Note: Descriptions are shown in the official language in which they were submitted.
~!L2~3~3
--1~
L--2220R/B
Title: POLYMERIC CO~5POSI~IONS~ OïL COMPOSITIONS
CONTAINING SAID POhYMERIC COMPOSITIOl~S,
TRANS~iISSION FLUIDS A~D ~YDRA~I.IC FLUIDS
~NICAL ~:LELI) OF THE I~VENTIQN
Thi~ invention relates to novel polymeric
compositions, transmission fluids (i~,e., automatic
transmission fluids and manual transmission fluids)
~nd hydraulic fluid~. More partic:ularly, the present
inv~ntion relates to automa~ic transmission fluid and
hydraul~c fluid compo~itions containing the polymeric
compositions of ~he presen~ invention and
characterized as having improved shear stabili~y.
Th~ problems assoclated with the lubrication
of automatic and manual transmissions and the
op~ration of hydrualic fluid ~ystems are well known to
those skilled in the art~ ~or e~ampl~, in the
lubrication o~ transmis~ion~, proper fluid
-
~L2437~3
viscosity at both low and high temperatures is
essential to successful operation, Good low
temperature fluidity eases cold weather starting and
insures that the hydraulic con~rol system will
properly "shi~t gears''9 ~igh viscosity at elevated
temperatures insures pumpability and the satisactory
functioning of converters, valves, clutches, gears and
bearing~.
In the operativn of hydraulic fluid systems,
proper fluid viscosity at both low and high
~emperatures is essential to successful operation.
High temperature visco~ity re~ention is beneficial in
lubrication, contributes to streamline flow and
reduces leakageO Good low temperature ~luidity
provides rapid control action, less heating loss and
lower pressure drop.
These conflic~ing fluidity requirements call
for a product that exhibits ~he following
characteristics~
~ A) high temperature viscosity retention,
(B) low temperature fluidity~ and
~C~ shear stability.
Tn order to preparQ lubricants having these
characteristics, it has bccome common practice to add
a variety of chemicals to the oil. For example, in
order to meet the viscosity requirements, compositions
have been added to the oils which are characterized by
relatively ~mall change in their viscosity with
chan~ing temperat~lre, and they are commonly graded
according to SAE s~andards according to the
viscosities at low ~e.g., 3F) and at high
temperatures ~e.g~, 210F~. ~s a result of the
3~2'~3~7~3
~3~
incorporation of such additives, the lubricating oi:l 5
are often referred ~o a~ being "multi-graded~. In
terms of widely accepted concepts, such multi-graded
luhricants have the de~irable properties are being
able to function immediately, ~hough cold, upon being
pu into service, and to continue to function
satisfactorily as they become heated during operationO
Although chemical compos itions have been
developed vhich improve the viscosi~y characteristics
of lubricating oil, it is often desirable ~o further
improve ~he low temperature characteri~tics by
including compositions which function as fluidity
modifiers at low temperatures. Fluidity modifiers are
capable of lowering the viscosity o~ a lubricating oil
at low temperatures generally by retarding the
formation o~ undesirable microcrystalline wax
substances.
In addition to the above improvements, it is
desirable~ if not necessary, that lubricating
compositions especially designed for use as
transmission fluids and hydraulic ~luids exhibit shear
stability. Shear stability means that the lubricating
oils will not degrade or lose ~heir desirable
viscosi~y characteristics as a result of the shearing
forces encountered during thelr use. Lubricating oil
compositions exhibiting desirable shear stability will
be found to generally have the viscosity within 85-95%
of their original viscosity after a number of hours,
~e.g~ 100 hours) of service. It has been recognized
that many ordinary viscosity index improvers commonly
added to crankcase lubrica ing oils, such as high
molecular weight polyi~obutene and polyacrylates, do
~2437~3
not possess the desired shear stability for use in
improving the viscosity characteristics of
transmission fluids and hydraulic ~luids.
It now has been ~ound ~hat multi-grade
lubrlcant exhibiting improved shear stability can be
made by utilizing the compositions of the present
invention. These lubrican~s are particularly useful
in providin~ transmission fluids and hydraulic fluids.
S~MM~ F T~E I~V~N~ION
Polymeric compos itions are described which
comprise a mixture of
~ A) at least one oil-soluble polymer which
is a homopolymer of a non-aromatic monoolefin or a
copolymer of said non-aromatic monoolefin with an
aroma~ic monoolefin, and
(B-l) at least one nitrogen-containing ester
of a carboxy-containing interpolymer, and/or
(B-2) at least one oil-soluble acrylate
polymerization product of at least one acrylate ester,
or a mixture of one or more of (B-l) and s-2). The
polymeric compositions of the invention also may
contain
~ C) an effective amount of at least one low
tempera~ure viscosity-reducing liquid organic diluent
such as a naphthenic oil or certain other natural and
synthetic oils having the desired low temperature
properties.
Polymeric compositions of the present
i~vention are useful as additive~ in transmission
fluidæ and hydraulic fluids, and the transmis~ion
fluids and hydraulic fluids containing the polymeric
composltions of the present invention exhibit improve~
shear stability while maintaining desirable high and
low temperature viscosity characteristics.
~2~3~3
The first component ~A~ of the polymeric
compositions of the invention i,s at least one oil-
soluble polymer which is a homopolymer of a non-
aromatic monoolein having at least 3 carbon atoms r or
a copolymer of said non-aromatic monoolefin with an
aromatic monoolefin, said polymer having a number
average molecular weight of about 500 to about
100,000, and more preferably, a number average
molecular weight of at least about 750. Still more
preferably, the number average molecular weight of the
polymer will be in the range of from about 750 to
about 10,000.
The characterization of these polymers as
oil-soluble does not necessarily mean they are soluble
in all base oils in all propor~ions. Rather, the
polymers are soluble in the base oils with which they
are formulated to a degree sufficient to allow the
lubricant composition to be mul~i-graded between SAE
75W and SAE 250.
The above-mention~d homopolymers can be
prepared from non aromatic monoolefins having at leas~
3 carbon atoms and preferably no more than 20 carbon
atoms by a number of polymerization techni~ues well
known to those of s~ill in the art~ It should be
noted that ~homopolymerW as used herein, describes
polymers made from monoolefins having the same number
of carbon atoms. Thus, polymers made from a mixture
of butene-l and isobu~ylene are, in the terms of this
specification and the appended claims, homopolymers of
butylene. When they con~in predominantly units
derived from a single isomer, they may be referred to
~2~379
--6--
as polymers of that isomer; but, such ~ermino}ogy ~oes
not exclude ~he possibility of the presence of a minor
amount of units derived from other isomersO Thus, a
"polyisobutylene polymer~ might contain units, 80~ of
which are derived from isobutylene, 15% from l-butene
and 5% from 2~butene.
Particularly preferred are homopolymers made
from C3 ko C2a monoolefins such as propene,
2-butene, isobutene, hexene-l, decene-3 9
tetradecene-4, etc. More preferable are homopolyme~s
derived from C4 ~o Cg alpha-olefins such as
butene, isobutene, pentene-l~ heptene-l, etc. The
most preferred homopolymers are those of propene and
the various butenes.
The oil-soluble polymer (A) of the polymeric
composition of this invention also may be copolymers
of said non-aromatic monoolefins with one or more
aromatic olefins. Copolymers containing at least 50%
by weight of said non-aromatic olefin and up to about
50% by weight of an aromatic olefin are useful. Th~
aromatic olefins are preferably vinyl aromatic
monomers of up to 12 carbon atoms including styrene
and substitu~ed styrenes such as the methyl styrenes,
alpha-halcstyrenes, lower alkyl-substituted styrenes
such as alpha-methylstyrene, alpha-ethylstyrene,
para-tert-butylstyrene and para-lower alkoxystyrenes.
Techniques such as Ziegler, cationic,
free-radical, anionic, emulsion polymerization and so
for~h can be used in appropriate circums~ances to
prepare these polymers. A particularly convenient
technique for polymerizing such olefins for use in
this invention is through the use of a Lewis acid
, ~
~2~37~3
catalyst such as aluminum chloride/ boron trifluoride,
titanium tetrafluoride and ~he like. These
polymerizations are well known in l:he art and need no~
be described further at this point.
Among the polymers ~hat are useful in the
compositions of the presen~ invention are the
~ollowing: a polyisobutene of Mn 1400, a poly~l-
octene) of Mn 4300, a poly (3-heptene~ of ~n 900, a
poly~l-eicosene3 of Mn of 9500, a poly~l nonene) of Mn
3700, a poly(2-methyl-1-pentene) of Mn 1700; a poly-
~5-ethyl-l~hexene) of Mn of 2~00, and a poly~8-methyl-
l-tetradecene) of Mn l900o
In general~ it is preferred ~ha~ the
homopolymers of the present invention, i.e., component
(A)~ for reason~ of oxidative stabili~y, contain no
more than 5~ unsaturation on the kasis of the total
number of carbon-to-carbon covalent llnkages present
within an average molecule. Such unsaturation can be
measured by a number of means well known to those of
skill in the art, su~h a~ infrared, NMR, e~c. More
preferably these polymers contain no discernable
unsaturation.
A particularly preferred polymer meeting all
of the above requiremen~s is polyisobutene, although
other polymers such as polypropylene may also prove
equally useful and desirable.
The transmission fluids of the invention
preferably contain from about 0~1% to about 20~ by
weight of component ~A). The hydraulic fluids of the
invention preferably contain from abou~ 001% ~0 abou~
20%, more preferably about 2~ to abou~ 10% by weight
by weight of component (A).
37~3
Component (B) of the polymeric composition of
the invention is at least one of ~he following:
(B-l~ at least one nitrogen-containing
ester of a carbo~y-containing interpolymer, said
interpolymer having a reduced specific viscosity of
from about 0~05 to about 2,
said ni~rogen-containing e~er being characterized by
the preC~ence wi~hin its polymer structure of the
following polar groups which are derived from the
carboxy groups of said interpolymer:
(a) at least one carbo~ylic ester group
having at least 8 aliphatic carbon atoms in the ester
group,
(b~ at least one carbonylpolyamino
group derived from a polyamino compound having one
primary or secondary amino group and optionally
(c) at least one carboxylic ester group
having no more than 7 aliphatic carbon atoms in the
ester group, or
(B 2) at least one oil-soluble acrylate
polymeri2ation product of at least one ester of the
formula
CH2=C~X)-COOR
wherein X is hydrogen or an alkyl or aryl group, and
R is a monovalent hydrocarbyl group
containing more than four carbon atoms, or an ether
derivative of said hydrocarbyl group.
Mixtures of B-l and B-2 also are useful
within the compositions of the invention, particularly
with respect to hydxaulic fluids.
"~
L3~f~33
As can be seen f rom the above, in one
embodiment of the invention, the nitrogen-containing
ester of a carboxy-containing interpolymer (B-l)
contains within its polymer structure, at l~ast two
polar groups which are derived from ~he carboxy groups
of said interpolymer. These polar groups are
(a3 at least one carboxylic ester group
having at least 8 aliphatic carbon atoms in the ester
group, and
(b) at lea~t one carbonyl-polyamino group
derived from a polyamino compound having one primary
or secondary amino group~
In a second embodiment, the nitrogen-containing ester
is characterized within its polymer s~ructure of the
above two groups identified as (a) and ~b) and a third
group (c) which is a carboxylic ester group having no
more than 7 aliphatic carbon atoms in the ester group.
In reference to the size of the ester groups,
it is poin~ed out that an ester group is represented
by the formula
-C~O)(OR)
and the number of carbon a oms in an ester group is
thus the combined to~al of the carbon atom of the
carbonyl group and the carbon atoms contained in the
(OR) group.
When the ni~rogen-containing es ter (B-l)
con~ains only polar groups ~a) and (b), ~he molar
ratio of (a) to (b) is generally within the range of
from about 85:15 to about 99:1, and an especially
preferred ratio is 95:5. When the nitrogen-containing
ester (B-~) con~ains all three polar groups, namely,
~3'793
--10--
(a), (b~ and~c), the polar groups are present at
molar ratiosof about (60 90): ~2-15): (10-30),
respectively.A preferred ratio is about (70-80~:
(5) ~ 253 .
It should be noted that the linkage described
as the carbonyl-polyamino group may be amide, imide~
or amidine, and inasmuch as any such linkages
contemplat~d within the present invention, the term
"carbonylpolyamino" is adop~ed as being a convenient,
generic expression useful for the purpose of defining
th~ polar groups (b). In a particularly advantageous
embodiment of the invention, the linkage is imide or
predominantly imide.
Another important element of component (B-l~
is the molecular weight of the carboxy containing
interpolymer. . For convenience, the molecular weight
is expre~sed in terms of the "reduced specific
YiscoSity" of the interpolymer which is a widely
recognized means of expressing the molecular size of a
polymeric substance. As used herein, the reduced
specific viscosity (abbreviated ~s RSV) is the value
o~tained in accordance with ~he formula
Rela~ive Viscosity -_
RSV ~ Concentration
wherein the relative viscosity is determined by
measuring, by means of a dilution viscometer, the
visco~ity of a solution of one ~ram of the
interpolymer in lOG ml. of acetone and the viscosity
o acetone at 30iO.021C. For purpose of computation
by the above formula, the concentration is adjusted to
0.4 gram of the interpolyMer per 100 ml. o~ acetone.
~2'~3793
A more detailed discussion of the reduc~d specific
viscosity, al o known as the sp~eciic viscosity, as
well as its relationship to thle average molecular
weight of an interpolymer, appears in Paul J. Fory,
P~in~ $ ~ Polym~r ~hçmis~ry, (1953 Edition) pages
308 et seq.
While interpolymers having a reduced specific
viscosity of from about 0.05 to about 1 are
con~emplated in the present invention, the preferred
interpolymers are those having a reducPd specific
viscosity of from about 0.2 or 0.35 to about 0.8 or l.
Interpolymers having a reduced specific viscosity of
from about 0.35 to about 0.5 or from about 0.65 to
about 0.75 are particularly useful.
Mixtures of two or more compatible (i.e.,
nonreactive to one another) interpolymers which are
separately prepared are ~ontemplated herein for use in
the esterification reaction, if each has a RSV as
above described. Thus, as used herein, and in the
appe~ded claims, the terminology ~interpolymer" refers
to either one separately pxepared interpolymer or a
mixture of two or more of such in~erpolymers. A
separately prepared interpolymer is one in which the
reactants and/or reaction conditions are different
from the preparation of another interpolymer.
The interpolymers are copolymers,
terpolym~rs, and other interpolymers of alpha, beta-
unsaturated dicarboxylic acids or derivatives thereof,
or mixtures of two or more of any of these, and one or
more vinyl aromatic monomers having up to l~ carbon
atoms. The derivatives of the dicarboxylic acid are
derivatives which are polymerizable with the
monoolefinic compound, and as such, may be the esters
~37~3
--12--
and anhydrides of the acids. Copolymers of maleic
anhydride and styrene are especially suitable, and
such interpolymers havi~g a RSV in the range f rom
about 0.3 to about 1.8 (particularly 0.3 to about 0.9
are preerred.
Suitable alpha, beta-unsaturated dicarboxylic
acids, anhydrides or lower alkyl esters thereof useful
in the preparation of the interpolymers include those
wherein a carbon-~o-carbon double bond is in an alpha,
heta-position to at lea~t one of the carboxy functions
(e.g., itaconic acid, anhydride or lower esters
thereof) and preferably, in an alpha~ beta-position to
both of the carboxy functions of the alpha, beta-
dicarboxylic acid ~ anhydride or the lower alkyl ester
thereof (e.g., maleic acid, anhydride or lower alkyl
esters thereof). Normally, the carboxy functions of
these compounds will be separated by up to 4 carbon
atoms, preferably 2 carbon atoms.
A class of preferred alpha, beta-unsaturated
dicarboxylic acid, anhydrides or the lower alkyl
esters thereof, includes those compounds corresponding
to the ~ormulae-
o
R--C--C--OR' ~I)
R--C C OR'
O
o
R----C--C\ ~II)
R--C --Cl
~37~3
--13~
(including the geome~ric isomers ~hereo~ iOe., cisand trans) wherein each R is independen~ly hydrogen;
halogen (e~g. t chloro, bromo, or iodo); hydrocarbyl or
halogen-substituted hydrocarbyl of up to about 8
carbon atoms, preferably alkyl, alkaryl or aryl;
(preferably, at least one R is hydrogen); and each R'
is independently hydrogen or lower alkyl of up to
abou~ 7 carbon atoms ~e.g., me~hyl, ethyl, butyl or
h~ptyl). These preferred alpha, beta-unsaturated
dicarboxylic acids, anhydrides or alkyl esters thereof
contain a total carbon con~ent of up to about 25
carbon atoms, normally up to about 15 carbon atoms.
Examples include maleic anhydride; benzyl maleic
anhydride; chloro maleic anhydride; heptyl maleate;
citaconic anhydride; ethyl fumarate; fumaric acid;
mesaconic acid ethyl isopropyl maleate; isopropyl
fumarate; he~yl methyl maleate; phenyl maleic
anhydride and the like. These and other alpha, beta-
unsaturated dicarboxylic compounds are well known in
the art. of these preferred alpha, beta-unsaturated
dicarboxylic compounds~ maleic anhydride~ maleic acid
and fumaric acid and the lower alkyl esters thereof
are preferred. Interpolymers derived from mixtures of
two or more of any of these can also be used.
Suitable vinyl aromatic monomers of up to
about 12 carbon atoms which can be polymerized with
the alpha, beta-unsaturated dicarboxylic acids,
anhydrides or lower esters thereof are well known.
~he nature of the vinyl aromatic monomer is normally
not a critical or essential aspect of this invention
as these compounds serve primarily as a connective
moiety for the alpha~ beta-unsaturated compounds in
~LZ437~3
form~n~ the l~terpolymer. The vinyl ~romatic
compou~d~ include 3tyrene and ~3ub~ti~ut~d -~tyrene~
such a~ alpha-halo~yrene~, 10~Br alkyl-substitu~ed
~tyrenes ~uch as alpha-methyl~tyrene~, para-t~rt-
butylstyrenes, alpha-ethyl~yrene~, and para-lo~er
alkoxy ~tyrenes. ~ixtures of two ~r more vinyl
aromatic monomer~ can ~e u8edO
Particularly preferred ~i~ed alkyl esters ~f
this invention are tho~e of interpoly~er~ made by
reacting maleic acid, or anhydride or the lower est~rs
thereof with s~yrene. Of the~e particularly preferred
~nterpolymer~ tho~e which are m~de of mal~ic anhydride
and tyrene and have a RSV in the range of about 0.3
to about 0O9 are especially u~e~ul, Of thes~ latter
preferred interpolymers~ copolym~r~ of maleic
anhydride and styrene having a molar ratio of the
maleic anhydride to ~tyrene of about 1:1 are
~specially prefexred. ~hey can be prepared according
to me~hod~ known in the art9 a~ for example, fre~
radical initiated ~eO~., by benzoyl pero~ide~ solution
p~lymerization. E~ample~ of Ruch suitable
interpolymerization technigues are described in ~.S.
Patents 2,938,016; 2,980,653; 3,085,994; 3,342,787;
3,418,292; 3,451,979; 3r536~461 3,558,570; 3,702,3~g;
and 3,723,375. Other preparative tec~miques are known
în the art.
The molecular weight ti.e., RSV) of such
interpolymers can be adjusted to the range required in
this .invention, if necessary, according to
~..
~37~3
-15-
conventional techni~uesy e.g., control o~ the reaction
conditions.
From the standpoint o utili~y, as well as
for commercial and economical reasons,
nitrogen-containing esters in which the ester group
~a) has from 8 to 24 aliphatic carbon atoms,
preferably about 12 to about 18 carbon atomsO and most
preferably about 14 or 15 carbon atoms, the ester
group ~c) has from about 3 ~o about 5 carbon atoms,
and the carbonyl polyamino group (b) is derived from a
prim~ry-aminoalkyl-substituted tertiary amine,
particularly heterocyclic amine, are preferred.
Specific examples of the carboxylic ester group
containing at least 8 carbon atoms, i.e., the (OR)
group of the ester radical ~i.e., -(O)(OR)) include
isooctyloxy, decyloxy, dodecylo~y, tridecyloxy,
tetradecyloxy, pentadecyloxy, octadecyloxy,
eicosyloxy, tricosyloxy, tetracosyloxy, etc. Specific
examples of low molecular weight groups include
methyloxy, ethylo~y~ n-propyloxy, iso-propyloxy,
~-butyloxy, sec-butyloxy~ iso-butyloxy, n-pentyloxy,
neo-pentyloxy, n-hexyloxy, cyclohexyloxy,
cyclopentyloxy, 2-methyl-butyl~l-oxy, 2,3~dimethyl-
butyl-l-oxy, etc. In mos~ in~tances, alkvxy groups of
suitable size comprise the preferred high and low
molecular weight ester groups. Polar substituents may
be present in such ester groups~ Examples of polar
substituents are chloro, bromo, ether, nitro, etc~
Mixtures of the foregoing carboxylic ester groups can
also be provided. For example, mixtur s of ester
groups having from 12 to 18 carbon a~oms have been
found to be useful. Mixtures of ester groups having
3793
--16--
14 and 15 carbon atoms have been found to be
particularly advantageous~
Examples of the carbonyl polyamino group
include those derived from polyamino compound~ having
one pr~mary or secondary amino group and at least one
mono-functional amino group such as tertiary-amino or
het~rocyclic amino group. Such c:ompounds may thus be
tertiary-amino substituted primary or ~econdary amines
or other substituted primary or secondary amines in
which the substituent is derived from pyrroles,
pyrrolidones, caprolactam~, oxazolidones, oxazoles,
thiazoles, pyrazoles, pyrazolines, imidazoles,
imidazolines, thiazine~, oxazines, diazines,
oxycarbamyl, thiocarbamyl, urac~ls, hydantoins,
thiohydantoins, guanidines, ureas, sulfonamides,
phosphoramides, phenolthiazines, amidines, etc.
Examples of such polyamino compounds include
dimethylamino-ethylamine, dibutylamino~ethylamine,
3-dimethylamino-l-propylamine, 4-methylethylamino-
l-butylamine, pyridyl-ethylamine~ N-morpholino-
ethylamine, tetrahydropyridylethylamine, bis-
(dimethylamino)propylamine, bis-(diethylamino)
ethylamine, N,N-dimethyl-p-phenylene diamine,
piperidyl~ethylamine~ l-aminoethyl pyrazole,
l-(methylamino)pyrazoline, l-m~thyl-4-aminooctyl
pyrazole, l-aminobutyl imidazole, 4-aminoethyl
thiazole, 2-aminoethyl triazine, dimethylcarbamyl
propylamin~, N-methyl-N-aminopropyl acetamide,
N-aminoethyl succinimide, N~methylamino maleimide,
~-aminobutyl-alpha-chlorosuccinimide, 3-aminoethyl
uracil, 2-aminoethyl pyridine, ortho-aminoethyl-N,N-
dimethyl~enzenesulfamide, N-aminoethyl phenothiazine,
~ ~ ~ 3~ ~ 3
-17-
N-aminoethylacetamidine r l-aminophenyl-2-methyl-
imidazoline, N-methyl-N-aminoethyl-S-ethyl-dithio-
carbama~e, etc. Preferred polyamino compoundæ include
the N-aminoalkyl-sub~tituted morpholines such as
N-3-aminopropyl morpholine. For the mo~t part, the
polyamino compounds are those which contain only one
primary-amino or secondary-amino group and, preferably
at least one tertiary-amlno group. The tertiary amino
group is preferably a heterocyclic amino group. In
some instances polyamino compounds may contain up ~o
about 6 amino groups although, in most instance~, they
contain one primary amino group and either one or t~o
tertiary amino group~. The po'yamino compounds may be
aromatic or aliphatic amines and are preferably
heterocyclic amine~ such as amino-alkyl-su~tituted
morpholinesl piperazine~ pyridines, benzopyrroles,
picolines, quinolines, pyrroles, pyrrolidinones, etc.
Th~y are usually alkyl amines having from 4 to about
30 carbon a oms, preferably from ~ to about 12 carbon
atoms. Polar substituents may lik wise be presen~ in
the polyamin~s.
In one embodiment, the nitrogen-containing
esters of the inven~ion (B-l) contain at least the two
polar groups ~a) and ~b) derived from the carboxy
groups of the interpolymer, and in another embodiment~
the nitrogen-containing esters are mixed esters
containing at least one of each of polar groups (a),
(b) and (c).
The nitrogen~containing esters of the
invention (B-l) are most conveniently prepared by
first esterifying the carboxy-con~aining interpolymer
with the higher molecular weight alcohol or a mix~ure
~2437~
-18-
of the high and lo~ molecular weight alcohols to
convert at least about 50~ and no more than about 99%
of the carboxy radicals of the interpolymer ~o ester
radicals, and than neutralizi~g the remaining carboxy
radicals with a polyamino compound such as described
above. When the mixed esters are prepared, the molar
ratio of the high molecular weight alcohol to the low
mol~cular weight alcohol used in the process should be
within the range of from about 2:1 to about 9:1. In
- most instances the ratio will be from about 2.5:1 to
about 5~ ore than one high molecular ~eight
alcohol cr low molecular weight alcohol may be used in
the process. Commercial alcohol mixtures such as the
so-called Oxo-alcohols which comprise, for example,
mixtures of alcohols having from 8 to about 24 carbon
atoms also may be used. A particularly useful class
of alcohols are the commercial alcohol mixtures or
mixtures of commercial alcohol mixtures comprising
octyl alcohol, decyl alcohol, d~decyl alcohol,
tridecyl alcohol, tetradecyl alcohol, pentadecyl
alcohol, hexadecyl alcohol~ hep~adecyl alcohol and
octadecyl alcohol. Commercial alcohol mixtures of
tetradecyl and pentadecyl alcohols are particularly
useful. Several ~uitable sources of these alcohols
mixtures are the technical grade alcohols sold under
A the ~ "~ odols" b~ Shell Chemical Corporation
and under the ~ "Alfols n by Continental Oil
Company. Other alcohols useful in the process are
illustrated by those which, upon esterification, yield
the ester groups exemplified above.
The extent of es~erification, as indicated
previously, may range from about 5~% to about 99%,
~;~437~313
--19--
pre~erably about 75% to about 97~, conversion of the
carboxy radical~ of the int~erpolymer to ester
radicals. In a preferred embodiment, the degree of
esterification is about 95~..
The esterif ication can be accomplished simply
by hea~ing the carboxy-containing interpolymer and the
alcohol or alcohol mixtures undar condi ions typical
for effecting esterification. Such conditions usually
include, for exam~le, a ~empera~ure of at least about
80C, preferably rom abou~ 1~0C to about 350C,
provided that the; temperature be below the
decomposition point of the reaction mixture, and the
removal of water of esterification as the reaction
proceedsO Such conditions may optionally include the
use of an excess of the alcohol reactant so as to
~acilitate esterification, the use of a solvent or
diluent such as mineral oil, toluene, benzene~ xylene
or the like and an esterification catalyst such as
toluene sulfonic acid, sulfuric acid, aluminum
chloride, boron trifluoride-triethylamine,
hydrochloric acid, ammonium sulate, phosphoric acid,
sodium methoxide or the like. These conditions and
variations thereof are well known in the art.
A particularly desirable method of effecting
esterification when mixed esters are desired involves
first reacting the carboxy-containing interpolymer
with the relatively high molecular weight alcohol and
then reacting the par~ially esterified interpolymer
with the relatively low molecular weight alcohol. A
variation of this technique involves initia~iny the
esterification with the relatively high molecular
weight alcohol and before such esteri~ication is
~437~3
-20-
complete, the relatively low molecular weight alcohol
is introduced into the reaction mass so as ~o achieve
a mixed esterification. In either event it has been
discovered that a two-step es~lerificatisn process
whereby the carboxy-containing interpolymer is first
esterified with the relatively high molecular weigh~
alcohol so as to convert from about 50% to about 75%
of the ~arboxy radicals to ester radicals and then
with a relatively low molecular weight alcohol to
achieve the finally desired dPgree of es~erification
results in products which have unusually beneficial
viscosity properties.
The esteriied interpolymer is then treated
with a polyamino compound in an amount so as to
neutralize substantially all of the unesterified
carboxy radicals of the interpolymer. The
neutralization is preferably carried out at a
temperature of a~ least about 80C, often from about
120C to about 300C, provided that the temperature
does not exceed the decomposition point of the
reaction mass. In mos~ instances the neutralization
temperature is between about 150C and 250C. A
slight ~cess of the stoichiometric amount of the
pnlyamino compound is often desirable, so as to insure
substantial completion of neutralization, i.e., no
more than about 2-5% of the carboxy radicals initially
present in the interpolymer remained unneutralized.
The following e~amples are illustrative of
the preparation of the nitrogen-containing esters and
mixed esters (B-l) used in the present invention.
Unless otherwise indicated, all parts and percentages
are by weight.
33
-21-
EXAMPLE l-B 1
A styrene-maleic interpolymer is obtained by
preparing a solution of styrene ~536 parts) and maleic
anhydride (505 par~s~ in toluene ~7585 parts) and
contacting the solution at a temperature of 99-101C
and an absolute pressure of 480~535 mm. Hg. with a
catalys~ solution prepared by dissolving ben20yl
peroxide (2.13 parts) in toluene (51.6 parts~. The
catalyst solution is added over a period of 1..5 hours
with the temperature maintained at 99~101C. Mineral
oil (2496 parts~ is added to the mixture. The mixture
is maintained at 99-101C and 480-535 mm. ~9. for 4
hours. The resulting product is a slurry of the
interpolymer in the solven~ mixture~ The resulting
interpolymer has a reduced specific vi~cosi~y of 0.42.
A toluene slurry ~2507 parts), having 11.06%
solids and 88.94~ volatiles, of this maleic
anhydride~styrene interpolymer ~eodol 45 (631 par~s),
a product o~ Shell Chemical Company identified as a
mix~ure of C14 and C1s linear primary alcohols,
mineral oil (750 parts), and Ethyl Antio~idant 733
(4.2 parts), a product of Ethyl identified as an
isomeric mixture of bu~yl phenols, ~r~ charged to a
vesselO The mixture i~ heated ~ith medium agita~ion
under nitrogen purge at 0.5 standard cubic feet per
hour until the temperature reaches 115C. 70% methane
sulfonic acid catalyst in water (10.53 parts) is added
dropwise over a period of 20 minutes. Nitrogen purge
is increased to 1.0 standard cubic feet per hour and
temperature is raised by removal of toluene-water
distilla~e. The mix~ure is maintained at a
temperaturP of 150C for five hours under a nitrogen
~Z~3793
--22--
purge o~ 0.1-0.2 standard cubic feet per hour.
Additional methane sulfonic acid solution (15.80
parts) is added to the mixture over a period of 15
minutes. The mixture is maintai.ned at 150C for 3.5
hours. The degree of esterification is 95/08%. ~mino
propylmorpholine (35.2 parts) i5 added to the mi~ture
dropwise over a period of 20 minutes. The mixture is
maintained at 150 C for an additional 30 minutes then
cooled with stirring. The mixture is stripped from
50C to 141C at a pressure of 102 mm. Hg. then
permitted to cool. At a tempera~ure of 100C, mineral
oil ~617 parts) is added. Cooling is continued to
60C, diatomaceous earth ~36 par~s) is added and the
mixture is heated to 100C. The mixture is maintained
at 100-105C for one hour with stirring and then
filtered to yield the desired product.
EXAMPLE 2-B-l
The procedure of Example l-B-l is repeated
with the exception that both ~eodol 45 (315~4 parts)
and Alfol 1218 ~312.5 parts), a product of Continental
Oil Company identified as a mixture of synthetic
primary straight chain alcohols having 12 to 18 carbon
atoms, are initially charged, rather than the 631
parts of Neodol 45 which were included in the initial
charge in Example 2.
EXAMPLE 3-B-l
A toluene slurry (1125 parts), having 13.46%
solids and 86.54% vola~iles, of the maleic
anhydride/s~yrene interpolymer of Example l-B-l
mineral oil (~50 parts) and Neodol 45 ~344 parts) are
charged to a vessel. The mixture is heated with
medium agitation under nitrogen sweep of 0.5 standard
~2~37~3
-23-
cubic ~eet per hour until the temperature reaches
110C. Para-toluene sulfonic acid (8055 parts) in
water (9 parts3 is added dropwise over a period of 24
minutes~ The tempera~ure of the mixture is increased
to 152C by removing toluene-water distillate. The
temperature is maintained at 152-.156C under nitrogen
sweep of 0.5 standard cubic feet per hour until the
net acid number indicates that esterification is at
least 95% complete. Aminopropylmorpholine (15.65
par~s) i~ added dropwise over a period of 10 minutes,
The temperature of th~ mi~ture is maintained at 155C
for one hour and then cooled under a ni~rogen sweepO
Ethyl Antioxidant 733 ~1.48 parts) is added to the
mixture. The mixture is s~rippPd at 143 C and 99 mm~
Hg. pressure. The mixture is cooled under nitrogen
sweep. Mineral oil is added to provide a total of 63%
dilution. Ethyl Antioxidant 733 (1.79 parts) is added
and the mixture is stirred for 30 minutes. The
mixture is heated to 60C while stirring with a
ni~rogen ~weep of 0.5 standard cubic feet per hour.
Diatomaceous earth (18 parts) is added to the
mixture. The mixture is heated to 90C. The
temperature of the mixture is maintained at 90-100C
for one hour and then filtered through a pad of
diatomaceous earth tl8 parts) in a heated funnel to
yield the desired product.
EXAMPLE 4-B-l
The procedure of Example 3-B-l is repeated
with the exception that both Neodol 45 tl72 parts) and
Alfol 1218 tl69 parts) are provided in the initial
charge, rather than the 344 parts of ~eodol 45
provided in Example 4~
37~3
-24-
EXAMPL~ 5-B-1
The product of Example 1 B 1 ~101 parts),
~eodol 91 (56 parts), a product o~ Shell Chemical
Company identified as a mixture of Cg, Cl~, and
Cl1 alcohols, TA-1618 ~9~ parts), a product of
Procter & ~am~le iden~ified as a mixture of C16 and
Clg alcohols, ~eodol 25 (62 parts), a produc~ of
Shell Chemical Company identifled as a mixture of
C12~ C13~ and Cls alcohols, and toluene
(437 parts) are charged to a vessel. The vessel is
stirred and the contents are hea~ed. Me~hane sulfonic
acid (5 parts) is added to the mixture. The mixture
is heated under reflux conditions for 30 hours~
Aminopropyl morpholine (12.91 parts) is added to the
mixture. The mixture is heated under reflux
conditions for an additional 4 hours. Diatomac~ous
earth ~30 parts) and a neutral paraffinic oil (302
parts) are added to the mixture which is then
stripped. The residue is filtered to yield 497.4
parts of an orange-brown ~iscous liquid.
EXAMPLE 6-B-l
The product of Example l-B-l (202 parts),
Neodol 91 (112 parts), TA 1618 ~184 par~s), Neodol 25
(124 parts) and toluene (875 parts) are charged to a
vessel. The mix~ure is heated and stirred. Methane
sulfonic acid (10 parts) is added to the mixture which
is then hea~ed undar reflux conditions for 31 hours.
Aminopropyl morpholine (27.91 parts) is added to the
mixture which is then heated under reflux conditions
for an additional 5 hours. Dia omaceous earth (6Q
parts) is added ~o the mixture which is then stripped,
600 parts of polymer remaining in the vessel. A
37~3
~25-
neutral par~ffinic oil (600 parts) is added to the
mixture which is ~hen homogenizled. The mixture is
filtered ~hrough a heated funnel ~o yield 1063 parts
of a clear orange-brown viscous liquid.
EXAMPLE 7-B-l
The produ~t of Example l-B-l (101 parts),
Alfol 810 (50 parts), a p~oduct of Continental Oil
Compa~y identified as a mi~ture of Cg and Cl~
alcohols, TA-1618 ~92 parts), Meodol 25 (62 parts) and
toluene ~437 parts) are charged to a vessel~ The
mixture is heated and stirr~d. Methane sulfonic acid
(5 parts~ is added to the mixture which is heated
under reflux conditions for 30 hours. Aminopropyl
morpholine tl5.6 parts) is added to the mixture which
is then heated und~r reflux conditions for an
additional 5 hours. ~he mi~ture is stripped to yield
304 parts of a yellow-orange viscous liquid.
Diatomaceous earth (30 parts) and a neutral paraffinic
oil (304 parts) are added to the mixture which is.~hen
homogenized. The mixture is filtered through a heated
funnel to yield 511 parts of a clear a~ber viscous
liquid.
EX~MPLE 8-B 1
A toluene slurry (799 parts) of a maleic
anhydride/styrene interpolymer ~17.82% polymer) is
charged to a vessel. The reduced specific viscosity
of the interpolymer if 0.69. The vessel is purged
with nitrogen while stirring the contents for 15
minutes. Alfol 1218 (153 parts), Neodol 45 (156
par~s) and 93% sullfuric acid (5 parts) are added to
the mixture~ Toluene ~125 parts) is ~hen added to the
mixture. The mi~ture is heated at 150-156C for 18
~43793
--2~--
hours. Aminopropyl morpholine (103 parts) i5 added to
the mixture which is ~hen heated for an addi~ional on
hour at 150 C O The mixture is cooled to 80 C O Ethyl
Antioxidant 733 (1.84 parts) is added to the mixture.
The mixture is stripped at 143 C and 100 mm~ ~g .
Mineral oil ~302 parts) and Ethyl An~ioxidant 733 (218
parts) are added and the mixture is stirred. The
temperature of the mixture is maintained at 90C and
is blown wi~h nitroyen~ Diatomaceous earth (44 parts)
is added to ~he mix~ure which is stirred for one hour
at 90-95C. The mixture i~ filtered through
diatomaceous earth to yield 1312 parts of a dark-brown
clear viscous liquid.
EXAMPLB 9-B-l
A toluene slurry (973 part~) of a maleic
anhydride/styrene interpolymer (17.2~ solids) is
charged to a vessel. The reduced specific viscosity
of the interpolymer is 0.69. The slurry is stirred
and blown with nitrogen at 0~75-1.0 standard cubic
feet per hour for 20 minutes. Neodol 45 (368 parts)
and 80% sulfuric acid (6.84 parts) are added to the
mi~ture. ~he mixture is heated at 150-156C for 23
hours. Additional 80% sulfuric acid (1 part~ and
toluene (50 parts) are added after approximately the
first 9 hours of heating. Additional 80% sulfuric
acid t2.84 parts) is added after about the first 13
hours of heating. Additional Neodol 45 (18.4 parts~
and 80% sulfuric acid (2 parts) are added after about
the flrst 16 hours of heating. Aminopropyl morpholine
(2.33 parts) is added to the mixture which is heated
at 153 154C for an additional one hour and 20
minutes. Ethyl Antioxidant 733 (2.06 parts) is added
~37~3
--27--
to the mixture. The mi~ture is stripped at 142C and
100 mm. ~g. Mineral oil t481 parts) is added to the
mixture. Ethyl Antioxidant 733 (2.5 parts) is added
to the mix~ure while ~he m.Lxture is stirred.
Diatomaceous earth (25 parts) is added to the
mixtuxe. ~he temperature of the mixture is maintainsd
at 70C for 45 minutes and th~n heated to 110C,
Diatomaceous earth (25 parts) is added to the
mixture~ The mixture is filtered through diatomaceous
earth to yield the desired product.
EXAMP~E 10-B-1
A toluene and mineral oil slurry (699 parts)
containing 17.28% solids of a maleic anhydride/styrene
interpolymer (reduced specific viscosity of 0.69),
Neodol 45 (139 parts), Alfol 1218 (138 par~s), Ethyl
Antioxidant 733 (2.9 part~) and ~oluene t5C parts) are
charged to a vessel. The mixture is heated under a
nitrogen purge at 0.5 standard cubic feet per hour.
70% me~hane sulfonic acid (3.9 parts) is added
dropwise over a period of 9 minutesO The mixture is
heated under reflux conditions for 35 minu~esO
Toluene ~51 parts) is added to the mix~ure which is
then heated for an additional 3 hours 15 minu~es under
reflux conditions. 70% methane sulfonic acid (3
parts) is added dropwise over a period of 3 minu~es.
The mixture is heated under reflux conditions for 3
hours 15 minutes. 70% methane ulfonic acid t3.9
parts) is added dropwise over a perîod of 12 minutes.
The mixture is heated at 150-152C for 3 hours 45
minutes. Aminopropyl morpholine tl4.3 parts) is added
to the mixture dropwise over a period of 15 minutes.
The mixture iq maintained at a temperature o~
~24~793
-28-
149-150C for an additional 30 minutes. The mixture
is stripped at 140C and 100 mm. ~g. The mixture is
cooled to 501::. Mineral oil ~338 parts) and
diatomaceous earth (19 parts) are added to the
mix ure. The temperature of the mixture is maintained
at 100 105C for 1.5 hours and then filtered through
additional diatomaceous ear~h (18 parts) ~o yield the
des i red p roduc t .,
EXA~PLE 11--B-l
styr~ne-maleic interpolymer is obtained by
preparing a solution of styrene ~16.3 parts by weight)
and maleic anhydride (12.9 par~s) in a ben~en -~oluene
solution (270 parts; weight ratio of b~nzene:toluene
being 66.5:33.5~ and contac~ing the solution at 86C
in nitrogen atmosphere for 8 hours with a catalyst
solution prepared by dissolving 70~ benzoyl peroxide
~0.42 part) in a similar benzene-toluene mixture (2,7
part~)~ The resulting product is a thick slurry of
the interpolymer in the solvent mixture~ To the
slurry there is added mineral oil (141 parts) while
the solvent mixture is being distilled off at 150C
and then at 150C/200 mm. Hg. To 209 parts of ~he
stripped mineral oil-interpolymer slurry tthe
interpolymer having a reduced specific viscosi~y of
0.72) there is add~d toluene (25.2 parts~, n-butyl
alcohol (4.8 parts), a co~nercial alcohol consisting
essentially of primary alcohols having f rom 12 to 18
carbon atoms (56.6 parts) and a commercial alcohol
consisting of primary alcohols having from 8 to 10
carbon atoms (10 parts) and to the resulting mixture
there is added 96% sulfuric acid (2.3 parts). The
mî~ure is then heated a~ 150-160C for 20 hours
~2~37~3
~2~-
whereupon water is distilled oi.f. An additional
amount of sulfuric acid ~0.18 part) together with an
additional amount of n-butyl alcohol ~3 part~) is
added and the esterification is continued until 9S~ of
the carboxy radicals of the polymer has been
esterifiedO To the esterified interpolymer, there is
then added aminopropyl morpholine (3.71 parts; 10~ in
excess of the ~toichiome~ric amount requi.red ~o
neutralize the remaining free carboxy radicals) and
the resulting mixture is heated to 150-160C/10 mm.
~g. ~o distill off toluene and any other volatile
component~. ~he stripped product is mixed with an
additional amount of mineral oil ~12 parts) and
filtered. The $iltrate is a mineral oil solution of
the nitrogen-containing mix~d ester having a nitrogen
content o~ 0.16-0.17~.
EXAMPLE 12-B-1
The procedure of Example ll-B-l is followed
except that the esteri~ication is carried out in two
steps, the first step being the esterification of the
styrene-maleic inkerpolymer with the commercial
alcohols having from 8 to 18 carbon atoms and the
second step being the further esterification of the
interpolymer with n-butyl alcohol.
EX~MPLE 13-B-l
The procedure of E~ample 11-B-l is followed
except that the esterification is carried out by first
esterifying the s~yrene~malPic interpolymer with the
commercial alcohols having from 8 to 18 carbon atoms
until 70% of the carboxyl radicals of the in~erpolymer
have been converted to e~ter radicals and thereupon
continuing the esterification with any yet~unreacted
~24~7~3
-30-
commercial alcohols and n-butyl alcohol until 95% of
the carbo~yl radicals of ~he int:erpolymer have been
converted to ester radicals.
EXAMPLE 14-B-l
The procedure of Example ll-B-l is followed
except that the interpolymer is prepared by
polymerizing a solution consisting of styrene t416
parts), maleic anhydride (392 parts) in benzene (2153
parts) and toluene t5025 parts) in the presence of
ben~.oyl peroxide (1.2 part~) at 65-106C. (The
resulting interpolymer has a reduced specific
viscosity o~ ~.45.)
EXA~PL~ 15-B-l
The procedure of Example ll-B-1 is followed
excep~ ~hat the styrene-maleic anhydride is obtained
by polymerizing a mixture of styrene (416 parts),
maleic anhydride (392 parts), benzene (6101 parts) and
toluene (2310 parts) in the presence of benzoyl
peroxide 11.2 parts) at 78 92C. (The resulting
interpolymer has a reduced speci~ic viscosity of
O .91 .)
EXAMPLE 16-B-l
The procedure of Example ll-B-l is followed
except that the styrene maleic anhydride is prepared
by the following procedure: Maleic anhydride (392
parts) is dissolved in benzene (6870 parts). To t~is
mixture there is added s~yrene ~416 parts) at 76C
whereupon benzoyl pero~ide (1.2 parts) is added. The
polymerization mixture is maintained at 80-821C for
about 5 hours. (The resulting interpolymer has a
reduced specific viscosity of 1.24.)
37~3
-31-
EXAMPLE 17-B~l
The procedure of Example 16-B-l is followed
except that aceton2 (1340 parts) is used in place of
benzene as the polymerization solvent and that
azobis-isobutyronitrile (0.3 part) is used in place of
benzoyl peroxide as a polymerization catalyst~
EXAMPLE 18-B-l
The procedure of Example ll-B-l is followed
except that toluene sulfonic acid (3.5 parts) is used
in place of sulfuric acid as the esterification
catalyst,
EXAMPLE l9-B-l
~ he procedure of Example ll-B-l is followed
except that phosphoric acid (2.5 parts) is used in
place of sulfuric acid as the e~terification catalyst~
EXAMPLE 2~B-l
The procedure of Example ll-B-l is followed
except that dodecyl alcohol (0.7 mole per carboxy
equivalent of the styrene-maleic anhydride
in~erpolymer) is used in place of the alcohol mixtures
havin~ 8 to 18 carbon atoms and isobutyl~ alcohol (0.2
mole per carboxy equivalent o~ the interpolymer) is
used ~n place of n-bu~yl alcohol.
EXAMPLE 21~B-l
The procedure of Example ll-B-l is followed
except tha~ eicosyl alcohol (0.8 mole consumed per
carboxy equivalent of interpvlymer) is used in place
of the commercial alcohols having from 8 to 18 carbon
atoms and n-pentyl alcohol ~0.15 mole consumed per
carboxy equivalent of ~he interpolymer) is used in
place of the n-butyl alcohol.
~ ~37 ~ 3
-32-
~XAMPLE 22-B 1
The procedure o Example ll~B-l is followed
except that octyl alcohol (008 mole consumed per
carboxy equivalent of the interpolymer) is used in
place of the commercial alcohols having fro~ 8 to 18
carbon atoms, isopentyl alcohol (0.1 mole consumed per
carboxy equivalent of the interpolymer) is used in
place of the n-butyl alcohol, and N-aminoethyl and
.l-methyl-4-aminoethyl piperazine ~0.1 mole consumed
per carboxy equivalent of the interpolymer) is used in
place of aminopropyl morpholine~
EX~MPLE 23-B-l
The procedure of Example ll-B-l is followed
except ~hat dimethylamino-ethylamine is substituted
for the aminopropyl morpholine used on a molar basis.
EXAMPLE 24-B-l
The procedure of Example ll-B-l is followed
except that dibutylamino-propylamina is substituted
for the aminopropyl morpholine on a molar basis.
EXAMPLE 25-B-l
An interpolymer (O.86 carboxyl equivalent) of
styrene and maleic: anhydride (prepared from an equal
molar mixture of styrene and maleic anhydride and
having a reduced specific viscosity of 0.67-0.68) is
mixed with mineral oil to form a slurry, and then
esterified with a commercial alcohol mixture (0.77
mole; comprising primary alcohols having from 8 to 18
carbon a~oms) at 150-160C in the presence of a
catalytic amount of sulfuric acid until abou~ 70% of
the carboxyl radicals are converted to ester
radicals. rhe partially esterified interpolymer is
then further esteri~ied with n-butyl alcohol (0.31
~2~3793
--33--
mole) until 95% of the carboxyl radicals of ~he
interpolym~r are converted to the mix~d ester
radicals, The esterified interpol~ymer is then treated
with aminopropyl morpholine (slight excess of the
stoichiometric amount to neutrali.~e the free carboxyl
radicals of the interpolymer) at 150-160C until the
resulting product is substantially neutral (acid
number of 1 to phenolphthalein indicator). The
resulting product is mixed with mineral oil so as to
form an oil solution containing 34% of the polymeric
product.
EXAMPhE 26-B-l
The procedure of Example ll-B-l is followed
except that the aminopropyl morpholine used is
replaced on a chemical equivalent basis with
N-aminoethyl pyrrole.
~XAMPLE 27-B~l
The procedure of Example ll-B-l is followed
except that the aminopropyl morpholine used is
replaced on a chemical e~uivalent basis with
N-aminopropyl thiopyrrolidone.
EXAMPLE 28 B-l
The procedure of Example ll-B-l is followed
except that the aminopropyl morpholine used is
replaced on a chemical equivalent basis with
N-aminoethyl caprolactam.
EXAMPLE 29-B-l
The procedure of Example ll-B-l is followed
except tha~ the aminopropyl morpholine used is
replaced on a chemical equivalent basis with
N-aminophenyl oxazolidone.
,
~ ~ ~37~ 3
-34-
EX~MPLE 30-B-l
The procedure of Example 11 B-l is followed
except that the aminopropyl morpholine used is
replaced on a chemical equ:Lvalent ba~is with
4-aminoethyl thiazole.
E~MPLE 31-B~l
The procedure o~ ~am~:Le ll-B l is followed
exc~pt that the aminopropyl morpholin~ used is
replaced on a chemical equivale~t basis with
2-cyclohexyl triazine.
~XAMPLE 32-B-l
The procedure of Exam~le 11-~-1 is followed
exc~p~ that the aminopropyl morpholine used is
replaced on a chemical equivalent ba~is with
l-aminoethyl-2-heptadecylimidazoline.
EXAMPLE 33-B-l
The procedure of E2ample ll-B-l i5 followed
except that the aminopropyl morpholine used is
replaced on a chemical equivalent basis with
N-aminooctyl succinamide.
EXAMPLE 34-B-l
~The procedure of Example ll~B-l is followed
:except that the aminopropyl morpholine used is
replaced on a chemical equivalent bas is with
3 -aminobutyl u rac il .
EXAMPLE 35--B--1
The procedure of E~ample ll-B-l is followed
except that the aminopropyl morpholine used is
replaced on a chemical e~uivalent basis with
4-aminobutyl pyridine.
The transmi3sion fluids of the inven~ion
prefer~bly contain from about 0.1~ to about
~437~3
-35~
10~ by weight of component (B-l). The hydraulic
fluids of the invention preferably contain from about
0.05% to about 10%, more preferably ~rom about 0.1~ to
about 4% by weight of component tB~l).
The polymeric compositions of the present
invention also may include as componen~ (B)~ at least
one oil-solubl~ acrylate polymerization product of at
least one ester of the formula
~2=C(X)-COOR (II~)
wherein X is hydrogen or an alkyl or aryl group, and R
is a monovalent hydrocarbyl group containing more than
4 carbon atoms, or an ether derivative of said
hydrocarbyl group. For convenience, these acrylate
polymerization products will be identified herein as
componen~ (B-2).
Compounds of the above types represented by
Formula III whose oil-soluble polymers are
particularly useful for ~he present purpose are the
esters of acrylic acid or of its alpha-alkyl or
alpha~aryl substitution products and monohydric
alcohols containing at least four c rbon atoms such as
the butyl, amyl, hexyl, heptyl, oc~yl, nonyl, decyl,
lauryl, myricyl, cetyl, or octadecyl esters of acrylic
acid, alpha-me~hacrylic acid, alpha-phenylacrylic
acid, and other alpha-substituted homologues of
acrylic acid. These esters are preferably those of
the normal, primary sa~urated aliphatic alcohols r but
the analogous esters of the corresponding secondary or
of the branched-chain alcohols can also be usedO The
esters of the above acids of the acrylic series with
~$43793
--36--
monohydric aromatic, hydroaromatic, or ether alcohols
may also be used, such as the benzyl, cyclohexyl,
amylphenyl, n-butyloxyethyl esters.
These esters are employed in the form of
their oil-soluble polymers which should be as free as
possible of unpolymerized monomeric es~ers, since the
presence of unsaturated or volatile compounds in the
transmission fluid may be objectionable.
Unpolymerized esters can be removed by hea~ing the
polymer or the mixture of lubricating oil and polymer
in vacuo to a temperature sufficiently high to
volatilize the monomeric ester, but preferably the
polymerization should bP carried out as completely as
possible and the latter operation dispensed with.
The most effective polymers for the present
purpose, from the point of view of availability and
power of increasing ~he desirable properties are the
polymerized esters of acrylic acid or
alpha-methacrylic acid and monohydric, saturated,
primary aliphatic alcohols containing from 4 to 22
carbon atoms in ~he molecule. The esters possessing
the highest solubility and stability in oils and
giving the highest viscosi~y index are those derived
from the straight chain, nohydric primary, saturated
aliphatic alcohols containing 8 to 20 carbon atoms
such as the normal octyl, lauryl, cetyl, or octadecyl
esters. ~hese esters need not be pure, but may be
pr~pared from technical mixtures of the higher
aliphatic alcohols such as are obtained commercially
from the catalytic high pressure hydEogenation of
fatty acids or their esters.
.:
~37~3
--37--
~ he acrylate ester ~onomers are prepared by
3tandard e~terificat~on techniques through the
reaction of acryli~ acid or ~ubstituted acrylic acid
~uch as ~ethacrylic ac~d with an alcohol or alcohol
mlxture ~uch a~ with technical grades of long chain
pri~ary alcohols. The~e co~nercially available
alcohol~ are mixtures of n-alkanols of variou~ cha~n
lengths contalning between abou~ 4 and 22 carbon~ in
1:he alkyl group. Several suitable sources of the~e
~lcohol mixtures are the technical grade ~lcohols sold
under the ~radename ~Neodols" by Shell Ch~mical
Corporatioxl and under the tradename WAlfols'' by
Continental Oil Company.
Any anîa:ture of two or more polymers of the
esters set forth herein can also be used. These may
be ~imple mi:ctures of such polymers~ or they may be
co polymers which can be prepared by polymerizing a
mixture of two or more of the monomeric esters.
The polymers are prepared for use in the
present process, preferably by heating ~he monomeric
esters at 70~100 C in the presence of small amounts o~
polym~rization-inducing catalyst~ ~uch a6 pero~ides or
ozonides. These are referred to as ~heat
polymerization product~-. Other catalysts may,
however~ be used, .such as anhydrous halides o~
: polyvale~t or amphoteric metals, according to the
known art of polymerizing vi~yl compounds.
Procedures for the preparation of acrylate
polymers (B-2) useful in thi~ inven~ion are known in
the art such as in U.S. Patents 2~100r993; 3~5~8r7367
and 3, 67 9 ,644 .
`
~,1
~ ~ ~3
-38-
The hydraulic fluids of the invention
preferably con~ain from about 0.1% to about 10%, more
preferably about 0.5% to about 5% by weight of
component (B-2).
The compo~itions of the present invention
also may, and preferably do, contain (C) an effec~ive
amount of at least one low t mperature visco~ity-
reducing liquid organic diluentO Generally, the
diluent (C) i~ characterized as having a viscosity at
40 C of les~ ~han 4 centistokes, and more prefe~ably a
viscos ity at 40 ~C of between about 2 . 0 and about 3 ~ 8
centistokes .
The dilu~nt ~C) may be any organic diluent
having the desired viscosity reducing characteristics,
and such diluents may be natural or synthetic
diluents~ Among the preferred organic diluents
exhibiting the desirable viscosity.characteris~ics are
the naphthenic oils, certain synthetic oils and
alkylated aromatic materials. ~he naphthenic oils
which are useful in the compositions of the invention
are those derived from naphthenic crudes such as found
in the Louisiana area. The viscosity of such
naphthenic oils at 40 C generally is 12ss than 4
centistokes aIld more generally within the range of
~rom about 3.0 to about 3.B centistokesc At 100C,
the viscosity of the desirable naphthenic crudes is
within the range of about 0 . 8 to about 1. 6
centistoke~. Such naphthenic oils have been found to
provide excellent fluidity characteristics to the
polymeric compositions of the invention~ particularly
at low temperature.
~2~37g3
3g-
The synthe~ic oils useful as diluent (C) are
those having a viscosity at 40C of from about 2.0 to
3.8 ~entistokes and preferably between about 2.0 and
3.0 centistokes. Examples of such oils include the
esters of dicarboxylic acids ~e.g., phthalic acid,
succinic acid~ alkyl succinic acids, azeleic acid,
malonic acid~ wi~h a variety of alcohols including,
or example, butyl alcohol~ dodecyl alcohol, etc~ The
~ynthetic oils, especially the ester.types, which are
useful as diluent (C) are described in more detail
below.
The alkylated aromatic materials that are
par~icularly useful as the diluent (C) in the
hydraulic fluid compositions of the invention. These
alkylated aroma~ic materials are preferably mono- or
di- (more prefer~bly mono-) substituted benzenes
wherein the substituent~ are hydrocarbon-based groups
of abou~ 8 to about 30, preferably about 10 to abou~
14 carbon atomsO An example is a commercially
available mixture of alkyla~ed benzenes containing a
2% maximum of <Clo, a 10% maximum of C10-12~
70-90% of C13_14, and a 5% maximum o:E ~C14
hydrocarbon groups.
The amou~t of low temperature viscosity
reducing liquid organic diluent included in the
compo~itions of the present invention is an amount
which is effective to reduce the viscosity of the
composition to the desired level at low temperatures,
particularly at temperatures below 0C~ According}y,
the amount of diluent ~C) included in the polymeric
compositions of the invention will depend upon the
amounts and relative amounts of components ~A) and ~s)
present 1~ the composition, the proparties of the
particular diluent, and the ViRCosity characteristics
~;2437~3
-4~-
desired in the final product. Generally, the weight
ratio of diluent (C) to the mixture of components ~A)
and (B) will be in the range of about 5:1 to about
1:5. In the case of transmission fluid~, the diluent
tC) is pre~erably pre~nt a~ a level of from about 1%
to about 90% by weight~ With hydraulic fluids, the
diluent (C) is preferably present at a level o~ ~rom
about 1% to about 35%, more preferably from abou~ 2%
to about 10% by weight.
The compositions of this invention comprising
mixtures of components (A), (B) and ~C) described
above are useful in a variety of lubricating
compositions formulated for a variety of u~es. In
particular, ~he compositions of this invention are
useful in the formulation of tran~mission fluids
(i~e., both automatic and manual transmission fluids)
and hydraulic fluids exhibiting improved and desirable
low temperature characteristics. The composi~ions of
khis invention provide excellent low temperature
fluidity.
Furthermore, the transmis~ion fluids and
hydraulic ~luids of the pre~en~ invention have the
une~pected combination of high shear stabili~y,
e~cellent low ~emperature fluidity, and 100C
viscosity equivalent to conventionally formulated
f luids .
When the compositions of the present
invention comprising components (A), (B) and (C) are
to be u~ilized in lubricating oil formulativns, and in
par~icular, in transmi~sion fluids and hydraulic
fluids/ th~ compo~i~ions of the present invention will
contain, in addition to components tA), tB) and (C),
other additives which impart certain desirable
~Z~37~3
--41--
proper . iesto the transmission fluids and hydraulic
fluids.Such additives include, for example,
detergentsand dispersants of the ash producing or
a hless type, corrosion- and oxidation-inhibiting
agents, pour point depressing agents~ extreme pressure
agents, anti-wear agents, rust-inhibi~ing agents, seal
swell agentsr friction modifiers~ color stabilizers
and anti-~oam agents.
The ash-producing de~ergents are exemplified
by oil-soluble neutral and basic salts of alkali or
alkaline earth metals with sulfonic acids, carboxylic
ac ids, o r organic phosphorus acid~ characterized by at
least one direct carbon-to-phosphorus linkage such as
those prepared by ~he treatment of an olefin polymer
~e.g., polyisobutene having a molecular weight of
1000) with a phosphorizing agen~ such as phosphorus
trichloride, phosphorus heptasulfide, phosphorus
pentasul;Eider phosphorus trichloride and sulfur, white
phosphoru and a sulfur halide, or phosphorothioic
chloride . The mo~t commonly used sal ts of such acids
are those of sodium, potassium, lithium, calcium,
magnesium, strontium and barium.
The term "basic salt" is used to designate
metal sal~s wherein the metal is present in
stoichiometrically larger amounts than the organic
acid radical. The commonly employed methods for
preparing the basic salts involve heating a mineral
oil solution o~ an acid with a stoichiometric excess
of a metal neutralizing agent such as the metal oxide,
hydroxide, carbonate, bicarbonate, or sulfide at a
temperature of abou~ 50C and filtering the resulting
37~3
--~2--
mass. The use of a Npromoter" in the neutrallzation
step to aid the incorporation of a large excess of
metal likewise is known~ Examples of compounds useful
as the promoter include phenolic substances ~uch as
phenol, naph hol, alkylphenol, thiophenol, sulfuriz~d
alkylphenol, and conden~ation produc~s of formaldehyde
with a phenolic substance; alcohols such as methanol,
2-propanolt octyl alcohol, cellosolve, carbitol,
ethylene glycol~ stearyl al ohol, and cyclohexyl
alcohol; and amines such as aniline, phenylenediamine,
phenothiazine~ phenyl-beta-naphthylamine, and
dodecylamine. A particularly effective method for
preparing the basic salts comprises mixing an acid
with an excess of a basic alkaline earth metal
neutralizing agent and at least one alcohol promoter,
and carbonating the mixture at an elevated temperature
such as 60-200~C.
Ashless detergent~ and dispersants are so
called despite the fact that, depending on its
constitution, the dispersant may upon combustion yield
a non-volatile material such as boric oxide or
phosphorus pentoxide; however, it does not ordinarily
contain metal and therefore does not yield a metal-
containing ash on combustion. Many types are known in
the art, and any of them are suitable for use in the
lubricant compositions of thi~ inv~ntion. The
following are illustrative:
(1) Reaction products of carboxylic acids
(or derivatives thereof) containing at least about 34
and preferably at least about 54 carbon atoms with
nitrogen containing compounds such as amine, organic
hydroxy compounds such as phenols and alcohols, and/or
.. ,
~ ~ ~37 ~ 3
-43-
basic inorganic materîals. Examples of these
~carboxylic dispersants~ are de,scribed in British
Patent 1,306,529 and in many U.SO patents including
the following: .
3,1~3,603 3,351,55~ 3,541,012
3,18~474 3,381,022 3,543,678
3,~15~7~7 3,39~,141 3,54~,68
3,21g,666 3,415,750 3,567t637
3,271,310 3,~33,7~4 3,574,101
3,272,746 3,444,170 3,576,743
3,281,357 3,448,048 3,630,904
3,306,908 3~448rO49 3,632,510
3,311,558 3,451,~33 3,632t511
3,316,177 3 r454 ,607 3,697~428
3,340,281 3,467,6~8 3,725,441
3,341,542 39501,405 4,234,435
3,346,493 3,522,179 Re 26,433
(2) Reaction products of relatively high
molecular weight aliphatic or alicyclic halides with
amines, preferably olyalkylene polyamines. These may
be characterized as ~amine dispersants" and ~xamples
thereof are de~cribed for example, in the following
UO~- patents:
3,275,554 3,454,555
3,438,757 3,565,804
(3) Reaction products of alkyl phenol~ in
which ~he alkyl group contains at least about 30
carbon atoms with aldehydes ~especially ~ormaldehyde)
and amines (especially polyalkylene polyamines~, which
may b~ characterized as ~Mannich dispersants~, The
material~ described in the following U.S. patents are
illustrative:
~37~3
2,459rll2 3,442,808 3,591,598
2 s 962 9 D.~2 3, 4~8 ~ 047 3 ~ 600, 372
2,984,550 3,454,497 3,634,515
3,036,003 3,D~59,661 3,649,229
3 ,166 ,516 3 ,461,172 3 i~97 ,57~
3,236,770 3,493~520 3r725~277
3,355,~70 3,539~633 3,7~5,480
3,368,97~ 3,558"743 3,726,882
3,~13,34~ 3,5~,629 3,g~0,569
(4) Productæ obtained by post treating the
carboxylic, amine or Mannich dispersants with such
~eagents as urea, thiourea, carbon disulfide,
aldehydes, ketones, carbo~ylic acids, hydrocarbon-
substituted succinic anhydrides, nitriles, epoxides,
boron compounds, phosphorus compounds or the like,
Exemplary materials of this kind are described in the
following U.S. patents:
3,036,003 3,282,955 3r493~520 3,639,242
3,087,936 3,31~,619 3, 502, 677 3,649,~29
3,2009107 3,3~6,569 3,513,093 3,649,659
3,216,~36 3,367,943 3r~3319~5 3,65~,836
3,~54,02S 3,373,111 3,539,633 3,697,574
3j256,185 3,403,102 37573,010 3,702,757
3,278,55~ 3,442~08 3,~79,450 3,703,53
3,280,234 3,455,831 3,591,598 3,704,308
3,281,428 3, 455,~32 ~,600,372 3,7~8,422
~5) Interpolymers of oil-solubilizing
monomers such as decyl m~thacrylate, vinyl decyl ether
and high molecular weight ole~ins with monomers
containing polar substituents, e.g~, aminoalkyl
acrylates or acrylamides and poly-(oxyethylene)
substituted acryla~es. These may be characteri~d as
~ ~3~ ~ 3
-45- ~
"polymeric dispersants~ and examples thereof are
disclosed in the following U.S. patents:
3,329,658 3,666,730
3,449,250 3,687,849
3,519,5fi5 3,702,300
The above-noted patents are incorporated by reference
herein for thei~ disclosures of ashless dispersants.
The deterge~ts/dispersant~, when employed,
are used at a level of from abou~ 0.01~ to about 20%
by w~ight, or higher depending on the nature of the
dispersant. Usually, such detergents/dispersants are
employed at a level of from about 0.1% to about 15% by
weight based on the total weight of the trans~nission
fluid.
Extreme pxe~sure agents and corrosion- and
oxidation-inhibiting agents which may be included in
the compositions of the inventio~ are exemplified by
chlorinated aliphatic hydrocarbons such as chlorinated
wax; organic sulides and polysulfides such as benzyl
disulfide, bis(chlorobenzyl)disulfide, dibutyl
tetrasulfide, sulfurized methyl ester of oleic acid,
sulfurized alkylphenol, sulfurized dipentene, and
sulfurized terpene; phosphosulfurized hydrocarbons
such as the reaction product of a phosphorus sulfide
with turpentine or methyl oleate, phosphorus esters
including principally dihydrocarbon and trihydrocarbon
phosphi~es such as dibutyl phosphite, diheptyl
phosphite,dicyclohexyl phosphite, pentylphenyl
phosphîte,dipentylphenyl phosphi~e, tridecyl
phosphite~ distearyl phosphite, dimethyl naphthyl
phosphite,oleyl 4-pentylphenyl phosphite,
polypropylene ~molecular weight 500)-substituted
~2~3793
~-~6--
phenyl phosphite, diisobutyl-substitutPd phenyl
phosphite; metal thiocarbamates, such as zinc
dioctyldithiocarbamate, and barium heptylphenyl
dithiocarbamate, Group II metal phosphorodithioates
such as zinc dicyclohexylphosphorodithioate, zinc
dioctylphosphorodithioate~ barium di~heptylphenyl)-
phospborodithioate, cadmium dinonylphosphorodithioate,
and the zinc salt of a phosphorodithioic acid produced
by the reaction of phosphorus pentasulfide wi h an
equimolar mixture of isopropyl alcohol and n-hexyl
alcohol~
Many of the above-mentioned extreme pressure
agents and corrosion o~idation inhibitors also serve
as anti-wear agents. Zinc dialkylphosphorodithioates
are a well known example.
Anti-wear agents that are particularly useful
in the hydraulic ~luid compositions of the invention
are those anti-wear agents made by contacting a salt
of a phosphorus acid of the formula (~10) 2PSSH,
wherein each R' is independently a hydrocarbon-based
group, or the phosphorus acid precursors thereof with
at least one phosphite of the formula (R"O)3P,
wherein R" is a hydrocarbon-based group, under
reaction condi~ions at a temperature of about 50C to
about 200C. Rl is preferably an alkyl group of about
3 to about 50 carbon atoms, and R" is preferably
aromatic. Th~ salt is preferably a zinc salt, but can
be a mixed salt of at least one of said phosphorus
acids and at least one carboxylic acid. These
anti-wear agents are described more fully in UOS.
Patent 4,263,150, which is incorporated herein by
reference~ Th~se anti-wear agents as well as the
3793
--~7--
anti~wear agents referred to above can be provided in
the hydraulic fluid compositions of the invention at
levels of about 0.1~ to about 5~, preferably about
0.25% to about 1% by weight based on the total weight
of said fluid compositions.
The oxidation inhibi~ors ~hat are particu-
larly useful in the hydraulic fluid compositions of
the invention are the hindered phenols ~e.g.,
2,6-di-~t-butyl)phenol); aromatic amines (eO9- r
alkylated diphenyl amines); alkyl polysulfides,
selenides; boxates (e.g., epoxide/boric acid reaction
products); phosphorodithioic acidsr esters and/or
salts; and ~he dithiocarbamate (e.g., zinc dithio-
carbamates). These o~idation inhibitors as well as
the oxidation inhibitors discussed above are
preferably present in the hydrauli~ fluids of the
invention at levels o~ about 0.05% to about 5%r more
preferably about 0.25 ~o about 2% by weight based on
the total weight of such comqpositions.
~ he rust-inhibitors ~hat are particularly
useful in the hydraulic fluid compositions of the
invention are the alkenyl succinic acids, anhydrides
and estersr preerably the tetrapropenyl succinic
acids, acid/esters and mixtures thereof; metal
(preferably calcium and barium) ~ulfonates; the amine
phosphates; and the imidazolines. These rust-
inhibitors are preferably present in the hydraulic
fluids of the invention at levels of about 0.01% to
about 5%, preferably about 0.02% to about 1% by weight
based on the total weight of said fluids.
Pour point depressants may be included in the
compoqitions described herein. The use of such pour
~ ~37~ 3
point depre~ant in oil ba~ed compogition~ to impr~ve
low temperature propertles of oil-based compositiDn~
iR ~ell known in th~ ar~O See, for e~ample, page 8 of
~ubricant Add$tive~ by C~V. Smalheer and R~ ~ennedy
5mith (Leziu~-~ile~ Co. publishers, Claveland, Ohio,
196~).
~ xample3 of u~eful pour point d~pres~ants are
polymethacrylate~; polyacrylate~; polyacry}amides;
condensation products of haloparaffin wa~s and
aromatic compounds; vinyl carboxylate polymers; and
terpolymers ~f d~alkylfumarates, vinyl esters of fatty
acid~ and alkyl vlnyl e~hers. Pour polnt depressant~
useful for the purpos~s of thi~ lnveAtion, tech~iques
for their preparation and their uses are de~cribed in
.S. Patents 2~387,501; 2,015,748; 2,655,479;
1,815,0~2~ 2,191,~98; 2,6~746; 2,721,877; 2,7~1,878;
and 3,250,7150
Anti-foam agent~ are u~d to reduce or
prevent the formatio~ o ~table foam. Typical
anti-foam agent~ include ~ilicone~ or organic
polymers. Additional anti-foam compo~itions are
described in ~Foam Control Agents", by Elenty T. Rerner
tNoyes Data Corporation, 1976), pages 125-162.
When additional additives are used with the
composition~ o~ the present invention in formulating
transmis~ion fluid and hydraulic fluid compositions,
the additional additives are used in concentrations in
which they are normally employed in the art. Thu~,
th~y will generally be used in a concentra~ion o~ from
about 0.001~ up ~o about 25~ by weight of the total
compo~ition, depending, of cour~e, upon the nature of
3793
--4~--
the additive and the nature of the automatic
transmi3sion fluid composition.
The transmission fluid and hydraulic fluid
compositions of the present invention may, of course,
be prepared by a variety of methods known in the art.
~n~ convenient method is ~o combine the composition of
the present invention comprising components ~A), (B) r
and ~C) described above and the additional additives
in the form of a concentrated solution or
O substantially stable dispersion ~i.e., an ad~itive
concentrate3 to a su~ficient amount of a base oil
which may be an additional a~ount of the diluent (C)
described above or any other natural or synthe~ic oil
normally used in the preparation of such transmission
fl~ids or hydraulic fluids to form the desired final
transmission fluid or hydraulic fluid composition.
Such concentrates contain the additives in proper
amounts so as to provide the desired concentration of
each additive in the final automatic txansmission
fluid or hydraulic fluid composition when blended with
a predetermined amount of a base oil.
As mentioned above; the compositions of the
present invention comprising components (A~, ~B) and
(C) and other optional and desirable additives may be
blended with additional diluent such as component ~C)
or other natural and synthetic base oils.
The base oils used in preparing the
transmission fluids and hydraulic fluids of the
invention can be natural oils or synthetic oils.
Natural oils include animal oll~ and vege~able oils
~e.g~, castor oil, lard oil) as well as mineral
~;~43793
--50--
lubricating oils such as liquid petroleum oils and
solven~-treated or acid-treated mineral lubricating
oils of the paraffinic9 naphthenic or mixed
paraffinic-naphthenic t~pes. Oils of lubricating
visco~ity derived from coal or shale are also useful.
Syn~he~ic lubricating oils include hydrocarbon oils
and halosub~tituted hydrocarbon oils such as
polymerized and interpolymerized olefins (e.g.,
polybutylenes, polypropylenes, propyleneiso~utylene
copolymers, chlorinated polybut~lenes, etc.);
poly(l-hexenes), poly(l-octenes), poly(l-aecenes),
etc~ and mixtures thereof, alkylbenzenes ~e.g.,
dodecylbenzenes, ~etradecylben-~enes, dinonylben~enes,
di-(2-ethylhexyl1-benzenes, etc.); polyphenyls (e.g.,
biphenyls, terphenyl~, alkylated polyph~nyls, etc.);
alkyla~ed diphenyl ethers and alkylated diphenyl
sulfides and the derivatives, analogs and homologs
thereof and the like.
Alkylene oxide polymers and interpolymers and
derivatives thereof where the terminal hydroxyl groups
have been modified by esterification, etherifica~ionr
etc., constitute another class of k~own synthetic
lubricating oils that can ba used. These are
exemplified by the oils prepared through
polymerization of ethylene oxide or propylene oxide,
the alkyl and aryl ethers of these polyoxyalkylene
polymers (e.g., methylpolyisopropylene glycol ether
having an average molecular weight of about 1000,
diphenyl ether of polyethylene glycol having a
molecular weight of about 500-1000, die~hyl ether of
polypropylene glycol having a molecular weight of
about 1000-1500, etc.~ or mono- and polycarboxylic
3793
--51--
esters thereof~ for example~ the acetic acid esters,
mixed C3-C$ fatty acid . esters, or the C130xo
acid diester of tetraethylene glycol.
Another suitable class of synthetic
lubricating oils that can be used comprises the esters
of dicarboxylic acids (e~g., phthalic ac~d, succinic
acid, alkyl succinic acids, alke~yl 9UCCi~iC aGidS,
maleic acid, azelaic acid~ suberic acid, sebacic acid,
fumaric acid, adipic acid, linoleic acid dimer,
malonic acid, alkyl malonic acids, alkenyl malonic
acids~ etc.~ with a variety of alcohols ~e.g., butyl
alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl
alcohol, ethylene glycol, diethylene glycol monoether,
propylene glycol, etc.~ 5pecific examples of these
esters include dibutyl adipate, di~2-ethylhexyl)
sebaca~e, di-n-hexyl fumarate, dioctyl sebacater
diisooctyl azelate, diisodecyl azelate, dioctyl
phthalatet didecyl phthalate, dieicosyl sebacate, the
2-ethylhexyl diester of linoleic acid dimer, the
complex es~er formed by reacting one mole of se~acic
acid ~ith ~wo mole of tetraethylene glycol and two
moles of 2-ethylhexanoic acid and the lik~.
Esters useful as synthetic oils also i~lcude
those made from Cs to C12 monocarbo~ylic acicls and
polyols and polyol ethers such as neopentyl glycol,
trimethylol propane, pentaery~hritol, dipentaery-
thritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-,
polyaryl-, polyalkoxy-t or polyaryloxy-siloxane oils
and silica~e oils compri~e ano~her useful class of
synthetic lubrican~s ~e.~., tetraethyl silicate,
tetraisopropyl silicate, tetra-(2-ethylhexyl3silicate,
375~3
--52--
tetra-~4-methyl-he~zyl)silicate~ tetra-~p-tert-butyl-
phenyl)~ilicate, hexyl~(4-methyl-2-pentoxy)disiloxane,
poly(methyl)siloxanes, poly~met.hylphenyl)siloxanes,
etc.). Other synthetic lubricating oils include
liquid esters of phosphoru ~-ontaining acids (e.gO,
tricresyl phospAate, ~rioctyl phosphate, diethyl ester
of decane phosphonic acid, e~c.), polymeric tetrahy-
drofurans and the like.
Unrefined, refined and rarefined oils, either
natural or syn~hetic (as well as mixture~ of two or
more of any of these) of the type disclosed herein-
above can be used in the concentra~es o ~he ~resent
invention. Unre~ined oils ar~ those obtained directly
from a natural or synthetic source without further
purification treatment. For example, a shale oil
obtained directly from retorting operations, a
petroleum oil obtained directly from primary
distillation or ester oil obtained directly from an
esterification process and used wi~hout fur~her
treatment would be an unrefined oil. R~fined oils are
imilar to the unrefined oils except they have been
further treated in one or more purification steps to
improve one or more properties. Many such
purification techniques are known ~o those skilled in
the art such as solvent extraction, secondary
distillation, acid or base extraction; filtration,
percolation, etc. Rerefined oils are obtained by
processes similar to tho~e used to obtain refined oils
applied to refined oils which have been already used
in service. Such rerefined oils are also known as
reclaimed or reprocessed oils and often are
additionally processed by tec.hniques directed to
removal of spent additives and oil breakdown products.
3~793
--53--
The following exampl~s illustrate the
compositions of the present invention. Unless
otherwise indicated, all parts and percentages are by
weight.
EX~MPLE A
A composition is prepared which comprises 35
parts by weight of a polyisobutylene having a number
av~rage molecular weight of 900 and 5 parts of a
nitrogen- and boron-containing compound of Example
l-B-l.
EXAMPLE B
A composition suitable for the formation of
an automatic transmission fluid is prepared which
comprises 35 parts of a polyisobutylene having a
number average molecular weight of 900, 5 parts of the
product of Example l-B-l and 30 parts of a naphthenic
hydrocarbon oil having a viscosity a~ 40C of about
3.5 centistoke~.
EXAMPLE C
A composition suitable for use in the
prepara~ion of automa~ic transmission fluids is
prepared comprising 35 parts of a polyisobutylene
having a number average molecular weight of about 900,
5 parts of the product of Example l-B-l, 29 parts of a
commercially available naphthenic oil having a
viscosity at 40~C of about 3.5 centistokes, 9.5~ parts
of the reactio~ product of polyisobutenyl succinic
anhydride with ethylene polyamine and carbon
disulfidP, 1.67 parts of a ~eal sweller prepared as in
U.S. Patent 4,029,587, and 1.33 parts of silicone
anti-foam agentO
~437~3
--54--
Exampl es of hyd raul i c ~1 u id f o rmulat ions o f
the invention are indicated in the table below. In
the following table, all numerical value~ are in parts
by weight.
lL. E _E_
100 ~eutral Mineral C)il 9202 88.17 91.11
Product of Example l-B-l 1.17 1.8 1.35
Polyi~obutylene (Mn=1400) 4.,24 6.52 4089
A Alkylate 230~ta produc~ of Mon-
santo identif ied as an alkylated
benzene having a molecular weight
of about 260) 1.05 1.61 1.21
Acryloid~150 ~a product of Rvhm
& ~aas identif ied as a meth-
acryla e copolymer) 0.052 0.081 0.060
~6
Acryloid 156 (a product of Rohm
& ~aas identif ied as a meth~
acrylate copolymer) 0.155 0.23~ 0.179
Zinc di(2-ethylhexyl)
dithiophosphate ~.371 0.53 0.371
Sodium petroleum sulfonate OrO506 o.a3 0.0506
Ant iox idan~ 7 3 2 ( p roduct o f
Ethyl identified as alkylated
phenol) 0.151 0.18 0.151
~olad 370 (product of ~etro-
lite identified as a solut~on
of a polyglycol in aromatic
hydrocarbons) 0.01 0O008 0.01
Sulfuriæed calcium ~alt of
dodecyl phenol 0.05 0.07 0.05
Tolyltriaæole 3~00165 0.001 0,00165
Acrylate ~rpolymer derived ~rom
2-ethylhexyl acrylate, ethyl
acrylate and vinyl acetate 0.015 --- O.OlS
Diluent oil 0.48 0.76 0.569
~ ~r~ k
~29L37~3
While the invention has been described herein
with respect to it~ preferred embodiments and
illu~trated by the presentation of specific examples,
it is to be understood that various modifications
thereof will be apparen~ to those skilled in the art
upon reading the specificationO I~ is intended that
such modifications are within the scope of the
invention which is limited only by the appended
claims.
