Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
This invention relates to lubricating oils and
more particularly to improved lubricating oils containing
additives, such as anti-wear and friction-reducing com-
pounds, corrosion inhibitors and oxidation inhibitors.
It is well recognized in the petroleum industry
that boron-containlny compounds are desirable additives for
for lubricating oils. One such boron con-taining compound
is disclosed in United States Patent 3,224,971 to Knowles
et al. which relates to intracomplexed borate esters and
to lubricating compositions containing said esters. The
borate esters are organo-boron compounds derived from boric
acid and a bis(o-hydroxy-alkylphenyl) amine or sulfide.
Another extreme pressure lubrication composition
is disclosed in U.S. Patent 3,185,644 to Knowles et al ,
which relates to lubricating compositions containing amine
salts of boron-containing compounds. The amine salts are
formed by reaction of a hydroxy substituted amine and a
trihydrocarbyl borate. The amine-borate compounds thus
formed are described as useful as load carrying additives
for mineral and synthetic base lubricating oils.
Boric-acid-alkylolamine reaction products and
lubricating oils containing the same are disclosed in
United States Patent 3,227,739 to Versteeg. These amine
type products are prepared by reacting equal molar propor-
tions of diethanolamine or dipropanolamine and a long
chain, 1, 2-epoxide. The intermediate reaction product
thus produced is reacted with boric acid to produce the
final reaction product. These compounds are added to
lubricants to prevent rust formation.
Another boron ester composition is described in
United ~tates Patent 3,269,853 to English et al. which
discloses a boron ester curing agent which consists of a
cyclic ring structure containing boron, oxygen, nitrogen,
carbon and hydrogen.
Another boron composition is disclosed in United
States Patent 3,598,855 to Cyba which relates to cyclic
borates of polymeric alkanolamines Eormed by reacting a
borylating agent with a polymeric alkanolamine. The com-
pounds thus formed are described as additives for a widevariety of petroleum products including lubricating oils.
Currently, there are phosphorus-containing
additives which provide extreme pressuxe, anti-wear and/or
friction-reducing properties to automotive engine oils.
However, with the advent of the catalytic converter,
alternative additives are needed. During combustion in an
automotive engine, any oil which leaks or seeps into the
combustion chamber yields phosphorus deposits which poison
the catalyst in the catalytic converter. ~s a result,
there is a need for automotive engine oil additives which
are phosphorus-free but provide useful extreme pressure,
anti-wear, and/or friction-reducing properties to the oil.
Briefly, the invention resides in a boron-
containing heterocyclic compound of the formula:
[R - \R2
~ ~r~
wherein M is an inorganic or organic radical; R, Rl and R2
are the same or different organic radical; and y is an
integer.
The invention further resides in a boron-
containing heterocyclic compound of the foxmula:
r /Rl O~
R2
Y
wherein y is an integer; M is a metal selected from the
periodic groups IB, IIB, IIIB, IVB, V~3, VIB, VIIB, VIII,
IIIA, IVA, VA; R is, an inorganic radical or a Cl to C50
organic radical; and Rl and R2 are the same or di~ferent
Cl to C50 organic radical.
The invention further resides in a boron-contain-
ing heterocylic compound of the formula:
- ~1 - -
R N~ ~B M~Y
2 i
y
wherein y is an integer; M is a Cl to C50 organic radical;
R is an inorganic radical or Cl to C50 organic radical;
and Rl and R2 are the same or different C3 or greater
substituted or unsubstituted organic radicals provided
that at least one of Rl and R2 is other than an unsub-
stituted or alkyl-substituted ortho-alkyl phenyl bridge
with the o~cygen connected to the phenyl carbon.
The invention further resides in a boron-
containing heterocyclic compound of the formula:
~7~
[ R - ~N < R~ O B- -O ]
wherein M is hydrogen; R is an inorganic radical
or a C1 to C50 orc~anic radical; and R1 and R2 are the same
or different C4 or greater substituted or unsubstituted
organic radicals provided at least one of R1 or R2 is
other than an unsubstituted or alkyl-substituted ortho-
alkyl phenyl bridye with the oxygen connected to the
phenyl carbon.
The invention additionally resides in an extreme
pressure, anti-wear and friction-reducing lubricating oil
and a minor amount of a boron~containing, heterocyclic
compound as above-described.
The boron-containing, heterocyclic compounds may
conveniently be prepared by reacting either a saturated or
unsaturated primary amine wi-th an organic epoxide, such as
an alkyl epoxide or an aromatic epoxide, to form a reaction
product. The reaction product thus formed is reacted with
boric acid to form a boron-containing, heterocyclic com-
pound. Next, the boron-containiny, heterocyclic compound
may be reacted with either a salt of a metal, metalloid,
or semi-metal to produce a metal derivative of the boron-
containing, heterocyclic compound or with an alcohol to
produce an ester-type derivative.
Alternatively, the boron-containing heterocyclic
compounds may be produced by reacting either sulfur and/or
a halogen and/or a sulfur halide with a horon-containing,
heterocyclic compound containing unsaturateds in the R,
R1, R2, and M radicals.
The above-described, boron-containing, hetero-
cyclic compounds impart extreme pressure, anti-wear and
friction-reducing properties to lubricating oils when
added to said oils at use concentrations.
Another embodiment of the invention resides in a
lubricatlng composition comprising a boron-containing,
heterocyclic compound of the invention, and optionally any
of (1) a polysulfide derivative of 2,5-dimercapto-1,3,~-
thiodiazole, (2) terephthalic acid, and 13) either a
bis(dithiobenzil) metal derivative, a sulfur bridged,
bis(hindered phenol) or an alkylated or dialkylated
diphenyl amine or a mixture thereof.
In still another embodiment of the invention, a
copper compound is used with a borate of the present
invention in a lubricating compound. The copper compound
enhances the anti-wear properties of such a composition.
The present invention resides in extreme pressure,
anti-wear and friction-reducing lubricating oil compositions
comprising a major amount of an oil of lubricating viscosity
and a minor amount of a boron-containing, heterocyclic com-
pound~ Alternatively, corrosion inhibitors and anti-oxidants
may be incorporated into the lubricating composition.
Anti-wear, friction-reducing and extreme pressure
(or "E.P.") additives, as they are commonly called, are
chemicals which are added to lubricating compositions to
reduce friction and reduce or prevent destructive metal-
to-metal contact in the lubrication of moving surfaces.
It has now been discovered -that certain novel
oil-soluble or dispersible boron-containing, heterocyclic
compounds, when added to lubricatiny oils or grease, not
only improve the ability of the lubricant to prevent
seizure of the parts being lubricated (i.e., good E.P.
properties) but in addition greatly reduce the amount of
friction and wear of such moving parts.
The boron-containlng, heterocyclic compounds
described herein may be incorporated in a wide variety of
lubricating oils, for example, mineral oil, crude oil,
synthetic oil, industrial lubricating oils, cutting oil,
metal working fluids and grease. Ano-ther use for the
additive of the invention is in those fuels, e.g., certain
aviation fuels and the like, wherein lubrication properties
are desired. ~lowever, the most preferred use for the lubri-
cating additive of the invention is in automotive engine
oils. In this application, the boron-containing additives
provide extreme pressure, anti-wear, and friction-reducing
properties to the oil, and, upon combustion, prove innocu-
ous to the conventional catalytic converter in modernautomobiles.
If desired, the boron-containing, heterocyclic
compounds described herein may be employed in conjunction
with other additives commonly used in petroleum products.
Thus, there may be added to the oil compositions of this
invention rust and corrosion inhibitors, emulsifying
agents, antioxidants or oxidation inhibitors, dyes, haze
inhibitors, anti-static agents, detergents, dispersants,
viscosity index improvement agents, pour point reducing
~X~
agents, and other extreme pressure and anti-wear additives,
such as the zinc dithiophosphate, txiphenyl phosphorothio-
nate, etc. Soaps or other thickening agents may be added
to the lubricating oil compositions to form compositions
having the consistency of a grease. When other additives
are employecl, it may be desirable, although not necessary,
to prepare additive concentrates comprising concentrated
solutions of the herein boron-containing, heterocyclic
compounds together with said other additives whereby the
several additives are added simultaneously. Dissolution
of the additive or additive concentrate into the oil
composition may be facilitated by mixing accompanied with
mild heating, but this is not absolutely essential.
The herein-described boron-containing, hetero-
cyclic compounds may be incorporated in the lubricating
oils in any convenient way. Thus, boron-containing,
heterocyclic compounds may be added directly to the oil by
dissolving the desired boron derivative in the lubricating
oil at the desired level of concentration.
Normally, the boron-containing, heterocyclic
compound is blended with the lubricating oil such that its
concentration is from about 0.1 to about 15 percent by
weight, preferably from about 0.5 to about 10 percent by
weight of the resultant oil composition. Alternatively,
the compounds may first be blended with suitable solvents
to form concentrates that may readily be dissolved in the
appropriate oil at the desired concentration. If a
concentrate is prepared, it is presently preferred that
such concentrate comprise about 75 percent by weight of
6~3~
the compound, with the balance being a solvent. Sultable
solvents which may be used for this purpose are naphtha,
light mineral oil (iOe., 150 neutral -to ~50 neutral) and
mixtures thereof. The particular solvent selected should,
of course, be selected so as not to adversely affect the
other desired properties of the ultimate oil composition.
The boron-containiny, heterocyclic compounds of
the present invention are represented generically by the
following formula (I):
R 1 -
(I) R2 M Y
y
In the foregoing formula, R is an inorganic radical, e.g.,
hydrogen, chlorine, bromine, etc., or an organic radical
having rom about 1 to about 50 carbon atoms, typically
about l to 30 carbon atvms, and preferably from about 1 to
about 20 carbon atoms. Preferablyl R is derived from ali-
phatic, alicyclic, or aromatic compounds. Most preferably,
R is a substituted or unsubstituted hydrocarbyl group,
particularly an alkyl, alkenyl, alkynyl, aryl, alkyLaryl
or arylalkyl radical having from about 1 to about 30
carbon atoms, preferably from about 1 to about 20 carbon
atoms, especially from about 9 to about 20 carbon atoms.
Rl and R2 are the same or different organic radicals
bridging the nitrogen and oxygen atoms and have from about
1 to about 50 carbon atoms and preferably from about 2 to
about 30 carbon atoms, with R1 and R2 oftentimes containing
at least 3 or at least ~ carbon atoms. R1 and R2 are
--8~
typically derived from aliphatic, alicyclic, or aromatic
compounds and generally include at least two carbon atoms
bridged between the nitrogen and oxygen atoms. Usually,
Rl and R2 are the same or different substituted or unsub
stituted hydrocarbyl or hyclrocarbylo~y groups. Typical
hydrocarbyl groups, which Rl and R2 may be, are substituted
or unsubstituted al~ylaryl, aryl, arylalkyl, alkyl, alkynyl,
and alkenyl groups, with the most preferred radical bridging
the oxygen and nitrogen atoms (in this and all embodiments
hereinafter discussed with the exception of the embodiment
typified by formula (IV) hereinafter) being an alkylaryl
group wherein an ethylene radical bridges the oxygen and
nitrogen atoms and an unsubstituted phenyl radical is
bonded to the carbon closest to the oxygen atom, i.e.,
- N CH ~ CH - ~ - B -
Typical hydrocarbyloxy groups which may bridge the nitrogen
and oxygen atoms are those discussed hereinafter with
respect to formula (IV). y is an integer from 1 to 4 and
M is an organic or inorganic radical, but is usually
either hydrogen or a metal, typically selected from the
Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IIIA, IVA,
and VA of the Periodic Table, as found in the 1'Handbook of
Chemistry and Physics," CRC Publishing Co., 46th Edition.
Preferably, M is hydrogen or a transitlon metal having an
atomic number from 21 to 30 or a Group IVA metal of the
Periodic Table or mixtures thereof, and still more pref-
erably copper. If M is an organic radical, it is
typically of 1 to 50 carbon atoms and is derived from an
aliphatic, alicyclic, or aromatic compound. Preferred
radicals, when M is organic, are chosen from the group
consisting o~ substituted and unsubstituted alkyl,
alkynyl, alkenyl, aryl, arylalkyl, and alkylaryl ~roups of
between 1 and 50 carbon atoms, with methyl and cyclohexyl
radicals being among the most preferred groups. Also
among the most preferred groups, if M is organic, are
substituted and unsubstituted phenyl yroups, with
substituted phenyl groups being particularly preferred.
The phenyl group may be substituted with, for example, an
acetyl group, a methyl radical, or an O-CH3 group. One
of the most preferred substituted phenyl groups is the
hindered phenyl group wherein the phenyl group is
substituted at the 2 and 6 carbon atom of the phenyl ring
with an organic group having more than 3 carbon atoms,
e.g., the 2 r 6-di-tert-butyl phenyl groups, such as
~-methyl-2,6-di-tert-butyl phenyl. Hindexed phenyl groups
provide the compound with hydrolytic stability. It has
also been unexpectedly found that non-hindered phenyl
groups, whether substituted or unsubstituted, also provide
the compound with hydrolytic stability.
(It should be noted herein that the terms
"alkyl," "alkenyl," and "alkynyl" include cyclic species
thereoF, as well as the straight and branched chain
species thereof. Also, for purposes of this invention, an
"organic radical" is one which contains at least one
carbon atom whereas an "inorganic radical" contains none.
The term "inorganic radical," as used herein, is intended
to include metals, semi-metals, and metalloids, as well as
-10--
true inorganic radicals, e.g.l -Cl, -Br, ~ SO3, and
The metals, semi-metals, an~ meta].loids may be bond~d
ionically, covalently, or associatively.)
In one embodiment of the invention, useful when
M is either hydrogen or a metal, but particularly when
M is hydrogen, R is hydrogen or a substituted or unsubsti-
tuted hydrocarby.l. group and at least one of R1 and R2, if
both are aromatic, is other than an unsubstituted or alkyl
substituted ortho-alkyl phenyl bridge, with the oxygen
bonded at the ortho position relative to the alkyl group.
Usually, if both R1 and R2 are aromatic, at least one
contains no carbon atoms or three to five carbon atoms of
the same aromatic ring in a chain of atoms bridging (or
connecting) the oxygen atom to the nitrogen atom.
Generally in this embodiment, R contains at least 9 carbon
atoms if aliphatic and at least 7 carbon atoms if
aromatic; further, R in this embodiment, and sometimes
also R1 and R2, are organic radicals other than
hydroxyhydrocarbyl groups, and particularly other than
alkanol groups. Further still, it is preferred that at
least one of R1 and R2 in this embodlment and even more
preferably both are radicals other than an amino or
hydrocarbylamino group, and it is further preferred that
R1 and R2 contain only carbon atoms bridging the nitrogen
and oxygen atoms, with none of said bridging carbon atoms
being a member of an aromatic ring.
In a pre~erred embodiment, boron-containing,
heterocyclic compounds of the present invention are of
the followi.ng formula (II):
--1 1. ~
r~
1 4 ~5
(II~ R - 2~/ I R \B----O ~l~y
C - I O
R7 R6 - Y
In this formula, R3 is hydrogen or an organic radical
having from about 1 to about 30 carbon atoms, preferably
from about 1 to about 20 carbon atoms. Most preferably,
R3 is hydrogen or a substituted or unsubstituted alkyl,
alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radical
having from about 1 to about 30 carbon atoms, preferably
from about 1 to about 20 earbon atoms. R4, R5, R6 and R7
axe the same or different ancl are either an inorganic
radical such as hydrogen or an organic radical, such as
suhstituted or unsubstituted hydrocarbyl radicals having
from 1 to about 50 carbon atoms, preferably from about 1
to 30 carbon atoms, wherein at least one (and preferably
20 at least two) of the said R4, R5, R6 or R7 i9 an aryl,
alkylaryl or arylalkyl radical having from about 6 to
about 30 earhon atoms- R8, Rg, Rlo and Rll are the same
or different radicals selected from hydrogen or organic
radicals such as substituted or unsubstituted hydrocarbyl
groups; typieally, R8, R9, Rlo ancl Rll are either hydrogen
or an alkyl group having from about 1 to about 6 carbon
atoms. Yl is an integer from 1 to 4, and Ml is an inorganic
or organic radical, but is preferably selected from
hydrogen or a metal, typically selected from a transition
metal having an atomic number of 21 through 30 or a Group
IVA metal. If M1 is an organic radical, it is typically
of 1 to 50 carbon atoms and is derived from an aliphatic,
alicyclic, or aromatic compound. Preferred radicals, when
M is organic, are chosen from the group consisting of
substituted and unsubstituted alkyl, alkynyl, alkenyl,
aryl, arylalkyl, and alkylaryl groups o~ 1 to 50 carbon
atoms, with methyl and cyclohexyl radicals being among the
most preferred. ~lso among the most preferred groups, if
M is organic, are substituted and unsubstituted phenyl
groups, with substituted phenyl groups being particularly
preferred. The phenyl group may be substituted with, for
example, an acetyl group, a methyl radical, or an -O-CH3
group. One of the most preferred substituted phenyl
groups is the hindered phenyl group wherein the phenyl
group is substituted at the 2 and 6 carbon atom of the
phenyl ring with an organic group having more than 3
carbon atoms, e.g., 2,6-di-tert-butyl phenyl groups, such
as 4-methyl-2,6 di-tert-butyl phenyl. Hindered phenyl
groups provide the compound with hydrolytic stability. It
has also been unexpectedly found that non-hindered phenyl
groups, whether substituted or unsubstituted, also provide
the compound with hydrolytic stability.
In a preferred embodiment of the invention, R4,
R7~ R8, Rg, Rlo and Rll in formula (II) are hydrogen or
substituted or unsubstituted alkyl groups, with hydrogen
being especially preferred for all six radicals, and R5
and R6 are aromatic radicals, preferably such as alkylaryl,
arylalkyl, or aryl radicals, but most preferably are both
unsubstituted phenyl radicals. This embodiment of the
invention, i.e., the embodiment containing aromatic
~5~
radicals ~and particularly unsubstituted phenyl radicals),
has the added advantage of enhanced hydrolytic stability
and solubility in lubricating oils.
~ he ahove-described, boron containing, hetero-
cyclic compounds are produced by (A) reacting a primary
amine or ammonia with an alkylene oxide or epoxide or an
aromatic oxide. The resulting product is then reacted
with boric acid to give the corresponding boron~containing,
heterocyclic compound. Primary amines useful in preparing
the heterocyclic compounds of the present invention have
the chemical formula RNH2 wherein R is an organic or
inorganic radical, preferably where R contains I10 more
than 30 carbon atoms. Amines which are suitable for use
herein include saturated amines such as methylamine,
ethylamine, propylamine, butylamine, octadecylamine,
dodecylamine, cyclohexylamine, phenylamine, cocoamine, and
unsaturated amines such as tallowamine and oleylamine and
mixtures thereof. The organic radical associated with
such amines (e.g., the methyl group of methylamine, the
ethyl group of ethylamine, etc.) will ultimately be the R
group side chain emanating from the nitrogen atom o~ the
heterocyclic borate of the invention. Thus, the R group
side chain is determined by choice of amine, and if it is
clesired tha-t R be inorganic rather than organic, then one
may select ammonia to ensure that R is hydrogenl bromoamine
to ensure that R is bromine, chloroamine to ensure that R
is chlorine, hydroxylamine -to ensure that R is an OH
group, etc. However, since it is preferred in all embodi
ments of the invention that the R group side chain be
organic in nature, the preferred amines for use in prepar-
ing the he-terocyclic borates of the invention will be of
formula RNH2, wherein R is an organic radical.
A wide variety of alkylene oxides or epoxides
may be used to prepare the precursor for the heterocyclic
compounds herein. Typical alkylene oxides or epoxides
which are suitable for use include ethylene oxide,
propylene oxide, 1,2-epoxy-butane, cyclohexene oxide,
cyclooctene oxide, and cyclododecene oxide, and mixtures
thereof.
Generally, the primary amine (or ammonia) is
reacted with an alkylene oxide or epoxide, optionally in
the presence of a solvent, for example toluene, to produce
a dialkoxylated amine. The primary amine and alkene o~ide
or epoxide are reacted at a molar ratio typically of about
1:2. If added~ the solvent is introduced in sufficient
quantity to dissolve or disperse the reactants. After the
reaction proceeds to completion, the solvent is removed
from the reaction product, for example, by evaporation,
distillation, etc.
Next, the dialkoxylated amine is reacted with
boric acid at a typical molar ratio of about 1:1, option-
ally in the presence of a solvent, for example, xylenes,
benzene, toluene, etc~, to produce the heterocyclic
compound required herein. If used, the solvent w~ll
normally comprise from about 20 to about 50 weight percent,
especially from about 30 to about 40 weight percent of the
reaction mixture. The heterocyclic compound thus produced
will contain from about 0.5 to about 10 weight percent,
preferably from about 2 to about 5 weight percen-t of
boron. The reactions herein are typically conducted under
reflux at a temperature of from about 176 E'. (80 C.) to
about 392 F. (200 C.), especially from about 176 F.
(80 C.) to about ~00 F. (14~.~9 C.), at atmospheric
pressure for about 1 to about 5 hours.
It is also possible to prepare a suitable
heterocyclic compound herein from an aromatic oxide (or
aromatic epoxides). Aromatic oxides (or aromatic epoxides)
suitable for use herein preferably are of the following
formula (III):
(III) R12 ~ C - f Rl5
R13 ~14
wherein at least one of said R12, R13, Rl4 or Rl5 is aryl,
alkylaryl or arylalkyl with the remaining R groups being
independently hydrogen or an organic radical having 1 to
30 carbon atoms, preferably hydrogen or an alkyl radical
having 1 to 6 carbon atoms.
A wide variety of aromatic oxides may be used
to prepare the epoxide/primary amine adducts needed
to produce the boron compounds in the invention. Typical
aromatic oxides for use herein include styrene oxide,
alpha-methylstyrene oxide, ~ara tertiary-butylstyrene
oxide, cresyl glycidyl ether, ortho-methylstyrene oxide,
1,2-epoxybenzene, and para-methyl styrene oxide and
mixtures thereof. It should be noted that, of all the
embodiments of the invention, the most highly pre~erred
are those produced by borating the intermediate reaction
prod~ct of a primary amine or ammonia with styrene oxide,
with the resulting boron compound havlng a ring structure
-16-
wherein ethylene groups connect the nitrogen and oxygen
atoms of the ring and unsuhstituted phenyl groups are
attached to the carbon atom of said ethylene groups which
are bonded to the oxygen atoms.
When an aromatic oxide is selected as a starting
material, the primary amine may be reacted with the
aromatic oxide in the presence of a solvent, for example,
toluene, to produce an epoxide/amine adduct. The solvent
is added in sufficient ~uantity to dissolve or disperse
the reactants.
Generally, the primary amine and aromatic oxide
are reacted at a pressure of from about atmospheric
pressure to about 500 p.s.i.g. (35 atmospheres) at a
temperature of from 176 F. (80 C.~ to 392 F.(200 C.),
for 1 to 5 hours. The primary amine is preferably reacted
with the aromatic oxide at a molar ratio of 1:2 to produce
an epoxide/amine adduct. It may be desirable to react the
primary amine with two different aromatic oxides to
produce a mixed epoxide/amine adduct. In this embodiment
of the invention, one mole of the primary amine is reacted
with one mole each of two different aromatic oxides to
produce the desired tertiary amine. Yet another method of
producing the desired epoxide/amine adduct involves
reacting one mole of an aromatic-substituted alkene oxide
and one mole of an alkene oxide, for example ethylene
oxide, with a primary amine to produce an epoxide/amine
adduct having an aromatic moiety and an a]ky] moiety
attached to the nitrogen atom.
Next, the epoxide/amine adduct is reacted with
boric acid at a molar ratio of about 1:1, optionally in
the presence of a solvent, for example, xylene, benzene,
toluene, or -the ]ike, -to produce a boron~containing,
heterocyclic compound of the present invention~ If a
solvent is used, it will normally comprise from about 20
to about 50 weight percent, preferably from about 30 to
about 40 weight percent of the reaction mixture. The
reaction is conducted under reflux at a temperature of
from 176 F. (80 C.) to 392 F. (200 C.), F,referably
from 176 F. (80 C.) to 300 F. (148.89 C.)~ at a
pressure of from atmospheric pressure to about 500 p.s.i.g.
(35 atmospheres), for about 1 to about 5 hours. The
boron-containing heterocyc].ic compound thus produced will
contain from about 0.5 to about 10 weight percent, pref-
erably ~rom about 2 to about 5 weight percent of boron.
Typical boron-containing, heterocyclic compounds
herein which contain alkyl species in the heterocyclic
ring structure are selec-ted from the group consisting of
methylaminod.iethylate hydrogen horate, ethylaminodiethylate
hydrogen borate, propylaminodiethylate hydrogen borate,
butylaminodiethylate hydrogen borate, octadecylamino~
diethylate hydrogen borate, dodecylaminodiethylate hydrogen
borate, cyclohexylaminodiethylate hydrogen borate, phenyl-
aminodiethylate hydrogen borate, oleylaminodiethylate
hydrogen borate, cocoaminodiethylate hydrogen borate
tallowaminodiethylate hydrogen borate, dodecylamino
di(-2-methylethylate) hydrogen borate, and dodecylamino
di(-2-phenylethylate) hydrogen borate and mixtures thereof.
Representative boron-containing, heterocyclic
compounds which contain alkylaryl species on the hetero-
cyclic ring structure include the following compounds:
~5'~
l-hydroxy- 3,7-diphenyl-5-dodecyl-5-aza-l-bora-2,8-dioxa-
cyclooctane; l-hydroxy-4,6-diphenyl-5-dodecyl~5-aza-1-bora-
2,8-dioxacyclooctane; 1-hydroxy-4,7-diphenyl-5-dodecyl-5-
aza-l-bora-2,8- dioxacyclooctane; 1-hydroxy-3,7-dicresyl-5~
dodecy1-5-aza-1-bora-2,8-dioxacylooctane; 1-hydroxy-4,6-
dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;
l-hydroxy-~,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxa-
cyclooctane; l-hydroxy-3,7~dimethyl-3,7-diphenyl-5-dodecyl-
5-aza-1-bora-2,8-dioxacyclooctane;l~hydroxy-~,6-dimethyl-
4,6-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;
l-hydroxy-4,7-dimethyl-4,7-diphenyl-5-dodecyl-5-aza-1-bora-
2,8-dioxacyclooctane; 1-hydroxy-3,7-para-tertiary-butyl-
phenyl-5-dodecyl-5-aza-1-bora~2,8-dioxacyclooctane;
l-hydroxy-4,6-para-tertiary-butylphenyl~5-dodecyl-5~a~a-1-
bora-2,8-dioxacyclooctane; 1 hydroxy-4,7-p--ara-tertiary-
butyl-phenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;
l-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dloxa-
cyclooctane; and l-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-
bora-2,8-dioxacyclooctane and mixtures thereof. It should
be noted that the methyl, ethyl, propyl, butyl, cyclohexyl,
octadecyl, phenyl, steryl, oleyl, coco, tallow and the
like moieties may be substituted for the dodecyl moiety in
the above heterocyclic compounds.
Metal derivatives of the boron-containing,
heterocyclic compounds herein are conveniently prepared by
contacting the boron-containing, heterocyclic compound
with a metal or metal compound, usually a metal in salt
form. Thus, the metal acetates, proplonates, etc., are
suitable for use. The preferred metal compound for use in
incorporating the metal ion into the borate of the inven-
--19--
~ 3'~
tion is the metal acetate. Generally, the heterocycliccompounds are reacted with the metal compounds in a molar
ratio range of from about 1:1 to about 6:1, preferably
from about 1:1 to about 4:1, at a pressure of from about
atmospheric to about 500 p.s.i.g~ (35 atmospheresl and a
temperature of from about 176 F. (80 C.) to about 392
F. (200 C.). Water and, in the case where metal acetates
are used, acetic acid are then distilled from the reaction
mixture using a water-cooled condenser. (It should be
noted that not all metal salts are desirable for incorpo-
rating the metal ion into the boron-containing, heterocyclic
compound. The metal carbonates, nitrates, chlorides, and
sulfates, to name a few, are all undesirable as vehicles
for imparting metal ions into the boron-containing,
heterocyclic compound. These metal salts experlence solu-
bility problems and separation problems, and, in addition,
undesirable ions frequently contaminate the boron-contain
ing, heterocyclic compound.) Generally, the boron-contain-
iny, heterocyclic compounds are reacted with the metal
compounds herein in a molar ratio range of from about 1:1
to about 6:1, especially from about 1:1 to about ~:1.
Desirable metals are usually selected from
transition metals having an atomic number of 21 through 30
or Group IVA metals of the Periodic Table. Transition
metals which are suitable for use are selected from
scandium, titanium, vanadium, chromium, manganese, iron,
cobalt, nic~el, copper and ~inc and mixtures thereof.
Suitable Group IVA metals include lead and tin and mixtures
thereof. Other metals (or metalloids or semi-metals) may
also be selected, such as gallium, bismuth, and antimonyO
-20-
\~
7~
Normally, the metal will comprise from about 1 to about 17
weight percent, preferably from about 5 to about 9 weight
percent of the boron-containing, heterocyelic compound.
Representative metallic derivatives of the above
compositions include the following compounds: copper di--
(l-oxy~3-,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxa-
cyclooctane); copper di-(1-oxy-~,6-diphenyl-5-dodecyl-5-
aza-l-hora-2,8-dioxacyclooctane); copper di-~1-oxy-4,7-
diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxaeylooctane;
copper di~ oxy-3,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-
dioxacyclooetane); eopper di-(1-oxy-4,6-dieresyl-5--dodeeyl-
5-aza-1-bora-2,8-dioxacyclooctane); copper di-(1-oxy-4,7-
dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);
copper di- (l-oxy-3,7-dimethyl-3,7-diphenyl-5~dodecyl-5-
aza-l-bora-2,8-dioxacyclooctane); copper di-(1-oxy-4,6-
dimethyl-4,6-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxa-
cyelooctane); eopper di-(1 oxy-4,7-dimethyl-4,7-diphenyl-
5-dodecyl-5-aza-1-bora-2,8-dioxacyclooetane); copper
di-(1-oxy-3,7-para tertiary~butyl-phenyl-5-dodecyl-5~aza~
1-bora-2,B-dioxacyclooctane); copper di-(l-oxy-4,~ para
ter-tiary-butylphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclo
-
octane); copper di-(l-oxy-4,7-para tertiary-buty]-phenyl-5-
dodecyl-5-aza-1-bora-2,8-dioxacyclooctane); copper di-(l-
oxy-3,7-diphenyl-5-coco 5-aza-1-bora-2,8-dioxacyclooctane);
ancl copper di-(l-oxy-3,7-dlphenyl-5-tallow-5-aza-1-bora-
2,8-dioxacyclooctane). Other metals may be ineorporated
into the above compounds, i.e., substituted for the copper,
for example, scandium, titanium, chromium, manganese,
iron, cobalt, nickel, zinc, lead and tin ancl mixtures
thereof. In addition, methyl, ethyl, propyl~ butyl,
cyclohexyl/ octadecyl, phenyl, steryl, oleyl r COCO~ tallow
and the like moieties may be subs~ituted for the dodecyl
moiety in the above-described heterocyclic compounds.
If it is desired that M in ~ormula (I) herein-
before, and also for the corresponding M radical of any of
the borate of the invention formulas herein, be organic,
then one may employ the following procedure: the borate
of the invention is reacted under conditions as set forth
hereinbefore with respect to preparing metal derivatives,
but instead of using a metal salt, an alcohol of choice is
employed and no water is added to the reaction. For
example, if a methyl radical is desired for M, then
methanol is employed; if a cyclohexyl radical, then
cyclohexanol; and if an unsubstituted phenyl radical, then
phenol. Optionally, a solvent such as toluene or xylene
is also used. After the reaction is complete, water is
removed by distillation, and the desired borate oE the
invention is obtained.
Another proceduxe, preferred especially for
preparing borates of the invention with M as a substituted
phenyl group, involves reacting the alcohol of choice,
e.g., 2,6-tert-butyl phenol, optionally in the presence of
a solvent such as toluene or xylene, with boric acid in
the presence of an acid catalyst, e.g., para-toluenesulfonic
, acid, or other organic soluble acids (e.g., acetic) or an
ion exchange resin catalyst, Amberlyst 15, which is
strongly acidic. The reaction may be accomplished by
refluxing, which removes two moles of water for every mole
of boric acid which reacts with the phenol compound. rrhe
resulting product, a boric acid:phenol adduct is in turn
-22-
r~7~le ~n c~
76~3~j
reacted with an amine:epo~ide adduct, under conditions
hereinbefore specified for reacting boric acid with an
amine:epoxide adduct, and after water i~ removed by
distillation, the final desired product is recovered.
Another species of the heterocyclic compounds
here.in are the bisthydrocarbyloxy methylated) boron-
containing, heterocycl.ic compounds. These compounds are
of the following formula (IV):
R17
l
CH2
IIV) /CH2 -- CH - O \ M2+Y2
f
O
_ R18
Y2
where R16 .is an inorganic radical or an organic radical
having from 1 to about 50 carbon atoms , R17 and Rl~ are
the same or different organic radicals having from 1 to
about 50 carbon atoms, Y2 is an integer from 1 to 4, and
M2 is an organic or inorganic radical but preferably is
hydrogen or a metal, typically selected from a transition
metal having an atomic number of 21 through 30 or a Group
IVA metal as disclosed in the Periodic Table located in
the Handbook of Chemistry and Physics, 46th Edition. If
M2 is an organic radical, it is preferred that it be
~;~5~
chosen from the group co~sisting of substituted or unsub-
stituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, and
alkylaryl radicals having from 1 ~o 50 carbon atoms, wlth
methyl and cyclohexyl radicals being among the most
preferred groups. ~lso among -the most preferred groups,
if M is organic, are substituted and unsubstituted phenyl
groups, with substituted phenyl yroups being particularly
preferred. The phenyl group may be substituted with, for
example, an acetyl group, a methyl radical, or an -O-C~13
group. One of -the most preferred substituted phenyl
groups is the hindered phenyl group wherein the phenyl
group is substituted at the 2 and 6 carbon a-tom of the
phenyl ring with an organic group having more than 3
carbon atoms, e.g., 2,6-di-tert-butyl phenyl groups, such
as 4-methyl-2,6-di-tert-butyl phenyl. ~indered phenyl
groups provide the compound with hydrolytic stability. It
has also been unexpectedly found that non-hindered phenyl
groups, whether substituted or unsubstituted, also provide
the compound with hydrolytic stability.
When Rl6, Rl7 and Rl8 are organic radicals,
usually at least 65 percent, more usua]ly at least 75
percent, and most usually at least 90 percent of the atoms
composing said radicals will be carbon and hydrogen atoms.
Preferably, Rl6 is hydrogen or a substituted or unsubsti-
tuted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or
arylalkyl radical having from l to about 30 carbon atoms,
and more preferably, from l to about 24 carbon atoms. On
the other hand, Rl7 and Rl~ are preferably the same or
different radicals selected from a substituted or
unsubstituted alkyl, alkenyl, alkynyl, aryl, alkylaryl and
-24-
~ r~ t~
arylalkyl radicals having Erom 1 to about 50 carbon atoms,
and more preferably from 1 to about 30 carbon atoms, more
preferably still from 1 to about 20 carbon atoms, and most
preferably from 1 to about 10 carbon atoms.
In preparing the bis(hydrocarbyloxy methylated)
boron-containing, heterocyclic compounds, a primary amine
or ammonia (but preferably a primary amine) is reacted
with an alkyl, aryl, alkylaryl or arylalkyl glycidyl ether
to produce a bis(hydrocarbyloxy methylated) primary amine.
Glycidyl ethers suitable for use herein preferably are of
the following formula (V):
/ O\
(V) CH2 CH - CH ~- - R19
where Rlg is an organic radical ha~ing 1 to 50 carbon
atoms with said organic radical in a preferred mode
comprising at least 75 percent, preferably 90 percent of
carbon and hydrogen atoms. Preferably, R19 is a substi-
tuted or unsubstituted alkyl, aryl, alkylaryl or arylalkylradical ha~ing from 1 to about 50 carbon atoms, preferably
from 1 to about 30 carbon atoms, more preferably still
from 1 to about 20 carbon atoms, and most preferably from
1 to about 10 carbon atoms.
~ wide variety of glycidyl ethers may be used to
prepare the oxylated primary amines needed to produce the
he-terocyclic compounds hereinO Typical glycidyl ethers
for use herein include methyl glycidyl ether, ethyl
glycidyl ether, propyl glycidyl ether, butyl glycidyl
ether, phenyl glycidyl ether, cresyl glycidyl ether,
-25-
~ 3
phenyl methyl glycidyl ether, ethyl phenyl glycidyl ether
and phenyl ethyl glycidyl ether and mixtures thereof.
The primary amine may be reacted with the
glycidyl ether in the presence of a solvent, for example,
toluene to produce a dioxygenated amine. The solvent is
added in sufficient quantity to dissolve or disperse the
reactants.
Generally, the primary amine and glycidyl ether
are reacted at a pressure of from about atmospheric
pressure to about 500 p.s.i.g. (35 atmospheres) at a
temperature of from 176 F. (80 C.) to 392 F. (200 C.)
for 1 to 30 hours. The primary amine is preferably
reacted with the ~lycidyl ether at a molar ratio of 1:2 to
produce the bis(hydrocarbyloxy methylated) amine. It may
be desirable to react the primary amine with two different
glycidyl ethers to produce a mixed hydrocarbyloxy
methylated amine. In this embodiment of the invention,
one mole of the primary amine is reacted ~ith one mole
each of two different glycidyl ethers to produce the
desired mixed hydrocarbyloxy methylated amine. Yet
another method of producing the desired amine involves
reacting one mole of an aromatic glyciclyl ether and one
mole of an alkyl glycidyl ether with a primaxy amine to
produce an amine having an alkylaryl moiety and an alkyl
moiety attached to the nitrogen atom of the amine.
Next, the bis(hydrocarbyloxy methylated) amine
or mixed hydrocarbyloxy methylated amine is reacted with
boric acid at a molar ratio of from about l:1, optionally
in the presence of a solvent, for example, xylene, benzene,
toluene, or the like, to produce a bis(hydrocarbyloxy
-26-
~5~7f~
methylated) boron-con-taining, heterocyclic compound of the
present invention. Normally, the solvent, if used, will
comprise from about 20 to about 50 weight percen~, pref-
erably from about 30 to 40 weight percent of the reaction
mixture. The reaction is conducted under reflux at a
temperature of from 176 F. (80 C.) to 392 F. (200 C.),
at a pressure of from atmospheric pressure to about 500
p.s.i.g. (35 atmospheres) for about 1 to about 30 hours.
The compound thus produced will contain from about 0.5 to
about 10 weight percent, preferably from about 2 to about
5 weight percent of boron.
In a preferred mode the primary amine and
glycidyl ether are first reacted together and the inter-
mediate reaction produc-t thus produced is, next, reacted
with boric acid.
An alternative method of producing the bis(hydro-
carbyloxy methylated) boron-containing, heterocyclic
compounds herein involves reacting the primary c~nine,
glycidyl ether and boric acid in a one-step process.
Representative bis(hydrocarbyloxy methylated),
boron-containing, heterocyclic compounds produced in
accordance with the procedure herein include t~e following
compounds: 1-hydroxy-3,7-di-(methoxymethyl)-5-dodecyl-5-
aza~1-bora-2,8-dioxacyclooctane; 1-hydroxy-4,6-di-(methoxy
methyl)-5-dodecyl-5-aza-1-bora-2~8-dioxacyclooctane;
1-hydroxy-3,7-di-lethoxymethyl)--5-dodecyl-5-aza-1 bora-
2,8-di~xacyclooctane; 1-hydroxy-3,7-di-(propoxymethyl)-5-
dodecyl 5-a~a-1-bora-2,8-dioxacyclooctane;l-hydroxy-4,6-
di-(butoxymethyl~-5-clodecyl-5-aza-1-bora-2,8~dioxacyclo-
octane; 1-hydroxy-3,7 di-(methylphenoxymethyl)-5-dodecyl-
-27-
-
i(3~;
5-aza-l-bora-2,8-dioxacyclooctane; 1-hydroxy-4,6-di-(methyl-
phenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8~dioxacyclooctane;
1-hydroxy-3,7-di-(ethylphenoxymethyl)-5-dodecyl-5-aza-1-
bora-2,8-dioxacyclooctane; l-hydroxy-4,6-di-(phenylmethoxy-
methyl)-5-dodecyl-5-aza-1-bora-2,8- dioxacyclooctane; and
1-hydroxy-3,7-di (phenylethoxymethyl)-5-dodecyl-5-aza-l-
bora-2,8-dioxacylooctane and mixtures thereof. It should
be noted that the methyl, ethyl, propyl, butyl, cyclohexyl,
octadecyl, phenyl, steryl, oleyl, coco and tallow moieties
may be substituted for the dodecyl moiety in the above
heterocyclic compounds. This embodiment o~ -the i~vention
has the added advantage o~ enhanced extreme pressure
properties and a more pleasant odor.
Metal derivatives of the bis(hydrocarbyloxy
methylated), boron-containing, heterocyclic compounds,
herein are conveniently prepared by contacting -the compound
with a metal, usually in salt form. Thus, the metal
acetates, proprionates, etc., are suitable for use. The
preferred metal compound for use in incorporating the
metal ion into the bis(hydrocarbyloxy methylated) boron-
containing, heterocyclic compound is the metal acetate~
Generally, these compounds are reacted with the metal
compounds in a molar ratio range of from about 1:1 to
about 6:1, preferably from about 1:1 to about ~:1, at a
pressure of from about atmospheric to about 500 p.s.i.y.
(35 atmospheres) and a temperature of from about 176 F.
(80 C.) to about 392 F. (200 C.). Water ancl, in the
case where metal acetates are used, acetic acid are
distilled from the reaction mixture using a water-cooled
condenser.
-28
Representative of the metal compounds are: copper
cli[-l-oxy-2,7~di-(me-thoxymethyl~-5-dodecyl-5-aza-1-bora-
2,8-dioxacyclooctane]; copper di-[l~oxy-4,6-di~methoxy-
methyl)-5-dodecyl 5-aza-1-bora-2,8-dioxacyclooctane];
copper di-[l-oxy-3,7-di-(ethoxymethyl)-5-dodecyl~5-aza-1-
bora-2,8-dioxacyclo-octane]; copper di-[1-oxy-3,7-di-(pro~
poxymethyl)-5-dodecyl~5 aza l~bora~2,8~dioxacyclooctane];
copper di~[l~oxy~4,6-di~(butoxymethyl)~5~dodecyl~5-aza~l~
bora~2,8-dioxacyclooctane]; copper di--[]-oxy~3,7 di~(methyl-
phenoxymethyl)-5~dodecyl~5-aza-l~bora-2,~dioxacyclooctane];
copper di~[l-oxy-4,6 di-(methylphenoxymethyl~-5-dodecyl~5-
aza-l-bora-2,8~dioxacyclooctane]; copper di-[1-oxy-3,7-
di(ethylphenoxymethyl)-5-dodecyl-5~aza-1-bora 2,8-dioxa-
cyclooctane]; copper di-[l-oxy-4,6-di(phenylmethoxymethyl)-
5-dodecyl-5-aza-l~bora-2,8~dioxacyclooctane]; and copper
di [l-oxy~317-di-(phenyl-ethoxymethyl)~5~dodecyl-5-aza-l-
bora~2,a-dioxacyclooctane] and mixtures thereof. Other
metals may be incorporated into the above compounds, i.e.,
substituted for the copper, for e~ample, scandium, titanium,
vanadium, chromium, man~anese, iron, cobalt, nickel, zinc,
lead and tin and mixtures thereof. Semi-metals and
metalloids may also be incorporated into such compounds.
In addition, methyl, ethyl, propyl, butyl, cyclohexyl,
octadecyl, phenyl, steryl, oleyl, coco and tallow moieties
may be substituted for the dodecyl moiety in the above-
described compounds.
It should be noted that the foregoing bis(hydro-
carbyl methylated) boron-containing compounds of formula
lIV) have been found to be soluble in 450 neutral oil, at
least when prepared with tallowamine ox cocoamine. However,
-29-
the higher cost of preparing such compounds, particularly
in comparison to compounds of formula (II) structure
prepared with styrene oxide, makes the latter, i.e., the
formula (II) compounds prepared from styrene oxide, a more
preferred additive for automotive lubricating engines.
Also suitable herein are sulfohalogenated,
boron-containing, heterocyclic compounds of the following
formula (VI):
X
r I /R38 \
L f \ R39 - O ~ y7
(VI) (S)n2
. ~ /R40 \ .
R36 f~ R37 N \ / B O M8+Y8
Xl Y~3
wherein R3~ and R36 may be the same or different organic
or inorganic radicals but more typically R34 and R36 as
well as R35 and R37 are the same or different organic
radicals having from about 1 to about 30 carbon atoms,
R38~ R39, R40 and R41 are the same or different organic
radicals having from about 1 to about 50 carbon atoms, n2
is an integer from 1 to 4, preferably 1 or 2, X and X1 are
halogens independently selected from the group consisting
of chlorine, fluorine, bromine and iodine and mixtures
thereof, with chlorine being especially preferred. The
-30
34, R35, ~36 and R37 are typically s~lected from
the same or different, substituted or unsubstituted
hydrocarbyl groups, such as, substituted or unsubstituted
aliphatic and aromatic groups, particularly the alkyl,
alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radicals
having from about 1 to about 30 carbon atoms, preferably
from about 1 to about 20 carbon atoms. The organic
als P~3g, R39, R40 and R41 are typically selected from
the same or different, substituted or unsubstituted
hydrocarbyl groups, such as, substituted or unsubstituted
aliphatic and aromatic groups, particularly the alkyl,
alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl radicals
having from about l to about 50 carbon atoms, p.referably
from about 1 to about 30 carbon atoms. Preferably R38,
R39, R40 and R41 are alkylaryl or arylalkyl having from
about 8 to about 30 carbon atoms. More preferably, R3~,
R39, ~40, and R41 are alkylaryl groups and, most preferably,
are alkylaryl groups wherein ethylene radicals connect the
nitrogen and oxygen atoms and unsubstituted phenyl radicals
are bonded to the carbon atoms of the ethylene radicals
bonded to the oxygen atoms. y7 and Y8 are the same or
different integers from 1 to 4, and M7 and M8 may be an
organic or inorganic group, but preferably are either
hydrogen or a metal with the metal typically a transition
metal having an atom.ic number from 21 to 30 or a Group IVA
metal of the Periodic Table or mixtures thereof. If M7 or
M8 is an organic radical, it is preferred that it be
chosen from the group consisting of substituted and
unsubstituted alkyl, alkenyl, alkynyl, aryl, arylal.kyl,
a.nd alkylaryl radicals of between 1 and 50 carbon atoms,
~ ra~
with methyl and cyclohexyl radicals beiny among the most
preferred groups. Also among the mos-t preferred groups,
if M is organic, are substi~uted and unsubstituted phenyl
groups, with substituted phenyl groups being particularly
preferred. The phenyl group may be substituted with, ~or
example, an acetyl group, a methyl radical, or an -O-CH3
group. One of the most preferred substituted ph~nyl
groups is the hindered phenyl group wherein the phenyl
group is substituted at the 2 and 6 carbon atom of the
phenyl riny with an organic group having more than 3
carbon atoms, e.g., 2,6-di-tert-butyl phenyl groups, such
as 4-methyl-2,6-di-tert-butyl phenyl. ~lindered phenyl
groups provide the compound with hydrolytic stability. It
has also been une~pectedly found that non-hindered phenyl
groups, whether substituted or unsubstituted, also provide
the compound with hydrolytic stability. M7 and ~8 may be
the same physical atom or species, e.g., the two borated
radicals may be attached to the same metal atom or to-
gether may be one organic radical~
~lalogenated, boron-containiny, heterocyclic
compounds useful in the present invention are of the
following formula (VII):
~ 2 X3 /
(VII) ~2 IH C~l - R43 - N \ \ B - O Mg Y9
R45 O
Yg
wherein R~2 may be an inorganic radical bu-t more typically
R~2 and R~3 are the same or different organic radicals
-32~
having from about 1 to about 30 carbon atoms, R44 and R45
are the same or different organic radicals having from
about 1 to about 50 carbon atoms, X2 and X3 are halogens
selected from the group consisting of chlorine, fluorine,
bromine and iodine and mixtures thereof, with chlorine and
bromine being especially preferred. The radicals R42 and
R43 are typically selected from the same or different/
substituted or unsubstituted hydrocarbyl groups, such as
substituted or unsubstituted aliphatic and aromatic
groups, particularly the alkyl, alkenyl, alkynyl, aryl,
alkylaryl or arylalkyl radicals having from about 1 to
about 30 carbon atoms, preferably from about 1 to about 20
carbon atomsO The organic radicals R44 and R45 are
typically selected from the same or different, substituted
or unsubstituted hydrocarbyl groups, such as, substituted
or unsubstituted aliphatic and aromatic groups, particularly
the alkyl, aryl, alkylaryl or arylalkyl radicals having
from about 1 to about 50 carbon atoms, preferably from
about 1 to about 30 carbon atoms. Preferably, R4~ and R45
are alkylaryl or arylalkyl having from about 8 to about 30
carbon atoms. More preferably, R44 and R45 are alkylaryl
groups and, most preferably, are alkylaryl groups wherein
ethylene radicals connect the nitrogen and oxygen atoms
and unsubstituted phenyl radicals are bonded to the carbon
atorns of the ethylene radica1s bonded to the oxygen atoms.
yg is an integer from 1 to 4, and Mg may be an organic or
inorganic group, but preferably i5 either hydrogen or a
transition metal having an atomic number between 21 and 30
or a Group IVA metal of the Periodic Table and mixtures
thereof. If Mg is an organic radical, it i~ preferred
.;t)~
that it be chosen from the group consisting of substituted
and unsubstituted a]kyl, alkenyl, alkynyl, aryl, arylalkyl,
and alkylaryl radicals of between 1 and 50 carbon atoms,
with methyl and cyclohexyl radical being among the most
preferred groups. A]so amon~ the most preferred groups,
if M is organic, are substituted and unsubstituted phenyl
groups, with substituted phenyl groups being particularly
preferred. The phenyl group may be substituted with, for
example, an acetyl group, a methyl radical, or an -O-CH3
group. One oE the most preferred substituted phenyl
groups is the hindered phenyl group wherein the phenyl
group is substituted at the 2 and 6 carbon atom of the
phenyl ring with an organic group having more than 3
carbon atoms, e.g., 2,6~di-tert-butyl phenyl groups, such
as 4-methyl-2,6-di-tert-butyl phenyl. Hindered phenyl
groups provide the compound with hydrolytic ~tability. It
has also been unexpectedly found that non-hindered phenyl
groups, whether substituted or unsubstituted, also provide
the compound with hydrolytic stability.
~alogenated boron-containing, heterocyclic com-
pounds typically include 1-hydroxy-3,7-diphenyl--5-(9-10-
dichlorooctadecyl)-l-bora--2,8-dioxa 5-aza-cyclooctane;
1-hydroxy-3,7-diphenyl-5-(9-10-dichlorostearyl)-1-bora-
2,8-dioxa-5-aza-cyclooctane; and 1-hydroxy-3,7-diphenyl-5
(dichlorotallow)-1-bora-2,8-dioxa-5-aza-cyclooctane ancl
mixtures thereof. Other halogens which may be substituted
for the chlorine above include fluorine, bromine and
iodine and mixtures thereof.
Sulfurized forms of the borate of the invention
are of the following formula (VIII):
-34-
- -
R55 0\ Y1o
~VIII) ~54 N\ B O Mlo
R56 - O ylO
wherein R5~ is an inorganic or organic radical, R55 and
R56 are the same or different organic radicals, and M1o is
an organic or inorganic radical, with Y1o being the
valence of M1o, and preferably an integer from 1 to 4,
further provided that at least one of R54, R55, R56, and
M1o contains sulfur. Thus, for example, one or more of
R54, R55, R56, and M1o may contain a "sulfide group,"
which is herein defined as sulfur bonded (1) as an end
group as represented by a thio-group (-SH), ~2) as part
of the compound backbone (-CHX-S-CHx-), (3) as a pendant
from the compound as represented by an episulfide group
/s~
(-CHX CHX )
or (4) one or more sulfide or polysulfide bridges ( - S
or ~S(n~~, wherein ~S(n)~ represents two or more sulfur
atoms bonded in series) connected to an organic radical,
including another organic radical in formula (VIII) and an
organic radical in a second borate of the invention of
formula (VIII) structure or any of the borates of the
invention previously illustrated by formula.
The preferred sulfurized borate of the invention
contains a sulfide or polysulfide bridge connecting two
borates of the invention, with the most preferred location
of the bridge being between the two side R groups, i.e.,
as shown in -the following formula (IX):
-35-
,t~i
/ 58 \ Y
l R59 O , Mll
(IX) (S)nl Yll
¦ / 61 \ l Y12
\ R 6 2 /
wherein all of the R groups are the same or different
organic radicals and Mll and M12 are the same or different
organic or inorganic radicals and (S)nl represents one or
more sulfide or polysulfide bridges connecting R57 and
R60 .
As shown in formula (IX), one or more sulfur
bridges exist between two borates of the invention.
~Iowever, it is further contemplated in the invention that
the sulfurized borate of the invention may have three or
more borates of the invention, each of formula (VIII)
structure wherein the R side groups (shown in formula
(VIII) as R54) and the M radicals of the borates of the
invention may be the same or different inorganic or
organic radicals and the R groups bridging the oxygen and
nitrogen atoms (shown in formula (VIII) as R55 and R56)
are the same or different organic radicals. It is most
highly preferred that all sulfur bridges in the borate of
the invention connec-t the R group side chains ~R54 in
formula (VIII) and R57 and R60 in formula (IX)) emanating
from the nitrogen atom of each borate of the invention, in
which case the R group side chains would all be organic
-36-
~l~5~
radicals. Ilowever, it is also contemplated in alternative
embodiments that the sulfur bridge could connect elsewhere,
e.g., from the R group side chain to M, from one R group
connecting an oxygen and nitrogen atom to another, etc.
In formulas (VIII3 and (IX), R54, R57, and R60
are preferably organic radicals, usually having from 1 to
50 carbon atoms, and may, for example, be a substituted or
unsubstituted hydrocarbyl group~ particularly an alkyl,
alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl radical
having from 1 to 30 carbon atoms, often from about 9 to 20
carbon atoms- R5s~ R56~ R58~ R59~ R61' 62
generally organic radicals of 1 to 50 carbon atoms, and
may, for example, be a substituted or unsubstituted
hydrocarbyloxy group, e.g., the structure bridging the
nitrogen and oxygen atom in formula (IV), or a hydrocarbyl
group such as an alkyl, alkenyl, alkynyl, aryl, alkylaryl,
or arylalkyl radical. Preferably, R55, R56, R58, R
R61, and R62 are alkylaryl groups wherein ethylene
radicals connect the nitrogen and oxygen atoms and
unsubstituted phenyl radicals are bonded to the carbon
atoms of the ethylene radlcals bonded to the oxygen atom.
Mlor Mll, and M12 are typically inorganic
radicals such as hydrogen or a metal having an atomic
number from 21 to 30, or a Group IVA metal. Other metals
(or metalloids or semi-metals~ may also be selected, such
as gallium, bismuth, and antimony. Mlo, Mll, and M12 may
also be organic radicals, preferably chosen from substi-
tuted or unsubstituted alkyl, alkenyl, alk.ynyl~ aryl,
arylalkyl, and alkylaryl radicals with methyl and cyclo-
hexyl radicals being among the mos-t preferred. Also among
-37-
~ ~r t~J~
the most preferred groups, if M is organic, are substituted
and unsubstituted phenyl groups, with substituted phenyl
groups being particularly preferred. The phenyl group may
be substituted with, for example, an acetyl group, a
methyl radical, or an -O-CH3 group. One of the most
preferred substituted phenyl groups is the hindered phenyl
group wherein the phenyl group is substituted at the 2 and
6 carbon atorn of the phenyl ring with an organic group
having more than 3 carbon atoms, e.g., 2,6 di-tert-butyl
phenyl groups, such as 4-methyl-2,6-di-tert-butyl phenyl.
Hindered phenyl groups provide the compound wlth
hydrolytic stability. It has also been unexpectedly found
that non-hindered phenyl groups, whether substituted or
unsubstituted, also provide the compound with hydrolytic
stability. Also, Mll and M12 may be the same physical
atom or species, e.g., the two borate radicals may be
attached or bonded to the same metal atom or together may
be one organic radical.
One of the advantages of the sulfurized form of
the borates of the invention is that of increased oxidation
stability, as well as substantially enhanced extreme
pressure properties. Generally, the sulfurized compounds
exhibit the same or superior extreme pressure properties
when used at weight percen-t concentrations substantially
less than other heterocyclic, boron-containing compounds
disclosed herein.
The sulfurized, halogenated or sulfohalogenated
compounds herein are produced in accordance with the
procedure described before for producing -the boron-contain-
ing, heterocyclic compounds with the added stipulation
-38
3 d
that the primary amine used to form the heterocyclic
compound is unsaturated. Elemental sulfur is reacted with
the heterocyclic compound in toluene, xylene, or the like
to produce a sulfurized compound. The sulfohalogenated
form of the compound may be produced by substituting a
sulfur halicle for the elemental sulfur above, for example,
a sulfur chloride such as sulfur monochloride, sulfur
dichloride, etc. The halogenated form of the heterocyclic
compound is produced by substituting a halogen for the
sulfur above.
The sulfurized compounds of the invention are
preferably prepared by reacting one mole of sulfur with
one equivalent of unsaturateds in the R side group of the
boron heterocyclic compound or its metal derivative. For
example, if l-hydroxy-3,7-diphenyl-5-tallow-5-aza-l~bora-
2,8-dioxacyclooctane is the chosen boron compound to be
sulfurized, then 1 mole of sulfur is reacted with about
2.5 moles of the boron compound (because the boron
compound contains about 0.40 equivalents of unsaturateds
in the ~ group side chain). The reaction is conducted in
the presence of a solvent such as toluene or xylene, usiny
at least 3 moles of solvent for every mole of boron
compound reacted. The reaction is conduc-ted at elevated
temperature with refluxing, with the time and temperature
of reaction being dependent to a great extent upon the
solvent chosen. If toluene, sulfurization is usually
achieved in four hours at 110 C. under atmospheric
pressure conditions; if xylene, then sulfurization is more
rapid, occurring in 1 hour of refluxing at 137 to 140 C.
under atmospheric pressure conditions. To prevent
-39-
~ ~rjDJ~
oxidation of the sulfur during said reactions, an inert
gas blanket, such as nitrogen or argon, may be employed.
In an alternative embodiment of the invention,
the elemental sulfur is first reacted with the unsaturated
primary amine followed by subse~uent reaction with the
desired epoxide, which is in tuxn followed by reaction
with boric acid. Alternative].y still, an unsaturated
amlne:epoxide adduct may be produced first, followed by
reaction with the elemental sulfur, which is in turn
followed by reaction with boric acid. Reaction conditions
for these embodiments typically are commensurate with
those specified above for sulfurization reactions, reac-
tions with boric acid, and reactions between amines andepoxides.
As stated above, the sulfurized versions of the
borates of the invention typically form one or more
sulfur bridges between R side groups emanating from the
nitrogen atom. Such sulfur bridges, which may contain one
sulfur atom or several in series, typically bond to carbon
atoms immediately adjacent to a phenyl ring or alkenyl or
alkynyl unsaturation. In other words, the sulfur bridge
connects one R side group of a first borate of the invention
with that of a second at locations formerly occupied by
benzylic hydrogen (in the case of phenyl unsaturation) or
an allylic hydrogen (in the case of alkenyl or alkynyl
unsaturation). Thus, it will be understood that, by
"unsaturateds" in the R side group, it is meant in the
present specification and claims the number of allylic and
benzylic hydrogens available in said R side group for
substitution by a sulfur atom. And since the R side group
-40-
originates in the primary amine, it will be understood
that "unsaturated" in the term "unsaturated primary amine"
refers to the number of allylic and benzylic hydrogens
available in the R group of the amine (of formula RNH2)
for substitutlon by a sulfur a-tom.
(~f course, it will also be understood that, if
the R groups connecting the nitrogen and oxygen atoms
contain significant allylic and benzylic hydrogens, some
bonding of sulfur a-toms at such locations may also occur.
But in the preferred embodiment, wherein styrene oxide is
the epoxide chosen for reaction with the amine, and
particularly when the phenyl ~roups of said styrene oxide
ultimately are attached to the carbon atoms of the hetero-
cyclic ring nearest the oxygen atoms, sulfur substitution
is minimal, being impeded structurally by the ring itself
and the influence of the oxygen atom.~
If desired, the sulfurization of the boron
compound may be hastened by use of a vulcanization catalyst.
The presently preferred catalyst is zinc bis(clibutylthio-
carbamate), which is employed in the reaction mixture in aratio to the boron compound of 0.01 to 0.50 moles for each
mole of the boron compound.
The sulfohalogen compounds of the invention are
prepared in a similar manner to the sulfurized versions,
with the exception that no solvent is employed and,
instead of sulfur as a reactant, a compound such as a
sulfur monochloride (S2Cl2) is employed. The molar ratio
of sulfur monochloride to boron compound is preferably the
same as that for the sulfur to boron compound ratio
employed in preparing the sulfurized species.
~41-
The halogenated species of the invention is
typically prepared by introducing the boron compound to be
halogenated, said boron compound containing an unsaturated
R side group emanating from the nitrogen atom, in-to a 450
neutral oil or into a chlorinated hydrocarbon, e.g., carbon
tetrachloride, followed by bubbling of ch]orine or ~luorine
into the mixture at room temperature (25 C.). Generally,
the bubbling takes place for about 15 minutes, but longer
times are also suitable. If bromine is the desired halogen,
it is added to the mixture in liquid form, in sufficient
amoun-t to saturate a portion of or all the unsaturated
sites of the R side group. Bromination of the boron
compound can take place in as little as lO minutes at
120 C. at atmospheric pressure. If iodine is the desired
halogen, the procedure is modi~ied by adding the iodine in
sufficient quantity to saturate the unsaturated sites.
Sulfohalogenated, boron-containing, heterocyclic
compounds include 10,10'-dithiodi[9 chloro-1-(5-hydroxy-
3,7-diphenyl-1-aza 4,6-diocta~5-bora-cyclooctyl)-octadecane];
20 dithiodi[l-(5-hydroxy-3,7-diphenyl-1-aza-4,6-diocta-5-bora-
cyclooctyl) chlorotallow]; and dithiodi[l-(5-hydroxy-3,7-
diphenyl-l-aza-~,6-diocta-5--bora-cyclooctyl)chlorosoya]
and mixtures thereof. It should be noted that fluorine,
bromine and iodine may be substituted for the chlorine
above.
It will be noted in the foregoing descriptions
related to the preparation of boron heterocyclic compounds
of the invention that such descriptions relate to preparing
the compounds with solvents present during both reactions,
i.e., the reaction of a primary amine with an oxygen-
-42-
containing organic compound followed by the reaction of
the resulting in-termediate product with boric acid, which
yields the borated compound of the invention However,
the preferred embodiment of the invention as presently
contemplated is that the borated compound o~ the lnvention
be produced without any solvent being employed during
these two reactions. (It is, however, preferred that,
when preparing the sulfurized borated compounds previously
described, the sulfurizing step using elemental sulfur be
carried out in the presence of a solvent, e.g., toluene.)
The reason that the absence of solvent is preferred is
-that it has been discovered that a more complete reaction
to the desired borated product is accomplished when no
solvent is emplo~ed. The presence of solvent tends to
yield a mix of undesired and desired borates of the
invention whereas the absence of solvent tends to selec-
tively yield the desired borate of the invention.
The borates of the invention have, as stated
previously, excellent extreme pressure, anti-wear, and
friction-reducing properties. However, they have also
been found to increase the corrosiveness of automotive
lubricating engine oils, with the degree of corrosiveness
depen~ing on the purity of the borate of the invention
employed, the amount employed, and the particular borate
of the invention chosen. Some borates of the invention
herein are less corrosive than others; for example, a
borate of the invention of formula (I) structure herein-
before, wherein Rl and R2 are ethylene groups, is more
corrosive than the borate of the invention of formula (II)
30 structure wherein P~4, R7, R~, Rg, R1o, and R11 are
-~3
~5~6~)~
hydrogen ancl R5 and R6 are both unsubstituted phenyl
radicals. On the other hand, some of the sulfurized
borate of the invention compounds described hereinbefore
are significantly more corrosive than either of the
aforementioned formulae (I) and (II) compounds, but this
disadvantage is compensated for by the fact that only
about one-half as much of the sulfurized compounds is
needed to provide similar anti-wear, friction-reducing,
and extreme pressure properties as said formulae (I) and
(II) compounds.
In any event, if it is desired to lessen the
corrosiveness of the borates of the invention, the lubri-
cating oils into which they are added may be further
provided with one or more corrosion inhibitors. Such
corrosion inhibitors should impart lead and/or copper
corrosion-inhibiting properties, and this because the
bearings in automotive engines typically contain lead
and/or copper.
In one embodiment of the present invention,
copper corrosion in engine bearings is inhibited by adding
to the lubrication composition a corrosion inhibiting
amount, normally from 0.001 to about 5 weight percent,
preferably from 0.005 to about 2.5 weight percent of a
hydrocarbon polysulfide derivative of 2,5-dimercapto-
1,3,4-thiadiazole having the formula (X):
N N
Il 11
(X) ~6 (S)w - C f _ (S) - P~
S
_4a~_
~ 3~i
wherein R~6 and ~7 are the same or different moieties
selected from hydrogen or straight or branched chain
alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or
arylalkyl radicals having from 2 to about 30 carbon atoms,
and w and z are integers from 1 to 8. It should be noted
that R~6 ancl R47 cannot both be hydrogen because the
compound would be rendered insoluble in lubricating oils.
Thus, when R46 is hydroyen, R47 must be selected from one
oE the other moieties described above, and vice versa.
Suitable among such compounds are polysulfides
of 1,3,4-thiadiazole-2,5-bis(alkyl, di, tri or te-tra
sulfide) containing from 2 to about 30 carbon atoms.
Desirable polysulfides include 1,3,4-thiadiazole-2,5-
bis(octyldisulfide); 1,3,4-thiadiazole-2.,5-bis(octyltri~
sulfide); 1,3,4-thiadiazole- 2,5-bis(octyltetrasulfide);
1,3,4-thiadiazole-2,5-bis(dodecyldisulfide~; 1,3,4-thia-
diazole-2,5-bis(dodecyltrisulfide); 1,3,4~thiadiazole-
2,5-bistdodecyltetrasulfide); 2-lauryldithio 5-thio~
methyl-styryl-1,3,4-thiadiazole; 2~1auryltrithio~5~thio~
alpha~methyl~styryl~1,3,4-thiadiazole; 2~mercapto-5~octyl~
dithio-1,3,4~thiadiazole and 2-mercapto-5 dodecyldithio-
1,3,4-thiadiazole and mixtures thereof.
~ small amount of terephthalic acid is effective
as a lead corrosion inhibitor herein. The terephthalic
acid may be prepared in accordance with conventional
techniques and apparatus. Generally, the terephthalic
acid is incorporated into lubricating oils at a concentra-
tion of from about 0.001 to about 1 weight percent,
especially from about 0.005 to about 0.05 weight percent.
~45
An oxidation inhlbitor may also be employed in
conjunction wi-th the desired boron heterocyclic compound
or in conjunction with the boron heterocyclic compound and
corrosion inhibitors. Oxidation inhibitors are typically
added to lubricating oils to prevent oxidative deterlora-
tion of organic materials. Any oxidation inhibitor known
in the art may be employed, with suitable oxidation
inhibitors being selected ~rom the group consisting of
bis(dithiobenzil) metal derivatives; sulfur bridged,
bis(hindered phenols); and alkyl or diakyl, diphenyl-
amines, dithiocarbamates and mixtures thereof. These
compounds effectively limit or prevent the attack of
oxidants on copper/lead metal. In addition, these com-
pounds also help to control oil oxidation as manifested
by reduced sludge and varnish formation, and by reduced
oil thickening.
The bis~dithiobenzil) metal derivatives herein
preferably ha~e the formula (XI):
, _
S S
(XI) L~ I - c~ Mlo+t
H t
wherein Mlo is a first row transition metal and t is an
integer from 1 to 4. Suitable transition metals include
vanadium, chromium, manganese, iron, cobalt, nickel,
copper, zincr preferably iron, cobalt and nickel.
The bis(dithiobenzil) metal derivatives may be
prepared, for example, by reacting benzoin with a phos-
phorus sulfide in the presence of dioxane at elevated
temperature to produce the thiophosphoric ester of dithio-
benzoin. The desired divalent metal, for example,
~46-
metallic halide, is reacted with the above-described
thiophosphoric ester oE dithiobenzoin to produce the
bis(dithiobenzil) metal derivative.
It should be noted that the bis(dithiobenzil)
metal derivatives herein do not readily dissolve in
lubricant compositions. However, when the bis(dithiobenzil)
metal derivatives are mixed with the boron-containing,
heterocyclic compounds herein, especially dodecylaminodi-
(phenylethylate) hydrogen borate, the mixture goes into
solution in lubricant compositions such as motor oils.
The sulfur bridged, bis hindered phenols herein
preferably have the formula (XII):
(XII) [~O ~ (CH2)2 C-- O - (CH2)2 ~ S
R49 2
wherein R48 and R49 are selected from the same or
different alkyl groups having from 1 to 6 carbon atoms.
Sulfur bridged, bis(hindered phenols) which are
suitable for use as anti-oxidants include thiodiethyl
bis(3,5-dimethyl~4-hydroxy) hydrocinnamate; thiodiethyl-
bis(3,5-diethyl-4-hydroxy) hydrocinnamate; thiodiethyl
bis(3,5-dipropyl-4-hydroxy) hydrocinnamate; thiodiethyl
bis(3,5-dibutyl 4-hydroxy) hydrocinnama-te; thiodiethyl
bis(3,5-dipentyl-4-hydroxy) hydrocinnamate and thiodiethyl
bis(3,5-dihexyl-4-hydroxy~ hydrocinnamate and mixtures
thereof.
-47-
1~5~6~
One unexpected result in the present invention
is that, when a sulfur-bridged, bis hindered phenol is
employed as an oxidation inhibitor in the present invention,
lt further functions to reduce the corrosiveness of the
boron compounds of the invention towards lead and copper
automotive bearings. This discovery, which is illustrated
hereinafter in Examples 54 to 60, permits one, through the
introduction of a single additive, to take simultaneous
advantage of two desirable properties -- corrosion inhibi-
tion and oxidation inhibition.
Amines which are suitable for use asanti~oxidants or oxidation inhibitors herein have the
formula IXIII):
(XIII) R El R53
wherein R52 and R53 are hydrogen or the same or different
alkyl radicals having from about 1 to about 30 carbon
atoms, preferably from about 1 to about 20 carbon atoms,
with at least one of R52 and R53 being an alkyl group
(most preferably unsubstituted) having from about 1 to
about 30 carbon atoms, e.g., 8 carbon atoms.
Generally, the anti-o~idants herein are incorpo-
rated into lubricant compositions at concentrations of
from 0.01 to about 2 weight percent, preferably from 0.025
to about 0.10 weight percent, sometimes up to 1.0 weight
percent.
It has also been found that the presence of
copper compounds, dissolved in an automotive engine oil
-48-
~L~5~
25053-356
with borates of the invention, provides for enhanced anti-
wear properties. This embodiment of the invention allows
for the use of less of the borate of the invention for the
same level of desired anti-wear protection. The preferred
compounds for this use are copper carboxylates, such as
copper naphthenate, in concentrations of about lO0 to 125
wppm as Cu. However, even higher concentrations may be
used, for example, up to about 3 percent by weight if
desired.
This embodiment of the invention has an additional
advantage in that copper carboxylates, such as copper
naphthenate, has anti-oxidant properties. Other copper
compounds also ~unction in this manner, e.g., copper oleate.
And in U.S. Patent 4,122,033, teachings are presented for
employing copper compounds as anti-oxidants. Thus, the
use of copper compounds having anti-oxidant properties
functions in two ways in lubricating oils, first, as an anti-
oxidant and, second, for enhancement of the anti-wear
properties of the borate of the invention.
In addition to providing enhanced anti-wear
properties, it has also been found tha-t a lubrication oil
comprising a borate of the invention, and particularly a
sulfurized borate of the invention, with an oil-soluble
copper compound exhibits anti-oxidant properties better
than expected in comparison to the anti-oxidant properties
of a lubrication oil comprising either the borate or
copper compound alone.
.~S _ a~ g
~L~57~
The invention wi]l be further described with
reference to the following examples, which are intended to
illustrate -the invention, not to limit the claims.
Example 1
A boron-con-taining, heterocyclic compound
is prepared by adding 20 grams of boric acid, 95 grams of
Armak Ethomeen C/12 [bis(2-hydroxyethyl) cocoamine] and
250 ml of toluene to a single-necked one liter round-
bottomed flask. The toluene acts as a solvent and as anazeotrope for water produced during the reaction. It
should be noted that boric acid is not soluble in toluene
~D"~ or Ethomeen C/12. The flask is placed in a heating mantle
and fitted with a Dean-Stark trap that is topped with a
condenser. The mixture thus formed is then heated until
it begins to reflux. Next~ the mantle is adjusted to give
a moderate reflux rate. The reaction mixture is refluxed
for one hour, or until the stoichiometric amount of water
(12 ml.) collects in the Dean-Stark trap and all of the
boric acid has dissolved, after which the toluene is
distilled from the reaction product. The reaction product
(103 grams) has a clear golden color and is a fluid liquid
while hot but sets into a soft viscous material when
cooled to room temperature. The compound is readily
soluble in hydrocarbon solvents.
Example 2
A boron-containing, heterocyclic compound is
prepared by the following the procedure of Example 1 with
the following substitution:
-50-
e ~ r~
1~76~i
Armak Ethomeen T/12 [bis~2-hydroxyethyl) tallow-
amine] is substituted for the Armak Ethomeen C/12.
Substantially the same resu~ts are ob-tained.
Example 3
A boron-containing, heterocyclic compound is
prepared by mixing 20 grams of boric acid, 115 grams of
Armak Ethomeen 18/12 [bis~2-hydroxyethyl) octadecylamine]
ancl, as a solvent, 250 ml of toluene in a single-necked
one liter round-bottomed flask. The flask is placed in
a heating mantle and fitted with a Dean-Stark trap and
water-cooled condenser. The mixture is heated under
reflux for one hour, during which 12 ml of water collects
in the Dean-Stark trap. The toluene is then distilled
from the reaction product. The resulting compound is
readily soluble in hydrocarbon solvents.
Example 4
The procedure of Example 3 is followed to
prepare a boron compound of the invention with the follow-
ing exception: N,N-diethanol-n-methylamine (~6.3 grams)
is substituted for the Armak Ethomeen 18/12. The reaction
product thus produced is a liquid product with the consis-
tency of honey when hot and becomes a waxy semi~solid when
cooled to room temperature.
Example 5
Boric acid (20 grams), M,N-diethanol-N-phenylamine
(~6.3 grams) and 250 mls of toluene are mixed in a one liter
single-necked flask to prepare a boron--containing, hetero-
-51-
cyclic compound. The flask is equipped with a heatincJ
mantle, ~ean-Stark trap and water-cooled condenser. The
mixture is heated under reflux until the reaction is
completed (12 ml of water collects), approximately one
hour, and the toluene is distilled from the reaction
mixture. The product thus prepared is suitable for use an
extreme pressure, antiwear and friction-reducing additive
for lubrication compositions.
Example 6
A metal derivative of the reaction product
yielded in Example 1 is prepared by mixing 54 grams of the
product of Example 1, 400 ml of toluene, 24.6 grams of
nickel acetate and 150 ml of methanol in a single-necked,
one liter round-bottomed flask which is equipped with a
hea-ting mantle and water-cooled condenser. The mixture is
refluxed for four hours. Next, water, toluene, methanol
and acetic acid are distilled from the reaction product.
The product (59 grams) contained 7.8 weight percent nickel
as determinecl by emission spectroscopy and the resulting
product is a fluid green liquid when hot, which turns into
a solld upon cooling to room temperature. The product is
readily soluble in hydrocarbon solvents.
Example 7
A metal derivative of the compound of E~ample 2
is prepared by mixing the reaction product of Example 2
(54 grams), 400 ml of toluene~ 24 grams of nickel acetate
and 150 mls of methanol in a single-necked, one-liter
round-bottom flask, equipped with a heaking mantle, Dean-
-52-
~ ~3-J~
Stark trap and water-cooled condenser. The mixture is
refluxed for four hours and the toluene, water and acetic
acid are distilled from the reaction product.
Example 8
A zinc derivative of the reaction product of
Example 1 is prepared by mixing 5~ grams of said reaction
product with ~00 ml of toluene, 19.1 grams of zinc acetate
and 50 ml of methanol in a single-necked, one-liter round-
bottom flask, equipped with a heating mantle and water-
cooled condenser. The mixture is refluxed for four hours
and the toluene, methanol, water and acetic acid are
distilled. The resulting product is suitable for use as
an extreme pressure, anti-wear, friction-reducing additive
for lubrica-ting compositions.
Example 9
Another metal derivative is prepared by following
the procedure of Example 7 with the following exception:
zinc acetate is substituted for the nickel acetate.
Example 1 0
The extreme pressure, anti-wear and friction-
reducing additives produced in Examples 1 and 6 in a 1:1
ratio mixture are mixed with ~50 neutral oil and evaluated
for performance~ The additive mixture is mixed with the
~50 neutral oil at 5 weight percent based on the total
weight of the lubricant composition. This oil mixture is
compared to Arco graphite lubricant and ASTM high reference
-53-
~s~o~
oil, SAE 20W/30 for friction xeduction and extreme pressure
properties.
The lubricants are tested in accordance with the
procedure disclosed in ASTM D3233-73 (Reapproved 1978)
using a Falex lubricant tester. The test is performed
by applying resistance to a revolvin~ metal journal.
Resistance is applied by two V-Blocks equipped with a
ratchet mechanism which steadily increases pressure on the
journal. The metal journal and V-Blocks are composed of
steel in this example. The metal journal and V-Blocks are
submerged in the lubricating composition to be tested.
The results are indicated in the following ~able 1:
Table 1
LUBRICANT
Torque on Journal lbs-in. (Newton-Meters)
450 Neutral
Oil with 5 wt.
to-tal of
Examples
l ana 6
True 450 Neutral Compounds
Load Oil ~ No in a Arco ASTM
Lbs.(Newtons) Additives~ atio Graphite SAE 20W/30
300 (1,334)8 (0.904)4 (0.452)6 (0.678)6 (0.678)
500 (2,224,ll (1.243)6 (0.678)8 (0.904)7 (0.791)
750 (3,336)16 (1.808)9 (1.017)16 (1.808)12 (1.356)
1,000 (4,448)Journal14 (1.582)21 (2.373)20 (2.260)
Shear
1,250 (5,560) --- 21 (2.373)26 (2.937)24 (2.712)
1,500 (6,672) -~- Journal Journal Journal
Shear Shear Shear
It should be noted that substantially the same
results are obtained when the nickel derivative of Exam~le
7 is substituted for the nickel derivative oE Example 6.
~ -54~
~ra c~ ~7c~ y ,~
.5~
Example 11
The lubricant of Example 10 containing the two
compounds of the invention is tested in accordance with
the procedure set forth in Example 10 with the following
exception: the metal journal and V-Blocks are constructed
from cast iron. The results are indicated in the following
Table 2:
Table 2
I.UBRICANT
Torque on Journal lbs-in. (Newton-Meters~
450 Neutral
Oil with 5 wt.%
total of
Examples
1 and 6
True Compounds
Load ln a Arco ASTM
Lbs.(Newtons)1:1 ratio Graphite _ SAE 20W/30
300 (1,334) 3 (0.339)6 10.678) 6 (0.678)
500 (2,224) 4 (0.~52~7 (0.791) 7 (0.791)
750 (3,336) 7 (0.791)13 (1.469) 10 (1.130)
1,000 (4,448)12 (1.356)15 (1.6g5) 1~ (1.582)
1,250 (5,560)14 11.582)17 (1.921~ 17 (1.921)
1,500 (6,672)16 (1.808)20 (2.260) 19 (2.146)
1,750 (7,784)18 (2.034)23 (2.599) 21 (2.373)
2,000 (8,896)Journal Wear24 (2.712)Journal Wear
2,250 (10,008) --~ Journal Wear ~-
. .
The nickel derivative of Example 7 may conven-
iently be substituted for the nickel derivative of Example
6 with substantially the same results.
Example 12
The lubricant of Example 10 containing the two
compounds of the invention is tested in accordance with
the procedure set forth in Example 10 with the following
exception: the journal is constructed from cast iron and
the V-Blocks are constructed from chrome. The lubricant
-55-
properties are comparecl with those of Arco graphite and
ASTM, SAE 20W/30 lubricants. The lubricant compositions
are tested in accordance with -the procedure disclosed in
ASTM:D3233 73 ~Reapproved 1978) using a Falex lubricant
tester. The results axe lndicated in the following
Table 3:
Table 3
LUBRICANT
Torque on Journal lbs-in. (Newton-Meters)
450 Neutral
Oil wi-th 5 wt.%
total of
Examples
1 and 6
True Compounds
Load in a Arco ASTM
Lbs.(~Jewtons) 1:1 ratio Graphite _ _SAE 20W/30
300 (1,334) 5 (0.565) 4 (0.452) 5 (0.565)
500 (2,224) 6 (0.678) 5 (0.565) 7 (0.791)
750 (3,336) 7 (0.791) 8 (0.904) 10 (1.130)
1,000 (4,448) 12 (1.356) 11 (1.243) 1~ (1.582)
1,250 15,560) 15 (1.695) 16 (1.808) 20 (2.260)
1,500 _(6,672? Journal WearJournal Wear Journal Wear
Example 13
An extreme pressure, anti-wear and friction-
reducing lubricant composition is prepared by mixing 5weight percent of the zinc additive of Example 8 with 450
neu-tral oil. The lubricant composition reduces wear and
frictioIl of metal components in moving contact with each
other and~ in addition, lubricates said metal surfaces
under extreme pressure or boundary lubrication conditions.
Example 14
The zinc derivative additive of Example 9 is
admixed with 450 neutral oil at 5 percent by weight based
upon -the total lubricant composition to prepare an extreme
-56-
~ 5~tJ~
pressure, anti-wear and friction-reducing lubricant
composition. The zinc derivative additive imparts extreme
pressure, anti-wear and friction-reducing properties to
the 450 neutral, lubricating oil~
Example 15
A lubricant composition containing the nickel
heterocyclic compound of Example 6 and 450 neutral oil is
tested for extreme pressure, anti-wear and ~riction-reducing
properties in a 1973 Chevrolet 350 cu. in. displacement
V-8 engine which is run continuously for 196 hours on a
single fill of the lubricating composition. The lubrica-
ting oil does not contain conventional zinc dialkydithio-
phosphate anti-wear additives. The lubricant composition
is disclosed in detail in the following Table 4:
Table 4
Weight Percent
450 neutral oil ------~-------------- ------ 89.945
Example 1 Compound ---~ --- 2.500
Mickel Compound of Example 6 ----~ ------- 2.500
Oronite OLOA 12001 ) ------------------~---- 4.000
Chlorowax 40( ) ---------------------------- 1.000
UNAD 242(C) --------------____________ 0.010
Terephthalic Acid( ) ----------------------- 0.025
Quinizarin(E) _____________ _ ______________ 0.020
(A) Oronite OI,OA 1200 - alkyl succinimide type ashless
dispersant.
(B) Chlorowax 40 - Chlorinated paraffin containing 40%
chlorine.
(C) UNAD 242 - Silicone type defoamant with kerosene.
(D) Terephthalic acid - Corrosion inhibitor.
(E) Quinizarin - Antioxidant.
-57-
~-fad'e ~ J k
5~6~3~
The Chevrolet engine is programmed to run in a
repeating cycle that averaged approximately 40 MPEI. The
cycle is disclosed in the following Table 5:
Table 5
Cycle RPM Speed MPH (Kilometers/~r.) Time(MIN.)
1 700 0 (0) 2.0
2 1,700 ~5 (72.4) 3.0
3 1,200 30 (48.3~ 4.0
4 2,225 60 (96.5) 0.12
2,400 65 (104 6) 3.0
After the 196 hour engine test is comple-ted,
several areas in the engine which are subject to wear are
closely examined. These areas include: main bearings,
top end bearings, cam shaft bearings, valve lifters and
cam shaft lobes.
The length of the engine run is equivalent to
approximately 8,000 miles of driving. A detailed examina-
tion of the above-described components indicated no
abnormal or excessive wear.
Example 16
The extreme pressure, anti-wear and friction-
reducing additives of Example 1 and ~xample 2 are individ-
ually mixed with SAE lOW/40 mokor oil containing 0.15
weight percent of phosphorus and 0.17 weight percent of
zinc. In addition, the motor oil contains 0.21 weight
percent of calcium.
The resulting lubricant compositions are tested
in accordance with khe procedure disclosed in ASTM D3233-73
(Reapproved 1978) using a Falex lubricant tester. The test,
in accordance with the above ASTM designation, is performed
by applying resistance to a revolving metal journal. A
rachet mechanism movably attached to two V-blocks applies
-58-
resistance by steadily increasing pressure on the journal.
The metal journal and ~-blocks (steell are submerged in
the lubricant composition to be tested. The results are
set forth in the following Table 6:
Table 6
Torque on Journal,lb.-in ~lewtons-Meters?
SAE 10W/40( ) ~AE 10W/40(a) SAE 10W/40(a)
True LoadWithout Plus 1 wt.% of Plus 1 wt.~ of
lbs (Newtons) Additive Ex.l Compound _ Ex.2 Compound
100 (445)8 (0.904)7 1/2 (0.8~7)7 1/2 (0.847)
250 (1,112) 12 (1.356) 10 (1.130) 9 (1.017)
500 (2,224) 19 (2.147) 15 (1.695) 14 (1.582)
750 (3,336) 22 (2.486~ 18 (2.034) 19 (2.146)
1,000 (4,~481 25 (2.825) 22 (2.486) 22 (2.486)
1,250 (5,560) 35 (3.954) 25 (2.825) 25 (2.~25)
1,500 (6,672) Journal Shear 27 (3.050) 27 (3.050)
1,750 (7,784) ~~ Journal Shear 33 (3.728~
2,250 (10~008) -~ -- Journal Shear
~a) Union Super Motor Oil, marketed commercially by the
Union Oil Company of California.
Example 17
A metal heterocyclic compound is prepared by
following the procedure of Example 6 with the following
changes: 31 grams of reaction product yielded in Example
1 is mixed with 19 grams of lead (II) acetate, 150 ml. of
toluene and 25 ml of methanol. The mixture is refluxed
for 2 hours, after which, the toluene, methanol, water and
acetic acid (produced from acetate) are distilled using
conventional techniques and apparatus. The resultlng
lead-containing product (32.6 grams) is a golden colored
oil with the consistency of honey.
Example 18
~ he extreme pressure, anti~wear and friction-
reducing additive, lead derivative produced in accordance
with the procedure of Example 17 is blended with 450
neutral oil at 5 percent by weight based on the total
-59-
7 ~
weight of the lubricant composition. The above lubricant
composition is compared to Arco graphite lubricant and
ASTM hi~h reference oil, SAE 20W-30 for friction reduction
and e~treme pressure properties.
The lead derivative and 450 neutral oil mixture
is compared to Arco graphite and ASTM, SAE 20W/30 in
accordance with the procedure disclosed in ASTM:D3233-73
(Reapproved 1978) using a Falex lubricant tester. The
test is performed by applying resistance to a revolving
metal journal. Resistance is applied by two V-Blocks
equipped with a ratchet mec~anism which steadily increases
pressure on the journal. The metal journal and V-Blocks
- are composed of steel in this e~ample. The metal journal
and V Blocks are submerged in the lubricating composltion
to be tested. The results are indicated in the following
Table 7:
Table 7
Torque on Journal lbs-in. (Newton-Meters) _
450 Neutral
Oil with
True l,oacl Lead Arco ASTM
Lbs.(Newtons~DerivativeGraphite SAE 20W/30
300 (1,334)7 (0.791) 6 (0.678) 6 (0.678)
500 (2,224)11 (1.243) 8 (0.904) 7 (0.791)
750 (3,336)14 (1.582) 16 (1.808) 12 (1.356)
1,000 (~,448)20 (2.260) 21 l2.373) 20 (2.260)
1,250 (5,560)23 (2.599t 26 (2.937) 24 (2.712)
1,500 (6,672)40 (4.520) Journal ShearJournal Shear
1,750 (7,784)85 (9.605)
2,000 (8,896) 94 (10.622)
2,250 (10,000)90 (10.170)
2,500 (11,120)71 (8.023)
2,750 (12,232)79 (8.927)
3,000 (13,344)70 (7.345)
3,250 (~4,456)70 (7.345)
__ Stopped due to inabilit~ -to increase load.
-60-
~7~ 6
Example 19
A copper-heterocyclic compound is prepared by
adding 62 grams of the boron-containing, heterocyclic
reaction product yieldecl in Example 1, 150 ml of toluene,
50 ml of water and 18.2 grams of cupric acetate to a 500
ml., single-necked round-bottom flask equipped with a
Dean-Stark trap and condenser. The mixture is refluxea
for 8 hours, after which, water, toluene and produced
acetic acid (from acetate) are disti]led leaving 68 grams
of a green solid.
Example 20
The copper derivative additive produced in
Example 19 is admixed with 450 neutral oil at 5 weight
percent based on the total weight of the lubricant composi-
tion and evaluated for performance in accordance with the
procedure of Example 18 with the following exception: the
lubricant properties of the copper derivative-450 neutral
oil mixture are compared with those of 450 neutral oil and
SAE lOW/40 lubricants. The results are indicated in the
following Table 8:
-61-
.~ 5
Table 8
Torque on Journal lbs.-in (Newton-Meters)
True Load 450 Neutral Oil 450 Neutral SAE
lbs. (Newtons) with Copper Com- Oil Without 10W - 40
pound from Ex.l9 Additive
300 (1,33~) 9 (1.017) 10 (1.130)
500 (2,224)11 (1.243~ 15 (1.695) 17 (1.921)
750 (3,336)17 (1.921) 23 (2.599) 21 (2.3733
1,000 (4,44~)20 (2.260) Journal28 (3.163)
Shear
1,250 t5,560)28 (3.163) 33 (3.728)
1,500 (6,672)55 (6.214) Journal
Shear
1,750 (7,784)5S (6.214)
2,000 (8,896)55 (6.214)
2,250 (10,008) 60 (6.779)
2,500 (11,120) 65 (7.345)
2,750 (12,232) 70 (7.909)
3,000 (13,344) 75 (8.474)
3,250 (14,456) 80 (9 038) (Stopped for inspection)
Example 21
The boron-containing, heterocyclic compound,
1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-~,8-dioxacyclo-
octane, is prepared by adding 14,889 grams of cocoamine(1)
and 17,516 grams of styrene oxide to a 65 liter round
bottomed flask that contains 13 liters of toluene and 1
liter of water. The flask is placed in a heating mantle
and fitted with a water-cooled condenser. The mixture
thus formed is heated until it begins to reflux. Next,
the temperature is adjusted to give a moderate reflux rate
and the reaction mixture is refluxed for 24 hours. The
reaction mixture is cooled to room temperature and 4,595
grams of boric acid are added to the flask. Then, the
flask is equipped with a Dean-Star]c trap topped with a
water-cooled condenser and the reaction mixture is refluxed
until water stops collecting in the trap. Toluene is
distilled from the reaction product -to an end point at a
temperature of ~00 F. (204 C.). The reaction produces
-62-
~5~6~
34,373 grams ~f 1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-
2,8-dioxacyclooctane.
(1) Cocoamine is a mixture of primary amines consist-
ing of approximately 52 percent dodecylamine, 19
percent of tetradecylamine, 9 percent of hexadecyl
amine, 6.5 percent of octylamine, 6 percent of
decylamine, 2 percent of octadecyl amine and 5
percent of a mixture of octadecenylamine and
octadecadienylamine. Cocoamine is produced
commercially by the ~rmak Company under the
æ~/e ~na, k
t~a~=~ of Armeen CD.
.~
Example 22
A boron-containing, heterocyclic compound is
prepared by adding 17,605 grams of tallowamine(2) and
15,362 grams of styrene oxide to a 65-liter round-bottomed
flask that contains 11.34 liters of toluene and 1 liter of
water. The flask is fitted with a water cooled condenser
and placed in a heating mantle. The mixture thus formed
is refluxed at a moderate rate for 24 hours. The reaction
is cooled to room temperature and 4,033 grams of boric
acid are added to the flask. Next, the flask is fitted
with a Dean-Stark trap, topped with a water-cooled condenser
and the reaction mixture is refluxed until water stops
collecting in the trap~ Toluene is distilled from the
reaction product to an end point temperature of 400 F.
(204 C.). The reaction produces 34,695 grams of l-hydroxy
3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane.
-63-
~L~5~
(2) Tallowamine is a mixture of amines consisting of
approximately 29 percent hexadecylamine, 20.5
percent octadecylamine, 44 percent of a mixture
of octadecenylamine and octadecadienylamine, 3
percent tetradecylamine, 1.5 percent
hexadecenylamine, 1 percent heptadecylamine and
0.5 percent tetradecenylamine. Tallowamine is
produced commercially by the Armak Company under
the tradename Armeen T.
Example 23
l-hydroxy-3,7-diphenyl-5~dodecyl-5-aza-1-bora-
2,8-dioxacyclooctane is prepared by adding 13,502 grams of
dodecylamine and 17,516 grams of styrene oxide to a
65-liter round-bottomed flask that contains 13.34 liters
of toluene and 1 liter of water. The flask is placed in a
heating mantle and fitted with a water-cooled condenser.
The mixture thus formed is heated until it begins to
reflux. Next, the temperature is adjusted to give a
moderate reflux rate and the reaction mixture is refluxed
for 24 hours. The reaction mixture is cooled to room
temperature and 4,595 grams of boric acid are added to the
flask. Then, the flask is equipped with a Dean-Stark trap
topped with a water-cooled conclenser and the reaction
mixture is refluxed until water stops collecting in the
trap. Toluene is distilled from the reaction product to
an end-point temperature of 400 F. The reaction produces
32,986 grams of 1-hydroxy-3,7-diphenyl-5-dodecyl-5-aza-1-
bora-2,8-dioxacyclooctane.
-64-
~57~)t~
E xam~ 4
The compound, l-hydroxy--3,6-dieresyl-5-dodecyl-5-
aza-l-bora-2,8-dioxacyclooctane, is prepared by adding 21
grams of boric acid with 61.7 grams of dodecylamine, 89.3
grams of para methylstyrene oxide and 250 ml of toluene to
a single necked, one-liter, round-bottomed flask. The
toluene acts as a solvent and as an azeotrope for water
produced during the reaetion. It should be noted that
borie aeid is not soluble in toluene. The flask is plaeed
in a heating mantle ancl fitted with a Dean-Stark trap that
is topped with a water-eooled condenser. The mixture thus
~ormecl is heated until it begins to reflux. Mext, the
mantle heat is adjusted to give a moderate reflux rate.
The reaetion mixture is refluxed for one hour, or until
the stoiehiometric amount of water (12 ml) collects in the
Dean-Stark trap and all of the boric acid has dissolved,
after which the toluene is distilled from the reaction
product. The reaction produces 160 grams of product.
Example 25
The compound, 1 hydroxy-3,7--dimethyl-3,7-diphenyl-
5-dodecyl-5-aza-1~bora- 2,8-dioxaeyclooctane, is prepared
by followincJ the proeedure of Example 23 with the following
substitution:
Alpha methyl styrene oxide is substituted for
the styrene oxide with substantially the same results.
Example 26
Boric acid (21 grams), para-tertiary-butyl
styrene oxide (119.3 grams~, dodeeylamine t61.7 grams) and
250 ml of toluene are mixed in a one-liter, single-neeked
flask ~o prepare 1-hydroxy-3,7-para-tertlary-butylphenyl-
5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane. The flask is
equipped with a heating mantle, Dean~Stark trap and water
cooled condenser. The mixture is heated under reflux
until the reaction is completed; 12 ml of water collects
in the Dean-~tark trap. Next, toluene is distilled from
the reaction mixture. The product thus prepared is
suitable for use as an extreme pressure, anti-wear and
friction-reducing additive for lubricating compositions.
It should be noted that the other primary amines
herein may be substituted for the dodecylamine above, to
form the corresponding boron heterocyclic compound.
Example 27
A copper derivative of l-hydroxy-3,7~diphenyl-5-
coco 5-aza-1-bora-2,8-dioxacyclooctane is prepared by
following the procedure Example 21 with the following
exception: the above-described compound (47 grams), 100
ml of toluene, 20 ml of triethyl amine and 10 grams of
cupric acetate are mixed in a single-necked, 500 ml round-
bot-tomed flask, equipped with a heating ~lantle and water-
cooled condenser. The mixture is refluxed for 16 hours,
then filtered and the toluene, amine, water and acetic
acid (produced in situ) are distilled from the re~ction
product. Using the above-procedure, copper di-[l-oxy-
3,7-diphenyl-5-coco-5-aza--1-bora-2,8-dioxacyclooctane] is
produced.
-66-
~57606
Example 28
~ nickel derivative of 1-hydroxy-3,7-diphenyl--
5-coco-5-aza-1-bora-2,8-dioxacyclooctane is prepared by
following the procedure of Example 27 with the following
exception:
An equivalent amount of nickel acetate is
substituted for the cupric acetate. The reaction produces
nickel cli-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-
dioxacyclooctane].
Example 29
Lead di-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-
2,8-dioxacyclooctane] is prepared in accordance with the
procedure of Example 21 with the following exception:
The reaction product produced in Example 21
(23.5 grams), 100 ml of toluene, 9.5 grams of lead acetate
and 10 ml of triethylamine are mixed in a single-necked
500 ml round bottomed flask, equipped with a water-cooled
condenser and heating mantle. The mantle heat is adjusted
until a moderate rate of reflux is obtained. The mixture
thus formed is refluxed for 18 hours. Next, the mixture
is filtered, and toluene, water, triethylamine and acetic
acid (produced in the reaction) are distilled from the
reaction product. The reaction produces lead di-[1-oxy-
3,7-diphenyl-5-coco-5-aza~1-bora-2,8-dioxacyclooctane.
Example 30
Iron di-(1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,
8-dioxacyclooctane) is prepared according to the procedure
of Example 21 with the following exception~
-67--
~57~
A mixture comprisin~ 23.5 ~rams of the reaction
product produced in Example 21, 100 ml of toluene, 4.3 grams
of ferrous acetate and 10 ml of triethylamine are introduced
into a single-necked, 500-ml, round-bottomed flask, equipped
with a water-cooled condenser and heating mantle and Dean-
Stark trap.
Example 31
A boron compound of the invention is prepared by
adding 17,093 grams of octadecylamine and 15,362 grams of
styrene oxide to a 65-liter, round-bottomed flask that
contains 13 liters of -toluene and 1 liter of water. The
flask is fitted with a water-cooled condenser and placed
in a heating mantle. The mixture thus formed is refluxed
at a moderate rate for 24 hours. The reaction is cooled
to room temperature and 4,033 grams of boric acid are
added to the flask. Next, the flask is fitted with a
Dean-Stark trap, topped with a water-cooled condenser and
the reaction mixture is refluxed until water stops
collecting in the trap. Toluene is distilled from the
reaction product to an end-point temperature of 400 F.
The reaction produces 34,183 grams of 1-hydroxy-3,7-
diphenyl-5-octadecyl-5-aza-1-bora-2,8-dioxacyclooctane.
Example 32
The procedure of Example 31 is followed to
~roduce l-hydroxy-3,7-diphenyl-5-phenyl-5-aza-1 bora-2,8-
dioxacyclooctane with the following exception:
An e~uivalent amoun-t of phenylamine is substi-
tuted for octadecylamine.
-68-
o~-i
Example 33
~ inc di-[l-oxy-3,7-diphenyl 5-coco-5-aza-1 bora-
2,8-dioxacyclooctane] is produced according to the proce-
dure of Example 27 except that an equivalent amount of
zinc acetate is substituted for the cupric acetate.
Example 34
Tin di-[l-oxy-3,7 diphenyl-5-coco-5-aza-1-bora-
2,8-dioxacyclooctane] is prepared by substituting an
equivalent amount of tin acetate for the cupric acetate in
Example 27.
Example 35
Lead di-[l-oxy-3,7-diphenyl-5-dodecyl-5-aza-1-
bora-2,8-clioxacyclooctane] is prepared in accordance with
the procedure of Example 23 with the following exception:
The reaction product produced in Example 23
(23.95 grams), 100 ml of toluene, 9.5 grams of lead
acetate, and 10 ml of triethylamine are mixed in a single-
necked, 500-ml, round-bottom flask, equipped with a
water-cooled condenser, heating mantle and Dean-Stark
trap. The mantle heat is adjusted until a moderate rate
of reflux is obtained. The mixture thus formed is refluxed
for 18 hours. Next, the mixture is filtered and the
toluene, triethylamine, water and acetic acid (produced
in-situ) are distilled from the reaction product. The
reaction produces lead di[-l-oxy-3,7-diphenyl-5-dodecyl-
5-aza-1-bora-2,8-dioxacyclooctane].
-69-
)6
Example 36
A nickel derivative of l-hydroxy-3,7-dicresyl-5-
dodecyl-5-aæa-1-bora-2,8-dioxacyclooctane is prepared by
following the procedure of Example 35 with the following
exception:
~ n equivalent amount of paramethyl styrene oxide
is substituted for styrene oxide and niekel acetate is
substituted for lead acetate. The reaction produces
niekel di[-1-oxy-3,7 dicresyl 5-dodeeyl-5-a2a-l-bora-2,8-
dioxacyclooctane].
Example 37
Iron di-[l-oxy-3,7-di-para-tertiary-butyl-phenyl-
5-dodecyl-5-aæa-1-bora-2,8-dioxacyclooetane] is prepared
according to the procedure of Example 26 with the following
exception:
A mixture eomprising 28.4 grams of the reaction
produet produced in Example 26, 100 ml of toluene, 4.3 grams
of ferrous acetate and 10 ml of triethylamine are introdueed
into a single-neeked, 500~ml, round-bottom flask, equipped
with a Dean-Stark trap, water-eooled eondenser and heating
mantle. The heating mantle is adjusted to give a moderate
rate of reflux of the reaetion mixture. The mixture is
refluxed for 18 hours, filtered, and the toluene, triethyl-
amine, water and aeetic acid (produced in-situ) are distilled
from the reactlon product.
-70-
~57~0~j
Example 38
Zinc di~ oxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-
2,8-dioxacyclooctanel is produced according to the procedure
of Example 35 except that zinc acetate is substituted ~or
lead acetate.
Example 39
Tin di-[1-oxy-3 t 7-diphenyl-5-dodecyl-5-aza-1-bora-
2,8-dioxacyclooctane] is prepared by substituting tin
acetate for lead acetate in Example 35.
Examples 40 to 46
Extreme pressure, anti-wear and friction-reducing
additives produced according to the procedure of Examples
21, 27, 29, 30, 33 and 34 are mixed with separate portions
of 450 neutral oil at concentrations of 2 weight percent.
Each lubricant composition is tested in accordance
with the procedure disclosed in ASTM:D3233-73 (Reapproved
1978) using a Falex lubricant tester. The test, in
accordance with the above ASTM designation, is performed
by applying resistance to a revolving metal journal. A
rachet mechanism movably attached to two V blocks applies
resistance by steadily increasing pressure on the journal.
The me-tal journal and V-blocks (steel) are submerged .in
the lubricant composition to be tested. A summary of the
results obtained is disclosed in the following Table 9:
71-
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o~
Examples 47 and ~8
The extreme pressure, anti-wear and friction-
reducing additive produced in accordance with the pxocedure
of Example 21 is mixed at a concentration oE 2 weight
percent with SAE 30 motor oil which contains 0~05 weight
percent phosphorus. A sample of the SAE 30 motor oil which
does not contain the additive of Example 21 is used as a
control. This control was blended 6.5 volume percent
(7.05 weight percent) Amoco PCO-059 in ~nion 450 neutral.
(See footnote (E~ in Table 12 hereafter.)
Each lubricant composition is tested in accord-
ance with the procedure disclosed in ASTM D3233-73 (Reap-
proved 1978) using a Falex lubricant tester. A su~nary of
the results in disclosed in the following Table 10:
Table 10
Torque on Journal lbs.-in (Newton-Meters?
Example 47 48
True ~oad Control (SAE 30SAE 30 Motor Oil
lbs. (Newtons)Motor Oil)with Additive of Ex.21
300 (1,33~)9 (1.017~ 8 (0.904)
20500 (2,224)14 (1.5~2)12 (1.356)
750 (3,336)20 (2.260~17 (1.921)
950 (4,404)Journal Shear ---
1,000 (4,448) --- 22 (2.486)
1,250 (5,560) --- 28 (3.163)
1,400 (6,227) --- Journal Shear
The extreme pressure property of SAE 30 motor
oil is substantially enhanced in Table 10 above when 2
weight percent of l-hydroxy-3,7-diphenyl-5-coco-5-aza-1-
bora-2,8-dioxacyclooctane is added to said SAE 30 motor
oil.
~73-
--fr~ ~ c, r~
o~
Example 49
A copper corrosion inhibltor comprising 1,3,4-
thiadiazole-2,5-bis(dodecyldisulfide) is prepared by
chlorinating 284 grams of n-dodecyl mercaptan in 0.6 liter
of carbon tetrachloride with 1.47 moles of chlorine over a
two-hour period at a temperature of about 23 F. (-5 C.)
to about 32 F. (0 C.). ~ext, sulfenyl chloride which
forms as a reaction product is stripped with nitrogen to
remove hydrogen chloride, and the resultant compound is
added to 86 grams of a 2,5-dimercapto-1,3,4-thiadiazole
slurry. The mixture is heated at 86 F. (30~ C.) for 1
and 1/2 hours and the resultant compound (1,3,4-thia-
diazole-2,5-bis(dodecyldisulfide) is recovered by washing
with water and sodium bicarbonate and vacuum stripping to
remove carbon tetrachloride.
Example 50
The procedure of Example 49 is followed to
prepare 1,3,4-thiadiazole-2,5-bis (octyldisulfide) with
the following exception: octyl mercaptan is substituted
for the dodecylmercaptan.
Example 51
The oxidation inhibitor, thiodiethyl bis-(3,5-di-
t-butyl-4-hydroxy) hydrocinnamate, is prepared by melting
together 17.95 weight percent of beta,beta'~dihydroxy-
diethyl sulfide, 81.41 weight percent of (3,5-di~t~butyl-
4-hydroxy) hydrocinnamate acid and 0.64 weight percent of
sodium methylate under a nitrogen atmostphere at 266 E~.
(130 C.) for two and one-half hours. Methanol thus
-74-
6Q~i
formed is separated from the reaction mixture and condensed
in a dry-ice -trap using nitrogen gas as a carrier. The
reactants are heated at 149 F. (65 C.) for three hours
and the reaction product is dissolved in warm benzene,
filtered and the benzene filtrate is washed three times
with sa-turated sodium chloride solution. The filtrate is,
next, dried over anhydrous sodium sulfate and the solvent
evaporated using conventional techniques. Thiodiethyl
bis~(3,5-di-t-butyl-4-hydroxy) hydrocinnamate is isolated
and purified by successive recrystallization from hexane
and a mixture of hexane and t-butanol.
Example 52
The oxidation inhibitor, bis(dithioben~il) iron
(II), is prepared by adding 400 grams of ben~oin and 600
grams of phosphorous sulfide to a single-necked, 5-liter,
round-bottomed flask equipped with heating mantle and
water-cooled condenser and containing 1,500 ml of dioxane.
The mixture thus formed is refluxed for two hours. Next,
20 200 grams of hydrated ferrous chloride dissolved in 500 ml
of water is added to the 5 liter flask and the mixture is
heated on a steam bath at 212 F. (100 C.) for 2 hours.
The reaction product thus formed (169.5 grams) is filtered
and washed with methanol.
~ample 53
Dodecylamino di~phenylethylate) hydrogen borate
is prepared by adding 34.85 pounds (15,808 grams) of
dodecylamine (1 e~uivalent) and 41.0 pounds (18,597 grams)
30 of styrene oxide (2 equivalents) to a 17 U.S. gallon (64.3
-75-
~5~ 6
liters~ round bottomed flask equipped with a water-cooled
condenser and containing 3 U.S. gallons (11.36 liters3
toluene and 1 liter o~ water. The reaction is exothermic
and begins immediately upon addition of the above
reactants. Additional heat is applied and the reaction
mixture is refluxed for a total o~ 24 hours; however, as
little as 2 hours may result in complete reaction. The
reaction is cooled -to room temperature, 10.49 pounds
(4,758.16 yrams) of boric acid (1 equivalent) is added and
the flask is equipped with a Dean-Stark trap. Heat is
again applied and -the reaction mixture refluxed until
water stops collecting in the trap. Toluene is, then,
distilled from the reaction product at a temperature of
400 F. (204 C.) or less. About 6 liters of water
collect in the Dean-Stark trap. The reaction produces
approximately 75 pounds (34,019 grams) of product.
Examples 54 to 60
~ lubricant composition containing dodecylamino
di(phenylethylate) hydrogen borate, 1,3,-4-thiodiazole-
2,5-bis(octyldisulfide), terephthalic acid, and thiodiethyl
bis-(3,5-di-t-butyl-~-hydroxy) hydrocinnamate is tested
for copper and lead corrosion inhibition and anti~oxidant
properties using a single-cylinder Labeco CLR Test Engine
equipped with sintered copper (65 wt.%)/lead (35 wt.%)
connecting rod bearings, in accordance with the procedure
of Federal Test Method Standard ~o. 791B, method 3405.2.
The same lubricant composition, but containing bis(dithio--
benzil)irontII) substituted for the hydrocinnamate compound,
is also tested by the same procedure.
~5~
The copper-lead corrosion tests are conducte~ in
accordance with the test conditions of the following Table
1 1 :
Table 11
Operating Conditions
Test Duration, Hours 40
Speed, RPM 3150 + 25
Load, BHP 6.5a
(KW) (4.85)
Fuel, Flow, Lb/Hr. 4.75 + 0.25
(gm/Hr.) (2,155 + 53
Air/Fuel Ratio 14.0 + 0.5
Jacket Outlet Coolant Temp.,F. 200 + 2
(C.) (93.33 -~ 1.113
Gallery Oil Temp., F. 290 + 2
IC.)(143.33 ~ loll~
Spark Advance, BTDC 35 + 1
Oil Pressure, PSIG 40 + 2
(atmospheres) (3~72)
Crankcase Vacuum, in. H O2 + 0.5
(cm. ~2) (5.08 ~ 1.27)
Exhaust Back Pressure, in. Hg. 0.5 ~ 0.5
(cm. Hg) (1.27 + 1.27)
Crankcase Off-Gas, CFH 30 + 1
tCMH)(0.83 ~ .03)
Oil Charge, Pints 3.5
(Liters) (1.66~
The test is conducted by charging 3.5 pints
(1.66 liters) of the test lubricant to the engine sump.
Test duration eonsists of 40 hours operation at the
prescribed test conditions of Table 11 above. When the
prescribed gallery oil temperature is reached, the test
time begins. Interim oil acljustments are made at the end
of 10, 20 and 30 hours of test operation. A copper/lead
bearing weight loss (BWL) of about 40 mg of lower is
considered acceptable. All of the tests are eonducted on
blends based upon the control using SAE 30 motor oil
further containing the additives and/or compouncls, at the
concentrations in the following Table 12:
tj
o o o ~r ~ oo
~ o r~ D a)
O ~ ~ C~ t~ r~
_ ~ r~
u~
O c~ ~ In Lf)
D In O
~ ~ 8
~ -- ,d
O Ln Ln LO U~ Ln In ~ ~-rl a)
oooooooo ~o~
~_ o o o o o o o o .
d,~r
C~O I ~ ~
r ¦ i ~ O O &
oP ,~ r~
~1 0 r-l r--l ;~
~,_ I I o o o o o o . a) n ~
~.~ I I o o o o o o
~ ~~ ~ ~
~ o~O I I L~O. ~ ~ ~`~
52 ~ I I o o o o o o
H l l O O O O O O
~ O
2;~ 1 ~
3 ~ ô\o
~ L ) I r-l r I r ~ r I o r~ o 1~ 1 I rz O u~ rl 11
3 l~i --' ¦ ~ i t'J N ~
o ~ ~y r~
~ $ ~ o ~ o 11
~lo ~ 3 ~ !~
~ ~' Lt~ ~D ~ ~ ~ O ,_ ~ ~ _ _ _
~ ~ Ln n n
--78--
r 5i 7 ~ 6
Example 61
The bis(hydrocarbyloxy methylated) boron-
containing heterocyclic compound, 1-hydroxy-3,7-di(methyl
phenoxy methyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane r
is prepared by adding 278.5 grams of cocoamine and 450.5
grams of cresyl glycidyl ether to a 2-liter round-bottomed
flas]c that contains 250 ml of toluene and 22 ml of water.
The flask is placed in a heating mantle and fitted with a
water-cooled condenser. The mixture thus formed is heated
until it begins to reflux. Next, the temperature is
adjusted to give a moderate reflux rate and the reaction
mixture is refluxed for 18 hours. The reaction mixture is
cooled to room temperature and 86.0 grams of boric acid
are added to the flask. Then, the flask is placed in a
heating mantle and fitted with a water-cooled condenser.
The mixture thus formed is heated until it begins to
reflux. Next, the temperature is adjusted to give a
moderate reflux rate and the reaction mixture is refluxed
for 18 hours. The reaction mixture is cooled to room
temperature and 86.0 grams of boric acid are added to the
flask. Then the flask is equipped with a Dean-Stark trap
topped with a water-cooled condenser and the reaction
mixture is refluxed until water stops collecting in the
trap. Toluene is distilled from the reaction product to
an end-point temperature of 400 F. (20~ C.). The
reaction produces 758.5 yrams of 1-hydroxy-3,7-di(methyl-
phenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane.
-79-
5~7~
Exam~le_62
The bis(hydroxycarbyloxymethylated) boron-
containing, heterocyclic compound, 1-hydroxy-3,7-di(methyl-
phenoxymethyl~-5-oleyl-5-aza 1-bora-2,8-dioxacyclooctane,
is prepared by adding 55.6 grams of oleyl amine and 66.0
grams of cresyl glycidyl ether to a 1 liter round-bottomed
flask that contains 250 ml of toluene. The flask is
placed in a heating mantle and fitted with a water~cooled
condenser. The mixture thus formed is heated until it
begins to reflux. Next, the temperature is adjusted to
give a moderate reflux rate and the reaction mixture is
refluxed for 18 hours. The reaction mixture is cooled to
room temperature and 12.~ grams of boric acid are added to
the flask. Then, the flask is equipped with a Dean-Stark
trap topped with a water-cooled condenser and the reaction
mixture is refluxed until water stops collecting in the
trap. Toluene is distilled from the reaction product to
an end point temperature of 400 F. (20~ C.). The
reaction produces 97 grams of 1-hydroxy-3,7-di (methyl-
20 phenoxymethyl)-5 oleyl-5-aza-1-bora-2,8-dioxacyclooctane.
~xample 63
The compound, 1-hydroxy-3,7-di(methyl phenoxy
methyl)-5-dodecyl-5 aza-1-bora 2,8-dioxacyclooctane, is
prepared in accordance with the procedure of Example 61
with the following exception: one mole of dodecylamine is
substituted for each mole of cocoamine used.
-80-
1~5~ 3~i
Example 64
The compound, l-hydroxy-3,7-di(methyl phenoxy
methyl)-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane, is
prepared in accordance with the procedure of Example 62
with the following exception: one mole of tallowamine i5
substituted for each mole of oleyl amine used.
Example 65
A copper derivative of l-hydroxy-3,7-di(methyl
10 phenoxy methyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane
is prepared by following the procedure of Example 61 with
the following exception: the compound of Example 61 147
grams), 100 ml of toluene, 20 ml of triethyl amine and 10
grams of cupric acetate are mixed in a single-necked, 500
ml round bottom flask, equipped with a heating mantle,
Dean-Stark trap and water-cooled condenser. The mixture
is refluxed for 16 hours, then filtered and the toluene,
amine, water and acetic acid (produced in situ) are
distilled from the reaction product. Using the above
procedure, copper di[l-oxy-3,7-di(methyl phenoxy methyl)-
5-coco-5-aza-1 bora-2,8-dioxacyclooctane] is produced.
Examples 66 to 71
The compound l-hydroxy-3,7-di-(methylphenoxy-
methyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane produced
in accordance with the procedure of Example 61 is tested
for extreme pressure, anti-wear and friction-reducing
properties admixed with separate portions of 450 neutral
oil and SAE 30 motor at concentrations of 1 and 2 weight
percent respectively. Samples of 450 neutral oil and the
~81-
control SAE 30 motor oil [Example 47) without the compound
1-hydroxy-3,7~di-(methylphenoxymethyl)-5-coco~5-aza-1-
bora-2,8-dioxacyclooctane serve as controls of the experi-
ments.
Each lubricant composition is tested in accord-
ance with the procedure disclosed in ASTM:D3233-73 (Reap-
proved 1978) using a Falex lubricant tester. The test, in
accordance with the above ASTM designation, is performed
by applying resistance to a revolving metal journal. A
rachet mechanism movably attached to two V-blocks applies
resistance by steadily increasing pressure on -the journal.
The metal journal and V-blocks(steel) are submerged in the
lubricant composition to be tested. A summary of the
results obtained is disclosed in the following Table 13:
-8~-
' tj~t
~ ,~ o~o ~ o ~ ~ ~9 r~
r~ r~ v r~ J~ r~ ~ N C;~
O ~ ~ ~ ~ N
~ r~ r~ N
10 1~'~ 3
r~ ~r r~) ~ r~l
r~~ ~_ r~ ~ O 7
F ~ o\o r-~ ~D ro r~l ~3
~i r~ æ ~ r~ i o
o u~ ~ ~o 1~ r~
2 o ~ . rJ ~ r~
G .,; ~ ~
~O ~; O r-i ~ l~
r r r
rt~ r~l ~D ~ u) ~ cn ~o r
r7 r~ ~o r~ In r r u~ ~D
a) ~ 1 ~ ~ o }~
o o o u~ o o o r o
r o ~ r~
-83-
~ 3~
As shown in Table 13, the addition of 1-hydroxy-3,
7-di-(methylphenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxa-
cyclooctane to 450 neutral oil and to the control SAE 30
motor oil (Example 473 at concentrations of one and two
weight percent, respectively, imparts extreme pressure
properties to the oils~
Example 72
A lubricant composition is tested for copper and
lead corrosion inhibi-tion properties using a single-
cylindered Labeco CLR Test Engine equipped with sintered
copper (65 wt.~)/lead (35 wt.~) connec-ting rod bearings, in
accordance with the procedure of Federal Test Method
Standard No. 791B, Method 3405.2.
The test is conducted in accordance with the test
conditions of Table 11 in previous Examples 54 to 60.
In additionl the test is conducted by charging
3.5 pints (1.7 liters) of the test lubricant to the engine
sump. Test duration consists of 40 hours operation at the
prescribed test conditions of Table 11 above. When the
prescribed gallery oil temperature is reached, the test
time begins. Interim oil adjustments are made at the end
of 10, 20 and 30 hours of test operation. A copper/lead
hearing weight loss (BWL) of about 40 mg or lower is
considered acceptable.
The lubricant composition tested in this Example
72 is a standard 450 neutral oil containing the additives
and concentrations shown in Tab]e 14. Also shown in Table
14 is the result of the experiment.
-84
J~
8 ~ ~
ô o
o, ~ o ~ o
U~ ,~ ~ ~ ~` 52
~ ~
_ -U ~ $
~L~
o ~
co ~ ~ O ,~a
.~ U
'~ ~ ~ ~
~ o ~
E-l ~ ~ . N ,C ~ O
~- I o I ~ 0 ~
O ~1 0
~~
0~ I ~ ~40
O m^ ,~
2 0 ~ h ~`P u~
O O ~ r~ a) ~
o E~ ~ 0
~ H o
~ ~, O
O -~ ~ -- H ~) ' ;~ -~
~r~ o~O ~. ~ 0~
~1
~- ~ O~-o ~ ~ ~
~ UO 11
~1 ~ ~
~1 ` ~ â:~ v c ~
~5-
~7~ 6
Example 73
A lubricant composition containing 450 neutral
oil, l-hydroxy-3,7-diphenyl-5-coco~5-aza-1-bora-2,8-dioxa-
cyclooctane, and octyl diphenyl amine is tested for
extreme pressure properties, and resistance to oxidation
stability, and corrosion using a single cylinder Labeco
CLR Test Engine equipped with sintered copper (65 wt.~)/
lead (35 wt.%) connecting rod bearings, ln accordance with
the procedure ASTM STP 509A, Part IV and the engine
10 operating conditions of Examples 54 to 60 and 72. The
total phosphorus content was 0.075 weight percent.
The results are summarized in the following
Table 15:
-86-
~L;2t~
.~
~1
~ . -
~
_
_ ~ ~1 ~ ~ ~
~ I ~
cA ~
' o ~ '
_ ~ U ~1
~ ¦ ~ ~ u
,1~
d~ ~ $ ~ ~ ~
U 3 o o
,1 h L~ U
~ o $ ,~ ,~ o OU a~ ~ ~
2 0~ o ,~
I ,~ ~ h
~_ ~ 4~
Il ~ o~ LO
-~... o ~ ~ ~ o ~ ~ ~ 8
~; ~ 3 ~ h
~ o ~ ~ ~ 8 ~ N LO ~
r~J .~ ~ U ~ 1I h
O h 1~ ~ ~ 11
~ 'g ~
r~
~ ~ -- ~ ~ ~ ~
~ ~ ~ u
-87-
~L~5~
Example 74
The lubricant composition disclosed in Table 15
of E~ample 73 is tested in a 1977 Oldsmobile~ -8 engine
- for 64 hours in accordance with the following 1977 General
Motors Lubricant Evaluation Sequence III D test.
Prior to each test run, the engine is completely
disassembled, solvent cleaned, measured and rebuilt in
strict accordance to furnished speciEications. Following
the preparation, the engine is installed on a dynamometer
test stand equipped with the appropriate accessories for
controlliny speed, load, temperatures and other various
engine operating conditions.
The engine is operated on a 4-hour break-in-
schedule aEter which oil is sampled and leveled. The
engine is then operated under non-cyclic, moderately high
speed, high load and temperature conditions for a test
duration of 64 hours, with oil leveling and oil additions
each 8 hours.
In the following Table 16 is a summary of these
operating conditions:
fr~de ~n~7~
-88--
~L ~ r~
Table 16
Speed, rpm 3000 + 20
Load, bhp 100 t 2
(Kw) l74.6 + 1.49)
Oil, to engine, after filter, F. 300 + 2
(C.) ~149 + 1.1)
Oil pump outlet, psig min 40
(atmospheres min) (3.72)
Coolant, jacket out, F. 245 + 1
(C.)(18.3 + 0.6)
jacket in, F. 235 -~ 1
(C.)(112.8 + 0.6)
jacket flow rate, gpm 60 ~ 1
(lpm) (227 + 3.8)
rocket cover out, F. 240 + 3
(C.) (115.56 ~ 1.67)
at gpm per cover at 1.5 + 0.5
(lpm~ (5.7 + 1.9)
breather tube out, F. 100 + 2
(C.) (37.8 + 1.1)
at gpm at 3.0 + 0.5
(lpm) (11.36 + 1.9)
Air-fuel ratio 16.5 -~ 0.5
Caxburetor, air temperature ,F. 80 t 2
(C.) (26.7 ~ 1.1)
Carburetor, air humidity, grains
per lb of dry air80 + 5
(grams per gram of dry air~ (0.01143 ~ 0.0007)
Carburetor, pressure, in. of water 0.1 to 0.3
(cm)(.3 to .8)
Blowby rate, cfm at 100F. and 29.7 in. 2.0 + 0.3
(37.78 C.) and (75.4 cm) of ~y (0.0566 + 0.0085)
Intake manifold vacuum, in. of ~Ig 7 ~ 2
(cm)(17.78 + 5.08)
Exhaust back pressure, in. of water 30 + 2
(cm)(76.2 + 5.08)
Exhaust back pressure, max differential,
in.(cm) of water 0.2 (0.51)
After every 8 hours of testing, a 25-minute
shutdown period is provided for oil sampling, additions
and level adjustments. The total running test time for
Sequence IIID is 64 hours. The results are su~mari~ed in
the following Table 17:
-89-
C~
Table 17
Test Result ~PI "SF" Limit
(A) Engine Sludge Rating ~10=clean) 9~ 9.2 min.
(B) Piston Varnish (10=clean) 9.4 9.2 min.
(C) Cam & Lifter Wear (inch) 0.0019 0.0080 max.
(D) 64 hour Viscosity increase, ~ 1~2 375 max.
(E) Oil Consumption, quarts 3.06 6.38 max.
The engine tests are performed in accordance
with the Coordinating Research Council (CRC) rating and
techniques located in CRC Manual NOS 9 and 12.
Example 75
A sul~urized, boron-containlng, heterocyclic
compound is prepared by mixing 12 yrams of oleylamine, 9~6
grams of styrene oxide and 200 ml of toluene for 30
minutes at room temperature (25 C.) in a single-necked
one-liter round-bottomed flask. The flask is placed in a
heating mantle and equipped with a water-cooled condenser.
The mixture is heated under reflux for three hours produc-
ing an oleylamine/styrene oxide adduct.
The adduct is cooled to room temperature and
2O~7 grams of boric acid is added to the flask. Next, the
resulting mixture is refluxed until 1.4~ ml of water
collects in an added Dean-Stark trap. rrhe Elask and
contents are moved to a rotary evaporator where toluene is
stripped from the boron-containing, heterocyclic compound
(18 grams).
Sulfur (0.96 grams) and 75 ml of toluene are
added to the round-bottomed flask and the resulting
mixture i9 heated to reflux temperature with mixing for
four hours, after which the toluene is distilled off under
vacuum, to yield the desired reaction product.
--90--
Example 76
The reaction product of Example 75 is tested for
extreme pressure properties in 450 neutral oil in accord-
ance with the procedure disclosed in ASTM:D 32 33-73
(Reapproved 19781 using a Falex lubricant tester. The
test is performed by applying resistance to a revolving
metal journal. A rachet mechanism movably attached to two
V-blocks applies resistance by steadily increasing pressure
on the journal. The metal journal and V-blocks (steel)
are submerged in the lubricant composition to be tested.
The results are summarized in the following Table 18:
Table 18
Torque on Journal lb.-in.(Newtons-Meters)
450 Neutral Oil (A)
True Load 450 Neutral Oil (A) with 2.25 wt.
lbs.(Newtons)without additive additive
-
300 (1,334) 9 (1.017) 2 (0.226)
500 (2,224) 12 (1.356) 4 (0.452)
750 (3,336) xx 8 (0.904)
1,000 ~4,448) 13 (1.469)
1,250 (5,560~ 18 (2.034)
1,500 (6,672) 23 (2.599)
l,750 (7,784) xx
(A) 450 Neutral Oil, marketed commercially by Union Oil
Company of California.
Example 77
A sulfochlorinated, boron-containing, hetero-
cyclic compound is produced by adding 20 grams of l-hydroxy-
3,7-diphenyl-5-oleyl-5-aza-1-bora-2,8-dioxacyclooctane, 10
ml of toluene and 1.76 grams of sulfur monochloride to a
one liter round-bottomed flask equipped with heating
mantle and water- cooled condenser. The mixture thus
formed is heated at 200 F. (93.33 C.) for 45 minutes,
30 then 6.3 grams of 450 neutral oil is added to the flask
--91--
and the toluene evaporated. The compound 10,10'-dithio-
di[9-chloro-1-(5-hydroxy-3,7-diphenyl-1-aza-4,6-dlocta-5-
bora-cyclooctyl)-octadecane] is produced in this reaction.
Example 78
The compound dithiodi-[1-(5-hydroxy-3,7-diphenyl-
1-aza-4,6 diocta-5-bora-cyclooctyl)-chlorotallow] is
produced in accordance with the procedure of Example 75
with the following exception:
20 grams of 1-hydroxy-3,7-diphenyl-5-tallow 5~
aza~1-bora-2,8-dioxacyclooctane and 1.215 grams of sulfur
monochloride are added to the one liter round-bottomed
flask.
Examples 79 to 81
The compounds produced in Examples 77 and 78 are
tested for extreme pressure properties by admixing each
compound with separate portions of 450 neutral oil at
concentrations of 2 weight percent. A sample of ~50
neutral oil without an additive (compound) serves as a
control in the experiment.
Each lubricant composition is testecl in accord-
ance with the procedure disclosed in ASTM:D 32 33-73
(Reapproved 1978) using a Falex lubricant tester contain-
ing a steel journal and V-blocks. A summary of the
results obtained dlsclosed in the following Table 19:
-92-
7~0~
r~
rl rr
v r~
,~ ~o ~ co o ~ ~r
~ ~ ~ r~ r~ c~ ~ I` ~ ~
r~ h d~ ~ ~ o ~ u~ 1--
CO Z O O ~ r~ ~ ~ ~ _ ~
~ 11-1 e:r ~O o e;l~ CC\ r-l('~) ~
U~,~ ~ l ~)
_
~ r~'~
rl r U~
r~ I~
~:1 ~ ~ ~r~) o
Z h ~P ~ ~o ~~r ~r x
_ O ~ ~) X O OOr~lr--l r1 r-l ~ r~
i~ ~ l _ _ _ _ _ _ _ 1
~H ~ ~ 0~ ~ ~ ~ ~ b~
~11 ~ O O r-~r~
~ ~ ~.~ .~
ZV .1_~
~ v
2 0 ~cn ~ ~ ~i
~r
.~1
~ $
u~ ~ D CO O ~ ~' ~ o 'r~
~ ~ ~ ~ ~t' ~ I~ 0~ ~ O
rl l ~3 ~ ~ ~ ~r n ~ ~ ~ O .,
~ 3 r-l t~ x
'~1 '~ ~ -- ---- -- -- -- -- -- _ X
~ O g Ln O Ln O Ln O Ln
~ Q ~) ~ ~ O ~I Lnt-- O t` J r
li ~ i--1 r-~ r-lr-l r~ l
~93~
~r~7~
Example 82
A chlorinated, boron-containing, heterocyclic
eompound is prepared by placing 71.3 grams of A mixture
eontaining 75 weight pereent of 1-hydroxy-3,7-diphenyl-5-
tallow-5-aza-1-bora-2,8-dioxaeyelooctane and 25 weight
pereent o~ 450 neutral oil into a 250 ml Pyrex ~lask
equipped with a side arm. Chlorine gas is introduced into
the flask through a Tygon tube attaehed to a glass tube
equipped with a rubber stopper and extending to the bottom
of the flask. The chlorine gas is bubbled through the
heterocyelic compound with ayitation. Excess c3as is
vented through the side arm of the flask, Tygon tubing and
glass tubing into an aqueous solution of 10% potassium
hyciroxide. The ehlorine gas was bubbled through the
system for 15 minutes giving a total weight gain of 3.2
grams to the heterocyelie eompound. The eompound thus
produced is l-hydroxy~3,7-diphenyl-5-(perehlorotallow3-1-
bora-2,8-dioxa-5-aza~cyclooctane.
~xample 83
A brominated, boron-containing, heterocyclic
compound is prepared by plaeing 71.33 grams of a mixture
containing 75 weight percent of 1-hydroxy-3,7-diphenyl-5-
tallow-5-aza-1-bora-2,8-dioxacyclooctane and 25 weight
percent of 450 neutral oil into a 250 ml Pyrex flask
equipped with a heating mantle and thermometer.
Liquid bromine (6.37 grams) is added to the
Pyrex flask and the mixture is agitated for ten minutes.
Next the mixture is heated at 120~ F. (49 C.) for ten
minutes. The eompound l-hydroxy-3,7-diphenyl-5-(perbromo-
tallow)-1-bora-2,8-dioxa-5-aza-eyclooctane is produced.
-94-
C
Example 8~ to 88
The compounds produced in Examples 82 and 83 are
tested for extreme pressure properties by admixing each
compound with separate portions of SAE 30 motor oil contain-
ing 0.05 weight percent phosphorus (added as zinc dialkyl-
dithiophosphate) and the concentration of additive indicated
in Table 20 below. A sample of the control SAE 30 motor
oil (Example 47) without an additive (borate of the
present invention) serves as a control in the experiment.
Each lubricant composition is tested in accord-
ance with the procedure disclosed in ASTM:D 32 33-73
(Reapproved 1978) using a Falex lubricant tester contain-
ing a steel journal and V-blocks. A summary of results
obiained is disclosed in the following Table 20:
-95
~ oP
r~ ~ _ _ ~ _ _ .
~ L~ 1~ O LO O ~
CD ~1 _ ~ ~ ~ 7 1 ~ 7 . I ~ .L.
CD Ei ~ o o r I I ~ 1
~ 00 ~t) CO N ~ Q .~
~ _ ~U~
r~ ~oP ~ ~ O N C~ ~ .~
~ O ~r ~D r--I CO S~l I r -IJ
~_ rd ~ (`~I N ~ I
1-- ~H -- O r; ~ N I ~ ~ 7 ~) ,p
i: lGO ~ O ~ a
IJ N l l l r~
.~ 00 CO r--l O ~ O
r-l ~j
!~ .,~ oo
i~,~
O ~ .~ _ _ _ _ '~ ~
lrT~ r-~ LD ~ N ~1rl
r--i P IL9 ~ ~I r--~ O ~ N ~ 7 i I ~ ~
~Q ~_i CO Or--l r-l N I I N a) I I i ~) ~
~5$ ~i ~i N i 5 ~ , I I ~ ~
r~ i r--l N N ~ ~
-ri r--i
O ~
'~ O
~ r ~ ~ ~ ~_ ~ ~
2 0 ~ ~ r--l O ~'~ I S-l I I I I I O O
Ln I i r~ a~ Ln N i I } } I } ~ UJ
r--i r1 ~ $
'O
r
r-i r--i â~ C~ ~
O O ~ 0 00 O
~i ~r ~o ~ h I I I I I I O h
~ O ~ I~ r; ~i ~) ~3 i 1 7 7 , I
co ~ c) ~ ~ o i 7 ¦ I I i . rJi
~ ~1 r--l ~'f) ~i
_ ~r-i
_ ~ O ~î 0-- ~ ~
~ ~ N ~ Ln N ~ ~ ~O COLn r~ ~
ra $ ~ N ~ ~ N ~r CO Ln r~ ~n~r~
~ 3 r-J N ~ ~ ';1' Ln L
r--i I--i ~ _ _ _ _ _ _ _ _ _ _ r-
_ o o o Ln o o o o o o tti ~n
' o o Ln L~ Ln o o Ln o Ln U~
~U~ ~) Ln 1` 1~ a~ o r--l (~ ~ ~ ~ ~)
¦~ l~ r-i r; r-!r i r-l rl ~;
--96--
~L~5~
Example ~9
Tests were conducted to determine the effects on
water stability of various boron-containing compounds of
formula (I) hereinbefore wherein R1 and R2 were unsubsti-
tuted ethylene groups, M was hydrogen, and R contained
between 8 and 20 carbon atoms and was either an alkyl
group or an alkenyl group with only one double bond in the
chain. The same tests were also conducted to determine
the water stability of various boron-containing compounds
of formula (II) hereinbefore wherein R4, R7, R8, Rg, R1o,
R11, and M were hydrogen, R5 and ~6 were unsubstituted
phenyl radicals (i.e., a benzene ring), and R3 varied as R
in formula tI~ discussed above.
The purpose of the experiment was to determine
if, in the presence of water, said boron compounds would
form an emulsion. A11 lubricating oils contain water (or
come into contact with water) to some extent, and to the
degree that the boron compound resists forming an emulsion
in oil-water mixtures, to that same extent is it a more
desirable additive for engine lubricating oils.
The tests were conducted as follows:
Into a test tube was placed sufficient water and
lubricatiny oil containing the boron compound to be tested
so that the water and oil each formed about 50 percent of
the contents of the test tube. The contents were then
shaken vigorously, after which the test tube was visually
inspected to see if an emulsion had formed (indicative of
water instability) or if two separate, clearly defined
phases settlecl out (indicative of water stability).
-97-
~L~5~iO~
Upon visual inspection of the various samples,
it was found that the boron compound of formula (II)
consistently produced a clearly defined, two-phase liquid
indicative of a boron additive stable to water in a
lubricating environment. In contrast, the formula (I~
compound consistently formed an emulsion indicative of
instability in the presence of water in a lubricating
environment.
In yet other tests, it was found that the
formula (II) compounds were less corrosive to lead and
copper bearings in automotive engines and the like than
the above-described formula (I) compounds.
From these tests, and the data shown in previous
examples, the following was concluded: although the
formula tI) compound is a highly useful lubricating oil
additive, particularly in situa-tions wherein the water
concentration of the oil can be minimized, the formula
(II) compound possessed unexpectedly superior properties
thereto with respect to water stability and corrosion
inhibi.tionO
Example 90
I'he boron-containing heterocyclic compounds
listed in Table 21 below were tested for oil solubility by
adding 2 grams of each compound and separate samples of 98
grams of ~50 neutral oil to 250 ml Pyrex beakers equipped
with teflon~coated, maynetic stirring bars which had
lengths of 1-1/2 inches and diameter of 1/4 inch. The
Pyrex beakers were placed on Model PC-351 Corning hot
plates and the boron--containing heterocyclic compound-450
-98-
~5~
neutral oil mixtures were heated at temperatures of
120 F. with stirring (400 RPM of stirring bars) for ten
minutes.
The Pyrex beakers were removed from the hot
plates and the boron-containing heterocyclic cornpound-450
neutral oil mixtures were examined for oil solubility of
said compound in each sample. The results are summarized
in the following Table 21:
-99
760~ 25053-356
~ , ~
-1 N ~ ~ U-) U~ I`
--100--
7~
The data in Table 21 show that boron-containing
heterocyclic compounds are not soluble in 450 neutral oil
at concen-trations of 2 weight percent when the ~ group
attached to the nitrogen atom of said compounds contains 8
or less carbon atoms. In contrast, boron-containing
heterocyclic compounds axe soluble in 450 neutral oil at
concentrations of 2 weight percent when the R group
contains 12 or more carbon atoms.
Based on these data, it is concluded that the oil
solubility of the boron-containing heterocyclic compounds is
directly related to the length of the carbon chain in the
R group attached to the nitrogen a-tom of the amine moiety
in said boron-containing heterocyclic compound, and that
boron-containing heterocyclic compounds with 9 or more
carbon atoms in the R group attached to the nitrogen atom
of the amine moiety of said compounds are more soluble in
oil than when said R group contains 8 or less carbon atoms.
Several other factors should also be considered
when assessing the data in Table 21. One such is that the
data are indicative of solubilities in a specific oil,
i.e., a 450 neutral oil, and that for other oils, e.g.,
silicone synthetic oils, some of the boron compounds shown
as insoluble may prove soluble. Thus, the data indicate
the relative solubility of one boron compound versus
another, not the absolute solubility of boron compounds in
all oils. Another factor to be considered is the effect
oE the length of the Rl and R2 groups. The data clearly
indicate, when these groups contain only about 4 carbon
atoms or less, that the solubility of the compound will be
a function of the length of the R carbon chain. However,
--101--
one can also increase the soluhility of the boron compounds
by altering the Rl and R2 groups. For example~ compounds
of formulae (II) and lIII) hereinbefore are soluble in 450
neutral oil, even when the R group side chain is relatively
small. As an illustration, it is now known that a compound
falling wi-thin foxmula (II), i.e., l-hydroxy--3,7-diphenyl-
5-butyl-5-aza-1--bora-2,8-dioxacyclooc-tane, is known to be
readily soluble in 450 neutral oil, despite the fact that
the R group side chain is a relatively small butyl group.
Thus, the relative solubility of boron compounds herein
are dependent on both the length of the R group side chain
and the length and nature oE the Rl and R2 groups.
_xample 91
This Example compares the solubility and extreme
pressure properties of boron compounds of the invention
versus those disclosed in U.S. Patent 3,227,739.
The procedure described in Example 1 of U.S.
Patent 3,227,739 was followed to prepare M,N-diethanol
2-hydroxy C16-C18 amine with the following exception:
Since the EMC Corporation no longer commercially
produces the C16-C18 epoxide used, 1,2 epoxyoctadecane was
substituted for the FMC epoxide. The reaction produced
N,N-diethanol, 2-hydroxy C18 amine.
The procedure described in Example 2 of U.S.
Patent 3,227,739 was followed to prepare the boric acid
adduct of N,N~diethanol, 2--hydroxy C18 amine. The product
thus produced (Compound A) was so]id at room temperature.
-102-
~5~
Test No. 1
The boric acia adduct of N,N-diethanol,
2-hydroxy C18 amine and the tallowaminodiethylate hydrogen
borate (Compound B) produced in Example 2 hereinbefore
were tested for oil solubility by adding the weight
percentages indicated in Table 22 below to 450 neutral
oil. The designated samples, including 450 neutral oil
(100 grams ~otal), were added to 250 ml Pyrex beakers
equipped with teflon-coated, magnetic stirring bars which
had lengths of 2-1/2 inches and diameters of l/4 inch.
The Pyrex beakers were placed on Model PC-351 Corning hot
plates and heated to the temperatures indicated in Table
22 with stirring (400 RPM of stlrring bars) for ten
minutes.
The Pyrex beakers were removed from the hot
plates, and the 450 neutral oil mixtures were examined for
oil solubility of the respective compounds in each sample.
The results are su~marized in the following Table 22:
-103-
1~ 5 7 ~
o
o ~ r r rY r-
a~ ~ u~
~ ~ u~ O O 'O ,Y
~3 l -I r~ r I r~ r-l l~i
cn o C~ U V~ C~ O
r~
r~ ~ u
O O o o .~ o o o r~
~ ~4 ~ r
~ O ~ r ~
O ~ _ _ _ _ _ _ p~ CO
~ ~ ~ 14 h h h h h .~ Il
~ E~ ~ o o o o o o o~ ~
a~ ~ ~; ~9 w ~ r~ ~ ~ ~ ,_1
~ ~P ~ ~
~ _ r~ 1~
~ ~ U~ O O Ln O o~ r4
O ~ o ,~ ~ o ,~ ~ .~i
~1- $
O ~ ,~
m m m '~
a ~ U ~ ~
u
~r~
,; ~ ~ ~r ~ u~ *
--104--
~5~
Several temperatures were used in an attempt to fully
dlssolve Compound ~, i.e., the boric acid adduct of
N,N-diethanol, 2-hydroxyamine, in 450 neutral oil. At
temperatures of 130 F. (54.44 C.), 200 F. (93.33 C.)
and 225 F. (107.22 C.), the compound was insoluble in
450 neutral oil. The compound was soluble in 450 neutral
oil at 260 F.(126.~7 C.); however, upon cooling a cloudy
appearance and sediment in the oil was noted. A concen-
tration of 2 weight percent of Compound A produced a very
viscous, semi-gel when mixed with 450 neutral oil and was
unacceptable as an adclitive for the oil at this concentra-
tion.
Compound B, i.e., tallowaminedie-thylate hydrogen
borate, was fully soluble in all samples tested at the
standard 130 F. (54.44 C.) mixing temperature for oil
additives and did not precipitate from the oil upon
standing and cooling.
Test No. 2
The boric acid adduct of N,N-diethanol, 2-hydroxy
C18 amine and the tallowaminodiethylate hydrogen borate
were also tested for oil solubility in the low phosphorus
control SAE 30 motor oil (Example ~7) in accordance with
the procedure described above. The results are summarized
in the following Table 23:
-105-
7~0~i
~ ~ -5 ~
,~ ", .3
~ ~ ~ a
~o
o o o ~
~ ) O
r- ',~
~ _ ~_____
~ ~ C~ o o o o o ~ ~
~1 h ~ ~ ~ ~r ~r ~ ~ ~)
~ o ~ ~;cO
~ ~ ~ __ ____ .~
~ O 1l o o o o O r~
tu ~) ~1 O O O O O o r-l r-l
r j~j t~ ~I ~ ~ r-l ~1 ~ ~ ~
i~ ~ ~ ~
2 0 ~ _
O ~ U~ o o U~ o o
o r; N O ~i ~i r~
~H
0
r~
~ ~ t4
'~ D
~ ~ ~ ~r u~ .1~ 1
--106--
7 ~
As shown in Table 23, Compound A was insoluble
in the SAE 30 motor oil at all concentrations tested at
temperatures of 130 F. (54.44 C.), 200 F. (93.33 C.)
and 225 F. (107.22 C.). At a temperature of 260 F.
(126.67 C.), the compound did dissolve in the SAE 30
motor oil; however, upon standing, a sediment was noted in
each sample.
By comparison, Compound B was soluble in the SAE
30 motor oil in all samples tested at a temperature of
130 F. (54.44 C.). The compound remained in solution
and did not ~orm a precipitate or sediment in the oil upon
standing.
Test_No. 3
The boric acid adduct of N/N-diethanol, 2-hydroxy
C18 amine and tallowaminodiethylate hydrogen borate, both
described above, were tested for extreme pressure proper-
ties in accordance with the procedure disclosed in ASTM:D
3233-73 (Reapproved 1978) using a Falex lubricant tester.
The test, in accordance with the above ASTM designation,
was performed by applying resistance ttorque) to a revolv-
ing metal journal. A rachet mechanism movably attached to
two V-blocks applied resistance by steadily increasing
pressure on the journal. The metal journal and V~blocks,
both construc-ted of steel, were submerged in the lubricant
composition to be tested. The base oil in the experiments
was the control SAE 30 motor oil (E,xample ~7). The SAE 30
motor oil was chosen as the base oil because the boric
acid adduct of N,M-diethanol, 2-hydroxy C18 amine was
slightly more soluble in this oil and did not produce a
semi-gel at higher concentrations as compared to ~50
-107-
~L~5~
neutral oil. However, this compound was not tested in the
Fale~ luhricant tester at a concentration of 2 weight
percent because at this concentration severe solubility
problems were encountered in both the 450 neutral oil and
the SAE 30 motor oil. The results are summarized in the
following Table 24:
--10~--
~L~5~
K ~ ~
~ ~1 O t~ OD O
o ~ ~ ~ n
3 o ~ $
o~
o
~o~
~3 ~ o
~ .
_ d, ~ ~ ~ _ _ .~
. O ~ Lrl ~ ~ N --1 00
~ U~ ~0. ~ ~ C)
E~ ~ ~ ~ ~ ~
20~ o~o~ ~ ~
0'~ ~ ~D O 'r~
~3~ o
~ ~ t~D O t ~ '~
~J t~) t.~l r-l t~ r-l ~ O ~ tl~
~ r-l t~ ~ tr) ~ t
_ O O O UO~ ~ O ~ ~ r
r~ 1 *
--109--
As shown in the foregoing Table 24, the compound
prepared in accordance with the procedure of U.S. Patent
3,227,739 had inferior extreme pressure properties when
compared with Compound B prepared according to the proce-
dure of Example 2 hereinbefore. In contrast, the data in
Table 24 show that tallowaminodiethylate hydrogen borate
exhibits superior extreme pressure properties when added
to SAE 30 motor oil as compared to the boric acid adduct
of N,N-diethanol, 2-hydroxy C18 amine. And based on the
data in Tables 22 and 23 above, compounds of the type
disclosed in U.S Patent 3,227,73g experience oil solubility
problems in 450 neutral oil and S~E 30 motor oil at
concentrations of 0.5, 1.0, and 2.0 weight percent. In
contrast, the tallowaminodiethylate hydrogen borate is
completely soluble at such concentrations.
Exam~le 92
This example compares the solubility and extreme
pressure properties of a compound disclosed in U.S. Patent
20 3,224,971 against the boron compounds produced according
to Examples 1 and 2 hereinbefore.
The tris (borate ester) of bis (o-hydroxy-octyl-
phenylmethyl) amine was prepared in accordance with the
procedure in Example 3 (column 3, lines 39 to 69) of U.S.
Patent 3,224,971.
The borate ester was prepared by mixing 205
grams o~ 5-octylphenol, 23.4 grams of hexamethylene-
tetramine and 500 ml of toluene in a single-necked one-
liter round~bottomed flas}c. The flask was placed in a
heating mantle and fitted with a Dean-Stark trap and
-110~
~.~sc~jt7~
water-cooled condenser. The mixture was refluxed for 24
hours. Next, 20.6 grams of boric acid were added to the
flask and the mixture was refluxed for an additional four
hours during which water produced in the reaction was
collected in the Dean-Stark trap.
Test No. 1
An experiment was performed to compare the boron
compounds of Examples 1 and 2 hereinbefore with the borate
ester described above in the Ryder~Gear Test disclosed in
column 6, lines 1 to 48 and Table 6 of U.S. Patent
3,224,971. The base oil used in the -test was di-2-ethyl-
hexyl sebacate.
A one-gram sample of the boron compound of
Example 1 hereinbefore was admixed with 99 grams of
di-2-ethyl-hexyl sebacate at 120 F. (48.89 C.) in a
250-ml Pyrex ~lass beaker. The boron compound did not
dissolve in the base oil. The mixture ~ormed was cloudy
and the boron compound settled to the bottom of the beaker
upon standiny. The mixture was heated to 300 F. (148.89
C.); however, the boron compound did not dissolve in the
di-2-ethyl-hexyl sebacate.
Next, a one-gram sample of the boron compound of
Example 2 hereinbefore was admixed with 99 yrams of di-2-
ethyl-hexyl sebacate at 120~ F. (48.89 C.) in a 200~ml
Pyrex ylass beaker. This boron compound did not dissolve
in the base oil. The base oil and boron compound mixture
was heated to 300 F. (148.89 C.), but the boron compound
still did not dissolve in the base oil.
~r~de ~c~/~J~
--111--
Additional experiments to determine the effective-
ness of the two boron compounds as extreme pressure agents
in the Ryder Gear Test were not conducted, because the
compounds would not go into solution in the di-2-ethyl-
hexyl sebacate base oil. However, experiments were
conducted to compare the effectiveness in an SAE 10W 40
motor oil of these compounds and the tris borate esters of
U.S. Patent 3,2249971 as extreme pressure agents in a
Falex lubricant tester.
Test No. 2
The boron compounds of Examples 1 and 2 and the
tris (borate ester) of bis (o-hydroxy-octylphenylmethyl)
amine described above were tested in accordance with the
procedure disclosed in ASTM D3233-73 (Reapproved 1978)
using a Falex lubricant tester. The test was performed by
applying resistance to a revolving metal journal. A
rachet mechanism movably attached to two V-blocks applied
resistance by steadily increasing pressure on the journal.
The metal journal and V-blocks, both constructed of steel,
were submerged in the lubricant composition to be tested.
The base oil in the experiments was an SAE 10W/40 motor
oil marketed co~mercially by the Union Oil Company of
California~ The results are summari~ed in the following
Table 25:
-112-
5~
Table 25
Highest Jaw Load
Before Failure,
Composition Lbs.(Newtons)
(1) SAE lOW/40 oil without any 1,400 (6,227)
additive
(2) SAE lOW/40 oil plus 1.0 wt.~ 1,700 (7,562)
Example 1 compound
(3) SAE lOW/40 oil plus 1.0 wt.% 2,250 (10,008)
Example 2 compound
(4) SAE lO~/40 oil plus 1.0 wt.% 900 (4,003)
tris borate ester of bis (o-
hydroxy-octylphenylmethyl~ amine
(5) SAE lOW/40 oil plus 2.0 wt.% 900 (4,003)
tris borate ester of bis (o-
hydroxy-octylphenylmethyl) amine
As shown in Table 25 above, the Example 1 and 2
compounds substantially increased the load carrying
property (extreme pressure property) of SAE lOW/40 base
oil in the Falex lubricant tester, while bis (o-hydroxy-
octylphenylmethyl) amine had a detrimental effect upon the
base oil, reducing the load carrying property of said oil
by 500 pounds. The amount of bis (o-hydroxy-octylphenyl-
methyl) amine added to the base oil was doubled with the
same d~trimental effect noted.
Test No. 3
The boron compound of Example 1 hereinbefore and
the tris (borate ester) of bis (o-hydroxy-octylphenylmethyl)
amine described above were tested in accordance with the
-113-
1~5~6V~i
procedure of Test No~ 2 with the Eollowing exception: 450
neutral oil marketed by the Union Oil Company of California
was substituted for the SAE 10W/40 oil~ The results are
summarized in the following Table 26:
Table 26
Highest Jaw Load
Before Failure,
~E~ Lbs.(Newtons)
(1) 450 neutral without additive 700 (3,114]
(2) 450 neutral oil plus 1.0 wt.% 1,100 (4,893)
Example 1 compound
(3) 450 neutral oil plus 1.0 wt.% 700 (3,114)
tris borate ester of bis (o-
hydroxy-oc-tylphenylmethyl) amine
(4) 450 neutral oil plus 5.0 wt.% 700 (3,114)
tris borate ester o~ bis (o-
hydroxy-octylphenylmethyl) amine
As shown in Table 26 above, the boron compound
of Example 1 increased the load carrying property (extreme
pressure) of 450 neutral base oil in the Falex lubricant
tester. Bis (o-hydroxyoctylphenylme-thyl) amine did not
affect the base oil either positively or negatively; the
load-carrying property of the base oil was the same with
or without the additive.
Example 93
The combination of a solution of an oil-soluble
copper carboxylate such as cop~er naphthenate and a
boron-containing heterocyclic compound both sulfurized and
nonsulfurized gives better anti-wear protection in an oil
than either component separately.
In the four~ball wear test (40 kg., 600 rpm,
167 F. (75 C.), 1 hour (ASTM D 4172-~2 modified to run
at 600 rpm)), one loaded steel bal] rotates against three
-114-
7~ ;
stationary balls. The average wear scar diameter of the
three stationary balls is a measure of wear. The reported
wear scar diameters are the average scar diameters minus
the Hertz scar diameter ~the average diameter in millimeters
of an indentation caused by the deformation of the balls
under static load, calculated from Dh = 8.73 x 10 2(p)1/3
where Dh is the Hertz diameter of the contact area, and P
is the static applied load).
The four-ball wear scar test was performed on an
automotive oil (~50 neutral) containing the ingredients
indicated in Table 27, with the results of the tests also
being indicated therein. The borates of the invention all
give better wear protection than copper naphthenate.
However, a combination of copper naphthenate solution and
borates solution gives significantly better wear protection
than either component alone. Therefore, there is a
synergistic interaction between copper naphthenate and
the borates of the invention.
-115-
~5~0~
s~
N c~ co 0 N ~D
t~ 1 ~ ~1 ~1 ~1 0
~ OOOOOOO ~I
ro_ ~ ~ .
~ H ~ o O ~ ~
1 ~ I o I c~
2 0 ~
.~ ~ H ~1 ~ U
r~
- 1 1 6 -
25053-356
Example 94
Tallowamine ~distilled~ from Armak Chemlcal
Company (94.04 grams, 0.35 mole~, styrene oxide from Union
Carbide (94.21 grams~ 0.70 moles) and -toluene (200 ml)
were stirred at room temperature for 30 minutes in a
round-bottomed flask equipped with a reflux condenser.
The mixture (solution) was heated to the reflux temperature
of toluene for three hours producing an amine: styrene
oxide adduct~ The adduct was cooled in the flask to room
temperature (25 to 30C.) and boric acid (21.75 ~ram,
0.35 mole) was added. A Dean Stark-type water separation
apparatus was inserted between the flask and condenserO
After 12.5 ml of water was collected in the Dean Stark
sidearm, the reaction was presumed to be over. The flask
and contents were then moved to a rotary evaporator to
strip off the toluene leaving the product, l-hydroxy-3,7-
diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane. This
borate of the invention (75g~ and 100 ml of toluene are
refluxed in a round-bottom flask~ 2.2g of sulfur is
added to the refluxing mixture. The solution continued to
reflux for 4 hours, then cooled to room temperature where
25g of 450 neutral oil is added and the toluene is elim-
inated by rotary evaporation. The product is a brown,
viscous sticky oil, i.e., a sulfurized form of l-hydroxy-
3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane.
- 117 -
25053-356
Obviously, many modifications and variations of
this invention, as hereinbefore set for-th, may be made
without departing from the spirit and scope thereof. For
example, although the specification focused on the pre-
ferred embodiment relating to oils for use in gasoline-
powered automotive engines, the borates of the invention
are useful in lubricating oils for diesel engines. In
fact, it has been discovered that the borates of the
inventlon, and especially the sulfurized version of
1-h~droxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxa-
cyclooctane, the most preferred borate of the present
inven-tion, mar~edly reduce and/or prevent the formation of
deposits in the upper ring zone of diesel engines, such as
the caterpillar l-H2 Diesel Engine. Thus, it is intended
that this embodiment of the invention and other such
modifications and variations falling within the spirit and
scope of the appended claims are embraced within the
present invention.
- 118 -
