NO871306L - WATER-BASED FUNCTIONAL FLUID THICKNESS COMBINATIONS OF SURFACE ACTIVE AGENTS OF HYDROCARBYL-SUBSTITUTED succinic and / or anhydride / amine-terminated poly (oxyalkylone) reactor. - Google Patents

Description

The present invention relates to combinations of surface-active agents and water-dispersible materials produced by reacting at least one hydrocarbyl-substituted succinic acid and/or -anhydride with at least one amine-terminated poly(oxy-alkylene), as well as aqueous systems containing such combinations. The aqueous systems include both concentrates and water-based functional fluids, such as water-based lubricants, hydraulic fluids, cutting fluids and the like. The surface-active, water-dispersible hydrocarbyl-substituted succinic or -anhydride/amine-terminated poly(oxyalkylene) reaction product combinations are useful as thickeners for such aqueous systems; these combinations are stable under relatively high shear conditions.

The term "water-based functional fluid" is used here as a reference to water-based lubricants, hydraulic fluids, cutting fluids, etc. Water-based functional fluids are not a new concept. In recent times, however, the increasing price and scarcity of petroleum has made it increasingly desirable to replace oil-based functional fluids with water-based functional fluids where this is possible. Other beneficial effects can also be achieved from such replacements, such as reduced fire risk and environmental pollution problems. In many cases, however, it is not possible to make such replacements because the water-based functional fluids cannot be modified in their properties to thereby be effective to the same high degree as their oil-based counterparts. It has e.g. has often been difficult, if not impossible, to replace certain oil-based hydraulic fluids with water-based fluids even though the desirability of doing so is obvious.

One of the problems when formulating suitable water-based functional fluids has been the choice of thickeners that give the desired degree of thickening and at the same time are stable under high shear conditions. Various thickeners have been tried, but none have proven to be completely acceptable. Among the thickeners that have been tried are the polysaccharides, the cellulose ethers and -esters, and various synthetic polymers. The polysaccharides include natural gums such as agar gum, guar gum, gum arabic, algin, dextrans, xanthan gum and the like. The cellulose ethers and esters include hydroxyhydrocarbyl cellulose and hydrocarbyl hydroxycellulose and their salts. In this group are hydroxyethyl cellulose and the sodium salt of carboxymethyl cellulose. The synthetic polymers include polyacrylates, polyacrylamides, hydrolysed vinyl esters, water-soluble homo- and interpolymers of acrylamide doalkanesulfonates containing at least 50 mol-# of acrylamidoalkanesulfonate and other comonomers such as acrylonitrile, styrene and the like. Others include poly-n-vinyl pyrrolidones, homo- and copolymers, and water-soluble salts of styrene, maleic anhydride, and isobutylene maleic anhydride copolymers.

It has been proposed to use certain water-soluble hydroxy-terminated polyoxyalkylenes as thickeners. See e.g. US Patent 3,005,776; 3,346,501; 4,138,346; and 4,451,099. However, the degree of thickening provided by these polyoxyalkyls has not been found to be completely acceptable.

US patent 4,239,635 describes carboxylic acid-terminated diamides and alkali metal, ammonium or amine salts thereof obtained from the reaction of organic polycarboxylic acids with polyoxyalkylenediamines. The patent states that these diamides have lubricating properties and are useful in aqueous metalworking fluids.

US Patent 4,288,639 describes the use of certain alpha-olefin oxide-modified polyoxyalkylenes as thickeners for aqueous liquids. This patent states that these thickeners are obtained by end-capping a liquid straight-chain polyoxyalkylene hetero or -block copolymer intermediate with an alpha-olefin oxide.

There is a need for water-dispersible thickeners which can provide water-based functional fluids with desired levels of thickening and which are sufficiently stable for high shear applications.

Water-repellent combinations of surfactants and hydrocarbyl-substituted succinic acid and/or anhydride/amine-terminated poly(oxyalkylene) reaction products are provided according to the present invention. These combinations are useful as thickeners for water-based functional fluids and are relatively stable for high shear applications.

In general, the present invention relates to the provision of a composition comprising (A) at least one water-dispersible reaction product produced by the reaction of (A) (I) at least one hydrocarbyl-substituted succinic acid and/or anhydride represented by the formula:

where R is a hydrocarbyl group with from approx. 8 to approx. 40 carbon atoms, with (A) (II) at least one water-dispersible amine-terminated poly(oxyalkylene), and (B) at least one surfactant. Aqueous concentrates and water-based functional fluids comprising these compositions are also covered by the present invention.

The terms "dispersed" and "dissolved" (and related terms such as "dispersion", "dispersible", "dissolution", "soluble", etc.) are used in the present context to refer to the distribution of the present compositions in the aqueous systems to which they are added. While the practice of the present invention is not dependent on any particular theory or hypothesis to explain the invention, it is to be understood that in some cases the present compositions may dissolve in the aqueous phase to form true solutions, while in other cases micelle dispersions or micro-emulsions can be formed which visibly turn out to be real solutions. Whether a solution, micelle dispersion or micro-emulsion is formed depends on the particular composition used and the particular system to which it is added. In all cases, the terms "dispersed" and "dissolved" are used interchangeably in the present context to refer to solutions, micelle -dispersions, micro-emulsions etc.

With reference to a material used according to the present invention, the term "water dispersible" refers to a material which forms a solution, micelle dispersion or micro-emulsion when added to water at a level of at least approx. 1 g per 1 at 25°C.

The term "hydrocarbyl" is used herein to include substantially hydrocarbyl groups (eg, substantially hydrocarbyloxy, substantially hydrocarbyl mercapto, etc.), as well as pure hydrocarbyl groups. The description of these groups as essentially hydrocarbyl means that they do not contain any non-hydrocarbyl substituents or non-carbon atoms which significantly affect the hydrocarbyl properties of such groups in relation to their uses as described herein.

Examples of substituents which usually do not significantly change the hydrocarbyl properties of the general nature of the hydrocarbyl groups of the present invention are the following: Ether groups (especially hydrocarbyloxy such as methoxy, n-butoxy, etc.);

Oxo groups (eg -O bonds in the main carbon chain);

Nitro groups;

Thioether groups;

Thia groups (eg -S bonds in the main carbon chain);

Carbohydrocarbyloxy groups

Sulfonyl groups Sulfinyl groups

The overview shall be illustrative only and not exhaustive, and the omission of a certain class of substituents shall not mean that it is necessarily excluded. In general, if such substituents are present, there will be no more than two for every 10 carbon atoms in the essential hydrocarbyl group and preferably no more than 1 for every 10 carbon atoms. Nevertheless, the hydrocarbyl groups are preferably free of non-hydrocarbon groups, i.e. they are preferably pure hydrocarbyl groups consisting only of carbon and hydrogen atoms.

The term "substantially straight chain" is used in the present context to refer to hydrocarbyl groups which have straight chains and do not contain any branching which adversely affects the thickening properties of the reaction products of components (A) (I) and (A) (II). In the present context, e.g. a straight-chain C 1-4 alkyl group with a methyl group attached as a side or branch chain, and a straight-chain C 1-4 alkyl group, substantially similar in their properties with respect to their use in the present invention.

Component ( A) ( I) :

The hydrocarbyl-substituted succinic acids and/or anhydrides (A) (I) which are used for the production of component (A) in the present invention are represented by the formula:

where R is a hydrocarbyl group with from approx. 8 to approx. 40 carbon atoms, preferably from approx. 8 to approx. 30 carbon atoms, more preferably from approx. 12 to approx. 24 carbon atoms, and even more preferably from approx. 16 to approx. 18 carbon atoms. In a preferred embodiment, R is represented by the formula:

where R' and R" are independently hydrogen or straight-chain or substantially straight-chain hydrocarbyl groups, provided that the total number of carbon atoms in R is in the ranges indicated above. R' and R" are preferably alkyl or alkenyl groups. In a particularly preferred embodiment, R has from approx. 16 to approx. 18 carbon atoms, R' is hydrogen or an alkyl group with from 1 to approx. 7 carbon atoms, or an alkenyl group with from 2 to approx. 7 carbon atoms, and R" is an alkyl or alkenyl group with from about 5 to about 15 carbon atoms. Mixtures of two or more of these acids or anhydrides can be used.

The group R can be derived from one or more olefins with from approx.

8 to approx. 40 carbon atoms. These olefins are preferably alpha-olefins (sometimes referred to as mono-l-olefins) or isomerized alpha-olefins. Examples of alpha-olefins that may be used include 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1- octadecene, 1-nonadecene, 1-eicosene, 1-henicosene, 1-docosene, 1-tetracosene, 1-pentacosene, 1-hexa-cosene, 1-octacosene, 1-nonacosene, etc. Commercially to soluble alpha-olefin fractions which can used, include<c>15-18alpha-olefins, C^g-16alpha-olefins, 0^4-^5 alpha-olefins, Ci4_i3alpha-olefins, C^^.^<g>alpha-olefins, Ckj_ 2q alpha-olefins , Cg2-28alpha-olefins , etc. The C₁ and C₁₂ alpha-olefins are particularly preferred. Procedures for the production of these α-olefins are well known to those skilled in the art and are described e.g. under the heading "Olefins" in Encyclopedia of Chemical Technology, 2nd Edition, Kirk and Othmer, Supplement, pages 632-657, Interscience Publishers, Div. of John Wiley and Son, 1971.

Isomerized alpha-olefins are alpha-olefins that have been converted to internal olefins (ie, olefins in which the olefinic de-esterification is other than in the "-1-" or alpha position). The isomerized alpha-olefins suitable for use herein are generally in the form of mixtures of internal olefins with some alpha-olefins present. The methods for the isomerization of alpha-olefins are well known in the art. Briefly, these methods usually involve contacting an alpha-olefin with a cation exchange resin at a temperature in the range of e.g. 80 to approx. 130°C until the desired degree of isomerization is achieved. These products are described e.g. in US patent 4,108,889, and European patent application 20037.

In general, the hydrocarbyl-substituted succinic acids and anhydrides (A) (I) are prepared by reacting the above-mentioned alpha-olefins or isomerized alpha-olefins with the desired unsaturated carboxylic acid such as fumaric acid or its derivative such as maleic anhydride at a temperature in the area, e.g. from 160 to approx. 240°C, preferably from approx. 185 to approx. 210°C, and more preferably approx. 190°C. Generally, these reactions are carried out at atmospheric pressure, although pressures of up to 689.5 kPa can be used, particularly when the olefin has a relatively low molecular weight (eg Cg-C^g). Free radical inhibitors (eg t-butylcatechol) can be used to reduce or prevent the formation of polymeric by-products. The methods for preparing these hydrocarbyl-substituted succinic acids and anhydrides are well known to those skilled in the art, and are described e.g. in US Patent 3,412,111; Japanese Kokai Tokkyo Koho 81 12,382 and 82 35,580; Benn et al. "The Ene Reaction of Maleic Anhydride with Alkenes", J. C. S. Perkin II, (1977), pages 535-7; Remond, "Preparation-Properties et. Emplois de L'Anhydride Dodecenylsuccinique", Revue Des Produits Clinique (February 28, 1962), pages 57-64.

Component ( A) ( II) :

The water-dispersible amine-terminated poly(oxyalkylene)s are preferably alpha-omega-diaminopoly(oxyethylene)s, alpha-omega-diaminopoly(oxypropylene)poly(oxyethylene)poly(oxypropylene)s or alpha-omega-diaminopropylene oxide-terminated poly(oxyethylene )is. Component (A) (II) may also be a polyamino (eg, triamino, tetraamino, etc.) polyoxyalkylene provided that it is amine-terminated and that it is water dispersible. In the compounds containing both poly(oxyethylene) and poly(oxypropylene) groups, the poly(oxyethylene) groups predominate in order to achieve the desired water dispersibility. The terminal amines may be primary amines, e.g. —NIL?, or secondary amines, e.g. —NHR<*>where R<*>is a hydrocarbyl group with from 1 to approx. 18 carbon atoms, preferably from 1 to approx. 4 carbon atoms. RH is preferably an alkyl or an alkenyl group. These compounds usually have a number average molecular weight of at least approx. 2,000, preferably in the area from approx. 2,000 to approx. 30,000, more preferably in the range from approx. 2,000 to approx. 10,000, more preferably in the range from approx. 3,500 to approx. 6,500. Mixtures of two or more of these compounds can be used.

In a preferred embodiment, component (A) (II) is a compound represented by the formula:

where a is a number in the range from 0 to approx. 200; b is a number in the range from approx. 10 to approx. 650; and c is a number in the range from 0 to approx. 200. These compounds preferably have number average molecular weights in the range from approx. 2,000 to approx. 10,000, more preferably from approx. 3,500 to approx. 6,500. In another preferred embodiment, component (A) (II) is a compound represented by the formula:

where n is a number which is sufficient to give said compound a number-average molecular weight of at least approx. 2,000. These compounds preferably have number average molecular weights in the range from approx. 2,000 to approx. 10,000, more preferably from approx. 3,500 to approx. 6,500.

Examples of water-dispersible amine-terminated poly(oxy-ethylene)s which are useful in the present invention are described in US patents 3,021,232; 3,108,011; 4,444,566; and Re. 31,522.

Water-dispersible amine-terminated poly(oxyalkylene)s which are useful are commercially available from Texaco Chemical Company under the trade name Jeffamine.

Reaction of components ( AUD and ( A) ( II) to form component ( A) : The reaction of one or more of component (A) (I) with one or more of component (A) (II) to obtain the water-dispersible the reaction products (A) according to the invention can be carried out at temperatures varying from the highest of the melting temperatures of the reaction components up to the lowest of the decomposition temperatures of the reaction components or products. Usually it is carried out at a temperature in the range from about 60 to about 160°C, preferably from about 120 to about 160° C. Usually the reaction is carried out under amide-forming conditions, and the product thus formed is, for example, a semi-amide, i.e. an amide/acid.

In general, the ratio of equivalents of component (A) (I) to component (A) (II) varies from approx. 0.1:1 to approx. 8:1, preferably from approx. 1:1 to approx. 4:1, and advantageously approx. 2:1. The weight of 1 equivalent of component (A) (I) can be determined by dividing its molecular weight by the number of carboxylic functions present. With component (A) (I), the weight of 1 equivalent is equal to half of its molecular weight. The weight of 1 equivalent of the amine-terminated polyoxyalkyl (A) (II) can be determined by dividing its molecular weight by the number of terminal amine groups present. These can usually be determined from the structural formula of the amine-terminated polyalkyl or empirically through well-known methods.

The amide/acids formed by the reaction of components (A) (I) and

(A) (II) can be neutralized with e.g. one or more alkali metals, one or more amines, or a mixture

thereof, and thus converted into amide/salts. Furthermore, if these amide/acids are added to concentrates or functional fluids containing alkali metals or amines, amide/salts are usually formed in situ.

Among the alkali metals that can be used to neutralize these amides/acids and thus form such esters/salts are sodium, potassium and lithium. Suitable metal bases include the free metals and their oxides, hydroxides, alkoxides and basic salts. Examples are sodium hydroxide, sodium methoxide, sodium carbonate, sodium hydroxide, potassium carbonate, etc. Usually the ratio of the number of moles of alkali metal to equivalents of acid in the amide/acid is in the range from approx. 1:10 to approx. 2:1, preferably approx. 1:1. The weight of 1 equivalent acid in these amide/acids can be determined by dividing the molecular weight of the amide/acid by the number of —COOH groups present. These can usually be determined from the structural formula of the amide/acid or empirically using well-known titration methods.

Among the amines that can be used to neutralize these amide/acids are the N-(hydroxyl-substituted hydrocarbyl)-amines. These amines generally have from 1 to approx. 4, typically from 1 to approx. 2 hydroxyl groups per molecule. These hydroxyl groups are each attached to a hydrocarbyl group to form a hydroxyl-substituted hydrocarbyl group which is in turn attached to the amine part of the molecule. These N-(hydroxyl-substituted hydrocarbyl)amines can be monoamines or polyamines, and they can have a total of up to about 40 carbon atoms; generally they have a total of up to approx. 20 carbon atoms. They can be monoamines containing only a single hydroxyl group. These amines can be primary, secondary or tertiary amines, while the N-(hydroxyl-substituted hydrocarbyl) polyamines can have one or more of these types of amino groups. Mixtures of two or more of any of the above amines may also be used.

Specific examples of the N-(hydroxyl-substituted hydrocarbyl)-amines suitable for use in the present invention are N-(hydroxy-lower alkyl)-amines and polyamines, such as 2-hydroxyethylamine, 3-hydroxybutylamine, di-( 2-hydroxyethyl)amine, tri-(2-hydroxyethyl)amine, di-(2-hydroxypropyl)amine, N,N,N'-tri-(2-hydroxyethyl)ethylenediamine, N,N,N',N '-tetra(2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)plperazine, N,N,N' ,N'-tetra( 2-hydroxyethyl )ethylenediamine, N-(2-hydroxyethyl)piperazine , N , N' -di-(3-hydroxypropyl)piperazine, N-(2-hydroxyethyl)morpholine, N-(2-hydroxyethyl)-2-morpholine, N-(2-hydroxyethyl)-3-methyl-2-morpholine, N- (2-hydroxypropyl )-6-methyl-2-morpholino, N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone, N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone, N-( 2 -hydroxyethyl)-5-(N-butylcarbamyl)-2-piperidine, N-(2-hydroxyethyl)piperidine, N-(4-hydroxybutyl)piperidine, N,N-di-(2-hydroxyethyl)glycine, and ethers thereof with allphatic alcohols, especially lower alk noler, N,N-di(3-hydroxypropyl )-glycine, etc.

Additional amine alcohols are the hydroxy-substituted primary amines described in US patent 3,576,743 with the general formula:

where Ra is a monovalent organic radical containing at least one alcoholic hydroxy group. According to this patent, the total number of carbon atoms in Ra will not exceed approx. 20. Hydroxy-substituted aliphatic primary amines containing a total of up to approx. 10 carbon atoms, are useful. Generally useful are the polyhydroxy-substituted alkanol primary amines in which only one amino group is present, i.e. a primary amino group (having an alkyl substituent containing up to 10 carbon atoms and up to 4 hydroxyl groups. These alkanol primary amines correspond to RaNH2wherein Ra is a mono- or polyhydroxy-substituted alkyl group. It is typical that at least one of the hydroxyl groups is a primary alcoholic hydroxyl group. Trimethylolamlnomethane is a typical hydroxy-substituted primary amine. Specific examples of the hydroxy-substituted primary amines include 2-amino-l-butanol, 2-amino -2-methyl-l-propanol , p-(betahydroxyethyl )analine, 2-amino-l-propanol , 3-amino-l-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino- 2-ethyl-l,3-propanediol, N-(betahydroxy-propyl)-N'-(beta-aminoethyl)piperazine, 2-amino-l-butanol, ethanolamine, beta-(beta-hydroxyethoxy)ethylamine, glucamine, glucoamln , 4-amino-3-hydroxy-3-methyl-1-butene (which can be prepared according to methods known per se by ning of isoprene oxide with ammonia), N-3-( aminopropyl )-4 ( 2-

hydroxyethyl )-piperadine, 2-amino-6-methyl-6-heptanol, 5-amino-l-pentanol , N-beta-(hydroxyethyl )-1, 3-diIaminopropane, 1, 3-diamino-2-hydroxy- propane, N-(beta-hydroxyethoxyethyl)-ethylenediamine, etc. For further description of the hydroxy-substituted primary amines which are useful as the N-(hydroxyl-substituted hydrocarbyl)amines in the present invention, reference is made to US patent 3,576,743.

The amine is typically a primary, secondary or tertiary alkanolamine or mixture thereof. Such amines can be represented by the following respective formulas:

where each R is independently a hydrocarbyl group with from 1 to approx. 8 carbon atoms or hydroxyl-substituted hydrocarbyl group with from 2 to approx. 8 carbon atoms, and R' is a bivalent hydrocarbyl group with from approx. 2 to approx. 18 carbon atoms. The group —R'-OH in such formulas represents the hydroxyl-substituted hydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group. It is typically an acyclic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene group, etc. When two R groups are present in the same molecule, they may be joined by a direct carbon-to-carbon bond or through a heteroatom (eg, oxygen, nitrogen, or sulfur) to form a 5-, 6-, 7-, or 8-membered ring structure. Examples of such heterocyclic amines are N-(hydroxyl-lower alkyl)morpholines, -thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and the like. Typically, however, each R is a lower alkyl group of up to 7 carbon atoms.

The amine can also be an N-(hydroxyl-substituted hydrocarbyl)amine. Such amines can conveniently be prepared by reacting epoxides with the above-mentioned amines and can be represented by the formulas:

where x is a number from 2 to approx. 15, and R and R' have the meanings given above.

Polyamine analogues of these alkanolamines, especially alkoxylated alkylene polyamines (e.g. N,N-(diethanol)ethylenediamine) can also be used. Such polyamines can be produced by reacting alkylene amines (e.g. ethylenediamine) with one or more alkylene oxides (e.g. ethylene oxide, octadecene oxide) with from 2 to approx. 20 carbon atoms. Similar alkylene oxide-alkanolamine reaction products can also be used such as the products prepared by reacting the above-mentioned primary, secondary or tertiary alkanolamines with ethylene, propylene or higher epoxides in a molar ratio of 1:1 or 1:2. Reactant ratios and temperatures for carrying out such reactions are well known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines include N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, mono(hydroxypropyl)-substituted diethylenetriamine, di(hydroxypropyl) -substituted tetraethylenepentamine, N-(3-hydroxybutyl)-tetramethylenediamine, etc. Higher homologues obtained by condensation of the above illustrated hydroxyalkylene polyamines through amino radicals or through hydroxy radicals are also useful. Condensation through amino radicals results in a higher amine accompanied by removal of ammonia while condensation through hydroxy radicals results in products containing ether linkages accompanied by removal of water. Mixtures of two or more of any of the above-described mono- or polyamines are also useful.

In general, the ratio of the number of moles of amine to equivalents of amide/acid is in the range from approx. 1:10 to approx. 10:1, preferably approx. 1:1.

The alkali metal or amine is preferably added after the reaction between components (A) (I) and (A) (II) is complete, i.e. to the resulting amide/acid. In general, the addition of alkali metal or amine is carried out at a temperature in the range from the highest of the melting temperatures of the amide/acid, or amine or metal base for the alkali metal up to the lowest decomposition temperatures for such materials. The temperature is preferably in the range from approx. 60 to approx. 160°C, more preferably from approx. 120 to approx. 160.

The following examples describe exemplary preparations of water-dispersible hydrocarbyl-substituted succinic acid and/or

—anhydride/amine-terminated polyoxyalkylene reaction products (A) According to the invention. Unless otherwise stated, all parts and percentages are calculated by weight.

Example 1

Part A

2,960 parts C^, alpha-olefin and 100 parts Amberlyst 15 (a product of the Rohm & Haas Company Identified as a cation exchange resin) are added to a 5 liter flask equipped with a nitrogen scavenger (56.6 dm^ per hour), stirring , thermal well and water trap arranged under a cooler. The mixture

heated to 120°C for 1.5 hours with the stirrer operated at 350 rpm. The filtrate is the desired product.

Part B

367.5 parts of maleic anhydride are added to a 2 liter flask equipped with stirrer, thermowell, reflux cooler and gas inlet pipe. The maleic anhydride is melted and 765 parts of the product from part A are added. The mixture is heated to 180-200°C for 9.75 hours. The mixture is stripped under a vacuum of 30 mm Hg at 182°C, and then cooled to 115°C. The mixture is then stripped under a vacuum of 0.7 mm Hg at 145°C and then cooled to 50°C. The mixture is filtered with diatomaceous earth. The filtrate is the desired product.

Example 2

Part A

1100 parts of a C^^.^g alf a-olefin fraction and 14 parts Amberlyst 15 are added to a 2 liter flask equipped with a stirrer, thermowell, reflux condenser and stopper. The mixture is heated to 150-155°C for 3.25 hours, and is then filtered. The filtrate is the desired product.

Part B

412 parts of maleic anhydride and 920 parts of the product in part A are added to a 2 liter flask equipped with a stirrer, thermo-well, reflux condenser and stopper. The mixture is heated to 90°C. Stirring is started. The mixture is heated to 1190-195°C with stirring, and kept at this temperature for 11.5 hours and then cooled to 80°C. The mixture is stripped under a vacuum of 38 mm Hg at a temperature of 120°C.

The mixture is then stripped using a vacuum of 0.45 mm Hg at 180°C. The mixture is filtered with diatomaceous earth. The filtrate is the desired product.

Example 3

5,775 parts of a C±5-±& alpha-olefin fraction (with a carbon distribution of 1% C14, 29$ C15, 28$ C16, 27$ C17, 14$ C18 and 1% C-Lg) is passed through a 30, 5 cm column packed with activated aluminum oxide into a 12 liter flask containing maleic anhydride. The mixture is heated to 214°C and held at this temperature for 7 hours with a nitrogen spreader (5.7 dm<3>per hour) and then cooled to room temperature. The mixture is then heated to 209-212°C and held at this temperature for 7 hours, and then cooled to room temperature. 1,500 parts of textile alcohol are added, and the mixture is stirred for 1 hour. The mixture is filtered with diatomaceous earth. The mixture is stripped under a vacuum of 30 mm Hg at 121°C and then cooled to room temperature. The mixture is then stripped under a vacuum of 0.7 mm Hg at 168°C and then cooled to room temperature. The mixture is filtered with diatomaceous earth at room temperature. The filtrate is the desired product.

Example 4

A 20 liter boiler is flushed with nitrogen. 475 parts of a C^g_ 24&1 f a-olef inf raks j on is supplied to the boiler. The contents of the kettle are heated to 71°C and mixed. 189 parts of maleic anhydride are added. The mixture is heated to 200°C over a 6 hour period, the temperature increasing at a rate of 22°C per minute. hour. The mixture is then heated to 220°C over a 4 hour period, the temperature increasing at a rate of 5°C per minute. hour. The temperature is kept at 220°C for 10 hours. The mixture is blown with nitrogen until the level of unreacted maleic anhydride is approx. 0.05$ and then cooled to room temperature to provide the desired product.

Example 5

100 parts Jeffamine ED-4000 (a product of Texaco Chemical Co. identified as a diamine with an average molecular weight of about 4,000 and is a primary amine-terminated propylene oxide-terminated polyoxyethylene) and 16.3 parts of the product from Part B in Example 1 are mixed together, heated at a temperature of 130°C for 3 hours, and then cooled to room temperature to obtain the desired product.

Example 6

100 parts Jeffamine ED-6000 (a product of Texaco Chemical Co. identified as a diamine with an average molecular weight of about 6,000 and is a primary amine-terminated propylene oxide-terminated polyoxyethylene) and 10.8 parts of the product from Part B in Example 1 are mixed together, heated at a temperature of 130°C for 3 hours and then cooled to room temperature to obtain the desired product.

Example 7

20 parts of Jeffamine EDU-4000 (a product of Texaco Chemical Co. identified as a diamine with an average molecular weight of about 4,000 prepared by coupling urea with a primary amine-terminated propylene oxide-terminated polyoxyethylene) is melted at a temperature of 70°C and mixed with 3.4 parts of the product from part B in example 2. The mixture is heated at a temperature of 121°C for 4 hours, and then cooled to room temperature to obtain the desired product.

Example 8

20 parts of Jeffamine EDU-4,000 are melted at a temperature of 70°C and mixed with 6.8 parts of the product from part B of Example 2. The mixture is heated at a temperature of 121°C for 4 hours and then cooled to room temperature to obtain the desired product.

Example 9

37.3 parts Jeffamine ED-2001 (a product of Texaco Chemical Co. identified as a diamine with an average molecular weight of about 2,000 and is a primary amine-terminated propylene oxide-terminated polyoxyethylene) and 12.2 parts of the product from Part B in example 2 are mixed together, heated at 105-115°C for 3-4 hours, and then cooled to room temperature to obtain the desired product.

Component (B):

The surfactants (B) useful may be of the cationic, anionic, nonionic or amphoteric type. Many such surfactants of each type are known in the art. See e.g. McCutcheon's "Emulsifiers and Detergents", 1981, North American Edition, published by McCutcheon Division, MC Publishing Co., Glen Rock, New Jersey, USA.

Among the nonionic types of surfactants are the alkylene oxide treated products such as ethylene oxide treated phenols, alcohols, esters, amines and amides. Ethylene oxide/propylene oxide block copolymers are also useful nonionic surfactants. Glycerol esters and sugar esters are also known to be nonionic surfactants. A typical class of non-ionic surfactant useful in the present invention is the dialkylene oxide-treated alkylphenols such as the ethylene oxide-alkylphenol condensates sold by the Rohm & Haas Company. A specific example of these is Triton X-100, which contains an average of 9-10 ethylene oxide units per molecule, has an HLB value of approx. 13.5 and a molecular weight of approx. 628. Many other suitable nonionic surfactants are known, see e.g. the above MucCutcheon reference as well as the treatise "Non-ionic Surfactants" published by Martin J. Schick, M. Dekker Co., New York, 1967.

As mentioned above, cationic, anionic and amphoteric surfactants can also be used. In general, all of these are hydrophilic surfactants. Anionic surfactants contain negatively charged polar groups while cationic surfactants contain positively charged polar groups. Amphoteric dispersants contain both types of polar groups in the same molecule. A general overview of useful surfactants can be found in the Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition, Volume 19, pages 507 et seq., (1969, John Wiley & Son, New York) and the above works published under the name of McCutcheons.

Among the useful anionic types of surfactants are the well-known carboxylate soaps, the organosulfates, the sulfonates, the sulfocarboxylic acids and their salts, and the phosphates. Useful cationic surfactants include nitrogen compounds such as amine oxides and the well-known quaternary ammonium salts. Amphoteric surfactants include amino acid type materials and similar types. Various cationic, anionic and amphoteric dispersants are available from industry, particularly from such companies as Rohm & Haas and Union Carbide Corporation, both of America. Additional information on anionic and cationic surfactants can also be found in the textbooks "Anionic Surfactants", Parts II and III, edited by W. M. Linfield, published by Marcel Dekker, Inc., New York, 1976 and "Cationic Surfactants" edited by E. Jungermann, Marcel Dekker, Inc., New York, 1976.

In a preferred embodiment, the surfactant is

(B) the condensation product of a primary amine with ethylene oxide such as those commercially available from Armak under

the trade name Ethomeen.

In another preferred embodiment, the surfactant (B) is a polyalkylene glycol ether such as the polyethylene glycol ethers of primary and secondary alcohols available from Union Carbide under the trade name Tergitol.

In a further preferred embodiment, the surfactant (B) is a tallow oil such as the distilled tallow oil available from Union Camp under the trade name Unitol.

In a particularly preferred embodiment of the invention, the surfactant (B) is at least one nitrogen-containing phosphorus-free reaction product produced by reaction of (B) (I) at least one carboxylic acid acylating agent which has at least one hydrocarbyl-based substituent with at least from approx. 12 to approx. 500 carbon atoms with (B) (II) at least one (A) N-(hydroxyl-substituted hydrocarbyl)amine, (b) hydroxyl-substituted poly-(hydrocarbyloxy) analogue of said amine, or (c) mixtures of (a) and (b).

In general, the hydrocarbyl-based substituents present in the acylating agents (b) (I) are free of acetylenic deprotonation; ethylenic debonding, when present, will generally be such that no more than one ethylenic bond is present for every 10 carbon-to-carbon bonds in the substituent. Subst in tuen tene is often completely saturated and therefore contains no ethylenic extract.

The hydrocarbyl-based substituents present in the acylating agents (B) (I) can be obtained from olefin polymers or chlorinated analogues thereof. The olefin monomers from which the olefin polymers are derived are polymerizable olefins and monomers which are characterized by having one or more ethylenically unsaturated groups. They can be monoolefinic monomers such as ethylene, propylene, butene-1, isobutene and octene-1 or polyolefinic monomers (usually diolefinic monomers such as butadiene-1,3 and isoprene). Typically, these monomers are terminal olefins, i.e., olefins characterized by the presence of the group ^C=CH2- Certain internal olefins can also serve as monomers (these are sometimes referred to as medial olefins). When such medial olefin monomers are used, they are normally used in combination with terminal olefins to form olefin polymers which are interpolymers. The hydrocarbyl-based substituents may nevertheless also include aromatic groups (especially phenyl groups and lower alkyl- and/or lower alkoxy-substituted phenyl groups such as para(tertiary butyl)phenyl groups and alicyclic groups as would be obtained from polymerizable cyclic olefins or alicyclic-substituted polymerizable cyclic olefins .The olefin polymers are usually free of such groups.However, olefin polymers derived from such interpolymers of both 1,3-dienes and styrenes such as butadiene-1,3 and styrene or para(tertiarybutyl)styrene are exceptions to this general rule.

The olefin polymers are generally homo- or interpolymers of terminal hydrocarbyl olefins with from approx. 2 to approx. 26 carbon atoms. A more typical class of olefin polymers is selected from the group consisting of homo- and interpolymers of terminal olefins having 2-6 carbon atoms, especially those having 2-4 carbon atoms.

Specific examples of terminal and medial olefin monomers that can be used to prepare the olefin polymers from which the hydrocarbyl-based substituents in component (B) (I) are derived include ethylene, propylene, butene-1, butene-2, isobutene, pentene-1, hexene—1, heptene-1, octene-1, nonene-1, decene-1, pentene-2, propylene tetramer, diisobutylene, isobutylene trimer, butadiene-1,2, butadiene-1,3, pentadiene-1,2-pentadiene- 1,3-isoprene, hexadiene-1,5, 2-chlorobutadiene-1,3, 2-methylheptene-1, 3-cyclohexylbutene-1, 3,3-dimethylpentene-1, styrenedivinylbenzene, vinyl acetate, allyl alcohol, 1-methyl- vinyl acetate, acrylonitrile 1, ethyl acrylate, ethyl vinyl ether and methyl vinyl ketone. Of these, the pure hydrocarbyl monomers are more typical, and the terminal olefin monomers are particularly typical.

Often the olefin monomers are poly(isobutene)s such as are obtained by polymerization of a C4raffiner stream which has a butene content from approx. 35 to approx. 75 weight-$ and an isobutene content of approx. 30 to approx. 60 wt-$ in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. These polyisobutenes contain mainly (i.e. over 80$ of the total repeating units) isobutene repeating units with the configuration:

The hydrocarbyl-based substance in the carboxylic acid acylating agent (B) (I) is typically a hydrocarbyl, alkyl or alkenyl group with from 12 to approx. 500 carbon atoms. Useful acylating agents include substituted succinic acid- or anhydride-containing hydrocarbyl-based substituents with from about 20 to approx. 500 carbon atoms, more preferably from approx. 30 to approx. 500 carbon atoms, more preferably from approx. 50 to approx. 500 carbon atoms, more preferably from approx. 50 to approx. 90 carbon atoms, and even more preferably from approx. 60 to approx. 75 carbon atoms.

Often the agents (B) (I) used in the production of the surfactants (B) are substituted succinic acids or derivatives thereof which can be represented by the formula:

wherein "hyd" is the above-identified hydrocarbyl-based substituent. Such succinic acylating agents can be prepared by reacting maleic anhydride, maleic acid or fumaric acid with the above-mentioned olefin polymer. In general, the reaction only involves heating the two reactants at a temperature from approx. 150 to approx. 200°C. Mixtures of said polymeric olefins as well as mixtures of unsaturated mono- and di-carboxylic acids can also be used.

The N-(hydroxyl-substituted hydrocarbyl)amines (B) (II) generally have from 1 to about 4, typically from 1 to approx. 2 hydroxyl groups per molecule. These hydroxyl groups are each attached to a hydrocarbyl group to form a hydroxyl-substituted hydrocarbyl group which is in turn attached to the amine part of the molecule. These N-(hydroxyl-substituted hydrocarbyl)amines can be monoamines or polyamines, and they can have a total of up to about 40 carbon atoms; generally they have a total of up to approx. 20 carbon atoms. They can be monoamines containing only a single hydroxyl group. These amines may be primary, secondary or tertiary amines while the N-(hydroxyl-substituted hyrocarbyl)polyamines may have one or more of any of these types of amino groups. Mixtures of two or more of any of the above-described amines may also be used.

Specific examples of the N-(hydroxyl-substituted hydrocarbyl)amines which are suitable for use in the present invention are the N-(hydroxylower alkyl)amines and polyamines such as 2-hydroxyethylamine, 3-hydroxybutylamine, di-(2-hydroxyethyl)amine, tri-(2-hydroxyethyl)amine, di-(2-hydroxypropyl)amine, N,N,N'-tri-(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetra(2-hydroxyethyl) ethylenediamine, N-(hydroxyethyl)piperazine, N,N'-di-(3-hydroxypropyl)piperazine, N-(2-hydroxyethyl)morpholine, N-(2-hydroxyethyl)-2-morpholine, N-(2-hydroxyethyl) )-3-methyl-2-morpholino, N-(2-hydroxypropyl )-6-methyl-2-morpholino, N-(2-hydroxypropyl)-5-carbethoxy-2-piperidone, N-(2-hydroxypropyl)- 5-carbethoxy-2-piperidone, N-(2-hydroxyethyl)-5-(N-butylcarbamyl)-2-piperidone, N-(2-hydroxyethyl)piperidine, N-(4-hydroxybutyl)piperidine, N,N -di(2-hydroxyethyl)glycine, and ethers thereof with aliphatic alcohols, especially lower alkanols, N,N-di(3-hydroxypropyl)glycine, etc.

Additional amine alcohols are the hydroxy-substituted primary amines described in US patent 3,576,743 with the general formula:

where Ra is a monovalent organic radical containing at least one alcoholic hydroxy group. According to this patent, the total number of carbon atoms in Ra will not exceed approx. 20. Hydroxy substituted aliphatic primary amines containing a total of up to approx. 10 carbon atoms are useful. Generally useful are the polyhydroxy substituted alkanol primary amines in which only one amino group is present (ie, a primary amino group) having an alkyl substituent containing up to 10 carbon atoms and up to 4 hydroxyl groups. These alkanol primary amines correspond to RgNHg where Ra is a mono- or

polyhydroxy-substituted alkyl group. It is typical that at least one of the hydroxyl groups is a primary alcoholic hydroxyl group. Trismethylolaminomethane is a typical hydroxy-substituted primary amine. Specific examples of the hydroxy-substituted primary amines include 2-amino-l-butanol, 2-amino-2-methyl-1-propanol, p-(betahydroxyethyl )-anal In, 2-amino-l-propanol, 3-amino -l-propanol, 2-a,mino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(beta-hydroxypropyl 1 ) -N' - (betaaminoethyl ) piperazine, 2-amino-l-butanol, ethanolamine, beta-(betahydroxyethoxy)ethylamine, glucamine, glucoamine, 4-amino-3-hydroxy-3-methyl-l-butene (which can be prepared according to methods known in the art by reaction of isoprene oxide with ammonia), N-3-(aminopropyl)-4(2-hydroxyethyl)piperadine, 2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol, N-beta-(hydroxyethyl) -1,3-diaminopropane, 1,3-diamino-2-hydroxypropane, N-(betahydroxy-ethoxyethyl)-ethylenedamine, etc. For further description of the hydroxy-substituted primary amines which are useful as the N-(hydroxyl-substituted hydrocarbyl)amines in the present invention, reference is made to US patent 3,576,743.

The amine (B) (II) is typically a primary, secondary or tertiary alkanolamine or mixture thereof. Such amines can be represented, respectively, by the formulas:

where each R is independently a hydrocarbyl group with from 1 to approx. 8 carbon atoms or hydroxyl-substituted hydrocarbyl group with from 2 to approx. 8 carbon atoms, and R' is a bivalent hydrocarbyl group with from approx. 2 to approx. 18 carbon atoms. The group —R'-OH in such formulas represents the hydroxyl-substituted hydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group. It is typically an acyclic straight or branched alkylene group such as an ethylene, 1,2—

propylene, 1,2-butylene, 1,2-octadecylene group, etc. When two R groups are present in the same molecule, they may be joined by a direct carbon-to-carbon bond or through a heteroatom ( eg oxygen, nitrogen or sulphur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples of such heterocyclic amines include N-(hydroxylaveralkyl)-morpholines, —thiomorpholines, —piperidines, —oxazolidines, —thiazolidines and the like. However, each R is typically a lower alkyl group of up to 7 carbon atoms.

Amine (B) (II) can also be an ether-N-(hydroxyl-substituted hydrocarbyl)amine. Such amines can conveniently be prepared by reacting epoxides with the amines described above and can be represented by the formulas:

where x is a number from 2 to approx. 15, and R and R' have the meanings given above.

Polyamine analogues of these alkanolamines, especially alkoxylated alkylene polyamines, (eg N,N-diethanol)ethyldiamine) can also be used. Such polyamines can be prepared by reacting alkylene amines (e.g. alkylenediamine) with one or more alkylene oxides (e.g. ethylene oxide, octadecene oxide) with from 2 to approximately 20 carbon atoms. Similar alkylene oxide alkanol-amine reaction products can also be used such as the products prepared by reacting the above-described primary, secondary or tertiary alkanolamines with ethylene, propylene or higher epoxides in a molar ratio of 1:1 or 1:2. Reactant ratios and temperatures for carrying out such reactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines include N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, mono-(hydroxypropyl)-substituted diethylenetriamine, di( hydroxypropyl)-substituted tetraethylenepentamine, N-(3-hydroxybutyl)-tetramethylenediamine, etc. Higher homologues obtained by condensation of the three hydroxyalkylene polyamines illustrated above through amino radicals or through hydroxy radicals are also useful.

Condensation through amino radicals results in a higher amine accompanied by removal of ammonia while condensation through the hydroxy radicals results in products containing ether linkages accompanied by removal of water. Mixtures of two or more of any of the above-described mono- or polyamines are also useful.

Particularly useful examples of N-(hydroxyl-substituted hydrocarbyl)amines (A) (II) include mono-, ,1- and tri-ethanolamine, diethylethanolamine, di-(3-hydroxylbutyl)amine, N-(hydroxylbutyl)amine, N -( 4-hydroxylbutyl )amine , N,N-di-(2-hydroxylpropyl)amine, N-(2-hydroxylethyl)morpholine and its thioanalogue, N-(2-hydroxylethyl)cyclohexylamine, N-3-hydroxyl-cyclopentylamine, o-, m- and p-aminophenol, N-(hydroxylethyl)-piperazine, N,N'-di(hydroxylethyl)piperazine, etc. Preferred amines are diethylethanolamine and ethanolamine and mixtures thereof.

The reaction of the acylating agent (B) (I) with the hydroxylamine

(B) (II) can be carried out at temperatures varying from approx. 30°C to the decomposition temperature of the reaction components

and/or the products that have the lowest such temperature. In general, it is carried out at a temperature in the range from approx. 50 to approx. 150°C, but usually at a temperature below approx. 100°C. Often the reaction is carried out under ester-forming conditions

looks, and the thus formed product is e.g. an ester, salt, amide, imide, amine ester or mixture of such products. The salt can be an internal salt in which one of the carboxyl groups is ionically bound to a nitrogen atom in the same group, or it can be an external salt in which the ionic salt group is formed with a nitrogen atom that is not part of the same group that forms the ester group. Mixtures of acylating agents and/or mixtures of hydroxylamines can be used.

In general, the ratio of acylating agent (B) (I) to N-(hydroxyl-substituted hydrocarbyl)amine (B) (II) is in the range from approx. 0.5 to approx. 3 mol amine (B) (II) per equivalent acylating agent (B) (I). An equivalent acylating agent

(B) (I) can be determined by dividing its molecular weight by the number of carboxyl functions present. These can

usually determined from the structural formula of the acylating agent or empirically using well-known titration methods. A succinic anhydride or di(alkyl)ester acylating agent has e.g. an equivalent weight of half its molecular weight.

The reaction products produced by reacting components (B) (I) and (B) (II) are described in US patents 4,329,249; 4,368,133; 4,435,297; 4,447,348; and 4,448,703.

Example 10

To a charge of 1,000 parts of etpolyisobutene (Mn = 950)-substituted succinic anhydride heated in a resin kettle with stirring to approx. 90°C, 209 parts of N,N-diethylethanolamine are slowly added over a 2-hour period. Heating is continued for a further 1 hour at 90°C. The heated reaction mixture is cooled to room temperature to obtain the desired product.

Concentrates and water-based functional fluids

Components (A) and (B) are generally provided in the compositions according to the invention at weight ratios for (A): (B) in the range from approx. 1:5 to approx. 5:1, preferably from approx. 1:1 to approx. 3:1. Mixtures of more than one of the components (A) and/or (B) can be provided in such compositions. When such mixtures are provided for a component, the total amount of said component will usually still fall within the indicated weight ratios.

The invention includes aqueous systems or compositions characterized by an aqueous phase with components (A) and (B) dispersed in the aqueous phase. This aqueous phase is preferably a continuous aqueous phase. These aqueous systems usually contain at least approx. 30 wt-$ water. Such aqueous systems include both concentrates containing from approx. 30 to approx. 90$, preferably from approx.

50 to approx. 80$ water; and water-based functional fluids containing a main amount of water and a smaller thickening amount of present compositions, preferably from approx. 1.5 to approx. 10$, more preferably from approx. 3 to approx. 6 weight-$ of said compositions. The concentrates preferably contain from approx. 10 to approx. 70 weight-$ of the present compositions, more preferably from approx. 20 to approx. 50 weight-$ of said compositions. The concentrates generally contain less than approx. 50$, preferably less than approx. 25$, more preferably less than approx. 15$, and even more preferably less than approx. 6$ hydrocarbon oil. The water-based functional fluids contain less than approx. 15$, preferably less than approx. 5$, and more preferably less than approx. 2$ hydrocarbon oil. These concentrates and the water-based functional fluids may possibly include other conventional additives that are usually used in water-based functional fluids. These other additives include functional additives, corrosion inhibitors, shear stabilizers, bactericides, dyes, water softeners, odor masking agents, antifoam agents, etc., as well as additional surface-active agents beyond those specified as components

(B).

The concentrates are analogous to the water-based functional ones

the fluids with the exception that they contain less water and relatively more of the other components. The concentrates can be converted into water-based functional fluids by dilution with water. This dilution is usually done using standard mixing techniques. This is often an appropriate method because the concentrate can be shipped to the point of use before additional water is added. The costs of shipping a significant amount of water in the final water-based functional fluid are thus saved. Only the water that is necessary to formulate the concentrate (which is determined primarily on the basis of ease of handling and appropriateness factors) needs to be shipped.

In general, these water-based functional fluids are produced by diluting concentrates with water, where the ratio of water to concentrate is usually in the range from approx. 80:20 to approx. 99:1 calculated by weight. When dilution is carried out within these ranges, it will appear that the final water-based functional fluid contains at most an insignificant amount of hydrocarbon oil.

Included in the invention are also methods for producing aqueous systems, including both concentrates and water-based functional fluids, containing other conventional additives that are commonly used in water-based functional fluids. These methods include the steps: (1) Mixing the present composition with such other conventional additives either simultaneously or sequentially to form a dispersion or solution; optionally (2) combining said dispersion or solution with water to form said aqueous concentrate; and/or (3) dilution of said dispersion or solution, or concentrate with water whereby the total amount of water used is the amount required to give the desired concentration of the present composition and other functional additives in said concentrates or said water-based functional fluids. These mixing steps are carried out using conventional equipment and generally at room temperature or slightly elevated temperatures, usually below 100°C and often below 50°C. As indicated above, the concentrate can be formed and then shipped to the point of use where it is diluted with water to form the desired water-based functional fluid. In other cases, the finished water-based functional fluid can be formed directly in the same equipment that is used to form the concentrate or the dispersion or the solution.

The functional additives that can be used are typically oil-soluble, water-insoluble additives that function in conventional oil-based systems as E.P. agents, anti-wear agents, load-carrying agents, friction-modifying agents, lubricants, etc. They can also act as anti-slip agents, film formers and friction modifiers. As is known, such additives can act in two or more of the above ways; e.g. E.P. agents often act as load-carrying agents.

The term "oil-soluble, water-insoluble functional additive" refers to a functional additive that is not soluble in water above a level of approx. 1 g per 100 ml of water at 25°C, but is soluble in mineral oil to the extent of at least 1 g per liter at 25°C.

These functional additives may also include certain solid lubricants such as graphite, molybdenum disulfide and polytetrafluoroethylene and related solid polymers.

These functional additives may also include friction polymer formers. Briefly, these are potential polymer-formed materials that are dispersed in a liquid carrier at low concentration and that polymerize upon rubbing or contact with surfaces to form protective polymeric films on the surfaces. The polymerizations are believed to result from the heat developed by the rubbing and possibly from catalytic and/or chemical action of the newly exposed surface. A specific example of such materials are dilinoleic acid and ethylene glycol combinations which can form a polyester friction polymer film. These materials are known in the art and descriptions of them can be found, e.g. in the journal "Where", volume 26, pages 369-392, and in West German published patent application 2,339,065.

These functional additives are typically known metal or amine salts of organosulfur, phosphoric, boric or carboxylic acids which are the same as or of the same type as used in oil-based fluids. Such salts are typically carboxylic acids with 1-22 carbon atoms including both aromatic and aliphatic acids; sulfuric acids such as alkyl sulphonic acids and aromatic sulphonic acids and the like; phosphoric acid such as phosphoric acid, phosphoric acid, phosphinic acid, acid phosphate esters and analogous sulfur homologues such as thiophosphoric acid and dithiophosphoric acid and related acid esters; boric acids include boric acid, acid borates, etc. Useful functional additives also include metal dithiocarbamates such as molybdenum and antimony thiocarbamates; as well as dibutyltin sulphide, tributyltin oxide, phosphates and phosphites; boratamine salts, chlorinated waxes; trialkyl tin oxide, molybdenum phosphates and chlorinated waxes.

Many such functional additives are known in the art. Descriptions of additives useful in conventional oil-based systems and in present aqueous systems can be found, e.g. in "Advances in Petroleum Chemistry and Refining", Volume 8, published by John J. McKetta, Interscience Publishers, New York, 1963, pages 31-38; Kirk-Othmer "Encyclopedia of Chemical Technology; Volume 12, 2nd Edition, Interscience Publishers, New York, 1967, from page 575; "Lubricant Additives" by M.W. Raney, Noyes Data Corporation, Park Ridge, N.J. USA, 1973; and " Lubricant Additives" by J.V. Smalheer and R.K. Smith, The Lezius-Hiles Co., Cleveland, Ohio, USA.

In certain of the typical aqueous systems of the invention, the functional additive is a sulfur or chlorine-sulfur E-P agent known to be useful in oil-based systems. Such materials include chlorinated aliphatic hydrocarbons such as chlorinated waxes; organic sulfides and polysulfides such as benzyl disulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized spermaceti oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulphurised hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorous esters such as the dihydrocarbon and trihydrocarbon phosphites, ie, dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphite; metal thiocarbamates such as zinc dioctyl dithiocarbamate and barium heptylphenol dithiocarbamate; and Group II metal salts of phosphorus dithionic acid such as zinc dicyclohexyl phosphorodithionate, and the zinc salts of a phosphorodithionic acid.

The functional additive can also be a film former such as a synthetic or natural latex or emulsion thereof in water. Such latexes include natural rubber latexes and synthetic latexes of polystyrene butadienes.

The functional additive can also be anti-choking or anti-howling agents. Examples of the former are amide metal-dithiophosphate combinations as described in West German patent m 1,109,302; amine salt-azomethane combinations as described in British Patent 893,977; or amine dithiophosphate as described in US patent 3,002,014. Examples of anti-howling agents are N-acylsarcosines and derivatives thereof as described in US patents 3,156,652 and 3,156,653; sulfurized fatty acids and esters thereof as described in US patents 2,913,415 and 2,982,734; and esters of dimerized fatty acids as described in US patent 3,039,967.

Specific examples of functional additives useful in the present systems include the following commercially available products.

Mixtures of two or more of any of the functional additives described above can also be used. A functionally effective amount of the functional additive is typically present in the present aqueous systems. If the functional additive is primarily to serve as a load-carrying agent, it is e.g. present in a load-bearing amount.

Available aqueous systems often contain at least one inhibitor for corrosion of metals. These inhibitors can prevent corrosion of either ferrous or non-ferrous metals

(e.g. copper, bronze, brass, titanium, aluminium, etc.)

or both. The inhibitor can be of an organic or inorganic nature. Usually it is sufficiently soluble in water to give a satisfactory inhibitory effect, although it can function as a corrosion inhibitor without dissolving in water, and it therefore need not be water-soluble. Many suitable inorganic inhibitors useful in the present aqueous systems are known to those skilled in the art. Included are those described in "Protective Coatings for Metals" by Burns and Bradley, Reinhold Publishing Corporation, Second Edition, Chapter 13, pages 596-605. Specific examples of useful inorganic inhibitors include alkali metal nitrates, sodium di- and -tri-polyphosphate, potassium and dipotassium phosphate, alkali metal borate and mixtures thereof. Many suitable organic inhibitors are known to those skilled in the art. Specific examples include hydrocarbylamine and hydroxy substituted hydrocarbylamine neutralized acid compounds such as neutralized phosphates and hydrocarbyl phosphate esters, neutralized fatty acids (e.g., those having from about 8 to about 22 carbon atoms), neutralized aromatic carboxylic acids (e.g., eg 4-tertiarybutylbenzoic acid), neutralized naphthenic acids and neutralized hydrocarbyl sulphonates. Mixed salt esters of alkylated succinimides are also useful. Particularly useful amines are the alkanolamines such as methanolamine, diethanolamine, triethanolamine and the corresponding propanolamines. Mixtures of two or more of any of the above-described corrosion inhibitors

rer can also be used. The corrosion inhibitor is usually present in concentrations in which they are effective in inhibiting corrosion of metals with which the aqueous composition contacts.

Some of the aqueous systems according to the present invention (especially those used for cutting or shaping metals) can also contain at least one polyol with inverse solubility in water. Such polyols are those that become less soluble as the temperature of the water increases. Thus, they can act as surface lubricants during cutting and machining operations because, as the fluid heats up as a result of friction between a metal workpiece and tool, the inverse solubility polyol will "plate out" on the surface of the workpiece and thus improve the lubricating properties.

Present aqueous systems may also include at least one bacteriocide. Such bacteriocides are well known to those skilled in the art, and specific examples can be found in the aforementioned McCutcheon publication in the section entitled "Functional Materials" under the heading "Antimicrobials" on pages 9-20. In general, these bacteriocides are water-soluble, at least to the extent that they can act as bacteriocides.

Available aqueous systems can also contain such other materials as dyes, e.g. an acid green dye; water softeners, e.g. ethylenediaminetetraacetate sodium salt or nitrilotriacetic acid; odor masking agents, e.g. citronella, lemon oil, etc.; and antifoam agents such as the well-known slllkon antifoam agents.

The aqueous systems according to the invention can also include an antifreeze additive when it is desired to use the composition at a low temperature. Materials such as ethylene glycol and analogous polyoxyalkylene polyols can be used as antifreeze agents. It is clear that the amount used will depend on the degree of antifreeze protection desired, and will be known to a person skilled in the art.

As indicated above, the present aqueous systems may contain additional surfactants beyond those indicated as component (B). These additional surfactants are useful for improving the dispersibility of the above-mentioned other additives, especially the functional additives. Any one or more of the surfactants listed above as component (B) may be used. These surfactants, when used, are generally used in effective amounts to improve the dispersion of the above-mentioned additives in the present aqueous systems.

It should also be pointed out that many of the components described above for the production of the aqueous systems according to the invention are industrial products which exhibit or give more than one property to such aqueous systems. Thus, a single component can provide several functions and thereby eliminate or reduce the need for another additional component. Thus, e.g. an E.P. agent such as tributyltin oxide also functions as a bacteriocide.

Illustrative water-based functional fluids covered by the invention are described in tables II-IV. Tables II and III also contain formulations that are not covered by the invention for comparison purposes. These functional fluids are produced by mixing the components at a temperature in the range from approx. 50 to approx. 70°C using conventional mixing techniques. The thickeners of the present invention (if present) are first mixed with the water and sodium hydroxide (if present). These components are stirred for approx. 1/2 hour, and then add the remaining ingredients. The numerical values given in Tables II-IV are in parts by weight.

In Table II, formulations B-D are covered by the present invention, while formulation A is outside the scope of the invention. That is, formulations B-D include both components

(A) and (B), while formulation A only comprises component (A). Although the product of Example 6 (ie component (A)) is useful

alone as a thickening agent, the combinations provided in formulations B-D (i.e., component (A) plus one or more of component (B)) provide significantly improved thickening or higher viscosity relative to formulation A, (i.e., component (A) only) .

In table III, formula rings E, G, I and K are covered by the present, while formulations F, H, J and L lie outside the scope of the invention. That is, formulations E, G, I and K contain the product of Example 6 (ie component (A)) plus a number of surfactants (ie component (B)), while formulations F, H, J and L contain only the the surfactants (ie component (B)). Formulations E and F are identical with the exception that formulation E contains the product in example 6 and a correspondingly smaller amount of water; the kinematic viscosity at 50°C for formulation E was 17.9 est., while that of formulation F was only 1.0. Similar comparisons can be made between formulations G and H; I and J; and K and L. Table IV shows formulations M-U which are a number of thickened water-based functional fluids that are covered by the present invention and are useful as hydraulic fluids. Formulation 0 from Table IV is evaluated for shear stability using the Vickers pump test method (V-105C), the results being given in Table V. At various intervals during the pump test, Formulation 0 is removed from the pump and tested for kinematic viscosity. Viscosity data are also listed in Table V. The pump has a maximum pump speed of 30.3 liters/min., a 10 horsepower motor, a V-105C test cartridge, a 60 mesh screen, and a 5.1 liter sump using 11.4 liters of fluid. The experimental method involves the steps (1) weighing the cartridge and placing it in the pump, (2) increasing the torque to 0.35 kg/m in increments of 0.12 kgm, (3) placing formulation C in the reservoir and starting the pump, (4) ) the torque is readjusted to 0.35 kgm and the pressure is adjusted to 1,379 kPa as soon as positive flow is established, (5) the pump is run for 10 min. at 1,379 kPa, (6) the pressure is adjusted to 2,758 kPa, and the torque is increased to 0.86-0.92 kgm in steps of 0.12 kgm, (7) the pump is run for 10 min. at 2,758 kPa, (8) the pressure is adjusted to 4,137 kPa and the pump is run for 10 min., (9) the pressure is adjusted to 5,516 kPa and the flow rate is measured. The experiment is run for a total of 870 hours, being interrupted at the specified intervals to measure ring wear rate and viscosity.

Claims (55)

1. Composition, characterized in that it includes (A) at least one water-dispersible reaction product produced by reaction of (A) (I) at least one hydrocarbyl-substituted succinic acid and/or — anhydride represented by the formula: where R is a hydrocarbyl group with from approx. 8 to approx. 40 carbon atoms, with (A) (II) at least one water-dispersible amine-terminated poly(oxyalkylene), and (B) at least one surfactant. 2. Composition according to claim 1, characterized in that R has from approx. 8 to approx. 30 carbon atoms. 3. Composition according to claim 1, characterized in that R has from approx. 12 to approx. 24 carbon atoms. 4. Composition according to claim 1, characterized in that R has from approx. 16 to approx. 18 carbon atoms. 5. Composition according to claim 1, characterized in that R is an alkenyl group represented by the formula: <H> where R' and R" are independently hydrogen or straight or substantially straight hydrocarbyl groups. 6. Composition according to claim 5, characterized in that R has from approx. 16 to approx. 18 carbon atoms, R' is hydrogen or an alkyl group with from 1 to approx. 7 carbon atoms or an alkenyl group with from 2 to approx. 7 carbon atoms, and R" is an alkyl or an alkenyl group having from about 5 to about 15 carbon atoms. 7. Composition according to claim 1, characterized in that R is derived from an alpha-olefin or an isomerized alpha-olefin. 8. Composition according to claim 1, characterized in that R is derived from a mixture of olefins. 9. Composition according to claim 1, characterized in that said water-dispersible reaction product (A) is an amide/acid. 10. Composition according to claim 1, characterized in that said water-dispersible reaction product (A) is an amide/salt. 11. Composition according to claim 1, characterized in that component (A) (II) is an alpha-omega-diaminopoly(oxyethylene), an alpha-omega-diaminopoly(oxypropylene)poly(oxyethylene)poly(oxypropylene) or an alpha-omega -diaminopropylene oxide end-capped poly(oxyethylene). 12. Composition according to claim 1, characterized in that component (A) (II) is a urea condensate of an alpha-omega-diamino(polyoxyethylene), an alpha-omega-diaminopoly(oxypropylene)poly(oxyethylene)poly( oxypropylene) or an alpha-omega-diaminopropylene oxide end-terminated poly(oxyethylene). 13. Composition according to claim 1, characterized in that the terminal amines in component (A) (II) are represented by the formula NHg or —NHR <*> where R <*> is a hydrocarbyl group with from 1 to approx. 18 carbon atoms. 14. Composition according to claim 13, characterized in that R <»*> is a hydrocarbyl group with from 1 to approx. 4 carbon atoms. 15. Composition according to claim 1, characterized in that component (A) (II) is a compound represented by the formula: where a is a number 1 in the range from 0 to approx. 200; b is a number in the range from 10 to approx. 650; c is a number in the range from 0 to approx. 200. 16. Composition according to claim 15, characterized in that b is a number 1 in the range from approx. 50 to approx. 150. 17. Composition according to claim 15, characterized in that the sum of a + c is approx. 2.5. 18. Composition according to claim 1 where component (A) (II) is a compound represented by the formula where n is a number which is sufficient to give said compound a number-average molecular weight of at least approx. 2,000. 19. Composition according to claim, characterized in that each component (A) (II) has a number average molecular weight of at least approx. 2,000. 20. Composition according to claim 1, characterized in that component (A) (II) has a number average molecular weight in the range from approx. 2,000 to approx. 30,000. 21. Composition according to claim 1, characterized in that component (A) (II) has a number average molecular weight in the range from approx. 2,000 to approx. 10,000. 22. Composition according to claim 1, characterized in that component (A) (II) has a number average molecular weight in the range from approx. 3,500 to approx. 6,500. 23. Composition according to claim 1, characterized in that the ratio of equivalents of component (A) (I) to component (A) (II) varies from approx. 0.1:1 to approx. 8:1. 24. Composition according to claim 1, characterized in that the ratio of equivalents of component (A) (I) to component (A) (II) varies from approx. 1:1 to approx. 4:1. 25. Composition according to claim 1, characterized in that the ratio of equivalents of component (A) (I) to component (SA) (II) is approx. 2:1. 26. Composition according to claim 1, characterized in that components (A) (I) and (A) (II) are reacted at a temperature varying from the highest of the melting temperatures of components (A) (I) and (A) (II) up to the lowest of the decomposition temperatures for such components in the reaction product. 27. Composition according to claim 1, characterized in that components (A) (I) and (A) (II) are reacted at a temperature in the range of approx. 60 to approx. 160°C. 28. Composition according to claim 1, characterized in that component (B) is an anionic, cationic, non-ionic or amphoteric surfactant. 29. Composition according to claim 1, characterized in that component (B) is a cationic or non-ionic surfactant. 30. Composition according to claim 1, characterized in that component (B) is a condensation product of a primary amine with ethylene oxide. 31. Composition according to claim 1, characterized in that component (B) is a polyalkylene glycol ether. 32. Composition according to claim 1, characterized in that component (B) is a polyethylene glycol ether of a primary or secondary alcohol. 33. Composition according to claim 1, characterized in that component (B) is tallow oil. 34. Composition according to claim 1, characterized in that component (B) is a nitrogen-containing, phosphorus-free reaction product of (B) (I) at least one hydrocarbyl-substituted carboxylic acylating agent, where said hydrocarbyl substituent has from approx. 12 to approx. 500 carbon atoms, with (B) (II) at least one (a) N-(hydroxyl-substituted hydrocarbyl)amine, (b) hydroxyl-substituted poly(hydrocarbyloxy) analogue of said amine or (c) mixtures of (a) and (b). 35. Composition according to claim 34, characterized in that said acylating agent (B) (I) is represented by the formula: where hyd is said hydrocarbyl-based substituent in component (B) (I). 36. Composition according to claim 34, characterized in that said hydrocarbyl-based substituent in component (B) (I) is an alkyl or an alkenyl group with from approx. 12 to approx. 500 carbon atoms. 37. Composition according to claim 34, characterized in that said hydrocarbyl-based substituent in component (B) (I) is a poly(isobutene) with from approx. 12 to approx. 500 carbon atoms. 38. Composition according to claim 34, characterized in that said amine (B) (II) has from 1 to approx. 4 hydroxyl groups per molecule bound to a hydrocarbyl group, where the hydrocarbyl group is bound to the amine part of the molecule. 39. Composition according to claim 34, characterized in that said amine (B) (II) contains up to approx. 40 carbon atoms. 40. Composition according to claim 34, characterized in that said amine (B) (II) is a primary, secondary or tertiary alkanolamine with up to approx. 40 carbon atoms. 41. Composition according to claim 34, characterized in that said amine (B) (II) is a mixture of at least two alkanolamines with up to approx. 40 carbon atoms. 42. Composition According to claim 34, characterized in that said amine (B) (II) is a hydroxy-substituted primary amine with the formula: where Ra is a monovalent organic group containing at least one hydroxy group, with the total number of carbon atoms in Ra not exceeding approx. 20. 43. Composition according to claim 42, characterized in that the total number of carbon atoms in Ra does not exceed approx. 10. 44. Composition according to claim 42, characterized in that Ra contains up to approx. 4 hydroxyl groups. 45. Composition according to claim 42, characterized in that Ra is a monohydroxy-substituted alkyl group. 46. Composition according to claim 34, characterized in that the amine (B) (II) is selected from the group consisting of (a) primary, secondary and tertiary alkanolamines which can be represented similarly by the formulas: (b) hydroxyl substituted oxyalkylene analogues of said alkanolamines represented by the formulas: where each R independently is a hydrocarbyl group with from one to approx. 8 carbon atoms or hydroxyl-substituted hydrocarbyl group with from 2 to approx. 8 carbon atoms, and R' is a divalent hydrocarbyl group with from 2 to approx. 18 carbon atoms, and (c) mixtures of two or more thereof. 47. Composition according to claim 34, characterized in that the amine (B) (II) is a mixture of diethylethanolamine and ethanolamine. 48. Composition according to claim 34, characterized in that the amine (B) (II) is diethylethanolamine. 49. Composition according to claim 1, characterized in that component (B) is a reaction product of a polyisobutenyl succinic anhydride with n,n-diethylethanolamine, where the polyisobutenyl group in said polyisobutenyl-substituted succinic anhydride contains an average of from approx. 50 to approx. 90 carbon atoms. 50. Composition according to claim 49, characterized in that said polyisobutenyl group in said polyisobutenyl-substituted succinic anhydride has an average of from approx. 60 to approx. 75 carbon atoms. 51. Composition according to claim 49, characterized in that the molar ratio of said polybutenyl succinic anhydride to said N,N-diethylethanolamine is approx. 1:2, the reaction product (B) being mainly an ester/salt. 52. Composition according to claim 1, characterized in that the weight ratio for (A) to (B) is in the range from approx. 1:5 to approx. 5:1. 53. Composition according to claim 1, characterized in that the weight ratio for (A) to (B) is in the range from approx. 1:1 to approx. 3:1. 54. Concentrate, characterized in that it includes water and from approx. 10 to approx. 70 weight-$ of the composition according to claim 1. 55. Water-based functional fluid, characterized in that it comprises a main amount of water and a smaller thickening amount of the composition according to claim 1.