FI89179C - Polymer compositions and transmission fluids and hydraulic fluids containing them - Google Patents

Abstract

Polymeric compositions 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

1 89179

Polymer compositions and transmission fluids and hydraulic fluids containing them

TECHNICAL FIELD OF THE INVENTION This invention relates to novel polymeric compositions, transmission fluids (i.e., automatic transmission and manual transmission fluids), and hydraulic fluids. More specifically, this invention relates to automatic transmission fluid compositions and hydraulic fluid compositions comprising the polymer compositions of this invention and characterized in that they have improved shear strength.

Background of the invention

Problems with the lubrication of automatic and manual transmissions and the operation of hydraulic fluid systems are familiar to those skilled in the art. For example, in lubricating gearboxes, proper fluid viscosity at both low and high temperatures is essential for successful operation. Good fluidity at Mata-20 temperatures facilitates starting in cold weather and ensures that the hydraulic steering system "shifts gears" correctly. The high viscosity at high temperatures ensures pumpability and satisfactory operation of transformers, valves, switches, gears and bearings.

In the operation of hydraulic fluid systems, proper fluid viscosity at both low and high temperatures is essential for successful operation. Maintaining viscosity at high temperatures 30 is an advantage in lubrication, contributing to laminar flow and reducing leakage. Good fluidity at low temperatures means that the control operation is fast, the heat loss is lower and the pressure drop is smaller.

These opposing fluidity requirements require- · · ·. 35 a product having the following properties: 2 89179 (A) retention of viscosity at high temperatures, (B) flowability at low temperatures and (C) shear strength.

5 For the production of lubricants with these properties, it has become common practice to add various chemicals to the oil. For example, to meet viscosity requirements, oils have been added to compositions that are characterized by a relatively small change in their viscosity as the temperature changes and are usually classified according to SAE standards for low temperature [e.g. -18 ° C (0 ° F)] and high temperature [e.g. 99 eC (210 ° F)]. As a result of the addition of such additives 15, lubricating oils are often referred to as "multigrade oils". It is generally accepted that such multi-stage lubricating oils have the desired properties, that they are functional even in the cold immediately after they have been put into service, and that they are able to continue to function satisfactorily in use when heated.

Although chemical compositions have been developed that improve the viscosity properties of lubricating oil, it is often desirable to improve the properties of low temperatures by including compositions that act as flow modifiers at low temperatures. Fluidity modifiers are generally capable of lowering the viscosity of lubricating oil at low temperatures by slowing the formation of unwanted microcrystalline waxes.

In addition to the above improvements, it is desirable, if not essential, that lubricant compositions specifically intended for use as transmission fluids and hydraulic fluids have shear strength.

35 Shear strength means that lubricating oils do not degrade or lose their desired viscosity properties due to the shear forces encountered during use. Lubricating oil compositions having the desired shear strength can generally be found to have a viscosity of about 85-95% of their initial viscosity after many hours of use (e.g., 100 hours). It has been found that many conventional viscosity index improvers commonly added to crankcase lubricating oils, such as high molecular weight polyisobutylene and polyacrylates, do not have the shear strength desired from the viscosity enhancing properties of transmission fluids and hydraulic fluids.

It has now been found that multistage lubricants with improved shear strength can be prepared utilizing the compositions of this invention.

These lubricants are particularly useful in providing transmission fluids and hydraulic fluids.

20 Summary of the Invention

The invention relates to a polymer composition useful in gear fluids and hydraulic fluids, characterized in that it contains (A) about 0.1 to 20% by weight of at least one non-aromatic monoolefin containing at least 3 carbon atoms. an oil-soluble homopolymer having a number average molecular weight of about 750 to 10,000; and (B1) about 0.05 to 10% by weight of a nitrogen-containing ester of a copolymer containing at least one carboxyl group, the copolymer being formed of at least two monomers, one of said monomers being (i) an aliphatic olefin monomer or a vinyl aromatic monomer, .•• .35 and one of said monomers being 4 89179 (ii) at least one α, β-unsaturated aliphatic carboxylic acid or anhydride or ester thereof, and said copolymer having a viscosity number of about 0.05 to 2, wherein the nitrogen-containing ester has a polymer-5 the structure includes the following polar groups derived from the carboxyl groups of said copolymer; (a) at least one carboxylic acid ester group containing at least 8 aliphatic carbon atoms in the ester group; (B) at least one carbonyl polyamino group obtained by reacting the carboxyl group of said copolymer with a polyamino compound containing one primary or secondary amino group and at least one tertiary amino or heterocyclic amino group; and (C) about 1-90% by weight of at least one low temperature viscosity reducing liquid organic diluent.

The polymer compositions 20 of this invention are useful as additives in transmission fluids and hydraulic fluids, and the transmission and hydraulic fluids of this invention have improved shear strength while maintaining the desired high and low temperature viscosity properties.

25 Detailed Description of the Preferred Embodiments

The first component (A) of the polymer compositions of the invention consists of at least one oil-soluble polymer which is a homopolymer of a non-aromatic monoolefin having at least three carbon atoms, said polymer having a number average molecular weight of about 750 to 10,000.

The fact that these polymers are characterized as oil-soluble does not necessarily mean that they are soluble in all base oils in all proportions. Rather, the polymers of mink are soluble in the base oils into which they are blended in sufficient quantities to classify the lubricant composition between SÄE 75W and SÄE 250.

The aforementioned homopolymers can be prepared from non-aromatic monoolefins containing at least three and preferably up to 20 carbon atoms by a variety of polymerization procedures known to those skilled in the art. It should be noted that as used herein, "homopolymer" means polymers made from monoolefins containing the same number of carbon atoms. Thus, polymers prepared from a mixture of 1-butene and isobutylene are butylene homopolymers within the meaning of this specification and claims. When they contain mainly units from one isomer, they may be termed polymers of that isomer, but such expression does not exclude the possibility that they contain smaller amounts of units from other isomers. The "polyisobutylene polyol" could thus contain units, 80% of which are derived from isobutylene, 15% from 1-butene and 5% from 2-butene.

Particularly preferred are homopolymers made from C3.20 monoolefins such as propylene, 2-butene, isobutene, 1-hexene, 3-decene, 4-tetradecene, etc. Even more preferred are homopolymers made from C4.8 -alphaolefins such as butene, isobutene, 1-pentene, 1-heptene, etc. The most preferred homopolymers are polymers made from propylene and 30 different butenes.

Methods such as Ziegler, cationic, free radical, anionic and emulsion polymerization, etc. can be used, as appropriate, to prepare these polymers. A particularly convenient technique for polymerizing such olefins for use in the present invention is polymerization using a Lewis acid catalyst such as aluminum chloride, boron trifluoride, titanium tetrafluoride or the like. These polymerization methods are known in the art and need not be described in more detail here.

Some polymers useful in the compositions of this invention include: polyisobutylene with an Mn of 1,400, poly (1-octene) with an Mn of 4,300, poly (3-heptene) with an Mn of 900, poly (1-eicose) -10 ni) with an Mn of 9,500, poly (1-nonene) with an Mn of 3,700, poly (2-methyl-1-pentene) with an Mn of 1,700, poly (5-ethyl-1-hexene ) with an Mn of 2,200 and poly (8-methyl-1-tetradecene) with an Mn of 1,900.

In general, it is preferred that the homopolymers used in the compositions of this invention, i. component (A), do not contain more than 5% unsaturation due to oxidation stability, based on the total number of covalent carbon-carbon bonds in the average molecule. Such unsaturation can be determined by many means known to those skilled in the art, such as infrared, NMR, etc. Even more preferably, these polymers do not contain any detectable unsaturation.

A particularly preferred polymer that meets all of the above requirements is polyisobutylene, although other polymers, such as polypropylene, may prove equally useful and preferred.

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 about 0.1 to 20% by weight, more preferably from about 2 to 10% by weight, of component (A).

The hydraulic fluid composition of the invention contains, in addition to components (A) (B-1) and (C), (B-2)

Il: 7 89179 0.1 to 10% by weight of at least one oil-soluble acrylate polymerization product formed from at least one

CH 2 = C (X) -COOR

Of the formula 5, wherein X is hydrogen or an alkyl or aryl group and R is a monovalent hydrocarbon group having at least 4 carbon atoms or an ether derivative of said hydrocarbon group.

As for the size of the ester groups, it is noted that the ester group corresponds to the formula -C (O) (OR) and that the number of carbon atoms in the ester group is thus the sum of the carbon atom contained in the carbonyl group and the group (OR).

The molar ratio of the polar groups (a) and (b) contained in the nitrogen-containing ester (B-1) is generally in the range of about 85:15 to 99: 1, and a particularly preferred ratio is 95: 5.

It should be noted that the chain mentioned as the carbonyl polyamino group 20 may be an amide, imide or amidine, and since all such chains are possible within the scope of this invention, the term "carbonyl polyamino" has been introduced as a convenient general term for polar groups (b). the definition. In a particularly preferred embodiment of the invention, the chain is an imide or mainly an imide.

Another important element of component (B-1) is the molecular weight of the copolymer containing kar-V: cocyl groups.

For convenience, the molecular weight is expressed by the "viscosity number" of the copolymer, which is a generally accepted means of expressing the molecular size of a polymeric substance.

As used herein, the viscosity number [using ly - .. 1 reduced RSV (reduced specific viscosity)) is the value obtained from the equation 35 RSV = Relative Viscosity - 1

Concentration according to β 89179, where the relative viscosity is determined by measuring the viscosity and the viscosity of acetone at 30 ± 0,02 ° C in a solution containing 1 g of copolymer in 100 ml of acetone. For the calculation by the above formula, the concentration is adjusted to 0.4 g of copolymer per 100 ml of acetone. The viscosity number, also known as intrinsic viscosity, as well as its relationship to the average molecular weight of the copolymer, are discussed in more detail in Paul J. Fory, Principles of Polymer Chemistry (1953 edition), starting at page 308.

Although copolymers having a viscosity number of about 0.05 to 1 are possible in the context of this invention, preferred copolymers are those having a viscosity number of about 0.2 or 0.35 to about 0.8 or 1. : tea. Particularly useful are copolymers having a viscosity number of about 0.35 to 0.5 or 0.65 to 0.75.

In the esterification reaction, it is possible to use mixtures of two or more compatible (i.e. unreacted), separately prepared copolymers, provided that each copolymer has an RSV as described above. As used herein and in the claims, the term "copolymer" thus means either one separately prepared copolymer or a mixture of two or more such copolymers. A separately prepared copolymer is one in the preparation of which the starting materials and / or reaction conditions are different from those in the preparation of the second copolymer.

Copolymers are copolymers of ε, β-unsaturated dicarboxylic acids or their derivatives or mixtures of two or more such and one or more vinyl aromatic monomers containing up to 12 to 35 carbon atoms, terpolymers II 89179 or other copolymers. Such dicarboxylic acid derivatives are derivatives which are polymerizable with a monoolefin compound and as such may be esters and anhydrides of acids. Copolymers of maleic acid-5 polyanhydride and styrene are particularly suitable, and copolymers having an RSV of about 0.3 to 1.8 (especially about 0.3 to 0.9) are preferred.

Suitable α, β-unsaturated dicarboxylic acids or their anhydrides or (lower alkyl) esters which can be used in the preparation of copolymers are those in which the carbon-carbon double bond is located in the α, β-position of at least one α, β-dicarboxylic acid or its anhydride or alkyl) ester relative to the carboxyl function (e.g. itaconic acid or its anhydride 15 or lower esters) and preferably in the α, β position relative to both carboxyl functions [e.g. maleic acid or its anhydride or (lower alkyl) esters]. Normally there are up to four carbon atoms between the carboxyl functions of these compounds, preferably two carbon atoms.

A group of preferred α, β-unsaturated dicarboxylic acids or their anhydrides or (lower alkyl) esters form compounds corresponding to the formula • and 0 '

II

r-c-C-OR '(I)

B

R-C-C-OR

II

0 30 R — ps> RCC "^ ·; · n 35 o 10 891 79 including their geometric isomers, i.e. the cis and trans isomers, in which each R is independently hydrogen, halogen (e.g. chlorine, bromine or iodine) ) or a carbon-hydrogen group having up to about eight carbon atoms or a halogen-substituted hydrocarbon group, preferably alkyl, alkaryl or aryl (preferably at least one R is hydrogen), and each R 'is independently hydrogen or lower alkyl having up to about seven carbon atoms (e.g. methyl, ethyl, butyl or heptyl).

These preferred α, β-unsaturated dicarboxylic acids or their anhydrides or alkyl esters contain a total of up to about 25 carbon atoms, usually up to about 15 carbon atoms. Examples are maleic anhydride, benzylmaleic anhydride, chloromaleic anhydride, heptyl maleate, citraconic anhydride, ethyl fumarate, fumaric acid maleate acid, mesaconic acid, ethyl isopropyl maleate, ethyl isopropyl maleate, ethyl isopropyl maleate. These and other α, β-unsaturated dicarboxylic compounds are known in the art. Of these preferred α, β-unsaturated dicarboxylic compounds, maleic anhydride, maleic acid and fumaric acid and their (lower alkyl) esters are preferred. Copolymers derived from mixtures of two or more such compounds may also be used.

Suitable vinyl aromatic monomers containing up to about 12 carbon atoms and polymerizable with α, β-unsaturated dicarboxylic acids or their anhydrides or lower esters are known. The nature of the vinyl aromatic monomer is not normally critical or an integral part of this invention, as these compounds act primarily as a linking moiety for α, β-unsaturated compounds in the formation of copolymers. Vinyl aromatic compounds include styrene and substituted styrenes, li il 89179 such as α-halostyrenes, (lower alkyl) substituted styrenes such as α-methylstyrenes, pt-butylstyrenes and α-ethylstyrenes, and p- (lower alkoxy). ) styrenics. Mixtures of two or more vinyl aromatic monomers may be used.

Particularly preferred mixed alkyl esters of this invention are those copolymers prepared by reacting maleic acid or its anhydride or lower esters with styrene. Of these particularly preferred copolymers, those made from maleic anhydride and styrene and having an RSV of about 0.3 to 0.9 are particularly useful. Of these latter preferred copolymers, copolymers of maleic anhydride and styrene having a molar ratio of maleic acid to styrene of about 1: 1 are particularly preferred. They can be prepared according to methods known in the art, such as, for example, free radical-initiated (e.g., benzoyl peroxide-initiated) solution polymerization. Examples of such suitable copolymerization techniques are described in U.S. Patent Nos. 2,938,016, 2,980,653, 3,085,994, 3,342,787, 3,418,292, 3,451,979, 3,536,461, 3,558,570, 3,702,300, and 3,723,375. These patents are incorporated herein by reference for their content in the preparation of copolymers containing maleic anhydride and styrene suitable. Other manufacturing methods are known in the art.

: Molecular weight of copolymers (ie

RSV) can be adjusted to the range required by this invention, if necessary, by conventional procedures, for example by controlling the reaction conditions.

For utility, as well as for commercial and economic reasons, nitrogen - containing esters in which the ester group (a) contains 8 to 24 aliphatics. 35 carbon atoms, preferably about 12 to 18 carbon atoms, and most preferably about 14 to 15 carbon atoms, and the carbonyl polyamino group (b) derived from a (primary amino) alkyl-substituted tertiary amine, especially a heterocyclic amine, are preferred. Specific examples of carboxylic acid ester groups having at least about eight carbon atoms, i. ester groups [i.e. - (O) (OR)] (OR) groups are isooctyloxy, decyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, octadecyloxy, eicosyloxy, tricosyloxy, tetracosyloxy, etc. Specific examples of low molecular weight groups are methyloxy, ethyloxy, n-propyloxy, isopropyloxy, n-butyloxy, s-butyloxy, isobutyloxy, n-pentyloxy, neopentyloxy, n-hexyloxy, cyclohexyloxy, cyclopentyloxy, 2-methylbutyloxy-1-oxy, 2, 3-dimethylbutyl-1-oxy, etc. In most cases, suitably sized alkoxyl groups are preferred high and low molecular weight ester groups. Such ester groups may contain polar substituents. Pre-20 signs of polar substituents include chlorine, bromine, ether, nitro, etc. Mixtures of the above-mentioned carboxylic acid ester groups can also be formed. For example, mixtures of ester groups having 12 to 18 carbon atoms have been found to be useful. Mixtures of ester groups having 14 to 15 carbon atoms have been found to be particularly preferred.

Examples of carbonyl polyamino groups are groups derived from polyamino compounds containing one primary or secondary amino group .30 and at least one monofunctional amino group such as a tertiary or heterocyclic amino group. Such compounds may thus be primary or secondary amines substituted by a tertiary amino group or other substituted primary or secondary amines in which the substituent is derived from pyrroles, pyrr. 13,891 79 rolidones, caprolactams, oxazolidones, oxazoles, thiazoles, pyrazoles, pyrazolines, imidazoles, imidazolines, thiazines, oxazilines, diazines, oxycarbamyl, thiocanthase, thiocar-5-bamyl, thiocar-5-bamyl, ureas, sulfonamides, phosphoramides, phenolthiazines, amidines, etc. Examples of such polyamino compounds are (dimethylamino) ethylamine, (dibutylamino) ethylamine, 3-dimethylamino-1-propylamine, 4-methylethylamino-1-butylamine, morpholinoethylamine, tetrahydropyridylethylamine, bis (dimethylamino) propylamine, bis (diethylamino) ethylamine, N, N-dimethyl-p-phenylenediamine, piperidyl-ethylamine, 1-aminoethylpyrazole, 1- (methylamino) pyro, amino methyl 4-aminooctylpyrazole, 1-amino-butylimidazole, 4-aminoethylthiazole, 2-aminoethyltriazine, (dimethylcarbamyl) pro pyramine, N-methyl-N-aminopropylacetamide, N-aminoethylsuccinimide, N-methylaminomaleimide, N-aminobutyl-α-chlorosuccinimide, 3-aminoethyluracil, 2-aminoethylpyridine, o-aminoethyl-N, N-dimethylbenzenesulbenzene -aminoethylphenothiazine, N-aminoethylacetamidine, 1-amino-phenyl-2-methylimidazoline, N-methyl-N-aminoethyl- • 25-S-ethyldithiocarbamate, etc. Preferred polyamino compounds are N-aminoalkyl-substituted boronolines such as N-3 -aminopropyylimorfOliini. Polyamino compounds are mostly compounds containing only one primary or secondary amino group and preferably at least one tertiary amino group. The tertiary amino group is preferably a heterocyclic amino group. In some cases, polyamino compounds may contain up to about six amino groups, although in most cases they contain one primary amino group and either one of 35 or two tertiary amino groups. Polyamino compounds 89179 may be aromatic or aliphatic amines and are preferably heterocyclic amines such as aminoalkyl-substituted morpholines, piperazines, pyridines, benzopyrroles, picolines, quinolines, pyrroles, pyrrolidinones, etc. to about 30 carbon atoms, preferably from four to about 12 carbon atoms. Polyamines may also contain polar substituents.

The nitrogen-containing esters (B1) of the invention are most conveniently prepared by first esterifying a copolymer containing carboxyl groups with a higher molecular weight alcohol or a mixture of a high and low molecular weight alcohol such that at least about 50% and up to about 99% of the carboxyl group. -cyl groups are converted to ester groups and then the remaining carboxyl groups are then neutralized with a polyamino compound such as that described above. In the preparation of mixed esters, the molar ratio of high molecular weight alcohol to low molecular weight alcohol used in the process should be in the range of approximately 2: 1 to 9: 1. In most cases, the ratio is about 2.5: 1 to 5: 1. More than one high molecular weight alcohol or a low molecular weight alcohol may be used in the process. Commercial alcohol mixtures, such as the so-called oxoalcohols consisting of, for example, mixtures of alcohols having from eight to about 24 carbon atoms may also be used. A particularly useful alcohol group 30 is commercial alcohol mixtures or mixtures of commercial alcohol mixtures containing octyl alcohol, decyl alcohol, dodecyl alcohol, tri-decyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol. 35 octadecyl alcohol. Commercial alcohol mixtures containing tetradecyl and penis 89179 tadecyl alcohol are particularly useful. Suitable sources of these alcohol blends are technical grade alcohols sold under the tradename "Neodols" by Shell Chemical Corporation and 5 under the tradename "Alfols" by Continental Oil Company. Examples of other alcohols useful in the process are alcohols which, when esterified, give the ester groups mentioned above as examples.

The degree of esterification may, as previously mentioned, vary such that about 50-99%, preferably about 75-97%, of the carboxyl groups of the copolymer are converted to ester groups. In a preferred embodiment, the degree of esterification is about 95%.

The esterification can be carried out simply by heating the copolymer containing carboxyl groups and the alcohol or alcohol mixtures under conditions typical of the esterification process. Such conditions usually include, for example, a temperature of at least about 80 ° C, preferably about 150-350 ° C, provided that the temperature is below the decomposition point of the reaction mixture, and removal of the water formed in the esterification as the reaction proceeds. Such conditions may include the use of an excess of an alcoholic reagent to facilitate esterification, the use of a solvent or diluent such as mineral oil, toluene, benzene, xylene or the like, and an esterification catalyst complex such as toluenesulfonic acid, sulfuric acid, sulfuric acid, sulfuric acid, aluminum , use of ammonium sulfate, phosphoric acid, sodium methoxide or the like. These conditions and variations thereof are known in the art.

A particularly preferred method of esterification, when mixed esters are desired, first involves the reaction of a copolymer containing carboxyl groups with an alcohol of relatively high molecular weight, followed by the reaction of a partially esterified copolymer with an alcohol of relatively low molecular weight. A variation of this technique involves initiating esterification using an alcohol having a relatively high molecular weight, and before the reaction is complete, an alcohol having a relatively low molecular weight is added to the reaction mass to achieve the desired mixed esterification. In either case, it has been found that a two-step esterification process in which a copolymer containing carboxyl groups 10 is first esterified with a relatively high molecular weight alcohol to convert about 50-75% of the carboxyl groups to ester groups and then to a relatively low molecular weight alcohol achieving the desired degree of esterification results in products with exceptionally advantageous viscosity properties.

The esterified copolymer is then treated with an amount of the polyamino compound such that substantially all of the non-esterified carboxyl groups in the mixed ester are neutralized. The neutralization is preferably carried out at a temperature of at least about 80 ° C, often about 120-300 ° C, provided that the temperature does not exceed the decomposition temperature of the reaction mass. In most cases, the neutralization temperature is between about 150 ° C and 250 ° C. A small excess of polyamino compound relative to the stoichiometric amount is often desirable to ensure substantially complete neutralization, i. to ensure that no more than about 2-5% of the carboxyl groups originally contained in the copolymer remain neutralized. 30 without.

The following examples illustrate the preparation of the nitrogen-containing esters and mixed esters (B-1) used in this invention. Unless otherwise indicated, all parts and percentages are by weight.

17,891 79

Example 1-B-1

The styrene-maleic anhydride copolymer is obtained by preparing a solution containing styrene (536 parts) and maleic anhydride (505 parts) in toluene (7,585 parts) and bringing said solution to a temperature of 99-101 ° C and 480-535 mmHg. in absolute pressure on contact with a catalyst solution prepared by dissolving benzoyl peroxide (2.13 parts) in toluene (51.6 parts). Catalyst solution 10 is added over 1.5 hours while maintaining the temperature at 99-101 ° C. Mineral oil (2,496 parts) is added to the mixture. The mixture is maintained at 99-101 ° C and 480-535 mmHg for four hours. The resulting product is a slurry containing a copolymer in a solvent mixture. The resulting copolymer has a viscosity number of 0.42.

A toluene slurry (2,507 parts) of this maleic anhydride-styrene copolymer containing 11.06% solids and 88.94% volatile constituents, Neodol 45 (631 parts) of straight-chain primary alcohols containing 14 and 15 C-20 atoms, is placed in a vessel. a product of Shell Chemical Company defined as a mixture, mineral oil (750 parts) and Ethyl Antioxidant 733 (4.2 parts), a product of Ethyl defined as a mixture of butylphenol isomers. The mixture is heated with moderate stirring and nitrogen is introduced at a rate of 14 dm 3 / h until the temperature reaches 115 ° C. A catalyst (10.53 parts) containing 70% methanesulfonic acid in water is added dropwise over 20 minutes. The nitrogen supply is raised to 28 cm3 / h and the temperature is raised by distilling off the toluene-water mixture. The mixture is kept at 150 ° C for five hours under the same nitrogen at a rate of 2.8 to 5.7 dm 3 / h. Additional methanesulfonic acid solution (15.80 parts) is added to the mixture over 15 minutes. The mixture is kept at 150 ° C for 3.5 hours. The degree of esterification 35 is 95.08%. Aminopropylmorpholine (35.2 parts) is added dropwise to the mixture over 20 minutes. The mixture is kept at 150 ° C for an additional 30 minutes and then cooled with stirring. The mixture is stripped of volatiles at 50-141 ° C at 102 mmHg and then allowed to cool. At 100 ° C, mineral oil (617 parts) is added. Cooling is continued to 60 ° C, diatomaceous earth (36 parts) is added and the mixture is heated to 100 ° C. The mixture is kept at 100-105 ° C for one hour with stirring and then filtered to give the desired product.

Example 2-B-1

The procedure of Example 1-B1 is repeated with the exception that both Neo-dol 45 (315.4 parts) and Alfol 1218 (312.5 parts), which are synthetic, a product of Continental Oil Company, defined as a mixture of straight-chain primary alcohols, instead of the 631 parts of Neodol 45 included in the initial charge in Example 1.

20 Example 3-B-1

A toluene slurry (1,125 parts) of the maleic anhydride-styrene copolymer of Example 1-B-1 containing 13.46% solids and 86.54% volatile ingredients, mineral oil (350 parts) and 25 Neodol 45 (344 parts) is placed in a vessel. The mixture is heated with moderate stirring and nitrogen is introduced at a rate of 14 dm 3 / h until the temperature reaches 110 ° C. Add p-toluenesulfonic acid (8.55 parts) in water (9 parts) dropwise over 24 minutes. The temperature of the mixture is raised. 30 to 152 ° C by distilling off the toluene-water mixture. The temperature is maintained at 152-156 ° C by introducing nitrogen into the mixture at a rate of 14 dm 3 / h until the total acid number indicates an esterification rate of at least 95%. Aminopropylmorpholine (15.65 parts) is added dropwise over 10 minutes. 35 The temperature of the mixture is maintained at 155 ° C for one hour and ΐθ 89179 then the mixture is cooled under a nitrogen atmosphere. Ethyl Antioxidant 733 (1/48 part) is added to the mixture. The volatile components are removed from the mixture at 143 ° C and 99 mmHg. The mixture is cooled under a nitrogen atmosphere. An amount of mineral oil is added to achieve a 63% dilution. Ethyl Antioxidant 733 (1.79 parts) is added and the mixture is stirred for 30 minutes. The mixture is heated to 60 ° C with stirring and nitrogen is introduced at a rate of 14 dm 3 / h. Diatomaceous earth (18 parts) is added to the mixture li-10. The mixture is heated to 90 ° C.

The temperature of the mixture is maintained at 90-100 ° C for one hour and then the mixture is filtered through a pad of diatomaceous earth (18 parts) in a heated funnel to give the desired product.

15 Example 4-B-1

The procedure of Example 3-B-1 is repeated with the exception that both Neodol 45 (172 parts) and Alfol 1218 (169 parts) are included in the initial charge instead of the 344 parts Neodol 45 included in Example 3.

Example 5-B-1

The product of Example 1-B1 (101 parts), Neodol 91 (56 parts), a product of Shell 25 Chemical Company defined as a mixture of alcohols containing 9, 10 and 11 C atoms, TA-1618 (92 parts), is placed in a vessel. , a product of Procter & Gamble defined as a mixture of alcohols containing 16 and 18, Neodol 25 (62 parts), a product of Shell Chemical Company defined as a mixture of alcohols containing 12, 13, 14 and 15 C atoms, and toluene 30 (437 parts). The vessel is mixed and its contents heated. Methanesulfonic acid (5 parts) is added to the mixture. The mixture is heated at reflux for 30 hours. Aminopropylmorpholine (12.91 parts) is added to the mixture. The mixture is heated at reflux for an additional four hours. Diatomaceous earth (30 parts) and 20 891 79 neutral paraffin oil (302 parts) are added to the mixture and then the volatile constituents are removed from the mixture. The residue is filtered to give 497.4 parts of an orange-brown viscous liquid.

5 Example 6-B-1

The product of Example 1-B-1 (202 parts), Neodol 91 (112 parts), TA-1618 (184 parts),

Neodol 25 (124 parts) and toluene (875 parts). The mixture is heated and stirred. Methane-10 sulfonic acid (10 parts) is added to the mixture and then heated under reflux for 31 hours. Aminopropylmorpholine (27.91 parts) is added to the mixture and then heated under reflux for an additional five hours. Diatomaceous earth (60 parts) is added to the mixture and then the volatile constituents are removed; 600 parts of polymer remain in the container. Neutral paraffin oil (600 parts) is added to the mixture and then the mixture is homogenized. The mixture is filtered through a heated funnel to give 1,063 parts of a clear, orange-brown, viscous liquid.

Example 7-B-1

The product of Example 1-B1 (101 parts), Alfol 810 (50 parts), a product of Continental 25 Oil Company, defined as a mixture of alcohols having 8 and 10 carbon atoms, TA-1618 (92 parts), Neodol 25, is placed in a vessel: (62 parts) and toluene (437 parts). The mixture is heated and stirred. Methanesulfonic acid (5 parts) is added to the mixture and it is heated under reflux for 30 hours. Aminopropylmorpholine (15.6 parts) is added to the mixture and then heated under reflux for an additional five hours. The volatiles are removed from the mixture to give 304 parts of a yellow-orange viscous liquid. Diatomaceous earth (30 parts) and neutral paraffin wax (304 parts) are added to the mixture, and then the mixture is homogenized. The mixture is filtered hot. 2i 69179 through a riveted funnel to give 511 parts of a clear, amber-colored, viscous liquid.

Example 8-B-1

A toluene slurry of maleic anhydride-styrene-5 copolymer (799 parts; 17.82% polymer) is placed in a vessel. The viscosity number of the copolymer is 0.69. Nitrogen is introduced into the vessel while stirring its contents for 15 minutes. Alfoi 1218 (153 parts), Neodol 45 (156 parts) and 93% sulfuric acid 10 (5 parts) are added to the mixture. Toluene (125 parts) is then added to the mixture. The mixture is heated at 150-156 ° C for 18 hours. Aminopropylmorpholine (1.3 parts) is added to the mixture and then heated at 150 ° C for an additional hour. The mixture is cooled to 80 ° C. Ethyl An-15 thioxidant 733 (1.84 parts) is added to the mixture. The volatile constituents are removed from the mixture at 143 ° C and 100 mmHg. Mineral oil (302 parts) and Ethyl Antioxidant 733 (218 parts) are added and the mixture is stirred. The temperature of the mixture is maintained at 90 ° C and nitrogen is blown into it. 20 diatomaceous earth (44 parts) are added to the mixture and it is stirred for one hour at 90-95 ° C. The mixture is filtered through diatomaceous earth to give 1,312 parts of a dark brown, clear, viscous liquid.

Example 9-B-1

A toluene slurry of maleic anhydride-styrene-25 copolymer (973 parts; 17.28% solids) is placed in a vessel. The viscosity number of the copolymer is 0.69. The slurry is mixed and nitrogen is blown at a rate of 21-28 dm3 / h for 20 minutes. Neodol 45 (368 parts) and 80% sulfuric acid (6.84 parts) are added to the mixture.

The mixture is heated at 150-156 ° C for 23 hours. After approximately the first nine hours of heating, additional 80% sulfuric acid (1 part) and toluene: (50 parts) are added to the mixture. After about the first 13 hours of heating, an additional 80% sulfuric acid (2.84. ···. 35 parts) is added to the mixture. After about the first 16 hours of heating, more Neodol 45 (18.4 parts) and 80% sulfuric acid (2 parts) are added. Aminopropylmorpholine (2.33 parts) is added to the mixture and heated at 153-154 ° C for another hour and 20 minutes. Ethyl 5 Antioxidant 733 (2.06 parts) is added to the mixture. The volatile constituents are removed from the mixture at 142 ° C and 100 mmHg. Mineral oil (481 parts) is added to the mixture. Ethyl Antioxidant 733 (2.5 parts) is added to the mixture while stirring. Diatomaceous earth (25 parts) is added to the mixture. The temperature of the mixture is maintained at 70 ° C for 45 minutes and then the mixture is heated to 110 ° C. Diatomaceous earth (25 parts) is added to the mixture. The mixture is filtered through diatomaceous earth to give the desired product.

Example 10-B15 A toluene-mineral oil slurry (699 parts) containing 17.28% maleic anhydride-styrene copolymer solids (viscosity number 0.69), Neodol 45 (139 parts), Alfol 1218 (138 parts), Ethyl Antioxidant 733 is placed in a vessel. (2.9 parts) and toluene (50 parts). The mixture is heated while introducing nitrogen at a rate of 14 dm3 / h. 70% methanesulfonic acid (3.9 parts) is added dropwise over nine minutes. The mixture is heated to reflux for 35 minutes. Toluene (51 parts) is added to the mixture and then heated for a further three hours 15 minutes under reflux conditions. 70% methanesulfonic acid (3 parts) is added dropwise over three minutes. The mixture is heated under reflux for three hours 15 minutes. 70% methanesulfonic acid (3.9 parts) is added dropwise over 12 minutes. The mixture is heated at 150-152 ° C for three hours 45 minutes. Amino-propylmorpholine (14.3 parts) is added dropwise over 15 minutes. The mixture is maintained at 149-150 ° C for an additional 30 minutes. The mixture is stripped of 35 volatiles at 140 ° C and 100 mmHg.

li 23 89 1 79

The mixture is cooled to 50 ° C. Mineral oil (338 parts) and diatomaceous earth (19 parts) are added to the mixture. The temperature of the mixture is maintained at 100-105 ° C for 1.5 hours and then filtered through a portion of diatomaceous earth (18 parts) to give the desired product.

Example 11-B-1

The styrene-maleic anhydride copolymer is obtained by preparing a solution containing styrene (16.3 parts by weight) and maleic anhydride (12.9 parts by weight) in a benzene-toluene mixture (270 parts; benzene-toluene weight ratio 66.5: 33.5) and subjecting to a solution in a nitrogen atmosphere at 86 ° C for eight hours in contact with a catalyst solution prepared by dissolving 70% benzoyl peroxide (0.42 parts) in a similar benzene-toluene mixture (2.7 parts). The resulting product is a thick slurry containing a copolymer in a solvent mixture. Mineral oil (141 parts) is added to the slurry while distilling off the solvent mixture at 150 ° C and then at 150 ° C at a pressure of 200 mmHg. To 209 parts of a mineral oil copolymer slurry (the viscosity number of the copolymer is 0.72) from which the volatile components have been removed, toluene (25.2 parts), n-butyl alcohol (4.8 parts), commercial alcohol (56.6 parts) consisting of primary alcohols containing mainly 12 to 18 carbon atoms, and a commercial alcohol (10 parts) consisting of primary alcohols having 8 to 10 carbon atoms; and 96% sulfuric acid (2.3 parts) is added to the resulting mixture. The mixture is then heated at 150-160 ° C for 20 hours, after which the water is distilled off. Sulfuric acid (0.18 parts) and n-butyl alcohol (3 parts) are added and the esterification is continued until 95% of the carboxyl groups of the polymer are esterified. Aminopropylmorpholine (3.71 parts; 35 10% excess to the required stoichiometric amount to neutralize the remaining free carboxyl groups) is then added to the esterified copolymer and the resulting mixture is heated to 150-160 ° C at 10 mmHg. to distill off toluene and other volatile constituents. Additional mineral oil (12 parts) is added to the product from which the volatile constituents have been removed and filtered. The filtrate is a mineral oil solution of a nitrogen-containing mixed ester with a nitrogen content of 0.16-0.17%.

Example 12-B1 The procedure of Example 11-B1 is followed except that the esterification is carried out in two steps, the first step being the esterification of the styrene-maleic anhydride copolymer with commercial alcohols containing 8-18 carbon atoms and the second step being the further esterification of the copolymer with n-butylation. .

Example 13-B-1

The procedure of Example 11-B1 is followed, with the exception that the esterification is carried out by first esterifying the styrene-maleic anhydride copolymer with commercial alcohols containing 8-18 carbon atoms until 70% of the carboxyl groups of the copolymer have been converted to ester groups and then further esterified. with unreacted al-25 alcohols and n-butyl alcohol until 95% of the carboxyl groups in the copolymer are converted to ester groups.

Example 14-B-1

The procedure of Example 11-B1 is followed, except that the copolymer is prepared by polymerizing a solution containing styrene (416 parts) and maleic anhydride (392 parts) in benzene (2,153 parts) and toluene (5,025 parts), 65- At 106 ° C in the presence of benzoyl peroxide (1.2 parts). (The viscosity number of the resulting copolymer • 35 is 0.45).

li 25 891 79

Example 15-B-1

The procedure of Example 11-B1 is followed, except that the styrene-maleic anhydride copolymer is obtained by polymerizing a mixture of styrene-5ene (416 parts), maleic anhydride (392 parts), benzene (6,101 parts) and toluene (2,310 parts). At 92 ° C in the presence of benzoyl peroxide (1.2 parts). (The viscosity number of the resulting copolymer is 0.91.) Example 16-B-1

The procedure of Example II-B-1 is followed, except that the styrene-maleic anhydride copolymer is prepared by the following method: Maleic anhydride (392 parts) is dissolved in benzene (6,870 parts). To this mixture is added styrene (416 parts) at 76 ° C, followed by benzoyl peroxide (1.2 parts). The polymerization mixture is maintained at 80-821 ° C for about five hours. (The viscosity number of the resulting copolymer is 1.24,) Example 17-B-1

The procedure of Example 16-B-1 is followed, with the exception that acetone (1,340 parts) is used as the polyeneration solvent instead of benzene and azobisisobutyronitrile (0.3 parts) is used as the polymerization catalyst instead of benzoyl peroxide.

Example 18-B-1

The procedure of Example 11-B-1 is followed, with the exception that toluenesulfonic acid 30 (3.5 parts) is used as a catalyst for esterification in place of sulfuric acid.

Example 19-B-1

The procedure of Example 11-B-1 is followed, with the exception that phosphoric acid (2.5 to 35 parts) is used as a catalyst for the esterification instead of sulfuric acid.

26 891 79

Example 20-B-1

The procedure of Example 11-B1 is followed, with the exception that mixtures of alcohols having 8 to 18 carbon atoms are replaced by dodecyl alcohol (0.7 moles per carboxyl equivalent of styrene-maleic anhydride copolymer) and n-butyl alcohol is replaced by isobutyl alcohol (0.2 per carboxyl equivalent of copolymer).

Example 21-B1 The procedure of Example 11-B1 is followed, except that commercial alcohols having 8 to 18 carbon atoms are replaced by eicosyl alcohol (used 0.8 moles per carboxyl equivalent of copolymer) and n-butyl alcohol at t-15 n- pentyl alcohol (used 0.15 moles per carboxyl equivalent of copolymer).

Example 22-B-1

The procedure of Example 11-B1 is followed, except that commercial alcohols having 8 to 18 carbon atoms are replaced by octyl alcohol (used 0.8 moles per carboxyl equivalent of copolymer), n-butyl alcohol is replaced by isopentyl alcohol (used 0.1 mole per carboxyl equivalent of the copolymer) and aminopropyl: instead of morpholine, N-aminoethyl and 1-methyl-4-aminoethylpiperazine (used per 0.1 mol of carboxyl equivalent of the copolymer).

Example 23-B-1

The procedure of Example 11-B-1 is followed except that the aminopropylmorpholine is replaced with an equivalent molar amount of (dimethylamino) ethylamine.

Example 24-B-1: The procedure of Example 11-B-1 is followed. 35 with the exception that aminopropylmorpholine 27,891,79 is replaced by an equivalent molar amount of (dibutylamino) propylamine.

Example 25-B-1

Copolymer 5 (carboxyl equivalent 0.86) of styrene and maleic anhydride (prepared from an equimolar mixture of styrene and maleic anhydride and having a viscosity number of 0.67 to 0.68) is mixed with a mineral oil slurry and then esterified with 10 alcohols. primary alcohols containing carbon atoms, 0.77 mol) at 150-160 ° C in the presence of a catalytic amount of sulfuric acid until about 70% of the carboxyl groups have been converted to ester groups. The partially esterified copolymer is then further esterified with n-butyl alcohol (0.31 mol) until 95% of the carboxyl group of the copolymer is converted to miscellaneous ester groups. The esterified copolymer is then treated with aminopropylmorpholine (slightly in excess of a stoichiometric amount to neutralize the free carboxyl groups of the copolymer) at 150-160 ° C until the resulting product is substantially neutral (acid number 1 according to the phenolphthalein indicator). The resulting product is mixed with mineral oil to form an oil solution containing 34% polymeric product.

25 Example 26-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of N-aminoethylpyrrole.

30 Example 27-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of N-aminopropylthiopyrrolidone.

. · ·. 35 28 891 79

Example 28-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of N-aminoethylcaprolactam.

Example 29-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of N-aminophenyloxazolidone.

Example 30-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of 4-aminoethylthiazole.

Example 31-B-1

The procedure of Example 11-B-1 is followed, with the exception that the aminopropylmorpholine used is chemically replaced with an equivalent amount of 2-cyclohexyltriazine.

Example 32-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of 1-aminoethyl-2-heptadecylimidazoline.

Example 33-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of N-aminooctylsuccinamide.

Example 34-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of 3-aminobutyluracil.

li 29 891 79

Example 35-B-1

The procedure of Example 11-B-1 is followed, except that the aminopropylmorpholine used is chemically replaced with an equivalent amount of 4-aminobutylpyridine.

The transmission fluids of this invention preferably contain from about 0.1% to about 10% by weight of component (B-1). The hydraulic fluids of the invention preferably contain from about 0.05 to 10% by weight, more preferably from about 0.1 to 4% by weight of component (B-1).

The polymer compositions of this invention may also contain at least one oil-soluble acrylate polymerization product formed from at least one ester of the formula CH2 = C (X) -C00R) (III) wherein X is hydrogen or an alkyl or aryl group and R is a monovalent hydrocarbon group containing more than four carbon atoms or an ether derivative of said hydrocarbon group. For convenience, acrylate-20 drop polymerization products are referred to herein as component (B-2).

Compounds of the type corresponding to the above formula III, the oil-soluble polymers of which are particularly well suited for the purposes of this invention, are esters of acrylic acid or its o-alkyl or α-aryl substitution products and monohydric alcohols having at least four carbon atoms, such as butyl-30-, amyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, myristyl, cetyl, acetyl acid, α-phenylacrylic acid and other o-substituted homologues of acrylic acid. or octadeyl esters. These esters are preferably esters of normal, primary, saturated, aliphatic alcohols, but the corresponding esters of corresponding secondary or branched chain alcohols can also be used. Esters of the above-mentioned acrylic series acids with monohydric aromatic or hydroxyaromatic alcohols or ether alcohols, such as benzyl, cyclohexyl, amylphenyl and n-butyloxyethyl ester, can also be used.

These esters are used in the form of their oil-soluble polymers, the polymers of which should be as free as possible from non-polymerizable monomeric esters, since the presence of unsaturated or volatile compounds in the transmission fluid may be undesirable. The non-polymerized esters can be removed by heating the polymer or a mixture of lubricating oil and polymer under reduced pressure to a temperature high enough for the raonomeric ester to evaporate, but preferably the polymerization should be carried out as completely as possible and make the latter operation unnecessary.

The most effective polymers for this purpose are, given the availability and ability to enhance the desired properties, polymerized esters of acrylic acid or α-methacrylic acid and monohydric, aliphatic, saturated, primary alcohols having from 4 to 22 carbon atoms per molecule. Esters with the highest solubility in oils and the highest stability in oils and resulting in the highest viscosity index are esters obtained from straight-chain, saturated, aliphatic, monohydric, primary alcohols containing 8 to 20 carbon atoms, such as normal octyl, lauryl , cetyl or octadecyl esters.

30 These esters do not have to be pure, but can be prepared from technical mixtures of higher aliphatic alcohols, such as those obtained commercially from the catalytic high-pressure hydrogenation of fatty acids or their esters.

Acrylate ester monomers are prepared by conventional esterification procedures using a reaction between an acrylic acid or a substituted acrylic acid, such as methacrylic acid, and an alcohol or alcohol mixture, such as technical grade long chain primary alcohols. These commercially available alcohols are mixtures of n-alkanols of varying chain lengths containing from about 4 to 22 carbon atoms in the alkyl group. Suitable sources of these alcohol blends are technical grade alcohols sold by 10 Shell Chemical Corporation under the tradename "Neodols" and Continental Oil Company under the tradename "Alfols".

Mixtures of any two or more polymers of the esters disclosed herein may also be used. These may be simple mixtures of such polymers or may be copolymers which may be prepared by polymerizing a mixture of two or more monomeric esters.

For use in the process of this invention, the polymers are preferably prepared by heating the monomeric esters at 70-100 ° C in the presence of small amounts of polymerization catalysts such as peroxides or ozonides. These polymers are referred to as “thermal polymerization products.” However, other catalysts, such as anhydrous halides of polyvalent or amphoteric metals, may be used in the polymerization of vinyl compounds in accordance with known practice.

Procedures for preparing the acrylate polymers (B-2) useful in this invention are known in the art, for example, from U.S. Patent Nos. 2,100,993, 3,598,736, and 3,679,644. The contents of these patents are hereby incorporated by reference.

The hydraulic fluids of this invention preferably contain from about 0.1 to 10% by weight, more preferably from about 0.5 to 5% by weight of component (B-2>.

32 891 79 The compositions of this invention also contain (C) an effective amount of at least one liquid organic diluent that lowers the viscosity at low temperature. In general, the diluent (C) is characterized in that it has a viscosity at 40 ° C of less than 4 x 10 6 m2 / s and more preferably about 2.0 to 3.8 x 10 6 m2 / s.

The diluent (C) may be any organic diluent having the desired viscosity reducing properties and such diluents may be natural or synthetic diluents. Preferred organic diluents with the desired viscosity properties include naphthenic oils, certain synthetic oils and alkylated aromatics. Naphthenic oils useful in the compositions of the invention include those derived from naphthenic-containing crude oils, such as those found in the Louisiana area. The viscosity of such naphthenic oils at 40 ° C is generally less than 4x10 6 m2 / s and more generally about 3.0 to 3.8x10'6 m2 / s. Preferred naphthenic crude oils have a viscosity of about 0.8 to 1.6 x 10 6 m 2 / s at 100 ° C. Such naphthenic oils have been found to impart excellent flow properties to the polymer compositions of the invention, especially at low temperatures.

Synthetic oils useful as diluent (C) are oils having a viscosity at 40 ° C of about 2.0 to 3.8 x 10 6 m 2 / s and preferably about 2.0 to 3.0 x 10 6 m 2 / s. Examples of such oils are esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acids, azelaic acid and malonic acid) with various alcohols such as butyl alcohol, dodecyl alcohol, etc. Synthetic oils, especially ester type oils useful as diluent (C), are described in more detail below.

35 Alkylated aromatics are particularly

II

33 89 1 79 are useful as a diluent (C) in the hydraulic fluid compositions of the invention. These alkylated aromatics are preferably mono- or disubstituted (more preferably monosubstituted) benzenes, wherein the substituents are hydrocarbon-based groups containing from about 8 to 30, preferably from about 10 to 14 carbon atoms. One example is a commercially available mixture of alkylated benzenes containing up to 2% of less than 10 C atoms, up to 10% of 10-12 C atoms, 70-90% of 13-14 C atoms, and not more than 5% of hydrocarbon groups containing more than 14 carbon atoms.

The amount of low organic viscosity reducing diluent to be included in the compositions of this invention is such that it is sufficient to lower the viscosity of the composition to the desired level at low temperatures, especially below 0 ° C. Thus, the amount of diluent (C) to be included in the polymer compositions of the invention depends on the roar and relative amounts of components (A) and (B) in the composition, the properties of the diluent used and the desired viscosity properties for the final product. In general, the weight ratio of the diluent (C) to the mixture of components (A) and (B) is approximately in the range of 5: 1 to 1: 5. In the case of gear liquids, the diluent (C) is preferably present in an amount of about 1 to 90% by weight. In the case of hydraulic fluids, the diluent (C) is preferably present in an amount of about 1 to 35% by weight, more preferably about 2 to 10% by weight.

The compositions of this invention, consisting of mixtures of components (A), (B) and (C) described above, are useful in a wide variety of lubricant compositions formulated for a variety of uses. In particular, the compositions of this invention are useful in the formulation of transmission fluids (i.e., both automatic and manual transmission fluids) and hydraulic fluids with improved and desired low temperature properties. The compositions of this invention have excellent flowability at low temperatures.

In addition, the transmission fluids and hydraulic fluids of this invention unexpectedly combine high shear strength, excellent flowability at low temperatures, and the viscosity of conventionally formulated fluids at 100 ° C.

When using the compositions of this invention comprising components (A), (B) and (C) in lubricating oil formulations, and in particular in transmission and hydraulic fluids, the compositions of this invention contain other components in addition to components (A), (B) and (C). additives-15 that impart some desired properties to transmission and hydraulic fluids. Examples of such additives are detergents and dispersants, which may be of the ash-generating or ash-free type, corrosion and oxidation inhibitors, pour point depressants, high pressure additives, anti-wear agents, anti-corrosion agents, sealant swelling agents, friction modifiers, friction modifiers.

Examples of ash-generating detergents 25 are those oil-soluble neutral and basic salts formed by alkali or alkaline earth metals with sulfonic acids, carboxylic acids or organic phosphoric acids which are characterized by at least one direct carbon-phosphorus bond, such as those prepared with by treating the olefin polymer (e.g., polyisobutylene having a molecular weight of 1,000) with a phosphoring agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus, and sulfur halide or phosphorodithioic acid chloride. Salts of such acids commonly used in the eyes include sodium, potassium, lithium, calcium, magnesium, strontium and barium salts.

The term "basic salt" is used for metal salts containing a stoichiometrically greater amount of metal than an organic acid group. Commonly used methods for preparing basic salts include heating an acidic mineral oil solution with a stoichiometric amount of a metal-containing neutralizing agent, such as a metal oxide, hydroxide, carbonate, bicarbonate, or sulfide, at a temperature of about 50 ° C and filtering the resulting mass. The use of a "promoter" in the neutralization step to help incorporate a large excess of metal into the salts is also known. Examples of compounds useful as promoters include phenolic compounds such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products between formaldehyde and a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine and dodecylamine. One particularly effective method for preparing basic salts involves mixing the acid with a basic alkaline earth metal neutralizing agent used in excess and at least one alcohol solvent and carbonating the mixture at an elevated temperature such as 60-200 ° C.

30 Ashless detergents and dispersants are referred to as such despite the fact that, depending on their structure, such a dispersant may, on combustion, generate a non-volatile substance such as boron oxide or. phosphorus pentoxide; however, it does not usually contain 35 metals and therefore does not generate ash containing metal. Many types are known in the art and are all suitable for use in the lubricant compositions of this invention. Examples are the following: (1) Reaction products between carboxylic acids (or derivatives thereof) having at least about 34 and preferably at least about 54 carbon atoms and nitrogen-containing compounds such as amine, organic hydroxy compounds such as phenols and alcohols and / or basic inorganic substances. Examples of these "carb-10 carboxylic dispersants" are disclosed in GB Patent 1,306,529 and in many U.S. patents, including the following: 3,163,603 3,351,552 3,541,012 3,184,474 3,381,022 3,543,678 15 3 215 707 3 399 141 3 542 680 3 219 666 3 415 750 3 567 637 3 271 310 3 433 744 3 574 101 3 272 746 3 444 170 3 576 743 3 281 357 3 448 048 3 630 904 20 3 306 908 3 448 049 3 632 510 3 311 558 3 451 933 3 632 511 3 316 177 3 454 607 3 697 428 3 340 281 3 467 668 3 725 441 3 341 542 3 501 405 4 234 435: 25 3 346 493 3 522 179 Re 26 433 (2) Reaction products between aliphatic or alicyclic halides having a relatively high molecular weight and amines, preferably polyalkylene polyamines. These can be characterized as "amine dispersants" and examples are provided, for example, in the following U.S. Patents: 3,275,554 3,454,555 3,438,757 3,565,804. 35 li 37 89 1 79 (3) Reaction products between alkylphenols in which the alkyl group contains at least about 30 carbon atoms and aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines) which can be characterized as "Mannich dispersants". Examples are those disclosed in the following U.S. Patents: 2,459,112 3,442,808 3,591,598 2,962,442 3,448,047 3,600,372 10,984,550 3,454,497 3,634,515 3,036,003 3,459,661 3 649 229 3 166 516 3 461 172 3 697 574 3 236 770 3 493 520 3 725 277 3 355 270 3 539 633 3 725 480 15 3 368 972 3 558 743 3 726 882 3 413 347 3 586 629 3 980 569 (4 ) Products obtained by post-treatment of carboxylic dispersants, amine dispersants or Mannich dispersants with reagents such as urea, thiourea, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarboxylic acids, hydrocarbon-substituted epihydrides, hydrocarbons, . Examples of such substances are disclosed in the following U.S. Patents: 3,036,003 3,282,955 3,493,520 3,639,242 3,087,936 3,312,619 3,502,677 3,649,229 3,2007 3,366,569 3,513,093 3,649,659 ... 30 3 216 936 3 367 943 3 533 945 3 658 836 3 254 025 3 373 111 3 539 633 3 697 574 3 256 185 3 403 102 3 573 010 3 702 757 3 278 550 3 442 808 3 579 450 3 703 536 3 280 234 3 455 831 3 591 598 3 704 308 35 3 281 428 3 455 832 3 600 372 3 708 422 38 891 79 5) Polar sub-poles of oil-soluble monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins copolymers with monomers containing supports, for example aminoalkyl acrylates or acrylamides and poly (oxyethylene) substituted acrylates. These can be characterized as "polymeric dispersants" and are exemplified in the following U.S. Patents: 10,332,658 3,666,730 3,444,250 3,687,849 3,519,565 3,702,300

The above-mentioned patents are incorporated herein by reference for their content regarding ashless dispersants.

Detergents / dispersants are used, when used, in concentrations of about 0.01 to 20% by weight or higher, depending on the nature of the dispersant. Typically, such detergents / dispersants are used in concentrations of about 0.1 to 15% by weight based on the total weight of the transmission fluid.

Examples of high pressure additives and corrosion and antioxidants that may be included in the compositions of the invention include chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis (chlorobenzyl) disulfide, dibutyl tetra-sulfide, sulfurized oleic acid methyl ester, sulfurized alkylphenol, sulfurized dipentene and sulfurized terpene; phosphosulfurized hydrocarbons, such as phosphorus sulfide with turpentine or methyl oleate, the reaction product of a phosphorus containing esters, which are principally dihydrocarbon and 35 trihiilivetyfosfiitit, such as dibutyl li 39 79 891 phosphite, diheptyylifosfiitti, dicyclohexyl, pentylphenyl, dipentylphenyl, tridecyl phosphite, distearyl phosphite, dimetyylinaf-phosphite; oleyl (4-pentylphenyl) phosphite, poly-phosphite substituted with poly-5 polypropylene (molecular weight 500) and diisobutyl-substituted phenyl phosphite; metal thiocarbamates such as zinc (dioctyl thiocarbamate) and barium (heptyl phenyl dithiocarbamate); phosphorodithioates formed by Group II metals, such as zinc (dicyclohexylphosphorodithioate), zinc (dioctylphosphorodithioate), barium [di (heptylphenyl) phosphorodithioate], cadmium (dinonylphosphorodithioate) and phosphorodionate with a mixture of a molar amount of isopropyl alcohol and n-hexyl alcohol, a zinc salt.

Many of the high pressure additives and corrosion and oxidation inhibitors mentioned above also act as wear reducing agents. One known precursor is zinc (dialkyl phosphorodithioates).

Particularly useful anti-wear agents in the hydraulic fluid compositions of this invention are those used to contact (R'0) 2PSSH, wherein each R 'is independently a hydrocarbon-based group, a corresponding salt, or a phosphoric acid precursor thereof, with at least one phosphite. corresponding to the formula (RM0) 3P wherein R · 'is a hydrocarbon-based group, under reaction conditions at a temperature of about 50-200 ° C. R 'is preferably an alkyl group having about 30 to 50 carbon atoms and R "is preferably aromatic. The salt is preferably a zinc salt, but may be a mixed salt of at least one of said phosphoric acids and at least one carboxylic acid. These wear reducing agents are described. more specifically in U.S. Patent No. 40,891,792,263,150, which is incorporated herein by reference These wear reducing agents, as well as the above mentioned wear reducing agents, may be included in the hydraulic fluid compositions of the invention in an amount of about 0.1 to 5% by weight, preferably about 0, Concentrations of 25 to 1% by weight based on the total weight of said liquid compositions.

Antioxidants that are particularly useful in the hydraulic fluid compositions of this invention include hindered phenols [e.g. 2,6-di- (t-butyl) phenol], aromatic amines (e.g. alkylated diphenylamines), alkyl polysulfides, selenides, borates (e.g. epoxide / boric acid reaction products), phosphorodithioic acids, acid esters and / or acid salts 15 dithiocarbamates (e.g. zinc dithiocarbamates). These antioxidants, as well as the antioxidants discussed above, are preferably present in the hydraulic fluids of the invention in a concentration of about 0.05 to 5% by weight, more preferably 0.25 to 2% by weight, based on the total weight of such compositions.

Anti-corrosion agents that are particularly useful in the hydraulic fluid compositions of the invention include alkenyl succinic acids, acid anhydrides, acid esters, preferably tetrapropenyl succinic acids, acid half esters, and mixtures thereof; metal sulfonates (preferably calcium and barium sulfonates), amine phosphates; and imidazolines. These anti-corrosion agents are preferably present in the hydraulic fluids according to the invention in concentrations of about 0.01 to 5% by weight, preferably about 0.02 to 1% by weight, based on the total weight of said fluids.

Freezing point depressants may be included in the compositions described herein. The use of such pour point depressants in oil-based compositions to improve the low temperature properties of oil-based compositions 4i 8 9179 is known in the art. See, for example, C.V. Smal-Heer and R. Kennedy Smith, Lubricant Additives, Lezius-Hiles Co., Cleveland, Ohio, 1967, page 8.

Examples of useful pour point depressants are polymethacrylates, polyacrylates, polyacrylamides, condensation products between haloparaffin waxes and aromatic compounds, polymers of vinyl carboxylate re-vinyl esters of vinyl esters and vinyl esters of vinyl esters. Solidification point depressants suitable for the purposes of this invention and their use are described in U.S. Patent Nos. 2,387,501, 2,015,748, 2,655,479, 1,815,022, 2,191,498, 2,666,746, 15,271,877, 2,721,878 and 3,250,715. , which are hereby incorporated by reference in their entirety.

Defoamers are used to reduce or prevent the formation of permanent foam. Typical antifoams are silicones or organic polymers.

Other antifoam compositions are described in Henry T. Kerner, Foam Control Agents, Noyes Data Corporation, 1976, pp. 125-162.

When other additives are used in the formulation of transmission fluid and hydraulic fluid compositions in connection with the compositions of this invention, such additives are used in the concentrations conventionally used in the art. They are thus generally used in concentrations of about 0.001 to 25% by weight, based on the total composition, depending, of course, on the nature of the additive and the nature of the automatic transmission fluid composition.

The transmission fluid and hydraulic fluid compositions of this invention can, of course, be prepared by a variety of methods known in the art. One convenient method is to combine a composition of the present invention comprising components 42 891 79 (A), (B) and (C) described above and other additives in the form of a concentrated solution or a substantially stable dispersion (i.e., additive concentrate) in a sufficient amount. a base oil, which may be an Additional Batch of Diluent (C) described above, or another natural or synthetic oil normally used in the manufacture of transmission or hydraulic fluids to form the desired final transmission fluid or hydraulic fluid composition. Such concentrates contain additives in appropriate amounts to achieve the desired concentration of each additive in the final automatic transmission fluid or hydraulic fluid composition when mixed with a predetermined amount of base oil.

As mentioned above, the compositions of this invention containing components (A), (B) and (C) and other possible and desired additives may be mixed with an additional batch of diluent, such as component (C) or other natural or synthetic base oils.

The base oils used in the preparation of the transmission fluids and hydraulic fluids of the invention may be natural oils or synthetic oils. Natural oils include animal and vegetable oils (e.g., castor oil, lard oil) as well as mineral lubricating oils, such as liquid petroleum oils and solvent or acid-treated mineral lubricating oils, which may be of the paraffinic or naphthenic type. Oils from coal and shale, which have a viscosity of the lubricant, are also useful. Synthetic lubricating oils include hydrocarbon oils and halogen-substituted hydrocarbon oils such as polymerized and copolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.). poly (1-hex-35 fungi), poly (1-octenes), poly (1-decenes), etc., and mixtures thereof; alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl) benzenes, etc.); polyphenyls (e.g. biphenyls, terphenyls, alkylated polyphenyls, etc.); al-5 alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogs and homologues, and the like.

Alkylene oxide polymers and copolymers and their derivatives in which the terminal hydroxyl groups have been modified by esterification, etherification, etc. form another group of known synthetic lubricating oils which can be used. Examples of these are oils prepared by polymerizing ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl polyisopropylene glycol ether having an average molecular weight of about 1,000; polyethylene glycol having a molecular weight of about 1,000; , diphenyl ether, diethyl ether of polypropylene glycol having a molecular weight of about 1,000 to 20,500, etc.) or their mono- and polycarboxylic acid esters, for example acetic acid esters of tetraethylene glycol, mixed C3-8 fatty acid esters or C13-oxoacetic acid esters.

Another suitable group of useful synthetic lubricating oils are esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acid, maleic acid, linoleic acid, poacic acid, fatty acid, cork acid, cork acid, alkyl malonic acids, alkenyl malonic acids, etc.) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, (2-ethylhexyl) alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters are dibutyl adipate, di (2-ethylhexyl 444,191 yl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didoctyl phthalate, ethyl sebacate, a 2-ethylhexyl di-5 ester of a linoleic acid dimer, a complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include esters prepared from C5-12 monocarboxylic acids and polyols, as well as polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

Another useful group of synthetic lubricants are silicon-based oils, such as polyalkyl, polyaryl, polyalkoxy or polyaryloxysiloxane oils and silicate oils [e.g. tetraethyl silicate, tetraisopropyl silicate, tetra (2-ethyl-20-hexyl) silicate, tetra (4-methylhexyl) silicate, tetra (pt-butylphenyl) silicate, hexyl (4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxanes, poly (methylphenyl) siloxanes, etc.]. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymeric tetrahydrofurans, and the like.

The concentrates of this invention may use Refined Towers of the type described above, refined and re-refined, either natural or synthetic, oils (as well as mixtures of any two or more of such oils). Unrefined oils are oils obtained directly from a natural or synthetic source without further refining. For example, shale oil 45 8 91 79 obtained directly from the distillation steps, fuel oil obtained directly from the first distillation or ester oil obtained directly from the esterification process and used without further treatment would be crude oil. Refined oils are similar to crude oils, except that they have been further treated in one or more refining steps to improve one or more properties. Many such purification methods, such as solvent extraction, post-distillation, acid or base extraction, filtration, percolation, etc., are familiar to those skilled in the art. Refined oils are obtained by methods similar to those used to obtain refined oils when applied to refined oils already in use. Such refined oils are also known as regenerated or reprocessed oils and are often further treated by methods aimed at removing used additives and oil degradation products.

The following examples illustrate the compositions of this invention. Unless otherwise stated, all parts and percentages are by weight.

Example A

A composition is prepared containing 35 parts by weight of polyisobutylene having a number average molecular weight of 900 and five parts of the nitrogen-containing boron compound of Example 1-B-1.

Example B

A composition suitable for the formation of an automatic transmission fluid is prepared containing 35 parts of polyisobutylene having a number average molecular weight of 900, five parts of the product of Example 1-B1 and 30 parts of naphthenic hydrocarbon oil having a viscosity at 40 ° C of about 3.5 x 10 '. 6 m / s.

35 46 89 1 79

Example C

A composition suitable for use in the manufacture of automatic transmission fluids is prepared containing 35 parts of polyisobutylene having a number average molecular weight of Mole-5 of about 900, five parts of the product of Example 1-B1, 29 parts of a commercially available naphthenic oil having a viscosity of about 3 at 40 ° C. .5 x 10'6 m2 / s, 9.52 parts of the reaction product of polyisobutenyl succinic anhydride in a folder of ethylene polyamine and carbon disulphide, 1.67 parts of a sealant swelling agent prepared according to U.S. Pat. No. 4,029,587 and 1.33 parts of a silicone antifoam.

Examples of hydraulic fluid formulas according to the invention are shown in the table below. In the following table-15, all numerical values are parts by weight.

β £ 100 Neutral Mineral Oil 92.2 88.17 91.11

The product of Example 1-B-1 is 1.17 1.8 1.35

Polyisobutylene (Mn = 1,400) 4.24 6.52 4.89 20 Alkylate 230 (a product of Monsanto defined as alkylated benzene having a molecular weight of approximately 260) 1.05 1.61 1.21

Acryloid 150 (a product of Rohm & Haas 25 defined as a methacrylate copolymer) 0.052 0.081 0.060

Acryloid 156 (a product of Rohm & Haas defined as a methacrylate copolymer) 0.155 0.238 0.179 30 Zinc [di (2-ethylhexyl) dithiophosphate] 0.371 0.53 0.371

Sodium (petroleum sulphonate) 0,0506 0,03 0,0506

Antioxidant 732 (Ethyl product defined as alkyl-35 moiety) 0.151 0.18 0.151

II

47 89179

Tolad 370 (The petroleum product defined as the solution containing polyglycol in aromatic hydrocarbons) 0.01 0.008 0.01 5 Sulfurized calcium salt of dodecylphenol 0.05 0.07 0.05

Tolyltriazole 0.00165 0.001 0.00165

Acrylate terpolymer derived from (2-ethylhexyl) acrylate-10, ethyl acrylate and vinyl acetate 0.015 to 0.015

Dilution oil 0.48 0.76 0.569

Although the invention has been described herein in terms of preferred embodiments and illustrated by specific examples, it should be noted that various modifications will be apparent to those skilled in the art upon reading this specification. Such variations are intended to be within the scope of this invention.

Claims (13)

48 891 79 Claims A polymer composition useful in transmission fluids and hydraulic fluids, characterized in that it contains (A) about 0.1 to 20% by weight of at least one oil-soluble homopolymer of a non-aromatic monoolefin containing at least 3 carbon atoms, which the number average molecular weight is about 750 to 10,000; and 10 (B1) about 0.05 to 10% by weight of a nitrogen-containing ester of a copolymer containing at least one carboxyl group, which copolymer is formed of at least two monomers, one of said monomers being an aliphatic olefin monomer or a vinyl aromatic monomer, and wherein one of said monomers is (ii) at least one α, β-unsaturated aliphatic carboxylic acid or anhydride or ester thereof, and said copolymer has a viscosity number of about 0.05 to 2, wherein the polymer structure of the nitrogen-containing ester includes the following polar groups obtained carboxyl groups of said copolymer; (a) at least one carboxylic acid ester group which:. 25 contains at least 8 aliphatic carbon atoms in the ester group; (b) at least one carbonyl polyamino group obtained by reacting the carboxyl group of said copolymer with a polyamino compound containing one primary or secondary amino group and at least one tertiary amino or heterocyclic amino group; and (C) about 1-90% by weight of at least one low temperature viscosity reducing liquid organic diluent. 49 89179 Composition according to Claim 1, characterized in that (A) is a homopolymer formed from propylene or butene. Composition according to Claim 1 or 2, characterized in that the monomer (i) is styrene and the monomer (ii) is maleic acid, maleic anhydride or a mixture thereof. Composition according to any one of the preceding claims, characterized in that the viscosity of the diluent (C) at 40 ° C is less than 4 x 10 6 m 2 / s. Composition according to any one of the preceding claims, characterized in that the diluent (C) contains naphthenic oil or a synthetic oil having a viscosity at 40 ° C of about 2.0 x 10 * 6 to 3.8 x 10'6 m2 / s. Composition according to any one of the preceding claims, characterized in that the weight ratio of diluent (C) to combination (A) and (B) is from about 5: 1 to 1: 5. A transmission fluid composition having improved shear strength, characterized in that it contains (A) about 0.1 to 20% by weight of at least one oil-soluble homopolymer of a non-aromatic monoolefin containing at least 3 carbon atoms. having a number average molecular weight of about 750 to 10,000; (B1) about 0.05 to 10% by weight of a nitrogen-containing ester of a copolymer containing one carboxyl group, which copolymer is formed of at least two monomers, one of said monomers being (i) an aliphatic olefin monomer or a vinyl aromatic monomer, and the other said monomers being (ii) at least one α, β-unsaturated aliphatic carboxylic acid or anhydride or ester thereof, i.e. 89179, and said copolymer having a viscosity number of about 0.05 to 2, said nitrogen-containing ester being characterized by the following polymeric structure: groups derived from carboxyl groups of said copolymer: (a) at least one carboxylic acid ester group containing at least 8 aliphatic carbon atoms in the ester group; (b) at least one carbonyl polyamino group obtained by reacting the carboxyl group of said copolymer with a polyamino compound containing one primary or secondary amino group and at least one tertiary amino or heterocyclic amino group; and 15 (C) about 1-90% by weight of at least one low temperature viscosity reducing liquid organic diluent. Transmission test according to Claim 7, characterized in that the monomer (i) in the nitrogen-containing ester (B) is ethylene, propylene, isobutene or styrene and the monomer (ii) in the nitrogen-containing ester (B) is at least one of the compounds maleic -acid or maleic anhydride, itaconic acid or Itaconic anhydride or acrylic acid or acrylic acid ester. 25 Hydraulic fluid with improved shear strength, characterized in that it contains from 60 to 99% by weight of base oil (A) from 0.1 to 20% by weight of at least one oil-soluble polymer having at least 3 carbon atoms. a homopolymer of an aromatic monoolefin having a number average molecular weight of about 750 to 10,000; (B1) 0.05 to 10% by weight of a nitrogen-containing ester ester of a copolymer containing at least one carboxyl group, which copolymer is formed of at least two monomers, one of said monomers being si 89179 (i) an aliphatic olefin monomer or a vinylaromatic monomer, and one of said monomers is (ii) at least one α, β-unsaturated aliphatic carboxylic acid or anhydride or ester thereof, and said copolymer has a viscosity number of about 0.05 to 2, said nitrogen-containing ester being characterized by having the following polar structures in its polymeric structure: groups derived from carboxyl groups of said copolymer: (a) at least one carboxylic acid ester group containing at least 8 aliphatic carbon atoms in the ester group; (b) at least one carbonyl polyamino group obtained by reacting the carboxyl group of said copolymer with a polyamino compound containing one primary or secondary amino group and at least one tertiary amino or heterocyclic amino group; 20 (B-2) 0.1 to 10% by weight of at least one oil-soluble acrylate polymerization product formed from 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 hydrocarbon group having at least 4 carbon atoms or an ether derivative of said hydrocarbon group; (C) 1-35% by weight of at least one low temperature viscosity reducing liquid organic diluent. : V The liquid according to claim 9, characterized in that it further contains a small anti-rust amount of an anti-corrosion agent, a small antioxidant amount of an antioxidant and a small anti-wear amount of an anti-wear agent. 52 89179 A liquid according to claim 10, characterized in that said antiwear agent is prepared by contacting a salt of a phosphoric acid of formula (R'0) 2PSSH 5 wherein each R 'is independently a hydrocarbon-based group or a phosphoric acid precursor thereof with at least one phosphite of formula ( R "0) 3P wherein R" is a hydrocarbon-based group, under reaction conditions of about 50 to 200 ° C. A liquid according to claim 11, characterized in that R "is an aromatic group, each R 'is an alkyl group having about 3 to 50 carbon atoms, and said salt is a zinc salt. Liquid according to claim 12, characterized in that said anti-wear agent is zinc (dialkyl phosphorodithioate). li 53 89179