Note: Descriptions are shown in the official language in which they were submitted.
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Title: LUBRICANTS HAVING OVERBASED METAL
SALTS AND ORGANIC PHOSPHITES
Cross Reference to Related Application
This application claims priority from provisional application Serial No.
60/106,877, filed November 3, 1998, the entire disclosure of which is
hereby incorporated by reference.
Technical Field of the Invention
This invention relates to lubricants and especially for those lubricants
which are used in manual transmissions. More specifically, the lubricant
comprises (A) at least one basic metal salt of an acidic organic compound and
(B) at least one hydrocarbyi phosphite.
Background of the Invention
Manual transmissions are common for off road and heavy duty vehicles.
The manual transmission lubricants must provide protection to the components
of the transmission as well as desirable shift characteristics for the driver.
Many off road and heavy duty manual transmissions are non-synchronized
transmissions. These transmission rely on composite friction plates and steel
plates to provide shifting. These plates must slid over each other during the
shifting process. The lubricants must provide the needed friction properties
as
well as protecting against plate wear.
Manual transmission fluids, with synchronizers, require friction retention
to avoid a phenomenon known as synchronizer clashing (sometimes referred to
as crashing). Clashing of the synchronizer results when the dynamic co-
efficient
of friction building between the engaging synchronizer parts (plate to plate
or
ring to cone) falls below a critical minimum value. Below this critical
minimum
value the synchronizer parts do not attain zero relative velocity and the
lockup
mechanism (e.g., spline camphers) contacts the rotating member (e.g., cone
camphers) resulting in a loud noise (clashing/crashing).
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Thermal stability is the ability of the fluid to withstand high operating
temperatures without the formation of degradation or breakdown products from
the fluid's components. For lubricants, especially manual transmission fluids,
to be effective they must provide thermal stability. Additionally, the
lubricants
must have sufficient durability. Durability is a measure of the lubricants
ability
to provide antiwear and extreme pressure protection needed for transmission in
gears. For manual transmissions, one measure of durability is the Mack T2180
High Temperature Cycle Test.
It is desirable to have a fluid which provides the friction qualities for the
manual transmission while also providing thermal stability.
Summary of the Invention
This invention relates to a lubricant comprising (A) a basic metal salt of
an acidic organic compound and (B) a hydrocarbyl phosphite, provided that the
lubricant is free of metal deactivators. In one aspect the lubricant is a
manual
transmission fluid. The lubricants provide good friction, good antiwear and
thermal stability properties.
Detailed Description of the Preferred Embodiments
The term "hydrocarbyl" includes hydrocarbon, as well as substantially
hydrocarbon, groups. Substantially hydrocarbon describes groups which contain
non-hydrocarbon substituents which do not alter the predominately hydrocarbon
nature of the group.
Examples of hydrocarbyl groups include the following:
(1 ) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl),
alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, aromatic-, aliphatic-
and
alicyclic-substituted aromatic substituents and the like as well as cyclic
substituents wherein the ring is completed through another portion of the
molecule (that is, for example, any two indicated substituents may together
form an alicyclic radical);
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(2) substituted hydrocarbon substituents, that is, those substituents
containing non-hydrocarbon groups which, in the context of this invention, do
not alter the predominantly hydrocarbon substituent; those skilled in the art
will
be aware of such groups (e.g., halo (especially chloro and fluoro), hydroxy,
alkoxy, mercapto, alkylmercapto, vitro, nitroso, sulfoxy, etc.);
(3) hetero substituents, that is, substituents which will, while having
a predominantly hydrocarbon character within the context of this invention,
contain other than carbon present in a ring or chain otherwise composed of
carbon atoms. Suitable heteroatoms will be apparent to those of ordinary skill
in the art and include, for example, sulfur, oxygen, nitrogen and such
substituents as, e.g., pyridyl, furyl, thienyl, imidazolyl, etc. In general,
no more
than about 2, preferably no more than one, non-hydrocarbon substituent will be
present for every ten carbon atoms in the hydrocarbyl group. Typically, there
will be no such non-hydrocarbon substituents in the hydrocarbyl group. There-
fore, the hydrocarbyl group is purely hydrocarbon.
The lubricating compositions are free of metal deactivators. Metal
deactivators reduce the corrosion of metals, such as copper. Metal
deactivators
are also referred to as metal passivators. Metal deactivators are typically
nitrogen and/or sulfur containing heterocyclic compounds, such as
dimercaptothiadiazoles, triazoles, amino-mercaptothiadiazoles, imidazoies,
thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines,
thiophenes,
indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles,
oxatriazoles,
pyridines, piperazines, triazines, and derivatives of any one or more thereof.
IAl Basic Metal S~Its
The lubricating compositions of the present invention contain (A) at least
one basic metal salt of an acidic organic compound. These salts are generally
referred to as overbased materials or overbased metal salts. Overbased
materials are single phase, homogeneous Newtonian systems characterized by
a metal content in excess of that which would be present according to the
stoichiometry of the metal and the particular acidic organic compound reacted
with the metal. The basic metal salt is present in an amount up to about 3%
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by weight. Generally the lubricants contains from about 0.02% to about 5%,
or from about 0.05% to about 2%, or from about 0.1 % to about 1 %. Here and
elsewhere in the specification and claims, the range and ratio limits may be
combined.
The amount of excess metal is commonly expressed in terms of metal
ratio. The term "metal ratio" is the ratio of the total equivalents of the
metal to
the equivalents of the acidic organic compound. A neutral metal salt has a
metal ratio of one. A salt having 4.5 times as much metal as present in a
normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5. The
basic salts of the present invention have a metal ratio of about 1.5, more
preferably about 3, more preferably about 7, up to about 40, preferably about
25, more preferably about 20.
The basicity of the overbased materials generally is expressed in terms of
a total base number. A total base number is the amount of acid (perchloric or
hydrochloric) needed to neutralize all of the overbased material's basicity.
The
amount of acid is expressed as potassium hydroxide equivalents. Total base
number is determined by titration of one gram of overbased material with 0.1
Normal hydrochloric acid solution using bromophenolblue as an indicator. The
overbased materials of the present invention generally have a total base
number
from about 50 to about 1200, or from about 100 to about 1000, or from about
250 to about 900, or from about 500 to about 800.
In one embodiment, the inventors have discovered that when the ratio of
the equivalents of overbased material based on total base number to the equiva-
lents of hydrocarbyf phosphite based on phosphorus atoms is at least one the
lubricants have improved thermal stability. The equivalents of overbased
material is determined by the following equation: equivalent weight -
(56,1 OOltotal base number). For instance, an overbased material with a total
base number of 200 has an equivalent weight of 280.5 (eqwt = 56100/200).
The equivalents of phosphite are determined by dividing the molecular weight
of the phosphite by the number of phosphorus atoms in the phosphite.
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The overbased materials (A) are prepared by reacting an acidic material
(typically an inorganic acid or lower carboxylic acid, preferably carbon
dioxide)
with a mixture comprising an acidic organic compound, a reaction medium
comprising at least one inert, organic solvent (mineral oil, naphtha, toluene,
xylene, etc.) for said acidic organic material, a stoichiometric excess of a
metal
base, and a promoter.
The acidic organic compounds useful in making the overbased
compositions of the present invention include carboxylic acids, sulfonic
acids,
phosphorus-containing acids, phenols or mixtures of two or more thereof.
Preferably, the acidic organic compounds are carboxylic acids or sulfonic
acids
with sulfonic and salicylic acids more preferred. Throughout this
specification
and in the appended claims, any reference to acids, such as carboxylic, or
sulfonic acids, is intended to include the acid-producing derivatives thereof
such
as anhydrides, lower alkyl esters, acyl halides, lactones and mixtures thereof
unless otherwise specifically stated.
The carboxylic acids useful in making the overbased salts (A) of the
invention may be aliphatic or aromatic, mono- or polycarboxylic acid or
acid-producing compounds. These carboxylic acids include lower molecular
weight carboxylic acids (e.g., carboxylic acids having up to about 22 carbon
atoms such as acids having about 4 to about 22 carbon atoms or
tetrapropenyl-substituted succinic anhydride? as well as higher molecular
weight
carboxylic acids.
The carboxylic acids are preferably oil-soluble. Usually, in order to provide
the desired oil-solubility, the number of carbon atoms in the carboxylic acid
should be at least about 8, more preferably at least about 18, more preferably
at least about 30, more preferably at least about 50. Generally, these
carboxylic
acids do not contain more than about 400 carbon atoms per molecule.
The lower molecular weight monocarboxylic acids contemplated for use
in this invention include saturated and unsaturated acids. Examples of such
useful acids include dodecanoic acid, decanoic acid, oleic acid, stearic acid,
linofeic acid, tall oil acid, etc. Mixtures of two or more such agents can
also be
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used. An extensive discussion of these acids is found in Kirk- Othmer
"Encyclopedia of Chemical Technology" Third Edition, 1978, John Wiley & Sons
New York, pp. 814-871; these pages being incorporated herein by reference.
The monocarboxylic acids include isoaliphatic acids. Such acids often
contain a principal chain having from about 14 to about 20 saturated,
aliphatic
carbon atoms and at least one but usually no more than about four pendant
acyclic lower alkyl groups. Specific examples of such isoaiiphatic acids
include
10-methyl-tetradecanoic acid, 3-ethyl-hexadecanoic acid, and
8-methyl-octadecanoic acid. The isoaliphatic acids include mixtures of branch-
chain acids prepared by the isomerization of commercial fatty acids (oleic,
linoleic or tall oil acids) of, for example, about 16 to about 20 carbon
atoms.
High molecular weight carboxylic acids may also be used in the present
invention. These acids have a substituent group derived from a polyalkene. The
polyalkene is characterized as containing at least about 30 carbon atoms,
preferably at least about 35, more preferably at least about 50, and up to
about
300 carbon atoms, preferably about 200, more preferably about 150. In one
embodiment, the polyalkene is characterized by an Mn (number average
molecular weight) value of at least about 500, generally about 500 to about
5000, preferably about 800 to about 2500. In another embodiment, Mn varies
between about 500 to about 1200 or 1300.
The polyalkenes include homopolymers and interpolymers of polymerizable
olefin monomers of 2 to about 16 carbon atoms. The olefins may be
monoolefins such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or
a polyolefinic monomer, preferably diolefinic, monomer such 1,3-butadiene and
isoprene. Preferably the monomers contain from 2 to about 6 carbon atoms,
more preferably 2 to about 4, more preferably 4. The interpolymers include
copolymers, terpolymers, tetrapolymers and the like. Preferably, the
interpoiymer is a homopolymer. An example of a preferred homopolymer is a
polybutene, preferably a polybutene in which about 50% of the polymer is
derived from isobutylene. The polyalkenes are prepared by conventional
procedures.
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In one embodiment, the polyalkene is characterized as containing from
about 8 up to about 300, or from about 30 up to about 200, or from about 35
up to about 100 carbon atoms. In one embodiment, the polyalkene is
characterized by an n (number average molecular weight) of at least about 400
or at least about 500. Generally, the polyalkene is characterized by having an
n from about 500 up to about 5000, or from about 700 up to about 3000, or
from about 800 up to 2500, or from about 900 up to about 2000. In another
embodiment, Mn varies from about 500 up to about 1500, or from about 700
up to about 1300, or from about 800 up to about 1200.
The abbreviation Mn is the conventional symbol representing number
average molecular weight. Gel permeation chromatography (GPC) is a method
which provides both weight average and number average molecular weights as
well as the entire molecular weight distribution of the polymers. For purpose
of
this invention a series of fractionated polymers of isobutene, polyisobutene,
is
used as the calibration standard in the GPC. The techniques for determining Mn
and Mw values of polymers are well known and are described in numerous
books and articles. For example, methods for the determination of n and
molecular weight distribution of polymers is described in W.W. Yan, J.J.
Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatographs", J. Wiley
& Sons, Inc., 1979.
The higher molecular weight mono- and polycarboxylic acids suitable for
use in making the overbased salts (A) are well known in the art and have been
described in detail, for example, in the following U.S., British and Canadian
patents: U.S. Patents 3,024,237; 3,172,892; 3,219,666; 3,245,910;
3,271,310; 3,272,746; 3,278,550; 3,306,907; 3,312,619; 3,341,542;
3,367,943; 3,374,174; 3,381,022; 3,454,607; 3,470,098; 3,630,902;
3,755,169; 3,912,764; and 4,368,133; British Patents 944,136; 1,085,903;
1,162,436; and 1,440,219; and Canadian Patent 956,397. These patents are
incorporated herein by reference for their disclosure of higher molecular
weight
mono- and polycarboxylic acids and methods for making the same.
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Illustrative carboxylic acids include palmitic acid, stearic acid, myristic
acid, oleic acid, linoleic acid, behenic acid, hexatriacontanoic acid,
tetrapropyl-
enyl-substituted glutaric acid, polybutenyl-substituted succinic acid derived
from
a polybutene (Mn = 200-1500, preferably 300-1000), polypropenyl-substituted
succinic acid derived from a polypropene, (Mn = 200-1000, preferably 300-
900), octadecyl-substituted adipic acid, chlorostearic acid, 9-methyistearic
acid,
dichlorostearic acid, stearyl-benzoic acid, eicosanyl-substituted naphthoic
acid,
dilauryl-decahydronaphthalene carboxylic acid, mixtures of any of these acids,
their alkali and alkaline earth metal salts, and/or their anhydrides. A
preferred
group of aliphatic carboxylic acids includes the saturated and unsaturated
higher
fatty acids containing from about 12 to about 30 carbon atoms. Illustrative of
these acids are lauric acid, palmitic acid, oleic acid, linoleic acid,
linolenic acid,
oleostearic acid, stearic acid, myristic acid, and undecalinic acid,
alpha-chlorostearic acid, and alphanitrolauric acid.
In another embodiment, the carboxylic acid is an alkylalkyleneglycol-acetic
acid, more preferably alkylpolyethyleneglycol-acetic acid. Some specific
examples of these compounds include: iso-stearylpentaethyleneglycol-acetic
acid; iso-stearyl-O-(CH2CH20)5CH2C02Na; lauryl-O-(CHZCHZO)2,5-CHZCOzH;
lauryl-O-(CHzCH20)3.3CHZC02H; oleyl-O-(CH2C-H20)4 CHZCOZH; lauryl-0-
(CHZCH z0) 4,5CH ~O ~-i; lauryl-0-(CH ~H Q) ~~H ~O H; lauryl-O-
(CH2CHz0)zsCHZC02H; octyl-phenyl-O-(CH2CH20)8CH2COZH; octyl-phenyl-O-
(CH2CH2O),9CH2CO2H; 2-octyl-decanyl-O-(CH2CH20)BCHZC02H. These acids are
available commercially from Sandoz Chemical under the tradename Sandopan
acids.
In another embodiment, the carboxylic acids are aromatic carboxylic
acids. A group of useful aromatic carboxylic acids are those of the formula
X
(C-XH)b
(R,)a - Ar-(XH)~
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wherein R, is an aliphatic hydrocarbyl group of preferably about 4 to about
400
carbon atoms, a is a number in the range of zero to about 4, usually 1 or 2,
Ar
is an aromatic group, each X is independently sulfur or oxygen, preferably
oxygen, b is a number in the range of from 1 to about 4, usually 1 or 2, c is
a
number in the range of zero to about 4, usually 1 to 2, with the proviso that
the
sum of a, b and c does not exceed the number of valences of Ar. Preferably,
R, and a are such that there is an average of at least about 8 aliphatic
carbon
atoms provided by the R, groups. Examples of aromatic carboxylic acids include
substituted and non-substituted benzoic, phthalic and salicylic acids or
anhydrides.
The R, group is a hydrocarbyl group that is directly bonded to the
aromatic group Ar. R, preferably contains about 6 to about 80 carbon atoms,
preferably about 6 to about 30 carbon atoms, more preferably about 8 to about
25 carbon atoms, and advantageously about 8 to about 15 carbon atoms. R,
groups may be derived form one or more of the above-described polyalkenes.
Examples of R, groups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl,
5-chlorohexyl, 4-ethoxypentyl, 3-cyclohexyloctyl, 2,3,5-trimethylheptyl, and
substituents derived from polymerized olefins such as polyethylenes,
polypropylenes, polyisobutylenes, ethylene-propylene copolymers, chlorinated
olefin polymers, oxidized ethylene-propylene copolymers, propylene tetramer
and
tri(isobutene).
Examples of the R, groups include butyl, isobutyl, pentyl, octyl, nonyl,
dodecyl, and substituents derived from the above-described polyalkenes such
as polyethylenes, polypropylenes, polyisobutylenes, ethylene-propylene
copolymers, oxidized ethylene-propylene copolymers, and the like.
The aromatic group Ar may have the same structure as any of the
aromatic groups Ar discussed below. Examples of the aromatic groups that are
useful herein include the polyvalent aromatic groups derived from benzene,
naphthalene, anthracene, etc., preferably benzene. Specific examples of Ar
groups include phenylenes and naphthylene, e.g., methylphenylenes,
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ethoxyphenylenes, isopropylphenylenes, hydroxyphenylenes,
dipropoxynaphthylenes, etc.
Within this group of aromatic acids, a useful class of carboxylic acids are
those of the formula
(COOH)b
C~ T~' (R,)a
(OH1~
wherein R, is defined above, a is a number in the range of from zero to about
4, preferably 1 to about 2; b is a number in the range of 1 to about 4,
preferably
1 to about 2, c is a number in the range of zero to about 4, preferably 1 to
about 2, and more preferably 1; with the proviso that the sum of a, b and c
does not exceed 6. Preferably, R~ and a are such that the acid molecules
contain at least an average of about 12 aliphatic carbon atoms in the
aliphatic
hydrocarbon substituents per acid molecule. Preferably, b and c are each one
and the carboxylic acid is a salicylic acid.
The salicylic acids can be aliphatic hydrocarbon-substituted saficyclic
acids wherein each aliphatic hydrocarbon substituent contains an average of at
least about 8 carbon atoms per substituent and 1 to 3 substituents per
molecule. Overbased salts prepared from such salicyclic acids wherein the
aliphatic hydrocarbon substituents are derived from the above-described polyal-
kenes, particularly polymerized lower 1-mono-olefins such as polyethylene,
polypropylene, polyisobutylene, ethylene/propylene copolymers and the like and
having average carbon contents of about 30 to about 400 carbon atoms are
particularly useful.
The above aromatic carboxylic acids are well known or can be prepared
according to procedures known in the art. Carboxylic acids of the type
illustrated by these formulae and processes for preparing their neutral and
basic
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metal salts are well known and disclosed, for example, in U.S. Patents
2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092; 3,410,798; and
3,595,791.
The sulfonic acids useful in making the overbased salts (A) of the
invention include the sulfonic and thiosulfonic acids. Generally they are
salts of
sulfonic acids. The sulfonic acids include the mono- or polynuclear aromatic
or
cycloaliphatic compounds. The oil-soluble sulfonates can be represented for
the
most part by one of the following formulae: R2 T-(S03)a and R3-(S03)b, wherein
T is a cyclic nucleus such as, for example, benzene, naphthalene, anthracene,
diphenylene oxide, diphenylene sulfide, petroleum naphthenes, etc.; R2 is an
aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl, etc.; (RZ) +T
contains
a total of at feast about 15 carbon atoms; and R3 is an aliphatic hydrocarbyl
group containing at least about 15 carbon atoms. Examples of R3 are alkyl,
alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R3 are
groups
derived from petrolatum, saturated and unsaturated paraffin wax, and the
above-described polyalkenes. The groups T, R2, and R3 in the above Formulae
can also contain other inorganic or organic substituents in addition to those
enumerated above such as, for example, hydroxy, mercapto, halogen, vitro,
amino, nitroso, sulfide, disulfide, etc. In the above Formulae, a and b are at
least 1. In one embodiment, the sulfonic acids have a substituent (R2 or R3)
which is derived from one of the above-described polyalkenes.
Illustrative examples of these sulfonic acids include monoeicosanyl-
substituted naphthalene sulfonic acids, dodecylbenzene sulfonic acids,
didodecylbenzene sulfonic acids, dinonylbenzene sulfonic acids, cetylchloro-
benzene sulfonic acids, dilauryl beta-naphthalene sulfonic acids, the sulfonic
acid
derived by the treatment of polybutene having a number average molecular
weight (Mn) in the range of 500 to 5000, preferably 800 to 2000, more
preferably about 1500 with chlorosulfonic acid, nitronaphthalene sulfonic
acid,
paraffin wax sulfonic acid, cetyl-cyclopentane, sulfonic acid, lauryl-
cyciahexane
sulfonic acids, polyethylenyl-substituted sulfonic acids derived from
polyethylene
(Mn = 300-1000, preferably 750), etc. Normally the aliphatic groups will be
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alkyl and/or alkenyl groups such that the total number of aliphatic carbons is
at
least about 8, preferably at least 12 up to about 400 carbon atoms, preferably
about 250.
Another group of sulfonic acids are mono-, di-, and tri-alkylated benzene
and naphthalene (including hydrogenated forms thereof) sulfonic acids. Illus-
trative of synthetically produced alkylated benzene and naphthalene sulfonic
acids are those containing alkyl substituents having from about 8 to about 30
carbon atoms, preferably about 12 to about 30 carbon atoms, and
advantageously about 24 carbon atoms. Such acids include di-isododecyl-
benzene sulfonic acid, polybutenyl-substituted sulfonic acid, polypropylenyl-
substituted sulfonic acids derived from polypropene having an Mn = 300-1000,
preferably 500-700, cetylchlorobenzene sulfonic acid, di-cetylnaphthalene
sulfonic acid, di-lauryldiphenylether sulfonic acid, diisononylbenzene
sulfonic
acid, di-isooctadecylbenzene sulfonic acid, stearylnaphthalene sulfonic acid,
and
the like.
Specific examples of oil-soluble sulfonic acids are mahogany sulfonic
acids; bright stock sulfonic acids; sulfonic acids derived from lubricating
oil frac-
tions having a Saybolt viscosity from about 100 seconds at 100°F to
about 200
seconds at 210°F; petrolatum sulfonic acids; mono- and poly-wax-
substituted
sulfonic and polysulfonic acids of, e.g., benzene, naphthalene, phenol,
Biphenyl
ether, naphthalene disulfide, etc.; other substituted sulfonic acids such as
alkyl
benzene sulfonic acids lwhere the alkyl group has at least 8 carbons),
cetylphenol mono-sulfide sulfonic acids, dilauryl beta naphthyl sulfonic
acids,
and alkaryl sulfonic acids such as dodecyl benzene "bottoms" sulfonic acids.
Dodecyl benzene "bottoms" sulfonic acids are the material leftover after
the removal of dodecyl benzene sulfonic acids that are used for household
deter-
gents. These materials are generally alkylated with higher oligomers. The
bottoms may be straight-chain or branched-chain alkylates with a straight-
chain
dialkylate preferred.
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The production of sulfonates from detergent manufactured by-products
by reaction with, e.g., S03, is well known to those skilled in the art. See,
for
example, the article "Sulfonates" in Kirk-Othmer "Encyclopedia of Chemical
Technology", Second Edition, Vol. 19, pp. 291 et seq. published by John Wiley
& Sons, N.Y. ( 1969).
The phosphorus-containing acids useful in making the basic metal salts
(A) of the present invention include any phosphorus acids such as phosphoric
acid or esters; and thiophosphorus acids or esters, including mono and dithio-
phosphorus acids or esters. Preferably, the phosphorus acids or esters contain
at least one, preferably two, hydrocarbyl groups containing from 1 to about 50
carbon atoms, typically 1 to about 30, preferably 3 to about 18, more
preferably
about 4 to about 8.
In one embodiment, the phosphorus-containing acids are dithiophosphoric
acids which are readily obtainable by the reaction of phosphorus pentasulfide
(P2S5) and an alcohol or a phenol. The reaction involves mixing at a
temperature
of about 20° C to about 200° C four moles of alcohol or a phenol
with one mole
of phosphorus pentasulfide. Hydrogen sulfide is liberated in this reaction.
The
oxygen-containing analogs of these acids are conveniently prepared by treating
the dithioic acid with water or steam which, in effect, replaces one or both
of
the sulfur atoms with oxygen.
In another embodiment, the phosphorus-containing acid is the reaction
product of the above-described polyalkene and phosphorus sulfide. Useful
phosphorus sulfide-containing sources include phosphorus pentasulfide, phos-
phorus sesquisulfide, phosphorus heptasulfide and the like.
The reaction of the polyalkene and the phosphorus sulfide generally may
occur by simply mixing the two at a temperature above 80°C, preferably
between 100°C and 300°C. Generally, the products have a
phosphorus
content from about 0.05% to about 10%, preferably from about 0.1 % to about
5%. The relative proportions of the phosphorizing agent to the olefin polymer
is generally from 0.1 part to 50 parts of the phosphorizing agent per 100
parts
of the olefin polymer.
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The phosphorus-containing acids useful in the present invention are
described in U.S. Patent 3,232,883 issued to Le Suer. This reference is herein
incorporated by reference for its disclosure to the phosphorus-containing
acids
and methods for preparing the same.
The phenols useful in making the basic metal salts (A) of the invention
can be represented by the formula (R,)e-Ar-(OH)b, wherein R, is defined above;
Ar is an aromatic group; a and b are independently numbers of at least one,
the
sum of a and b being in the range of two up to the number of displaceable
hydrogens on the aromatic nucleus or nuclei of Ar. Preferably, a and b are
independently numbers in the range of 1 to about 4, more preferably 1 to about
2. R~ and a are preferably such that there is an average of at least about 8
aliphatic carbon atoms provided by the R, groups for each phenol compound.
While the term "phenol" is used herein, it is to be understood that this
term is not intended to limit the aromatic group of the phenol to benzene.
Accordingly, it is to be understood that the aromatic group as represented by
"Ar", as well as elsewhere in other formulae in this specification and in the
appended claims, can be mononuclear such as a phenyl, a pyridyl, or a thienyl,
or polynuclear. The polynuclear groups can be of the fused type wherein an
aromatic nucleus is fused at two points to another nucleus such as found in
naphthyl, anthranyl, etc. The polynuclear group can also be of the linked type
wherein at least two nuclei (either mononuclear or polynuclear) are linked
through bridging linkages to each other. These bridging linkages can be chosen
from the group consisting of alkylene linkages, ether linkages, keto linkages,
sulfide linkages, polysulfide linkages of 2 to about 6 sulfur atoms, etc.
The number of aromatic nuclei, fused, linked or both, in Ar can play a role
in determining the integer values of a and b. For example, when Ar contains a
single aromatic nucleus, the sum of a and b is from 2 to 6. When Ar contains
two aromatic nuclei, the sum of a and b is from 2 to 10. With a tri-nuclear Ar
moiety, the sum of a and b is from 2 to 15. The value for the sum of a and b
is limited by the fact that it cannot exceed the total number of displaceable
hydrogens. on the aromatic nucleus or nuclei of Ar.
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The metal compounds useful in making the basic metal salts (A) are alkali,
alkaline earth and transition metals. Preferably, any Group I or Group Il
metal
compounds (CAS version of the Periodic Table of the Elements). The Group I
metals of the metal compound include alkali metals (sodium, potassium,
lithium,
etc.) as well as Group IB metals such as copper. The Group I metals are prefer-
ably sodium, potassium, lithium and copper, more preferably sodium or
potassium, and more preferably sodium. The Group II metals of the metal base
include the alkaline earth metals (magnesium, calcium, barium, etc.) as well
as
the Group IIB metals such as zinc or cadmium. Preferably the Group II metals
are magnesium, calcium, or zinc, preferably magnesium or calcium, more
preferably magnesium. Generally the metal compounds are delivered as metal
salts. The anionic portion of the salt can be hydroxyl, oxide, carbonate,
borate,
nitrate, etc.
An acidic material is used to accomplish the formation of the basic metal
salt (A). The acidic material may be a liquid such as formic acid, acetic
acid,
nitric acid, sulfuric acid, etc. Acetic acid is particularly useful. Inorganic
acidic
materials may also be used such as HCI, S02, S03, C02, H2S, etc, preferably
COZ. A preferred combination of acidic materials is carbon dioxide and acetic
acid.
A promoter is a chemical employed to facilitate the incorporation of metal
into the basic metal compositions. Among the chemicals useful as promoters
are water, ammonium hydroxide, organic acids of up to about 8 carbon atoms,
nitric acid, sulfuric acid, hydrochloric acid, metal complexing agents such as
alkyl salicylaldoxime, and alkali metal hydroxides such as lithium hydroxide,
sodium hydroxide and potassium hydroxide, and mono- and polyhydric alcohols
of up to about 30 carbon atoms. Examples of the alcohols include methanol,
ethanol, isopropanol, dodecanol, behenyl alcohol, ethylene glycol,
monomethylether of ethylene glycol, hexamethylene glycol, glycerol, penta-
erythritol, benzyl alcohol, phenylethyl alcohol, aminoethanol, cinnamyl
alcohol,
allyl alcohol, and the like. Especially useful are the monohydric alcohols
having
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16
up to about 10 carbon atoms and mixtures of methanol with higher monohydric
alcohois.
Patents specifically describing techniques for making basic salts of the
above-described sulfonic acids, carboxylic acids, and mixtures of any two or
more of these include U.S. Patents 2,501,731; 2,616,905; 2,616,911;
2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162;
3,318,809; 3,488,284; and 3,629,109. The disclosures of these patents are
hereby incorporated in this present specification for their disclosures in
this
regard as well as for their disclosure of specific suitable basic metal salts.
(B1 Hydrocarbyl Phosl h~ ites
Compositions of the present invention also include (C) a hydrocarbyl
phosphate. The phosphate is present in an amount to deliver from about 0.01
to about 0.3%, or from about 0.03% to about 0.25% phosphorus to the final
lubricant. Typically the lubricant contains up to about 3% by weight of (B).
Generally the lubricants contains from about 0.05% to about 5%, or from about
0.02% to about 2%, or from about 0.1 % to about 2%, or from about 0.2% to
about 1.5%, or from 0.3% to about 1 % by weight of the lubricant.
The phosphate may be represented by the following formulae:
0
II
R50-P-OR5
H
or
(R50)3P
wherein each R5 is independently hydrogen or a hydrocarbyl group, provided at
least one R5 is hydrocarbyl. Preferably each R5 is independently a hydrogen or
hydrocarbyl group having from 1 to about 24, or from 1 to about 18, and or
from about 2 to about 8 carbon atoms. Each R5 may be independently alkyl,
alkenyl or aryl. When R5 is aryl it contains at least 6 carbon atoms;
preferably
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17
6 to about 18 carbon atoms. Examples of alkyl or alkenyl groups are propyl,
butyl, hexyl, heptyl, octyl, oleyl, linoleyl, stearyl, etc. Examples of aryl
groups
are phenyl, napthyl, heptylphenol, etc. Preferably each R5 is independently
propyl, butyl, pentyl, hexyl, heptyl, oleyl or phenyl, more preferably butyl,
oleyl
or phenyl and more preferably butyl or oieyl.
The R5 groups may also comprise a mixture of hydrocarbyl groups derived
from commercial alcohols. Examples of preferred monohydric alcohofs and
alcohol mixtures include commercially available "Alfol" alcohols marketed by
Continental Oil Corporation. Alfol 810 is a mixture containing alcohols
consisting essentially of straight-chain, primary alcohols having 8 to 10
carbon
atoms. Alfol 812 is a mixture comprising mostly C~2 fatty alcohols. Alfol 1218
is a mixture of synthetic, primary, straight-chain alcohols having from 12 to
18
carbon atoms. Alfol 20 + alcohols are mixtures of 18-28 primary alcohols
having mostly, on an alcohol basis, C2o alcohols as determined by GLC (gas-
liquid-chromatography).
Another group of commercially available alcohol mixtures includes the
"Neodol" products available from Shell Chemical Company. For example,
Neodol 23 is a mixture of C,2 and C~3 alcohols; Neodol 25 is a mixture of C,2
and C,5 alcohols; and Neodol 45 is a mixture of C,4 and C,5 linear alcohols.
Neodol 91 is a mixture of C9, C,o and C" alcohols.
Phosphites and their preparation are known and many phosphites are
available commercially. Particularly useful phosphites are dibutylhydrogen
phosphite, trioleyl phosphite and triphenyl phosphite. Phosphite esters are
generally dialkyl hydrogen phosphites.
A number of dialkyl hydrogen phosphites are commercially available, such
as lower dialkyl hydrogen phosphites, which are preferred. Lower dialkyl
hydrogen phosphites include dimethyl, diethyl, dipropyl, dibutyl, dipentyl and
dihexyl hydrogen phosphites. Also mixed alkyl hydrogen phosphites are useful
in the present invention. Examples of mixed alkyl hydrogen phosphites include
ethyl, butyl; propyl, pentyl; and methyl, pentyl hydrogen phosphites.
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18
In one embodiment, the lubricant includes minor amounts of other
phosphorus additives. These additives are present in amounts less than 2%, or
less than 1 %, or less than 0.5% by weight. In another embodiment, the
phosphate or mixture of phosphates is the sole source of phosphorus added by
components of the lubricant.
(C) Friction Modifier
In one embodiment, the lubricants include (C) at least one friction
modifier. The friction modifier is one which reduces friction. The friction
modifier is present in an amount from about 0.01 % to about 2%, or from about
0.05% to about 1 %, or from about 0.1 % to about 0.6% by weight. The
friction modifier may be any friction modifier known to those in the art.
Examples of friction modifiers include a fatty phosphate, a fatty acid amide,
a
fatty amine, a borated fatty amine, a borated fatty epoxide, a glycerol ester
and
a borated glycerol ester. Mixtures of friction modifiers may be used as well.
In one embodiment, the friction modifier is fatty acid esters of polyols.
The fatty acids are those having from about 8 to about 30, or from about 12 to
about 24 carbon atoms. Examples of these fatty acids include stearic acid,
oleic
acid, tallow acid, etc. The polyols generally has from about 2 to about 8, or
from about 3 to about 6 hydroxyl groups and form about 2 to about 18, or from
about 3 to about 12, or from 4 to 8 carbon atoms. The polyols include
alkylene,
such as ethylene or butylene, glycols, erythitol, pentaerythritol,
diethyleneglycol,
sorbitol, glycerol, etc. A particulary useful fatty ester of a polyols is a
glycerol
based esters such as glycerol mono-, di- or trioleate.
In one embodiment the fatty esters are glycerol esters. The glycerol
esters useful in the present invention are glycerol esters of fatty acids,
such as
fatty acids having from about 8 to about 22 carbon atoms, preferably about 12
to about 20. Examples of fatty acids useful in preparing the esters are oleic,
stearic, linoleic acids and the like. The esters may be mono-, di-, or
triesters of
fatty esters. Glycerol mono-oleate and glycerol taHowate are known commercial
materials. .It is generally recognized that esters of glycerol are actually
mixtures
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19
of mono- and diesters. A particularly useful ester is a mixture of mono- and
diester containing at least 40% of the monoester of glycerol. Preferably, the
mixtures of mono- and diesters of glycerol contain from about 40 to about 60%
by weight of the monoester. For example, commercial glycerol monoleate
contains a mixture of from about 45% to about 55% by weight monoester and
from 55% to about 45% of the monoester. Glycerol monoleate in its
commercially available mixtures are preferred.
The borated glycerol esters are also useful in the present invention and
are prepared by reacting the fatty acid ester of glycerol with boric acid and
removal of water. Preferably, the boric acid and the fatty acid ester are
reacted
such that each boron will react with from 1.5 to about 2.5 hydroxy groups
present in the mixture. The reaction may be carried out at a temperature in
the
range of from about 60°C. to about 135°C. in the absence or
presence of any
suitable organic solvent such as methanol, benzene, xylene, toluene, or the
like.
In another embodiment, the friction modifier (C) may be a fatty amide or
amine. The fatty amide or amine have substituent group analogous to the above
described fatty acids. Oleylamide and oleylamine are examples of these
friction
modifiers. The fatty acid amides which are useful in the present invention are
generally amides derived from fatty acids having from about 4 to about 28,
preferably about 12 to about 22, preferably about 16 to about 20 carbon atams.
A particularly useful fatty acid amide is oleyl amide, linoleyl amide, stearyl
amide
or tall oil amide, with oleyl amide being preferred. The fatty amines useful
as
friction modifiers are generally primary, secondary or tertiary amines having
alkyl, alkoxyl or polyoxyalkene groups. The borated fatty amines are prepared
by reacting a borating agent (described above) with a fatty amine (described
above). The borated fatty amines are prepared by reacting the amine with the
borating agent at about 50°C to about 300°C, preferably about
100°C to about
250°C, and at a ratio of 3:1 to 1:3 equivalents of amine to equivalents
of
borating agent.
In another embodiment, the friction modifier (C) may be a fatty phosphite.
The fatty phosphites include dialkyl hydrogen phosphites having alkyl groups
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having from about 8 to about 24, preferably about 12 to about 22, more pre-
ferably about 16 to about 20 carbon atoms in each alkyl group. A particularly
useful fatty phosphite is a dioleyl hydrogen phosphite.
In another embodiment, the friction modifier is a borated fatty epoxide.
The borated fatty epoxides are generally the reaction product of a boric acid
or
boron trioxide with at feast one epoxide. The epoxide is generally an
aliphatic
epoxide having at least 8 carbon atoms, more preferably from about 10 to about
20, more preferably 12 to about 20. Examples of useful aliphatic epoxides
include heptyl oxide, octyl oxide, stearyl oxide, oleyl oxide and the like.
Mixtures of epoxides may also be used, for instance commercial mixtures of
epoxides having from 14 to about 16 carbon atoms and 14 to about 18 carbon
atoms. The borated fatty epoxides are generally known and are disclosed in
Canadian Patent 1,188,704 issued to Davis. This patent is incorporated by
reference for its disclosure of borated fatty epoxides and methods for
preparing
the same.
U.S. Patent 4,792,410, issued to Schwind et al, described friction
modifiers and that disclosure is hereby incorporated by reference.
(D) Acylated Amine
The composition may contain an acylated amine. Typically, the acylated
amine has a total base number of at least about 30 TBN, or preferably at least
about 40 TBN, more preferably at least about 50 TBN. The basic nitrogen
compounds generally have a maximum TBN of about 350, preferably about 250.
In one embodiment, the acylated amine has a TBN from about 30 to about 200,
preferably from about 60 up to about 150, or more preferably from about 70 up
to about 100. The TBN is based on neat chemical. The acylated amine
includes reaction products of one or more carboxylic acylating agent and one
or
more amine, preferably a polyamine. In one embodiment, the acylated amines
are prepared by reacting an excess of amine with the carboxylic acylating
agent.
In one embodiment, greater than one equivalent of amine is reacted with each
equivalent-of carboxylic group of the acylating agent. The equivalents of the
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21
amine is based on the number of nitrogen atoms in the amine. The equivalent
weight of the carboxylic acylating agent is based on the number of carboxylic
groups (e.g. C001, such as acids, lower esters, etc. in each acylating agent.
In
one embodiment, at least about 1.2, preferably at least about 1.4 equivalents
of amine are reacted with each equivalent of carboxylic group of the acylating
agent. Typically, up to about 8, or preferably up to about 6, or more
preferably
up to about 4 equivalents of amine are reacted with each equivalent of
carboxylic group of the acylating agent.
The acylated amines are prepared from one or more amines and one or
more carboxylic acylating agents. The carboxylic acylating agents include
fatty
acids, isoaliphatic acids, dimer acids, addition dicarboxylic acids, trimer
acids,
addition tricarboxylic acids, and hydrocarbyl substituted carboxylic acylating
agents. In one embodiment, the carboxylic acylating agent is one of the above
described unsaturated fatty acids. The fatty acids may also be the saturated
analogs of the unsaturated fatty acids.
In another embodiment, the carboxylic acylating agents include
isoaliphatic acids. Such acids contain a principal saturated, aliphatic chain
typically having from about 14 to about 20 carbon atoms and at least one, but
usually no more than about four, pendant acycfic lower alkyl groups. Specific
examples of such isoaiiphatic acids include 10-methyl-tetradecanoic acid,
3-ethyl-hexadecanoic acid, and 8-methyl-octadecanoic acid. The isoaliphatic
acids include branched-chain acids prepared by oligomerization of commercial
tatty acids, such as oleic, linoleic and tall oil fatty acids.
The dimer acids include products resulting from the dimerization of
unsaturated fatty acids and generally contain an average from about 18 to
about
44, or from about 28 to about 40 carbon atoms. Dimer acids are described in
U.S. Patents 2,482,760, 2,482,767 , 2,731,481, 2,793,219, 2,964,545,
2,978,468, 3,157,681, and 3,256,304, the entire disclosures of which are
incorporated herein by reference.
In another embodiment, the carboxylic acylating agents are addition
carboxylic -acylating agents, which are addition (4 + 2 and 2 + 2) products of
an
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22
unsaturated fatty acid, such as tall oil acids and oleic acids, with one or
more
unsaturated carboxylic reagents, which are described below. These acids are
taught in U.S. Patent No. 2,444,328, the disclosure of which is incorporated
herein by reference.
In another embodiment, the carboxylic acylating agent is a tricarboxylic
acylating agent. Examples of tricarboxylic acylating agents include trimer
acylating agents and the reaction product of an unsaturated carboxylic
acylating
agent (such as unsaturated fatty acids) and an alpha,beta- unsaturated
dicarboxylic acylating agent (such as malefic, itaconic, and citraconic
acylating
agents, preferably malefic acylating agents). These acylating agents generally
contain an average from about 18, or about 30, or about 36 to about 66, or to
about 60 carbon atoms. The trimer acylating agents are prepared by the
trimerization of one or more of the above-described fatty acids. In one embodi-
ment, the tricarboxylic acylating agent is the reaction product of one or more
unsaturated carboxylic acylating agent, such as an unsaturated fatty acid or
unsaturated alkenyl succinic anhydride and an alpha,beta-unsaturated
carboxylic
reagent. The unsaturated carboxylic reagents include unsaturated carboxylic
acids per se and functional derivatives thereof, such as anhydrides, esters,
amides, imides, salts, acyf halides, and nitrites. The unsaturated carboxylic
reagent include mono, di , tri or tetracarboxylic reagents. Specific examples
of
useful monobasic unsaturated carboxylic acids are acrylic acid, methacrylic
acid,
cinnamic acid, crotonic acid, 2-phenylpropenoic acid, etc. Exemplary polybasic
acids include malefic acid, malefic anhydride, fumaric acid, mesaconic acid,
itaconic acid and citraconic acid. Generally, the unsaturated carboxylic
reagent
is malefic anhydride, acid or lower ester, e.g. those containing less than
eight
carbon atoms. In one embodiment, the unsaturated dicarboxylic acylating agent
generally contains an average from about 12 up to about 40, or from about 18
up to about 30 carbon atoms. Examples of these tricarboxylic acylating agents
include Empol° 1040 available commercially from Emery Industries,
Hystrene°
5460 available commercially from Humko Chemical, and Unidyme° 60
available
commercially from Union Camp Corporation.
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In another embodiment, the carboxylic acylating agent is a hydrocarbyl
substituted carboxylic acylating agent. The hydrocarbyl substituted carboxylic
acylating agents are prepared by a reaction of one or more olefin or
polyafkene
with one or more of the above described unsaturated carboxylic reagents. The
hydrocarbyl group generally contains from about 8 to about 300, or from about
12 up to about 200, or from about 16 up to about 150, or from about 30 to
about 100 carbon atoms. in one embodiment, the hydrocarbyl group contains
from about 8 up to about 40, or from about 10 up to about 30, or from about
12 up to about 24 carbon atoms. In one embodiment, the hydrocarbyl group
may be derived from an olefin. The olefins typically contain from about 3 to
about 40, or from about 4 to about 24 carbon atoms. These olefins are
preferably alpha-olefins (sometimes referred to as mono-1-olefins or terminal
olefins) or isomerized alpha-olefins. Examples of the alpha-olefins include 1-
octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-penta-
decene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-
eicosene, 1-heneicosene, 1-docosene, 1-tetracosene, etc. Commercially
available alpha-olefin fractions that can be used include the C,5_,g alpha-
olefins,
C~2_,s alpha-olefins, C~~~s alpha-olefins, C~4_,8 alpha-olefins, C,6_~8 alpha-
olefins,
C,s-ao alpha-olefins, C~e_24 alpha-olefins, C22_28 alpha-olefins, etc.
In another embodiment, the hydrocarbyl group is derived from one or
more of the above described polyalkenes. In one embodiment, the polyalkenes
have a Mn from at least about 1300, or from about 1500, or from about 1700.
In one embodiment, the polyalkenes have a Mn from about 1500 up to about
3200, or from about 1500 up to about 2800, or from about 1500 up to about
2400. In a preferred embodiment, the polyalkene has a Mn from about 1700
to about 2400. The polyalkenes also generally have a Mw/Mn from about 1.5
to about 4, or from about 1.8 to about 3.6, or from about 2.0 to about 3.4, or
from about 2.5 to about 3.2. The hydrocarbyl substituted carboxylic acylating
agents are described in U.S. Patent 3,219,666 and 4,234,435, the disclosures
of which is hereby incorporated by reference.
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In another embodiment, the acylating agents may be prepared by reacting
one or more of the above described polyalkenes with an excess of malefic
anhydride to provide substituted succinic acylating agents wherein the number
of succinic groups for each equivalent weight of substituent group, i.e.,
polyalkenyl group, is at least about 1.3, preferably at least about 1.4, or
more
preferably at least about 1.5. The maximum number will generally not exceed
about 4.5, or preferably about 3.5. A suitable range is from about 1.4 up to
about 3.5, or from about 1.5 up to about 2.5 succinic groups per equivalent
weight of substituent groups.
The carboxylic acylating agents are known in the art and have been de-
scribed in detail, for example, in the following: U.S. Patents 3,215,707
(Reuse);
3,219,666 (Norman et al); 3,231,587 (Reuse); 3,912,764 (Palmer); 4,1 10,349
(Cohen); and 4,234,435 (Meinhardt et al); and U.K. 1,440,219. The disclosures
of these patents are hereby incorporated by reference. These patents are
incorporated herein by reference for their disclosure of carboxylic acylating
agents and methods for making the same.
The above-described carboxylic acylating agents are reacted with amines
to form the acylated amines. The amines may be monoamines or polyamines
preferably the amine is a polyamine, such as an alkylenepolyamine or a
condensed amine. Useful amines include those amines disclosed in U.S. Patent
4,234,435 at Col. 21, line 4 to Col. 27, line 50, these passages being
incorporated herein by reference.
In one embodiment, the amine is a fatty amine. Fatty amines are those
containing from about 8 to about 30, or from about 12 to about 24 carbon
atoms. The fatty amines include n-octylamine, n-decylamine, n-dodecylamine,
n-tetradecylamine, n-hexadecylamine, n-octadecylamine, stearylamine,
oleyamine, tallowamine, soyaamine, etc. Also useful fatty amines include
commercially available fatty amines such as "Armeen" amines (products
available from Akzo Chemicals, Chicago, Illinois), such as Akzo's Armeen C,
Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD,
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wherein the letter designation relates to the fatty group, such as cocoa,
oleyl,
tallow, or stearyl groups.
Other useful amines include primary ether amines, such as those
represented by the formula, R,(OR2)x NHZ 111, wherein R, is a hydrocarbyl
group
from about 1 to about 150, or from 5 to about 24 carbon atoms, R2 is a
divalent
alkylene group having about 2 to about 6 carbon atoms; and x is a number from
one to about 150, or from about one to about five, or one. An example of an
ether amine is available under the name SURFAM° amines produced and
marketed by Mars Chemical Company, Atlanta, Georgia. Etheramines include
those identified as SURFAM P14B (decyloxypropylamine), SURFAM P16A (linear
C,6), and SURFAM P17B (tridecyloxypropylamine). The carbon chain lengths
(i.e., C,4, etc.) of the SURFAMS described above and used hereinafter are
approximate and include the oxygen ether linkage.
In another embodiment, the amine is a tertiary-aliphatic primary amine.
Generally, the aliphatic group, and in one embodiment an alkyl group, contains
from about 4 to about 30, or from about 6 to about 24, or from about 8 to
about 22 carbon atoms. Usually the tertiary alkyl primary amines are
monoamines represented by the formula R,-C(R2)2-NH2 (II), wherein R, is a
hydrocarbyl group containing from 1 to about 28 carbon atoms and R2 is a
divalent hydrocarbylene group, preferably an alkylene group, containing from 1
to about 12 carbon atoms. Such amines are illustrated by tert-butylamine,
tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine,
tent-decylamine, tert-dodecylamine, tent-tetradecylamine, tert-hexadecylamine,
tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.
Mixtures of amines are also useful for the purposes of this invention.
Illustrative of amine mixtures of this type are "Primene 81 R" which is a
mixture
of C~~-C,4 tertiary alkyl primary amines and "Primene JMT" which is a mixture
of C,$ C22 tertiary alkyl primary amines (both are available from Rohm and
Haas
Company). The tertiary alkyl primary amines and methods for their preparation
are known to those of ordinary skill in the art. The tertiary alkyl primary
amine
useful for the purposes of this invention and methods for their preparation
are
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26
described in U.S. Patent 2,945,749, which is hereby incorporated by reference
for its teaching in this regard.
In another embodiment, the polyamine is a fatty diamine. The fatty
diamines include mono- or dialkyl, symmetrical or asymmetrical
ethylenediamines, propanediamines ( 1,2, or 1,3), and polyamine analogs of the
above. Suitable commercial fatty polyamines are Duomeen C
(N-coco-1,3-diaminopropane), Duomeen S (N-soya-1,3-diaminopropane),
Duomeen T (N-tallow-1,3-diaminopropane), and Duomeen O (N-oleyl-1,3-di-
aminopropane). "Duomeens" are commercially available from Armak Chemical
Co., Chicago, Illinois.
In another embodiment, the polyamines are polyoxyalkylene polyamines,
e.g. polyoxyalkylene diamines and polyoxyalkylene triamines, having average
molecular weights ranging from about 200 to about 4000, or from about 400
to about 2000. The preferred polyoxyalkylene~ polyamines include the
polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene
triamines. The polyoxyalkylene polyamines are commercially available and may
be obtained, for example, from the Texaco Chemical Company, Inc. under the
trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403, etc.". U.S.
Patents 3,804,763 and 3,948,800 are expressly incorporated herein by
reference for their disclosure of such polyoxyalkylene polyamines and acyiated
products made therefrom.
In another embodiment, the polyamines are hydroxy-containing
polyamines. Hydroxy-containing polyamine analogs of hydroxy monoamines,
particularly alkoxylated alkylenepolyamines, e.g., N,N'-
(dihydroxyethyl)ethylene
diamines can also be used. Such polyamines can be made by reacting the
above-described alkylene amines with one or more alkylene oxides, such as
ethylene, propylene or butylene oxide. Similar alkylene oxide-alkanol amine
reac-
tion products may also be used such as the products made by reacting the
above described primary, secondary or tertiary alkanol amines with ethylene,
propylene or higher epoxide in a 1.1 to 1.2 molar ratio. Reactant ratios and
temperatures for carrying out such reactions are known to those skilled in the
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art. Specific examples of hydroxy-containing polyamines include
N-(2-hydroxyethyf)ethylenediamine, N,N'-bis(2-hydroxyethyl)ethylenediamine,
1-(2-hydroxyethyl)piperazine, mono(hydroxypropyl)-substituted tetraethylene-
pentamine, N-f3-hydroxybutyl)tetramethylenediamine, etc. Higher homologs
obtained by condensation of the above illustrated hydroxy-containing
polyamines
through amino groups or through hydroxy groups are likewise useful.
Condensation through amino groups results in a higher amine accompanied by
removal of ammonia, while condensation through the hydroxy groups results in
products containing ether linkages accompanied by removal of water. Mixtures
of two or more of any of the above described polyamines are also useful.
In another embodiment, the polyamine is a heterocyclic polyamine. The
heterocyclic polyamines include aziridines, azetidines, azolidines, tetra- and
dihydropyridines, pyrroles, indoles, piperidines, imidazoles, di- and tetra-
hydroimidazoles, piperazines, isoindoles, purines, morpholines,
thiomorpholines,
N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines,
N,N'-diaminoalkylpiperazines, azepines, azocines, azonines, azecines and tetra-
,
di- and perhydro derivatives of each of the above and mixtures of two or more
of these heterocyclic amines. Preferred heterocyclic amines are the saturated
5- and 6-membered heterocyclic amines containing only nitrogen, oxygen and/or
sulfur in the hetero ring, especially the piperidines, piperazines,
thiomorpholines,
morpholines, pyrrolidines, and the like. Piperidine, aminoalkyl substituted
piper-
idines, piperazine, aminoalkyl substituted piperazines, morpholine, aminoalkyl
substituted morpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines,
are
especially preferred. Usually the aminoalkyl substituents are substituted on a
nitrogen atom forming part of the hetero ring. Specific examples of such
heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine,
and N,N'-diaminoethylpiperazine. Hydroxy heterocyclic polyamines may be used
and include N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine,
parahydroxyaniline, N-hydroxyethylpiperazine, and the like.
The amine used in preparing the acylated amine may be an alkylenepol-
yamine. _ Alkyienepolyamines are represented by the formula
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incorporated by reference for its disclosure to the condensates and methods of
making. A particularly useful amine condensate is prepared from HPA Taft
Amines (amine bottoms available commercially from Union Carbide Co. with
typically 34.1 % by weight nitrogen and a nitrogen distribution of 12.3% by
weight primary amine, 14.4% by weight secondary amine and 7.4% by weight
tertiary amine), and tris(hydroxymethyl)aminomethane (THAM).
Acylated amines and methods for preparing the same are described in
U.S. Patents 3,219,666; 4,234,435; 4,952,328; 4,938,881; 4,957,649; and
4,904,401. The disclosures of acylated nitrogen dispersants and other
dispersants contained in those patents are hereby incorporated by reference.
The following Examples relate to basic nitrogen containing compounds
and methods of preparing the same.
Example N-1
A polyisobutenyl (Mn = 850) succinic anhydride having an acid number of
113 (corresponding to an equivalent weight of 500). To a mixture of 500
grams ( 1 equivalent) of this polyisobutenyl succinic anhydride and 160 grams
of toluene there is added at room temperature 55.5 grams (1.5 equivalents) of
an ethylene amine mixture having a composition corresponding to that of
triethylenetetramine. The addition is made portionwise throughout a period of
15 minutes. The mixture then is heated and a water-toluene azeotrope distilled
from the mixture. When no more water would distill the mixture is heated to
150°C at reduced pressure to remove the toluene. The residue is diluted
with
350 grams of mineral oil. The resulting product has a nitrogen content of
1.9%.
Example N-2
The procedure of Example N-1 is repeated using 55.0 grams (1.5
equivalents) of triethylenetetramine as the amine reactant. The resulting
product
has a nitrogen content of 2.9%.
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31
Example N-3
A mixture of 86.4 grams of an alkylenepolyamine mixture, comprising
80% of ethylene polyamine bottoms from Union Carbide and 20% of a
commercial mixture of ethylenepolyamines corresponding in empirical formula
to diethylenetriamine, and 390 grams of 100 neutral mineral oil is heated to
100°C under nitrogen. To this mixture is added 800 grams of polybutenyl
(n =1000) substituted succinic anhydride and 200 grams of 100 neutral mineral
oil. The reaction mixture is heated to 290-300°F and the temperature is
maintained for one hour, with submerged nitrogen blowing. The reaction
product is then filtered and the filtrate is the desired product. The desired
product is a 40% oil mixture having 2% nitrogen, and a 45 TBN.
Example N-4
To a mixture of 140 grams of toluene and 400 grams (0.78 equivalent)
of a polyisobutenyl (Mn = 850) succinic anhydride, having an acid number of
109, there is added at room temperature 63.6 grams ( 1.55 equivalents) of an
ethyleneamine mixture having an average composition corresponding to that of
tetraethyfenepentamine and available from Union Carbide under the trade name
"Polyamine H." The mixture is heated to distill the water-toluene azeotrope
and
then to 150°C. at reduced pressure to remove the remaining toluene. The
residual polyamide has a nitrogen content of 4.7%.
Example N-5
Following the procedure of Example N-3, 1 16 grams of the polyamine
mixture of Example N-3 and 388 grams of 100 neutral mineral oil are reacted
with 800 grams of the polybutenyl succinic anhydride of Example N-3 and 200
grams of a 100 neutral mineral oil. The desired product is a 40% oil mixture
having 2.5% nitrogen and a 70 TBN.
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Example N-6
The procedure of Example N-1 is repeated using 46 grams (1.5
equivalents) of ethylene diamine as the amine reactant. The product which
resulted has a nitrogen content of 1.5%.
Example N-7
A reaction vessel is charged with 1000 grams of the polybutenyl succinic
anhydride of Example N-3 and 400 grams of 100 neutral mineral oil. The
mixture is heated to 88°C where 152 grams of a polyamine prepared from:
1299 grams of HPA Taft Amines famine bottoms available commercially from
Union Carbide Co. with typically 34.1 % by weight nitrogen and a nitrogen
distribution of 12.3% by weight primary amine, 14.4% by weight secondary
amine and 7.4% by weight tertiary amine), 727 grams of 40% aqueous
tris(hydroxymethyl)aminomethane (THAM), and 23 grams of 85% H3P04 which
are heated to 120°C over 0.6 hour, then are heated to 150°C over
1.25 hour,
then to 235°C over 1 hour, then the temperature is maintained at 230-
235°C
for 5 hours, then heated to 240°C over 0.75 hour, and then held at 240-
245°C
for 5 hours, followed by filtration through diatomaceous earth. The mixture is
heated to 152 ° C over 5.5 hours. At temperature, the reaction mixture
is blown
subsurface with nitrogen until the percent water is a maximum of 0.3. Diluent
oil (342 grams of 100 neutral mineral oil) is added to the reaction mixture
and
the reaction mixture is filtered through diatomaceous earth. The filtrate is
the
desired product. The desired product is a 40% oil mixture having 2.1 %
nitrogen
and a 48 TBN.
Example N-8
An acid producing compound is prepared by heating chloromaleic
anhydride (1 equivalent) and 1 equivalent of a chlorinated polyisobutene
having
a chlorine content of 4% and a molecular weight of 2500 at 150 -200°C.
The
product of the reaction is then mixed with tetraethylenepentamine (2.5
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33
equivalents) at 50°C and the mixture is heated at 180 -210°C to
form an
acylated polyamine.
The lubricants may contain other additives such as dyes, cold flow
modifiers, auxiliary antiwear agents such as metal dithiophosphates (such as
zinc dithiophosphates), phosphate esters or salts, such as tricresylphosphate
or
2-ethylhexyl phosphates and salts thereof, sulfurized CZ_~Z olefins,
sulfurized
fatty acids or oils, etc.
In one embodiment, the lubricants consist essentially of (A) and (B). In
another embodiment, the lubricant consists essentially of (A). (B) and (C). In
these embodiment, the components provide durability in the Mack MT-1
transmission test and have improved antiwear and thermal stability properties.
The following examples relate to the lubricants which contain at least a
basic metal salt and a hydrocarbyl phosphate. Unless otherwise indicated, in
the
following examples as well as elsewhere in the specification and claims,
temperature is in degrees Celsius, parts and percentages are by weight and
pressures are atmospheric.
Example 1
A lubricant is prepared by blending 0.75% of di-2-ethylhexyl hydrogen
phosphate and 0.7% of a calcium benzene sulfonate, having 53% 100 neutral
mineral oil, a total base number or 41, a metal ratio of 12, and 2.5% of
calcium
methylene coupled heptylphenate having 2.2% calcium and a total base number
of 65 into a base stock prepared from combining 73%v of 750 neutral mineral
oil and 27%v of 150 bright stock.
Example 2
A lubricant is prepared as described in Example 1 except that 1.5% of
dioleyl phosphate is used in place of di-2-ethylhexyl phosphate.
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Example 3
A lubricant is prepared as described in Example 1 except that 0.6% of
dibutyl phosphate is used in place of di-2-ethylhexyl phosphate.
Example 4-6
A lubricant is prepared as described in Example 1-3 except that 0.6% of
a magnesium benzene suffonate having 42% 100 neutral mineral oil, 9.4%
magnesium, a metal ratio of 14.7, a total base number of 400 and 5% of
polyisobutylene (Mn = 980) succinic anhydride is used as the only basic salt.
White the invention has been explained in relation to its preferred
embodiments, it is to be understood that various modifications thereof will
become apparent to those skilled in the art upon reading the specification.
Therefore, it is to be understood that the invention disclosed herein is
intended
to cover such modifications as fall within the scope of the appended claims.
