CA1243793A - Polymeric compositions, oil compositions containing said polymeric compositions, transmission fluids and hydraulic fluids - Google Patents

Abstract

Title: POLYMERIC COMPOSITIONS, OIL COMPOSITIONS
CONTAINING SAID POLYMERIC COMPOSITIONS, TRANSMISSION FLUIDS AND HYDRAULIC FLUIDS

ABSTRACT OF THE DISCLOSURE
Polymeric compositions 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 aromatic monoolefin, and (B-1) at least one nitrogen-containing ester of a carboxy-containing interpolymer, 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-1) and B-2). The polymeric compositions of the invention also may contain (C) an effective amount of at least one viscosity-reducing liquid organic diluent such as a naphthenic oil or an alkylated aromatic material.
Polymeric compositions of the present invention are useful as additives in transmission fluids (both automatic and manual) and hydraulic fluids, and the transmission fluids and hydraulic fluids containing the polymeric compositions of the present invention exhibit improved shear stability while maintaining desired high and low temperature viscosity characteristics.

Description

~!L2~3~3 --1~

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 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 (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 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 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 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 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~

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 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 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.

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 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 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 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 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~

~24~793 149-150C 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~.

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 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 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 ~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 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 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 .

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 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 ~ 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 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 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 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 --~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 --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 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 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 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 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 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.

Claims (63)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A polymeric composition comprising a mixture of (A) at least one oil-soluble polymer which is a homo-polymer of a non-aromatic mono olefin having at least three carbon atoms, or a copolymer of said non-aromatic mono-olefin with an aromatic mono-olefin, said polymer having a number average molecular weight of about 500 to about 100,000, and (B-1) at least one nitrogen containing ester of a carboxy-containing interpolymer derived from at least two monomers, one of said monomers being (i) an aliphatic olefin or a vinyl aromatic monomer, and the other of said monomers being (ii) at least one alpha, beta-unsaturated aliphatic carboxylic acid, anhydride or ester thereof, said interpolymer having a reduced specific viscosity of from about 0.05 to about 2, said nitrogen-containing ester being characterized by the presence within its polymer structure o. the following polar groups which are derived from the carboxy groups of said interpolymer;
(a) at least one carboxylic ester group having at least 8 aliphatic carbon atoms in the ester group, (b) at least one carbonyl-polyamino group derived from reacting a carboxy group of said interpolymers with a polyamino compound having one primary or secondary amino group and at least one tertiary amino or heterocyclic amino group.

2. The polymeric composition of claim 1 wherein the molar ration of (a):(b) is from about 85:15 to about 99:1.

3. The polymeric composition of claim 1 wherein (A) is a homopolymer and is derived from a C3-C20 olefin.

4. The polymeric composition of claim 3 wherein the homopolymer is derived from a C4-C8 alpha-olefin.

5. The polymeric composition of claim 4 wherein the homopolymer is derived from propene or a butene.

6. The polymeric composition of claim 5 wherein the polymer has a number average molecular weight of about 750 to about 10,000.

7. The polymeric composition of claim 1 wherein the monomer (i) is selected from the group consisting of ethylene, propylene, isobutene and a styrene.

8. The polymeric composition of claim 6 wherein monomer (i) is a styrene.

9. The polymeric composition of claim 1 wherein the monomer (ii) is at least one of maleic acid or anhydride, itaconic acid or anhydride, or acrylic acid or ester.

10. The polymeric composition of claim 1 wherein the monomer (ii) is maleic acid, maleic anhydride or a mixture thereof.

11. The polymeric composition of claim 1 wherein the carboxylic ester group (a) contains from about 8 to about 24 aliphatic carbon atoms.

12. The polymeric composition of claim 1 wherein the interpolymer is a styrene-maleic anhydride interpolymer having a reduced specific viscosity of from about 0.3 to about 1.

13. The polymeric composition of claim 1 wherein the carbonyl polyamino group (b) is derived from a primary-aminoalkyl-substituted tertiary amine.

14. The polymeric composition of claim 13 wherein the tertiary amine is a primary-aminoalkyl-substituted heterocyclic amine.

15. The polymeric composition of claim 1 wherein the weight ratio of (A):(B) is from about 20:1 to 1:10.

16. A polymeric composition comprising a mixture of (A) from about 0.1% to about 20% by weight of at least one oil-soluble homopolymer of a non-aromatic mono-olefin having at least three carbon atoms, said homopolymer having a number average molecular weight of from about 850 to about 10,000, (B) at least one nitrogen-containing ester of a carboxy-containing interpolymer derived from at least two monomers, one of said monomers being (i) an aliphatic olefin or a vinyl aromatic monomer, and the other of said monomers being (ii) at least one alpha, beta-unsaturated aliphatic carboxylic acid, anhydride or ester thereof, said interpolymer having a reduced specific viscosity of from about 0.05 to about 2, said nitrogen-containing ester being characterized by the presence within its polymer structure of the following polar groups which are derived from the carboxy groups of said interpolymer:
(a) at least one carboxylic ester group having at least 8 aliphatic carbon atoms in the ester group, (b) at least one carbonylpolyamino group derived from reacting a carboxy group of said interpolymer with a polyamino compound having one primary of secondary amino group and at least one tertiary amino or heterocyclic amino group; and (C) an effective amount of at least one low temperature viscosity reducing liquid organic diluent.

17. The composition of claim 16 wherein the diluent (C) is characterized as having a viscosity at 40° C. of less than four centistokes.

18. The composition of claim 16 wherein the diluent (C) is a naphthenic oil or a synthetic oil having a viscosity at 40° C. of from about 2.0 to about 3.8 centistokes.

19. The polymeric composition of claim 16 wherein the weight ratio of diluent (C) to the combination of (A) and (B) is from about 5:1 to about 1:5.

20. A polymeric composition comprising a mixture of (A) at least one oil soluble homopolymer of a nonaromatic mono-olefin having at least three carbon atoms, said homopolymer having a number average molecular weight of about 750 to about 50,000 and (B-1) at least one nitrogen-containing interpolymer derived from at least two monomers, one of said monomers being (i) an aliphatic olefin or a vinyl aromatic monomer, and the other of said monomers being (ii) at least one alpha, beta-unsaturated aliphatic carboxylic acid, anhydride or ester thereof, said interpolymer having a reduced specific viscosity of from about 0.05 to about 2 and said nitrogen-containing interpolymer being characterized by the presence within its polymer structure of at least one of each of the following polar groups which are derived from the carboxy groups of said interpolymer;
(a) at least one carboxylic ester group having at least 8 aliphatic carbon atoms in the ester group, (b) at least one carbonyl-polyamino group derived from reacting a carboxy group of said interpolymers with a polyamino compound having one primary or secondary amino group and at least one tertiary amino or heterocyclic amino group and (c) at least one carboxylic ester group having no more than 7 aliphatic carbon atoms in the ester group.

21. The polymeric composition of claim 20 wherein the molar ratio of (a):(b):(c) is about (60-90):(2-15):(10-30).

22. The polymeric composition of claim 21 wherein the homopolymer is derived from a C4-C8 alpha-olefin.

23. The polymeric composition of claim 22 wherein the homopolymer is derived from propene or a butene.

24. The polymeric composition of claim 23 wherein the polymer has a number average molecular weight of about 750 to about 10,000.

25. The polymeric composition of claim 20 wherein the monomer (i) is ethylene, propylene, isobutene or a styrene.

26. The polymeric composition of claim 25 wherein the monomer (i) is a styrene.

27. The polymeric composition of claim 20 wherein the monomer (ii) is at least one of maleic acid or anhydride, itaconic acid or anhydride, or acrylic acid or ester.

28. The polymeric composition of claim 27 wherein the monomer (ii) is maleic acid, maleic anhydride or a mixture thereof.

29. The polymeric composition of claim 20 wherein the carboxylic ester group (a) contains from about 8 to about 24 aliphatic carbon atoms, and the carboxylic ester group (c) contains from about 3 to about 5 carbon atoms.

30. The polymeric composition of claim 20 wherein the interpolymer is a styrene-maleic anhydride interpolymer having a reduced specific viscosity of from about 0.3 to about 1.

31. The polymeric composition of claim 20 wherein the carbonyl polyamino group (b) is derived from a primary-aminoalkyl-substituted tertiary amine.

32. The polymeric composition of claim 31 wherein the tertiary amine is a primary-aminoalkyl-substituted heterocyclic amine.

33. The polymeric composition of claim 20 wherein the weight ratio of (A) to (B) is from about 20:1 to about 1:10.

34. A transmission fluid composition having improved shear stability comprising (A) from about 0.1% to about 20% by weight of at least one oil-soluble homopolymer of a non-aromatic mono-olefin having at least three carbon atoms, said homopolymer having a number average molecular weight from about 850 to about 10,000, (B) at least one nitrogen-containing ester of a carboxy-containing interpolymer derived from at least two monomers, one of said monomers being (i) an aliphatic olefin or a vinyl aromatic monomer, and the other of said monomers being (ii) at least one alpha, beta-unsaturated aliphatic carboxylic acid, anhydride or ester thereof, said interpolymer having a reduced specific viscosity of from about 0.05 to about 2, said nitrogen-containing ester being characterized by the presence within its polymer structure of the following polar groups which are derived from the carboxy groups of said interpolymer:
(a) at least one carboxylic ester group having at least 8 aliphatic carbon atoms in the ester group, (b) at least one carbonylpolyamino group derived from reacting a carboxy group of said interpolymer with a polyamino compound having one primary or secondary amino group and at least one tertiary amino or heterocyclic amino group; and (c) from about 1% to about 90% by weight of at least one low temperature viscosity reducing organic diluent.

35. The transmission fluid of claim 34 wherein the homopolymer (A) is derived from a C4-C8 alpha-olefin.

36. The transmission fluid of claim 35 wherein the homopolymer is derived from a butene.

37. The transmission fluid of claim 36 wherein the homopolymer has a number average molecular weight of about 750 to about 10,000.

38. The transmission fluid of claim 34 wherein the monomer (i) in the nitrogen-containing ester (B) is ethylene, propylene, isobutene or a styrene.

39. The transmission fluid of claim 34 wherein the monomer (ii) in the nitrogen-containing ester (B) is at least one of maleic acid or maleic anhydride, itaconic acid or itaconic anhydride or acrylic acid or ester.

40. The transmission fluid of claim 34 wherein the carboxylic ester group (a) contains from about 8 to about 24 aliphatic carbon atoms, and the carboxylic ester group.

41. The transmission fluid of claim 34 wherein the interpolymer is a styrene-maleic anhydride interpolymer having a reduced specific viscosity of from about 0.3 to about 1.

42. The transmission fluid of claim 34 wherein the carbonyl polyamino group (b) is derived from a primary-aminoalkyl-substituted tertiary amine.

43. The transmission fluid of claim 34 wherein the carbonyl polyamino group (b) is derived from a primary-aminoalkyl-substituted heterocyclic amine.

44. The transmission fluid of claim 43 wherein the heterocyclic amine is an N-aminoalkyl-substituted morpholine.

45. The transmission fluid of claim 34 wherein the diluent (C) comprises at least some naphthenic oil.

46. A polymeric composition comprising a mixture comprising:
(A) an oil-soluble polymer selected from the group consisting of a homopolymer of a non-aromatic mono-olefin having at least three carbon atoms, and a copolymer of the non-aromatic mono-olefin with an aromatic mono-olefin, said polymer having a number average molecular weight of about 500 to about 100,000; and (B) which is a mixture containing both (B-1) and (B-2), wherein (B-1) is a nitrogen-containing ester of a carboxy-containing interpolymer derived from at least two monomers, one of said monomers being an aliphatic olefin or a vinyl aromatic monomer, the other of said monomers being (ii) at least one alpha, beta-unsaturated aliphatic carboxylic acid, anhydride or ester thereof, the interpolymer having a reduced specific viscosity of from about 0.05 to about 2, the nitrogen-containing ester being characterized by the presence within its polymer structure of the following polar groups which are derived from the carboxy group of the interpolymer:
(a) at least one carboxylic ester group having at least 8 aliphatic carbon atoms in the ester group, and (b) at least one carbonyl-polyamino group derived from reacting a carboxy group of said interpolymer with a polyamino compound having one primary or secondary amino group and at least one tertiary amino or heterocyclic amino group; and (B-2) is an oil-soluble acrylate polymerization product of at least one ester of the formula CH2-=C(X)-COOR (III) wherein X is hydrogen or an alkyl or aryl group, and R is a monovalent hydrocarbyl group containing at least four carbon atoms, or an ether derivative of said hydrocarbyl group.

47. The polymeric composition of claim 46 wherein (A) is a homopolymer and is derived from a C3-C20 olefin.

48. The polymeric composition of claim 47 wherein the homopolymer is derived from a C4-C8 alpha-olefin.

49. The polymeric composition of claim 48 wherein the homopolymer is derived from propene or a butene.

50. The polymeric composition of claim 49 wherein the polymer has a number average molecular weight of about 750 to about 10,000.

51. The polymeric composition of claim 46 wherein the weight ratio of (A):(B) is from about 20:1 to 1:10.

52. The composition of claim 51 wherein X is hydrogen or a methyl group, and R contains from about 8 to about 20 carbon atoms.

53. The composition of claim 46 wherein (B-2) is a mixture of esters derived from a mixture of alcohols.

54. The composition of claim 46 further comprising:
(C) an effective amount of low temperature viscosity reducing liquid organic diluent.

55. The composition of claim 54 wherein the diluent (C) is characterized as having a viscosity at 40° C. of less than four centistokes.

56. The composition of claim 55 wherein the diluent (C) is a naphtenic oil or a synthetic oil having a viscosity at 40° C. of from about 2.0 to about 3.8 centistokes.

57. The polymeric composition of claim 54 wherein the weight ratio of diluent (C) to the combination of (A) and (B) is from about 5:1 to about 1:5.

58. The polymeric composition as claimed in claim 46, further comprising an oxidation inhibitor selected from the group consisting of hindered phenols, aromatic amines, alkyl polysulfides, selenides, borates, phosphorodithioic acids, esters and salts thereof, and dithiocarbamates.

59. The polymeric composition as claimed in claim 58, wherein the oxidation inhibitor is present in an amount in the range of from about 0.05 to about 5% based on the total weight of the composition.

60. The polymeric composition as claimed in claim 59, wherein the oxidation inhibitor is present in an amount in the range of from about 0.25% to about 2% by weight based on the weight of the composition.

61. The polymeric composition as claimed in claim 58, further comprising a rust inhibitor selected from the group consisting of alkenyl succinic acids, anhydrides, and esters thereof, metal sulfonates, amine phosphates, and imidazolines.

62. The polymeric composition as claimed in claim 61, wherein the rust inhibitor is present in an amount in the range of from about 0.01% to about 5% by weight based on the weight of the composition.

63. The polymeric composition as claimed in claim 62, wherein the rust inhibitors are present in an amount in the range of from about 0.02% to about 1% by weight based on the weight of the composition.