluene, xylene, n-hexane, cyclohexane,
naphtha, diethyl ether carbitol, dibutyl ether dioxane,
chlorobenzene, nitrobenzene, carbon tetrachloride, chloroform,
polyalphaolefin, base oil, and process oil.
[0037] The disclosed process further comprises providing a
nitrogen-containing compound. The nitrogen-containing compound can
help promote the sulfurization of the disclosed
phosphorus-containing compound and/or can help neutralize any
acids. Any nitrogen-containing compound can be used so long as it
is soluble in the lubricating composition which can comprise a base
oil. Non-limiting examples of the nitrogen-containing compound
include an amide, an amine, and a heterocyclic compound comprising
a basic nitrogen, such as pyridine. In an aspect, the
nitrogen-containing compound is an amine, which can be primary,
secondary, or tertiary.
[0038] In an aspect, the hydrocarbyl amines can be primary
hydrocarbyl amines comprising from about 4 to about 30 carbon atoms
in the hydrocarbyl group, and for example from about 8 to about 20
carbon atoms in the hydrocarbyl group. The hydrocarbyl group can be
saturated or unsaturated. Representative examples of primary
saturated amines are those known as aliphatic primary fatty amines.
Typical fatty amines include alkyl amines such as n-hexylamine,
n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine,
n-pentadecylamine, n-hexadecylamine, n-octadecylamine (stearyl
amine), etc. These primary amines are available in both distilled
and technical grades. While the distilled grade can provide a purer
reaction product, amides and imides can form in reactions with the
amines of technical grade. Also suitable are mixed fatty
amines.
[0039] In an aspect, the amine salts of the disclosed compounds can
be those derived from tertiary-aliphatic primary amines having at
least about 4 carbon atoms in the alkyl group. For the most part,
they can be derived from alkyl amines having a total of less than
about 30 carbon atoms in the alkyl group.
[0040] Usually the tertiary aliphatic primary amines are monoamines
represented by the formula ##STR5## wherein R.sup.1, R.sup.2, and
R.sup.3 can be the same or different and can be a hydrocarbyl group
containing from about one to about 30 carbon atoms. Such amines are
illustrated by tertiary-butyl amine, tertiary-hexyl primary amine,
1-methyl-1-amino-cyclohexane, tertiary-octyl primary amine,
tertiary-decyl primary amine, tertiary-dodecyl primary amine,
tertiary-tetradecyl primary amine, tertiary-hexadecyl primary
amine, tertiary-octadecyl primary amine, tertiary-tetracosanyl
primary amine, tertiary-octacosanyl primary amine.
[0041] Mixtures of amines are also useful for the purposes of this
disclosure. Illustrative of amine mixtures of this type can be a
mixture of C.sub.8-C.sub.16 tertiary alkyl primary amines and a
similar mixture of C.sub.14-C.sub.24 tertiary alkyl primary amines.
The tertiary alkyl primary amines and methods for their preparation
are well known to those of ordinary skill in the art and,
therefore, further discussion is unnecessary. The tertiary alkyl
primary amine useful for the purposes of this disclosure and
methods for their preparation are described in U.S. Pat. No.
2,945,749, which is hereby incorporated by reference for its
teaching in this regard.
[0042] Primary amines in which the hydrocarbon chain comprises
olefinic unsaturation also can be quite useful. Thus, the R groups
can contain at least one olefinic unsaturation depending on the
length of the chain, usually no more than one double bond per 10
carbon atoms. Representative amines are dodecenylamine,
myristoleylamine, palmitoleylamine, oleylamine and
linoleylamine.
[0043] Secondary amines include dialkylamines having two of the
above alkyl groups including fatty secondary amines, and also mixed
dialkylamines where R' can be a fatty amine and R'' can be a lower
alkyl group (1-9 carbon atoms) such as methyl, ethyl, n-propyl,
i-propyl, butyl, etc., or R'' can be an alkyl group bearing other
non-reactive or polar substituents (CN, alkyl, carbalkoxy, amide,
ether, thioether, halo, sulfoxide, sulfone). The fatty polyamine
diamines can include mono-or dialkyl, symmetrical or asymmetrical
ethylene diamines, propane diamines (1,2, or 1,3), and polyamine
analogs of the above. Suitable fatty polyamines include
N-coco-1,3-diaminopropane, N-soyaalkyl trimethylenediamine,
N-tallow-1,3-diaminopropane, and N-oleyl-1,3-diaminopropane.
[0044] In an aspect, the nitrogen-containing compound is not
triethyl amine or cyclohexyl amine.
[0045] The nitrogen-containing compound can be provided in any
amount nitrogen-necessary to drive the disclosed process to
completion, i.e., if enough containing compound is not present then
the phosphorus-containing compound does not completely sulfurize.
In an aspect, the nitrogen-containing compound can be provided in
an amount ranging from about 0.05 to about 2, and for example from
about 1 to about 1.5 molar equivalent per equivalent of
phosphorus-containing compound.
[0046] The disclosed process can occur at room about temperature
(23.degree. C.) or above, for example at least about 50.degree. C.,
and as a further example ranging from about 50.degree. C. to about
90.degree. C. Generally, mixing at room temperature for a period
ranging from about 1 minute to about 8 hours can be sufficient.
[0047] The resultant compound can be a compound of at least one
formulae (III) and (VI), both shown below. ##STR6##
[0048] wherein n is an integer from 1 to 5; and
[0049] wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 can be
independently selected from the group consisting of hydrogen,
cyano, and hydrocarbyl groups comprising from about 1 to about 30
carbon atoms, for example from about 1 to about 20 carbon atoms,
and as a further example from about 1 to about 10 carbon atoms.
[0050] In an aspect, in the compound of formula (III), R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 can be hydrogen;
R.sup.1 and R.sup.2 can be methyl; and R.sup.9 can be a tertiary
C.sub.12-.sub.14 alkyl group. In an aspect, in the compound of
formula (VI), R.sup.1 and R.sup.2 can be methyl; R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.7, and R.sup.8 can be hydrogen; R.sup.9 can
be a tertiary C.sub.12-.sub.14 alkyl group; and R.sup.10 and
R.sup.11 can be alkyl groups comprising from about 1 to about 6
carbon atoms.
[0051] Methods for the preparation of such salts are well known and
reported in the literature. See for example, U.S. Pat. Nos.
2,063,629; 2,224,695; 2,447,288; 2,616,905; 3,984,448; 4,431,552;
5,354,484; Pesin et al, Zhurnal Obshchei Khimii, 31(8): 2508-2515
(1961); and PCT International Application Publication No. WO
87/07638, the disclosures of which are hereby incorporated by
reference.
[0052] The salt of the sulfur-containing, phosphorus-containing
compound can be formed separately and then added to a lubricating
or functional fluid composition. Alternatively, the salt can be
formed when the phosphorus-containing compound, such as the
disclosed phosphite, is blended with other components to form the
lubricating or functional fluid composition. However, if the salt
is formed in situ then it is important to restrict the acids, such
as anti-rust components, present in the composition because the
acids can react with the nitrogen-containing compound and stop the
sulfurization and salt formations.
[0053] The salt of a sulfur-containing, phosphorus-containing
compound can be oil-soluble, i.e., the hydrocarbyl chains of the
salt can be of sufficient length, such as at least six carbon
atoms, so that the resultant compound is soluble in a formulated
composition. The incorporation of hydrophobic groups can lead to an
increase in solubility in a non-polar media. Non-limiting examples
of a salt of a sulfur-containing, phosphorus-containing compound
include diisobutyl thiophosphoric acid C.sub.8-16 tertiary alkyl
primary amine salt, di-2-ethylhexyl-thiophosphoric acid C.sub.8-16
tertiary alkyl primary amine salt, and neopentyl glycol
thiophosphoric acid C.sub.8-16 tertiary alkyl primary amine salt.
In an aspect, there is contemplated a salt of a dithiophosphoric
acid.
EXAMPLES
Example 1
Sulfurization of Neopentyl Glycol Phosphite (NPGP) with a Branched
Amine
[0054] A 1L reactor equipped with a pressure equalizing addition
funnel was charged with sulfur (53.3 g, 1.7 mol), a
nitrogen-containing compound (PRIMENE.RTM. 81R) (320.7 g, 1.7 mol)
and 4 cSt polyalphaolefin (375.6 g). The addition funnel was then
charged with liquid NPGP (250.04 g, 1.7 mol). The NPGP is a solid
at standard conditions and has a melting point ranging from about
60.degree. C. to about 65.degree. C. The additional funnel was
heated to avoid solidification.
[0055] With stirring and under a blanket of nitrogen, the NPGP was
added to the reactor while keeping the mass temperature from about
60 to about 90.degree. C. The rate of the addition was governed by
the ability of the reaction system to control the exotherm. The
process is exothermic; therefore, cooling of the reaction mass
during the addition was required. After the addition was completed,
the reaction mixture was stirred at 70 to 90.degree. C. for 2 to 6
hours until all of the sulfur was consumed.
[0056] The observed P-31 NMR chemical shift (ppm) of the sulfurized
NPGP was 52.96.
[0057] As discussed above, any sulfur-containing compound can be
used as the sulfur source so long as there is free and active
sulfur. For example, it is envisaged that the following process
would also make the disclosed compounds.
[0058] A 2 L reactor equipped with a pressure equalizing addition
funnel can be charged with
2,5-bis-(t-nonyldithio)-1,3,4-thiadiazole (396.8 g, 0.85 mol),
PRIMENE.RTM. 81R (320.7 g, 1.7 mol) and 4Cst PAO (375.6 g). The
addition funnel could then be charged with liquid NPGP (250.04 g,
1.7 mol). The NPGP is a solid at standard conditions and has a
melting point ranging from about 60.degree. C. to about 65.degree.
C. to melt. The additional funnel could be heated to avoid
solidification.
[0059] With stirring and under a blanket of nitrogen, the NPGP
should be added to the reactor while keeping the mass temperature
from about 60 to about 90.degree. C. The rate of the addition is
governed by the ability of the reaction system to control the
exotherm. After the addition is completed, the reaction mixture can
be stirred at from about 70 to about 90.degree. C. for about 2
hours.
Example 2
Sulfurizing of Neopentyl Glycol Phosphite (NPGP) with a Linear
Amine
[0060] A 1 L reactor equipped with a pressure equalizing addition
funnel can be charged with sulfur (53.3 g, 1.7 mol), a
nitrogen-containing compound (ARMEEN.RTM. OL) (464.1 g, 1.7 mol)
and 4cSt polyalphaolefin (375.6 g). The addition funnel can then be
charged with liquid NPGP (250.04 g, 1.7 mol). The NPGP is a solid
at standard conditions and has a melting point ranging from about
60.degree. C. to about 65.degree. C. to melt. The additional funnel
should be heated to avoid solidification. With stirring and under a
blanket of nitrogen, the NPGP can be added to the reactor while
keeping the mass temperature from about 60 to 90.degree. C. The
rate of the addition can be governed by the ability of the reaction
system to control the exotherm. The process is exothermic;
therefore, cooling of the reaction mass during the addition can be
required. After the addition is complete, the reaction mixture can
be stirred at from about 70 to about 90.degree. C. for about 2 to
about 6 hours until all of the sulfur is consumed.
Example 3
Antiwear Effectiveness
[0061] The potential of the antiwear effectiveness was measured by
the duration of the phosphorous species at an elevated temperature.
A fully formulated gear fluid was placed in a heated bath at about
325.degree. F. Aliquots of the fully formulated gear fluid were
pulled at timed intervals and the .sup.31Phosphorus Nuclear
Magnetic Resonance (NMR) spectrum was taken. The phosphorus species
observed in the .sup.31Phosphorus NMR spectrum were plotted versus
time and thermal decomposition. A profile for the phosphorus
antiwear species was created. The rate or amount of decomposition
of the phosphorus species was dependant on the chemical structure
of the hydrocarbyl chain. Examples of the phosphorus antiwear
components were the dialkylthiophosphoric acid amine salts. The
changes to the alkyl branching changed the thermal decomposition
rate of the dialkylthiophosphoric acid amine salts in the heat bath
at 325.degree. F. The thermal stabilization was most effective when
the beta carbon to the phosphorus-oxygen bond was branched with
methyl or a high homolog alkyl group. Examples of the increased
stability as demonstrated by a shallower slope are shown in FIG.
1.
[0062] For the purposes of this specification and appended claims,
unless otherwise indicated, all numbers expressing quantities,
percentages or proportions, and other numerical values used in the
specification and claims, are to be understood as being modified in
all instances by the term "about." Accordingly, unless indicated to
the contrary, the numerical parameters set forth in the following
specification and attached claims are approximations that can vary
depending upon the desired properties sought to be obtained by the
present disclosure. At the very least, and not as an attempt to
limit the application of the doctrine of equivalents to the scope
of the claims, each numerical parameter should at least be
construed in light of the number of reported significant digits and
by applying ordinary rounding techniques.
[0063] It is noted that, as used in this specification and the
appended claims, the singular forms "a," "an," and "the," include
plural referents unless expressly and unequivocally limited to one
referent. Thus, for example, reference to "an antioxidant" includes
two or more different antioxidants. As used herein, the term
"include" and its grammatical variants are intended to be
non-limiting, such that recitation of items in a list is not to the
exclusion of other like items that can be substituted or added to
the listed items.
[0064] While particular embodiments have been described,
alternatives, modifications, variations, improvements, and
substantial equivalents that are or can be presently unforeseen can
arise to applicants or others skilled in the art. Accordingly, the
appended claims as filed and as they can be amended are intended to
embrace all such alternatives, modifications variations,
improvements, and substantial equivalents.
* * * * *