AU620586B2 - Water-in-oil emulsions - Google Patents

Description

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PCT

INTERNATIONAL APP ANNOUNCEMENT OF THE LATER PUBLICATION OFAMENDED CLAIMS (AND, WHERE APPLICABLE, STATEMENT UNDER ARTICLE 19) w g. i v i rCii N1 .UUftKAIIlUN TREATY (PCT) (51) International Patent Classification 4 173/00, E21B 43/27 C06B 47/14 (C10M 173:00 129:93, 133:52) 40:08 (11) International Publication Number: WO 89/ 05848 (21) International Application Number: PCT/US88/04502 (22) International Filing Date: 16 December 1988 (16.12.88) (31) Priority Application Number: 137,542 (81) Designated States: AT (European patent), AU, BE (European patent), CH (European patent), DE (European patent), FR (European patent), GB (European patent), IT (European patent), LU (European patent), NL (European patent), SE (European patent).

Published With international search report With amended claims.

Date of publication of the amended claims: 27 July 1989 (27.07.89) (32) Priority Date: (33) Priority Country: 23 December 1987 (23.12.87) (71) Applicant: THE LUBRIZOL CORPORATION [US/ US]; 29400 Lakeland Boulevard, Wickliffe, OH 44092

(US).

(72) Inventor: FORSBERG, John, Wesley 8500 Barbara Drive, Mentor, OH 44060 (US).

(74) Agents: FRANKS, Robert, A. et al.; The Lubrizol Corporation, 29400 Lakeland Boulevard, Wickliffe, OH 44092 (US).

(54) Title: WATER-IN-OIL EMULSIONS (57) Abstract A water-in-oil emulsion is disclosed which comprises: a continuous oil phase; a discontinuous aqueous phase; a minor emulsifying amount of at least one salt derived from at least one hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derivative of said acid or anhydride, the hydrocarbyl substituent of having an average of from about 20 to about 500 carbon atoms, with ammonia, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; and a functional amount of at least one water-soluble, oilinsoluble functional additive dissolved in said aqueous phase.

WO 89/05848 PCT/US88/04502 -1- Title: WATER-IN-OIL EMULSIONS Technical Field This invention relates to water-in-oil emulsions and, more particularly, to water-in-oil emulsions containing nitrogen-containing salt emulsifiers and water-soluble, oil-insoluble functional additives. The utility of these emulsions is dependent upon the specific functional additives employed and includes that of hydraulic fluids, explosives and acidizing fluids.

Background of the Invention Water-in-oil emulsions have found wide acceptance as fire-resistant hydraulic fluids in general industry, coal mines and rolling mills where fire hazards exist. These hydraulic fluids are generally used in applications where the fluid could spray or drip from a break or leak onto a source of ignition, a pot of molten metal or a gas flame. This condition often exists in die-casting machines or in presses located near furnaces. Typically, these hydraulic fluids are constituted of a continuous oil phase, a discontinuous aqueous phase, at least one emulsifying agent, and one or more functional additives such as rust-inhibiting agents, extreme-pressure agents, foam inhibitors, freezing point depressants, bactericides, oxidation inhibitors, and the like. Examples of such hydraulic fluids are disclosed in U.S. Patents 3,255,108; 3,269,946; 3,281,356; 3,311,4561; 3,378,494; 3,629,119; and 4,225,447; these patents being incorporated herein by reference.

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WO 8905848 PCT/US88/04502, WO 89/05848 -2- A problem with water-in-oil hydraulic fluids is that they have a tendency to cause wear of metallic pump parts and other equipment with which they come into contact. The water phase, though dispersed in the oil phase, creates wear problems that are not encountered with straight petroleum oil compositions. Another problem is that the water phase tends to corrode the metallic parts it contacts. Water-phase additives which have been employed previously to reduce wear and/or corrosion have had the disadvantage that they tend to precipitate from the emulsion, particularly when the water content becomes reduced during use. The omission of water-phase additives, on the other hand, is undesirable since it is frequently impossible to obtain satisfactory wear- and/or corrosion-resistance by the use of additives which are dissolved only in the oil phase.

Explosive emulsions are typically constituted of continuous organic fuel or oil phase in which discrete droplets of an aqueous solution of an oxygensupplying source are dispersed as a discontinuous phase.

Suchi compositions are conventionally described as waterin-oil explosive emulsion compositions, and examples thereof have been described, inter alia, in U.S. Patents 3,447,978; 3,985,593; 4,008,110; 4,097,316; 4,104,092; 4,110,134; 4,149,916; 4,149,917; 4,218,272; 4,259,977; 4,357,184; 4,371,408; 4,404,050; 4,409,044; 4,453,989; and 4,534,809; and European Application Publication No.

0,155,800 Al, which are incorporated herein by reference. Formation of these explosive emulsions is generally effected in the presence of an emulsifier which is selected to promote subdivision of the droplets of the oxidizer phase and dispersion thereof in the continuous phase. While many of the emulsifiers described in the II 7 I ,WO 89/05848os PCT/US88/04502 -3prior art are meritorious, none have provided emulsion stability characteristics that are entirely satisfactory. Additionally, with most emulsifiers used in the prior art, selection of the fuel or oil for the continuous phase is generally limited to highly-refined, highly paraffinic oils such as white oils.

Acid treating or acidizing of porous subterranean formations penetrated by a well bore has been widely employed for increasing the production of fluids, e.g., crude oil, natural gas, etc., from the formations. The usual technique of acidizing a formation comprises introducing a nonoxidizing acid into the well under sufficient pressure to force the acid out into the formation where it reacts with the acid-soluble components of the formation. The technique is applicable to formations of high acid solubility such as limestone, dolomite, etc., as well as to other types of formations such as a sandstone containing streaks or striations of acid-soluble components such as the various carbonates. During the acid treating operation, passageways for fluid flow are created in the formation, or existing passageways therein are enlarged, thus stimulating the production of fluids from the formation. This action of the acid on the formation is often called etching. Acid treating or acidizing operations wherein the acid is injected into the formation at a pressure or rate insufficient to create cracks or fractures in the formation is usually referred to as matrix-acidizing. Various acidizing compositions have been disclosed in the prior art.

Examples are disclosed, inter alia, in U.S. Patents 4,136,739; 4,137,182; 4,137,400; 4,137,972; 4,143,007; 4,144,179; 4,146,486; 4,148,360; 4,148,736; 4,151,098; 4,152,274; 4,152,289; 4,153,066; 4,153,649; 4,160,483; i- !I I 1 WO 89/05848 PCT/US88/0450? -4- 4,163,727; 4,167,214; 4,169,797; 4,169,798; 4,169,818; 4,169,945; 4,172,041; 4,172,055; 4,174,283; 4,191,657; 4,200,151; 4,200,539; 4,200,540; 4,202,795; 4,203,492; 4,205,724; 4,206,058; 4,210,205; 4,210,206; 4,215,001; 4,217,231; 4,219,429; 4,225,445; 4,244,826; and 4,246,124, these patents being incorporated herein by reference. Examples of water-in-oil emulsions used in acidizing are disclosed in U.S. Patents 4,140,640 and 4,233,165, which are incorporated herein by reference.

Hydrocarbyl-substituted carboxylic acylating agents having at least 30 aliphatic carbon atoms in the substituent are known. The use of such carboxylic acylating agents as additives in normally liquid fuels and lubricants is discussed in U.S. Patents 3,288,714 and 3,346,354. These acylating agents are also useful as intermediates for preparing additives for use in normally liquid fuels and lubricants as described in U.S. Patents 2,892,786; 3,087,936; 3,163,603; 3,172,892; 3,189,544; 3,215,707; 3,219,666; 3,231,587; 3,235,503; 3,272,746; 3,306,907; 3,306,908; 3,331,776; 3,341,542; 3,346,354; 3,374,174; 3,379,515; 3,381,022; 3,413,104; 3,450,715; 3,454,607; 3,455,728; 3,476,686; 3,513,095; 3,523,768; 3,630,904; 3,632,511; 3,697,428; 3,755,169; 3,804,763; 3,836,470; 3,862,981; 3,936,480; 3,948,909; 3,950,341; 4,234,435; and 4,471,091; and French Patent 2,223,415.

Nitrogen-containing, phosphorus-free carboxylic solubilizers useful in high water based functional fluids are disclosed in U.S. Patents 4,329,249; 4,368,133; 4,435,297; 4,447,348; and 4,448,703. These solubilizers are made by reacting at least one carboxylic acid acylating agent having at least one hydrocarbyl-based substituent of at least about 12 to I i I ,WO 89/05848 PCT/US88/04502 about 500 carbon atoms with (II) at least one N-(hydroxyl-substituted hydrocarbyl) amine, hydroxyl-substituted poly(hydrocarbyloxy) analog of said amine or mixtures of and These patents indicate that the preferred acylating agents include the substituted succinic acids or anhydrides and-that the amines that are useful include the primary, secondary and tertiary alkanol amines. These solubilizers are useful in dispersing or dissolving oil-soluble, water-insoluble functional additives in water-based functional fluids.

These references indicate that a particularly preferred embodiment of the solubilizer is the reaction product of a polyisoubtenyl-substituted succinic anhydride with diethylethanolamine or a mixture of diethylethanolamine and ethanolamine.

Summary of the Invention An advantage of the present invention is that stable water-in-oil emulsions are provided which are useful as hydraulic fluids, explosives and acidizing solutions. A particular advantage of the invention with respect to hydraulic fluids relates to the provision of water-phase functional additives which improve the rustinhibition and anti-wear characteristics of such fluids.

A particular advantage with respect to explosives is an increased flexibility in the selection of oils or fuels for the continuous phase.

Broadly stated, the present invention contemplates the provision of a water-in-oil emulsion comprising: a continuous oil phase; a discontinuous aqueous phase; a minor emulsifying amount of at i, -6least one salt made by reacting component with component under saltforming conditions, component comprising at least one hydrocarbylsubstituted carboxylic acid or anhydride, or ester or amide derived from said acid or anhydride, the hydrocarbyl substituent of having an average of from about 20 to about 500 carbon atoms; and component comprising, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; and a functional amount of at least one water-soluble, oil-insoluble functional additive, dissolved in said aqueous phase; said functional additive being one or more oxygen-supplying salts, one or more non-oxidizing acids, or one or more borates, phosphates and/or molybdates.

Description of the Preferred Embodiments In the specification and claims the term "hydrocarbyl" is used herein to include substantially hydrocarbyl groups as well as purely hydrocarbyl groups.

15 The description of these groups as being substantially hydrocarbyl means that they contain no non-hydrocarbyl substituents or non-carbon atoms which significantly affect the hydrocarbyl characteristics or properties of such groups relevant to their uses as described herein. Non-limiting examples of substituents which do not significantly alter the hydrocarbyl characteristics or properties of the general nature of the hydrocarbyl groups of this invention include the following: B I 7 Oxo groups linkages in the main carbon chain);4502 Nitro groups; Thioether groups (especially hydrocarbyloxy such as phenoxy, benzyloxy, methoxy, n-butoxy, etc., and particularly alkoxy groups of up to about 10 carbon atoms);her); Thia groups linkages in the main main carbon chain); Sulfonylether groups -speciall- hydrocarbyl); thioether); Thia groups linkages in the main carbon chain); 0 0 0

II

Sulfinyl groups hydrocarbyl).

This list is intended to be merely illustrative and not exhaustive, and the omission of a certain class of substituent is not meant to require its exclusion. In general, if such substituents are present, there will not be more than two for each 10 carbon atoms in the substantially hydrocarbyl group and preferably not more than one for each 10 carbon atoms since this number of substituents usually will not substantially affect the hydrocarbyl characteristics and properties of the group.

Nevertheless, the hydrocarbyl groups are preferably free from non-hydrocarbon groups; that is, they are preferk i i

A

-8ably hydrocarbyl groups consisting of only carbon and hydrogen atoms.

The term "lower" as used in the present specification and claims, when used in conjunction with terms such as alkyl, alkenyl, alkoxy, and the like, is intended to describe such groups which contain a total of up to 7 carbon atoms.

In the specification and claims the term "water-soluble" refers to materials which are soluble in water to the extent of at least one gram per 100 milliliters of water at 25 C.

In the specification and claims the term "oil-soluble" refers to materials which are not soluble in mineral oil above a level of about one gram per 100 milliliters of oil at In the specification and claims the term "functional amount" refers to a sufficient quantity of an additive to impart desired properties intended by the addition of said additive. For example, if an additive is a rust-inhibitor, a functional amount of said rust-inhibitor would be an amount sufficient to increase the rust-inhibiting characteristics of the emulsion to which it is added. Similarly, if the additive is an anti-wear agent, a functional amount of said anti-wear agent would be a sufficient quantity of the anti-wear agent to improve the anti-wear characteristics of the emulsion to which it is added.

The oil phase of the water-in-oil emulsions of the invention is a 20 continuous oil phase, while the aqueous phase is a discontinuous aqueous phase dispersed in the oil phase The functional additive is dissolved in the dispersed aqueous phase The emulsifying salt stabilizes the emulsion.

The inventive emulsions preferably comprise: from about 2% to about 70% by weight, more preferably from about 4% to about 60% by weight based on the total weight of said Ik /A4d

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WO 89/05848 PCT/US88/04502 -teemulsion of component from about 1% to about 98% by weight, more preferably from about 3% to about 96% by weight of component and from about 0.05% to about by weight, more preferably from about 0.2% to about by weight, more preferably from about 0.2% to about by weight, more prefurably from about 0.2% to about by weight, more preferably from about 0.5% to about 2% by weight of component The level of addition of component is in the broad range of from about 0.05% to about 95% by weight based on the total weight of said emulsion. The level of addition of component is dependent upon the anticipated use of the inventive emulsion as discussed more fully below.

These emulsions have a variety of uses depending, inter alia, upon the specific functional additive that is used. For example, these emulsions can be used as hydraulic fluids. For such hydraulic fluids, the functional additive is preferably a rust-inhibiting and/or anti-wear agent such as, for example, a phosphate, borate or molybdate. In such hydraulic fluids, the oil phase is preferably present at a level in the range of from about 40% to about 70% by weight, more preferably from about 50% to about 65% by weight based on the total weight of said emulsion. The aqueous phase is preferably present at a level in the range of from about 30% to about 60%, more preferably from about to about 50% by weight based on the total weight of said emulsion. Component is preferably present in these hydraulic fluids at a level in the range of from about 2.5 to about 25% by weight, more preferably from about 5 to about 15% by weight based on the total weight of the oil phase The functional additive is preferably present at a level in the range of from about

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i' ItI 1~I I YIrC .WO 89/05848 PCT/US88/04502 lo 0.2 to about 20% by weight, more preferably from about to about 10% by weight based on the total weight of the aqueous phase These emulsions can also be used in enhanced oil recovery processes as acidizing fluids. For such acidizing fluids the functional additive is preferably a non-oxidizing acid. In such acidizing fluids the oil phase is preferably present at a level in the range of from about 20% to about 70% by weight, more preferably from about 40% to about 60% by weight based on the total weight of said emulsion. The aqueous phase is preferably present at a level in the range of from about to about 80% by weight, more preferably from about to about 60% by weight based on the total weight of said emulsion. Component is preferably present at a level in the range of from about 4% to about 40% by weight, more preferably from about 10% to about 20% by weight based on the total weight of the oil phase The functional additive is preferably present at a level in the range of from about 10% to about 90% by weight, more preferably from about 30% to about 80% by weight of the total weight of the aqueous phase These emulsions can also be used as explosive emulsions. For such explosive emulsions the functional additive is preferably an oxygen-supplying salt. In such explosive emulsions the oil phase is preferably present at a level in the range of from about 2% to about 15% by weight, more preferably from about 4% to about 8% by weight based on the total weight of said emulsion. The aqueous phase is preferably present at a level in the range of from about 85% to about 98% by weight, more preferably from about 92% to about 96% by weight based on the total weight of said emulsion.

WO 89/05848 PCT/US88/04502 2-- Component is preferably present at a level in the range of from about 4% to about 40% by weight, more preferably from about 12% to about 20% by weight based on the total weight of the oil phase The functional additive is preferably present at a level in the range of about from 70% to about 95% by weight, more preferably from about 85% to about 92% by weight, more preferably from about 87% to about 90% by weight based on the total weight of the aqueous phase These emulsions can also contain additional additives to improve the properties of said emulsions; these additional additives, which are dependent upon the intended use for the emulsion, are discussed more fully below.

The Oil The oil that is useful in the inventive emulsions can be a hydrocarbon oil having viscosity values from about 20 SUS (Saybolt Universal Seconds) at 40 0 C to about 2500 SUS at 40 0 C. Mineral oils having lubricating viscosities SAE 5-90 grade), can be used. Oils frcm a variety of sources, including natural and synthetic oils and mixtures thereof can be used.

Natural oils include animal oils and vegetable oils castor oil, lard oil) as well as solventrefined or acid-refined mineral lubricating oils of the paraffinic, naphthenic, or mixed paraffin-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful. Synthetic lubricating oils I include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins polybutylenes, polypropylenes, propyleneisobutylene copolymers, chlorinated polybutylenes, etc.); alkyl benzenes dodecylbenzenes, tetradei 0- x. 'WO 89/05848 PCT/US88/04502 \2_ 4-3cylbenzenes, dinonylbenzenes, di-(2-ethylhexyl) benzenes, etc.); polyphenols biphenyls, terphenyls, etc.); and the like. Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers methylpolyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3

-C

8 fatty acid esters, or the C 13 Oxo acid diester of tetraethylene glycol. Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids phthalic acid, succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.) with a variety of alcohols butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, pontaerythritol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, din-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid, and the like. Silicon-based oils such as the polyalrE 1 WO 89/05848 PCT/US88/04502 -1-4kyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants tetraethyl-silicate, tetraisopropyl-silicate, tetra-(2-ethylhexyl)-silicate, tetra-(4-methyl-2-tetraethyl)-silicate, tetra-(p-tertbutylphenyl)-silicate, hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(ethyl)-siloxanes, poly(aiethylphenyl)siloxanes, etc.). Other synthetic oils include liquid esters of phorphorus-containing acids tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.), polymeric tetrahydrofurans, and the like.

Unrefined, refined and rerefined oils (and mixtures of each with each other) of the type disclosed hereinabove can be used in the emulsions of the present invention. Unrefined oils are those obtained directly -from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtainec directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. In the case wherein the inventive emulsions are used as acidizing fluids in enhanced oil recovery processes, the oil can be unrefined oil obtained directly from the subterranean oil reservoir being treated with such fluids.

Refined oils are similar to the unrefined oils except that they have been further treated in one or more puriph fication steps to improve one or more properties. Many such purification techniques are known to those of skill in the art such as solvent extraction, acid or base extraction, filtration, percolation, etc. Rerefined oils are obtained by processes similar to those used to i? WO 89/05848 PCT/US88/04502 obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.

The Hydrocarbyl-Substituted Carboxylic Acid or Anhydride, or Ester or Amide Derivative The hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derivatives of said acid or anhydride, are made by reacting one or more alpha-beta olefinically unsaturated carboxylic acid reagents containing two to about 20 carbon atoms, exclusive of the carboxyl-based groups, with one or more olefin polymers containing at least about 20 carbon atoms, as described more fully hereinafter.

The alpha-beta olefinically unsaturated carboxylic acids may be either monobasic or polybasic in nature. Exemplary of the monobasic alpha-beta olefinically unsaturated carboxylic acids include the carboxylic acids corresponding to the formula:

R-CH=C-COOH

11

R

wherein R is hydrogen, or a saturated aliphatic or alicyclic, aryl, alkylaryl or heterocyclic group, preferably hydrogen or a lower alkyl group, and R 1 is hydro- AJ gen or a lower alkyl group. The total number of carbon atoms in R and R 1 should not exceed about 18 carbon atoms. Specific examples of useful monobasic alpha-beta olefinically unsaturated carboxylic acids include acrylic acid; methacrylic acid; cinnamic acid; crotonic acid; 3-phenyl propenoic acid; alpha, beta-decenoic acid, etc.

A

©I S) f- i" j WO89/05848 PCT/US88/04502

IS

hr.- The polybasic acids are preferably dicarboxylic, although tri- and tetracarboxylic acids can be used.

Exemplary polybasic acids include maleic acid, fumaric acid, mesaconic acid, itaconic acid and citraconic acid.

The alpha-beta olefinically unsaturated carboxylic acid reagents can also be the anhydride, ester or amide functional derivatives of the foregoing acids. A preferred alpha-beta olefinically unsaturated carboxylic acid reagent is maleic anhydride. Methods of preparing such functional derivatives are well known to those of ordinary skill in the art and they can be satisfactorily described by noting the reactants used to produce them.

Thus, for example, derivative esters for use in the present invention can be made by esterifying monohydric or polyhydric alcohols or epoxides with any of the aforedescribed acids or anhydrides. Derivative amides can be made by reacting any of the aforedescribed acids or anhydrides with ammonia, primary amines and secondary amines. The amines and alcohols described hereinafter can be used to prepare these functional derivatives.

In general, the hydrocarbyl substituents present in the hydrocarbyl-substituted carboxylic acids or anhydrides, or ester or amide derivatives are free from acetylenic unsaturation; ethylenic unsaturation, when present will generally be such that there is no more than one ethylenic linkage present for every ten carbonto-carbon bonds in the substituent. The substituents are often completely saturated and therefore contain no ki ethylenic unsaturation. These hydrocarbyl substituents have an average of from about 20 to about 500 carbon atoms, more preferably from about 30 to about 500 carbon atoms, more preferably from about 40 to about 500 carbon atoms, more preferably from about 50 to about 500 carbon *i y: ^!E 7

I

,WO 89/05848 PCT/US88/04502 atoms. These hydrocarbyl-based substituents are preferably hydrocarbyl, alkyl or alkenyl groups.

These hydrocarbyl substituents may be derived from olefin polymers or chlorinated analogs thereof.

The olefin monomers from which the olefin polymers are derived are polymerizable olefins and monomers characterized by having one or more ethylenic unsaturated groups.

They can be monoolefinic monomers such as ethylene, propylene, butene-l, isobutene and octene-1 or polyolefinic monomers (usually di-olefinic monomers such as butadiene-1,3 and isoprene). Usually these monomers are terminal olefins, that is, olefins characterized by the presence of the group >C=CH 2 However, certain internal olefins can also serve as monomers (these are sometimes referred to as medial olefins). When such medial olefin monomers are used, they normally are employed in combination with terminal olefins to produce olefin polymers which are interpolymers. Although the hydrocarbyl substituents may 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 such as would be obtained from polymerizable cyclic olefins or alicyclic-substituted polymerizable cyclic olefins. The olefin polymers are usually free from such groups.

Nevertheless, olefin polymers derived from such interpolymers of both 1,3-dienes and styrenes such as butadiene-1,3 and styrene or para(tertiary butyl) styrene are exceptions to this general rule.

Generally the olefin polymers are homo- or I interpolymers of terminal hydrocarbyl olefins of about two to about 16 carbon atoms. A more typical class of olefin polymers is selected from that group consisting

J

i o ii~~ 7 WO 89/05848 PCT/US88/04502

I

-7 -48of homo- and interpolymers of terminal olefins of about two to about six carbon atoms, especially those of about two to about four carbon atoms.

Specific examples of terminal and medial olefin monomers which can be used to prepare the olefin polymers from which the hydrocarbyl substituents are derived include ethylene, propylene, butene-l, butene-2, isobutene, pentene-l, hexene-l, heptene-l, octene-l, nonene- 1, docene-l, pentene-2, propylene tetramer, diisobutylene, isobutylene trimer, butadiene-1,2, butadiene-1,3, pentadiene-1,2, pentadiene-1,3, isoprene, 2-chlorobutadiene-l,3, 2-methylheptene-l, 3-cyclohexylbutene-l, 3,3-dimethylpentene-l, styrene-divinylbenzene, vinylacetate, allyl alcohol, 1-methylvinylacetate, acrylonitrile, ethylacrylate, ethylvinylether and methylvinylketone. Of these, the purely hydrocarbyl monomers are preferred and the terminal olefin monomers are especially preferred.

In a particularly advantageous embodiment of the invention, the olefin polymers are poly(isobutene)s such as obtained by polymerization of a C 4 refinery stream having a butene content of about 35 to about by weight and an isobutene content of about 30 to about by weight in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. These polyisobutenes preferably contain predominantly (that is, greater than about 80% of the total repeat units) isobutene repeat units of the configuration.

CH

3 CH2--C--

CH

3 u -18- Preferred acids and anhydrides are the hydrocarbyl-substituted succinic acids and anhydrides represented by the formulae: 0 hyd-CHCOOH or hyd-CHC

CH

2 COOH O

CH

2

C

O

wherein "hyd" is the hydrocarbyl substituent.

Preferably component comprises at least one ester and/or amide derived from the group consisting of primary, secondary and tertiary alkanol amines which can be represented correspondingly by the formulae

H

H\

R0 N-R'-OH

R

hydroxyl-substituted oxyalkylene analogs of said alkanol amines represented the formulae

H

SN-(R'-O)

2 -1 5

-H

H

H

-H

0R/ 19

R

N-(R'-O)215-H

R

wherein each R is independently a hydrocarbyl group of one to about 8 carbon atoms or a hydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms and R' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and (c) mixtures of two or more thereof.

The hydrocarbyl-substituted carboxylic adds, and anhydrides, and ester and amide derivatives thereof, can be prepared by any of several known procedures which are described in the following British and Canadian patents: U.S.

Patents 3,024,237; 3,087,936; 3,172,892; 3,215,707; 3,219,666; 3,231,587; 3,245,910; 3,254,025; 3,271,310; 3,272,743; 3,272,746; 3,278,550; 3,288,714; 3,307,928; 3,312,619; 3,341,542; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179; 3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169; 3,868,330; 3,912,764; and 4,368,133. British Patents 944,136; 1,085,903; S 1,162,436; and 1,440,219. Canadian Patent 956,397. These patents are incorporated herein by reference.

One procedure for preparing the hydrocarbyl-substituted carboxylic acids 0 and anhydrides, and ester and amide derivatives is illustrated, in part, in U.S.

Patent 3,219,666. This procedure is conveniently designated as the "two-step procedure". It involves first chlorinating an olefin polymer until there is an average of at least about one chloro group for each molecular weight of olefin polymer. (For purposes of this inven -1 u WO 89/05848 PCT/US88/04502 tion, the molecular weight of the olefin polymer is the weight corresponding to the Mn value.) Chorination involves merely contacting the olefin polymer with chlorine gas until the desired amount of chlorine is incorporated into the chlorinated polyolefin. Chlorination is generally carried out at a temperature of about 75 0 C *to about 125 0 C. If a diluent is used in the chlorination procedure, it should be one which is not itself readily subject to further chlorination. Polyand perchlorinated and/or fluorinated alkanes and benzenes are examples of suitable diluents.

The second step in the two-step chlorination procedure is to react the chlorinated polyolefin with the alpha-beta olefinically unsaturated carboxylic acid reagent at a temperature usually within the range of about 100 0 C to about 200 0 C. The mole ratio of chlorinated polyolefin to carboxylic acid reagent is usually about 1:1. (For purposes of this invention, one mole of a chlorinated polyolefin has the molecular weight of a chlorinated polyolefin corresponding to the Mn value of the unchlorinated polyolefin.) However, a stoichiometric excess of carboxylic acid reagent can be used, for example, a mole ratio of 1:2. If an average of more than about one chloro group per molecule of polyolefin is introduced during the chlorination steP, then more than one mole of carboxylic acid reagent can react per mole of chlorinated polyalkene. Because of such situations, it is better to describe the ratio of chlorinated polyolefin to carboxylic acid reagent in terms of equivalents. (An equivalent weight of chlorinated polyolefin, for purposes of this invention, is the weight corresponding to the Mn value divided by the average number of chloro groups per molecule of chlorinated polyolefin.

e' ;k

S~C~

i .il WO 89/05848 PCT/US88/04502 -21- An equivalent weight of a carboxylic acid reagent is its molecular weight.) Thus, the ratio of chlorinated p, -yolefin to carboxylic acid reagent will normally be such as to provide about one equivalent of carboxylic acid reagent for each mole of chlorinated polyolefin up to about one equivalent of carboxylic acid reagent for each equivalent of chlorinated polyolefin with the understanding that it is normally desirable to provide an excess of carboxylic acid reagent; for example, an excess of about 5% to about 25% by weight. Unreacted excess carboxylic acid reagent may be stripped from the reaction product, usually under vacuum, or reacted during a further stage of the process as explained below.

The resulting polyolefin-substituted carboxylic acid or anhydride, or ester or amide derivative, is, optionally, again chlorinated if the desired number of carboxylic groups are not present in the product. If there is present, at the time of this subsequent chlorination, any excess carboxylic acid reagent from the second step, the excess will react as additional chlorine is introduced during the subsequent chlorination.

Otherwise, additional carboxylic acid reagent is introduced during and/or subsequent to the additional chlorination step. This technique can be repeated until the total number of carboxylic groups per equivalent weight of substituent groups reaches the desired level.

Another procedure for preparing hydrocarbylsubstituted carboxylic acids and derivatives of the invention utilizes a process described in U.S. Patent 3,912,764 and U.K. Patent 1,440,219. Both of these patents are incorporated herein by reference. According to this procedure, the polyolefin and the carboxylic acid reagent are first reacted by heating them together WO 89/05848 PCT/US88/04502, -22in a direct alkylation procedure. When the direct alkylation step is completed, chlorine is introduced into the reaction mixture to promote reaction of the remaining unreacted carboxylic acid reagent. According to these patents, 0.3 to 2 or more moles of carboxylic acid reagent are used in the reaction for each mole of olefin polymer. The direct alkylation step is conducted at temperatures of about 180 0 C to about 250 0 C. During the chlorine-introducing stage, a temperature of about 160°C to about 225 0 C is employed.

A preferred process for preparing the hydrocarbyl-substituted carboxylic acids and derivatives of this invention, is the so-called "one-step" process. This process is described in U.S. Patents 3,215,707 and 3,231,587. Both of these patents are incorporated herein by reference. Basically, the one-step process involves preparing a mixture of the polyolefin and the carboxylic acid reagent containing the necessary amounts of both to provide the desired hydrocarbyl-substituted carboxylic acids or derivatives of this invention.

Chlorine is then introduced into the mixture, usually by passing chlorine gas through the mixture with agitation, while maintaining the rixture at a temperature of at least about 140 0 C. A variation on this process involves adding additional carboxylic acid reagent during or subsequent to the chlorine introduction. Usually where the polyolefin is sufficiently fluid at 140°C and above, there is no need to utilize an additional substantially inert, normally liquid solvent/diluent in the one-step process. However, as explained hereinbefore, if a solvent/diluent is employed, it is preferably one that resists chlorination. Again, the poly- and perchlorinated and/or -fluorinated alkanes, cycloalkanes, and benzenes can be used for this purpose.

V. WO8905P48 CT/US88/04502 -23- Chlorine may be introduced continuously or intermittently during the one-step process. The rate of introduction of the chlorine is not critical although, for maximum utilization of the chlorine, the rate should be about the same as the rate of consumption of chlorine in the course of the reaction. When the introduction rate of chlorine exceeds the rate of consumption, chlorine is evolved from the reaction mixture. It is often advantageous to use a closed system, including superatmospheric pressure, in order to prevent loss of chlorine so as to maximize chlorine utilization.

The maximum temperature at which the reaction in the one-step process takes place at a reasonable rate is about 140 0 C. Thus, the minimum temperature at which the process is normally carried out is in the neighborhood of 140 0 C. A preferred temperature range is between about 160C and about 220 0 C. Higher temperatures such as 250 0 C or even higher may be used but usually with little advantage. In fact, temperatures in excess of 220 0 C are often disadvantageous because they tend to "crack" the polyolefins (that is, reduce their molecular weight by thermal degradation) and/or decompose the carboxylic acid reagent. For this reason, maximum temperatures of about 200 0 C to about 210 0 C are normally not exceeded. The upper limit of the useful temperature in the one-step process is determined primarily by the decomposition point of the components in the reaction mixture including the reactants and the desired products. The decomposition point is that temperature at which there is sufficient decomposition of any reactant or product such as to interfere with the production of the desired products.

WO 89/05848 PCT/US88/04502 -24- In the one-step process, the molar ratio of carboxylic acid reagent to chlorine is such that there is at least about one mole of chlorine for each mole of carboxylic acid reagent to be incorporated into the product. Moreover, for practical reasons, a slight excess, usually in the neighborhood of about 5% to about by weight of chlorine, is utilized in order to offset any loss of chlorine from the reaction mixture.

Larger amounts of excess chlorine may be used but do not appear to produce any beneficial results.

The Alcohols Useful In Making the Hydrocarbyl-Substituted Carboxylic Acid Ester Derivatives The alcohols useful in making the hydrocarbylsubstituted carboxylic acid ester derivatives of this invention include those compounds of the general formula:

R

I

-(OH)m wherein R 1 is a monovalent or polyvalent organic group joined to the -OH groups through carbon-to-oxygen bonds (that is, -COH wherein the carbon is not part of a carbonyl group) and m is an integer of from 1 to about preferably 2 to about 6. These alcohols can be aliphatic, cycloaliphatic, aromatic, and heterocyclic, including aliphatic-substituted cycloaliphatic alcohols, aliphatic-substituted aromatic alcohols, aliphatic-substituted heterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols, cycloaliphatic-substituted heterocyclic alcohols, heterocyclic-substituted aliphatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols.

Except for the polyoxyalkylene alcohols, the mono- and .WO 89/05848 PCT/US88/04502 polyhydric alcohols corresponding to the formula R 1 (OH)m preferably contain not more than about 40 carbon atoms, more preferably not more than about 20 carbon atoms. The alcohols may contain non-hydrocarbon substituents or groups which do not interfere with the reaction of the alcohols with the hydrocarbyl-substituted carboxylic acids or anhydrides of this invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as and as in such groups as

-CH

2

CH

2

-X-CH

2

CH

2 where X is or Among the polyoxyalkylene alcohols suitable for use in the preparation of the ester derivatives of this invention are the commercially available polyoxyalkylene alcohols that include the polyoxyethylated amines, amides, and quaternary salts available from Armour Industrial Chemical Co. under the names ETHODUOMEEN polyethoxylated high-molecular-weight aliphatic diamines; ETHO- MEEN, polyethoxylated aliphatic amines containing alkyl groups in the range of about 8 to about 18 carbon atoms; ETHOMID, polyethoxylated high-molecular-weight amides; and ETHOQUAD, polyethoxylated quaternary ammonium chlorides derived from long-chain amines.

Useful polyoxyalkylene alcohols and derivatives thereof include the hydrocarbyl ethers and the carboxylic acid esters obtained by reacting the alcohols with various carboxylic acids. Illustrative hydrocarbyl groups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc., containing up to about 40 carbon atoms. Specific hydrocarbyl groups include methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenyl ethyl, cyclohexyl, anC the like. Carboxylic acids useful in preparing the ester derivatives are S i WO 89/05848 PCT/US88/04502 -26mono- or polycarboxylic acids such as acetic acid, valeric acid, lauric acid, stearic acid, succinic acid, and alkyl or alkenyl-substituted succinic acids wherein the alkyl or alkenyl group contains up to about 20 carbon atoms. Members of this class of alcohols are commercially available from various sources; PLURONICS, polyols available from Wyandotte Chemicals Corporation; POLYGLYCOL 112-2, a liquid triol derived from ethyleneoxide and propylene-oxide available from Dow Chemical Co.; and TERGITOLS, dodecylphenyl or nonylphenyl polyethylene glycol ethers, and UCONS, polyalkylene glycols and various derivatives thereof, both available from Union Carbide Corporation. However, the alcohols used must have an average of at least one free alcoholic hydroxyl group per molecule of polyoxyalkylene alcohol.

For purposes of describing these polyoxyalkylene alcohols, an alcoholic hydroxyl group is one attached to a carbon atom that does not form part of an aromatic nucleus.

Alcohols useful in this invention also include alkylene glycols and polyoxyalkylene alcohols such as polyoxyethylene alcohols, polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. These polyoxyalkylene alcohols (sometimes called polyglycols) can contain up to about 150 oxyalkylene groups, with the alkylene group containing from about 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols are generally dihydric alcohols. That is, each end of the molecule terminates with an OH group. In order for such polyoxyalkylene alcohols to be useful, there must be at least one such OH group. However, the remaining OH group can be esterified with a monobasic, aliphatic or aromatic carboxylic acid of up to about 20 carbon atoms such as acetic acid, f WO 89/05848 PCT/US88/04502 -27propionic acid, oleic acid, stearic acid, benzoic acid, and the like. The monoethers of these alkylene glycols and polyoxyalkylene glycols are also useful. These include the monoaryl ethers, monoalkyl ethers, and monoaralkyl ethers of these alkylene glycols and polyoxyalkylene glycols. This group of alcohols can be represented by the formula HO-(-RAO-)pRB-ORC wherein RA and Rg are independently alkylene groups of from about 2 to 8 carbon atoms; and RC is aryl phenyl), lower alkoxy phenyl, or lower alkyl phenyl, or lower alkyl ethyl, propyl, terbutyl, pentyl, etc.); and aralkyl benzyl, phenylethyl, phenylpropyl, p-ethylphenylethyl, etc.); p is from zero to about eight, preferably from about 2 to 4. Polyoxyalkylene glycols where the alkylene groups are ethylene or propylene and p is at least two as well as the monoethers thereof as described above are useful.

The monohydric and polyhydric alcohols useful in this invention include monohydroxy and polyhydroxy aromatic compounds. Monohydric and polyhydric phenols and naphthols are preferred hydroxyaromatic compounds.

These hydroxy-substituted aromatic compounds may contain other substituents in addition to the hydroxy substituents such as halo, alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like. Usually, the hydroxy aromatic compound will contain from 1 to about 4 hydroxy groups.

The aromatic hydroxy compounds are illustrated by the following specific examples: phenol, p-chlorophenol, p-nitrophenol, beta-naphthol, alpha-naphthol, cresols, resorcinol, catechol, carvacrol, thymol, eugenol, p,p'- PCT/US8$/04502 WO 89/05848 -28dihydroxy-biphenyl, hydroquinone, pyrogallol, phloroglucinol, hexylresorcinol, orcin, quaiacol, 2-chlorophenol, 2,4-dibutylphenol, propene-tetramer-substituted phenol, didodecylphenol, 4,4'-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-naphthol, polyisobutenyl-(molecular weight of about 1000)-substituted phenol, the condensation product of heptylphenol with about 0.5 mole of formaldehyde, the condensation product of octylphenol with acetone, di(hydroxyphenyl)oxide, di-(hydroxyphenyl)sulfide, di(hydroxyphenyl)-disulfide, and 4-cyclohexylphenol. Phenol itself and aliphitic hydrocarbonsubstituted phenols, alkylated phenols having up to 3 aliphatic hydrocarbon substituents are useful.

Each of the aliphatic hydrocarbon substituents may contain about 100 or more carbon atoms but usually will have from 1 to about 20 carbon atoms. Alkyl and alkenyl groups are the preferred aliphatic hydrocarbon substituents.

Further specific examples of monohydric alcohols which can be used include monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, beta-phenylethyl alcohol, 2-methylcyclohexanol, betachloroethanol, monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, monododecyl ether of triethylene glycol, monooleate of ethylene glycol, monostearate of diethylene glycol, sec-pentyl alcohol, tertbutyl alcohol, 5-bromo-dodecanol, nitro-octadecanol, and dioleate of glycerol. Alcohols useful in this invention may be unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, l-cyclohexene-3-ol and oleyl alcohol.

IL

i i 7 PCT/US88/04502 WO 89/05848 -29- Other specific alcohols useful in this invention are the ether alcohols and amino alcohols including, for example, the oxyalkylene-, oxyarylene-, aminoalkylene-, and amino-arylene-substituted alcohols having one or more oxyalkylene, aminoalkylene or amino-aryleneoxy-arylene groups. These alcohols are exemplified by the Cellosolves, (products of Union Carbide identified as mono- and dialkyl ethers of ethylene glycol and their derivatives), the Carbitols (products of Union Carbide identified as mono- and dialkyl ethers of diethylene glycol and their derivatives), phenoxyethanol, heptylphenyl-(oxypropylene) 6 -OH, octyl-(oxyethylene) 30

-OH,

phenyl-(oxyoctylene) 2 -OH, mono-(heptylphenyloxypropylene)-substituted glycerol, poly(styreneoxide), aminoethanol, 3-aminoethylpentanol, di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine, N-hydroxyethyl ethylenediamine, N,N,N',N'-tetrahydroxytrimethylenediamine, and the like.

The polyhydric alcohols preferably contain from 2 to about 10 hydroxy groups. They are illustrated, for example, by the alkylene glycols and polyoxyalkylene glycols mentioned above such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols and polyoxyalkylene glycols in which the alkylene groups contain from 2 to about 8 carbon atoms.

Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methyl ester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritol, arabitol, sor-

I-

WO 89/05848 PCT/US88/04502 bitol, mannitol, 1,2-cyclohexanediol, and xylene glycol.

Carbohydrates such as sugars, starches, celluloses, and so forth likewise can be used. The carbohydrates may be exemplified by glucose, fructose, sucrose, rhamose, mannose, glyceraldehyde, and galactose.

Polyhydric alcohols having at least 3 hydroxyl groups, some, but not all of which have been esterified with an aliphatic monocarboxylic acid having from about 8 to about 30 carbon atoms such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oil acid are useful. Further specific examples of such partially esterified polyhydric alcohols are the monooleate of sorbitol, distearate of sorbitol, monooleate of glycerol, monostearate of glycerol, di-dodecanoate of erythritol, and the like.

Useful alcohols also include those polyhydric alcohols containing up to about 12 carbon atoms, and especially those containing from about 3 to about carbon atoms. This class of alcohols includes glycerol, erythritol, pentaerythritol, dipentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid, 2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decanediol, digitalose, and the like. Aliphatic alcohols containing at least about 3 hydroxyl groups and up to about 10 carbon atoms are useful.

SUseful polyhydric alcohols are the polyhydric alkanols containing from about 3 to about 10 carbon atoms and particularly, those containing about 3 to about 6 carbon atoms and having at least three hydroxyl groups. Such alcohols are exemplified by glycerol, Hi i r 1 WO 89/05848 PCT/US88/0450 2 -31erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl-l,3-propanediol-(trimethyloletha ne),2-hydroxymethyl-2-ethyl-l,3-propanediol-(trimethylpropane), 1,2,4-hexanetriol, and the like.

The carboxylic acids or anhydrides can be reacted with the alcohols according to conventional esterification techniques to form the ester derivatives This normally involves heating the acid or anhydride with the alcohol, optionally in the presence of a normally liquid, substantially inert, organic liquid solvent/diluent and/or in the presence of esterification catalyst. Temperatures of at least about up to the decomposition temperature of the reaction component and/or product having the lowest such temperature can be used. This temperature is preferably in the range of about 50 0 C to about 130 0 C, more preferably about 80°C to about 100°C when a carboxylic anhydride is used as the carboxylic reactant. On the other hand, when the carboxylic reactant is an acid, the temperature is preferably in the range of about 100 0 C up to about 300 0 C with temperatures of about 140 0 C to 250 0 C often being employed. Usually, about 0.05 to about 0.95 equivalent of alcohol are used for each equivalent of acid or anhydride. Preferably, about 0.5 equivalent of alcohol per equivalent of acid or anhydride is employed. An equivalent an of alcohol is its molecular weight divided by the total number of hydroxyl groups present in the molecule. Thus, an equivalent weight of ethanol is its molecular weight while the equivalent weight of ethylene glycol is one-half its molecular weight. The number of equivalents of the acid or anhydride depends on the j total number of carboxylic functions carboxylic acid or carboxylic anhydride groups) present in the acid 1 ,'1 fl WO 89/05848 PCT/US88/04502 -32or anhydride. Thus, the number of equivalents of the acid or anhydride will vary with the number of carboxy groups present therein. In determining the number of equivalents of the acid or anhydride, those carboxyl functions which are not capable of reacting as a carboxylic acid acylating agent are excluded. In general, however, there is one equivalent of acid or anhydride for each carboxy group in the acid or anhydride. For, example, there would be two equivalents in an anhydride derived from the reaction of one mole of olefin polymer and one mole of maleic anhydride. Conventional techniques are readily available for determining the number of carboxyl functions acid number, saponification number) and, thus, the number of equivalents of acid or anhydride available to react with the alcohol can be readily determined by one skilled in the art.

Many issued patents disclose procedures for reacting carboxylic acid acylating agents with alcohols to produce acidic esters and neutral esters. These same techniques are applicable to preparing esters from the hydrocarbyl-substituted carboxylic acids and/or anhydrides thereof of this invention and the alcohols described above. All that is required is that the acid and/or anhydride, of this invention is substituted for the carboxylic acid acylating reagents discussed in these patents, usually on an equivalent weight basis.

The following U.S. Patents are expressly incorporated herein by references for their disclosure of suitable methods for reacting the'acids and/or anhydrides of this invention with the alcohols described above: U.S.

Patents 3,331,776; 3,381,022; 3,522,179; 3,542,680; 3,697,428; and 3,755,169.

WO 89/05848 PCT/US88/04502 -33- The Amines Useful In Making the Amide Derivatives The amines useful in making the hydrocarbylsubstituted acid amide derivatives include ammonia and the primary amines or secondary amines, with the secondary amines being preferred. These amines are characterized by the presence within their structure of at least one H-N< group and/or at least one -NH 2 group.

These amines can be monoamines or polyamines. Hydrazine and substituted hydrazines containing up to three substituents are included as amines suitable for preparing the derivatives Mixtures of two or more amines can be used.

The amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic, including aliphatic-substituted aromatic, aliphatic-substituted cycloaliphatic, aliphatic-substituted heterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphatic-substituted aromatic, cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic, heterocyclic-substituted aliphatic, heterocyclic-substituted cycloaliphatic and heterocyclic-substituted aromatic amines. These amines may be saturated or unsaturated. If unsaturated, the amine is preferably free from acetylenic unsaturation. The amines may also contain non-hydrocarbon substituents or groups as long as these groups do not significantly interfere with the reaction of the amines with the hydrocarbyl-substituted carboxylic acids and derivatives thereof of this invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl, mercapto, nitro, and interrupting groups K such as and as in such groups as

-CH

2

CH

2

CH

2

CH

2 where X is or WO 89/05848 PCT/US88/04502., -34- With the exception of the branched polyalkylene polyamines, the polyoxyalkylene polyamines and the high molecular weight hydrocarbyl-substituted amines described more fully hereinafter, the amines used in this invention ordinarily contain less than about 40 carbon atoms in total and usually not more than about 20 carbon atoms in total.

Aliphatic monoamines include mono-aliphatic and di-aliphatic-substituted amines wherein the aliphatic groups can be saturated or unsaturated and straight or branched chain. Thus, they are primary or secondary aliphatic amines. Such amines include, for example, mono- and di-alkyl-substituted amines, mono- and dialkenyl-substituted amines, and amines having one N-alkenyl substituent and one N-alkyl substituent, and the like. The total number of carbon atoms in these aliphatic monoamines preferably does not exceed about and usually does not exceed about 20 carbon atoms.

Specific examples of such monoamines include ethylamine, di-ethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine,' cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, octadecylamine, and the like.

Examples of cycloaliphatic-substituted aliphatic amines, aromatic-substituted aliphatic amines, and heterocyclicsubstituted aliphatic amines, include 2-(cyclohexyl)ethylamine, benzylamine, phenylethylamine, and 3-(furylpropyl) amine.

Cycloaliphatic monoamines are those monoamines wherein there is one cycloaliphatic substituent attached directly to the amino nitrogen through a carbon atom in the cyclic ring structure. Examples of cycloaliphatic monoamines include cyclohexylamines, cyclopentylamines,

I!I

n SWO 89/05848 PCT/US88/04502 cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamines, dicyclohexylamines, and the like. Examples of aliphatic-substituted, aromatic-substituted, and heterocyclic-substituted cycloaliphatic monoamines include propyl-substituted cyclohexylamines, phenylsubstituted cyclopentylamines and pyranyl-substituted cyclohexylamine.

Suitable aromatic amines include those monoamines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The aromatic ring will usually be a mononuclear aromatic ring one derived from benzene) but can include fused aromatic rings, especially those derived from naphthylene. Examples of aromatic monoamines include aniline, di(para-methylphenyl) amine, naphthylamine, N-(n-butyl) aniline, and the like. Examples of aliphatic-substituted, cycloaliphatic-substituted, and heterocyclic-substituted aromatic monoamines include paraethoxyaniline, paradodecylamine, cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.

Suitable polyamines include aliphatic, cycloaliphatic and aromatic polyamines analogous to the above-described monoamines except for the presence within their structure of another amino nitrogen. The other amino nitrogen can be a primary, secondary or tertiary amino nitrogen. Examples of such polyamines include N-aminopropyl-cyclohexylamine, N-N'-di-n-butyl- S] para-phenylene diamine, bis-(para-aminophenyl)-methane, 1,4-diaminocyclohexane, and the like.

Heterocyclic mono- and polyamines can also be Sused in making the hydrocarbyl-substituted carboxylic I acid amide derivatives As used herein, the terminology "heterocyclic mono- and polyamine(s)" is i 'i 1 WO 89/05848 PCT/US88/04502 -36intended to describe those heterocyclic amines containing at least one primary or secondary amino group and at least one nitrogen as a heteroatom in the heterocyclic ring. However, as long as there is present in the heterocyclic mono- and polyamines at least one primary or secondary amino group, the hetero-N atom in the ring can be a tertiary amino nitrogen; that is, one that does not have hydrogen attached directly to the ring nitrogen. Heterocyclic amines can be saturated or unsaturated and can contain various substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the total number of carbon atoms in the substituents will not exceed about Heterocyclic amines can contain heteroatoms other than nitrogen, especially oxygen and sulfur. Obviously they can contain more than one nitrogen heteroatom. The and 6-membered*heterocyclic rings are preferred.

Among the suitable heterocyclics are aziridines, azetidines, azolidines, tetra- and di-hydropyridines, pyrroles, indoles, piperadines, imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N,N'-di-aminoalkylpiperazines, azepines, azocines, azonines, azecines and tetra-, di- and perhydro-derivatives of each of the above and mixtures of two or more of these heterocyclic amines. Preferred Sheterocyclic amines are the saturated 5- and 6-membered Sheterocyclic amines containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like. Piperidine, aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substituted i I WO 89/05848 PCT/US88/04502 -37piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines, are useful. Usually the aminoalkyl substituents are substituted on a nitrogen atom forming part of the hetero ring. Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine, and N,N'-di-aminoethylpiperazine.

Hydroxyamines both mono- and polyamines, analogous to those described above are also useful provided they contain at least one primary or secondary amino group. Hydroxy-substituted amines having only tertiary amino nitrogens, such as in trihydroxyethyl amine, are thus excluded as amines, but can be used as alcohols as disclosed above. The hydroxy-substituted amines contemplated are those having hydroxy substituents bonded directly to a carbon atom other than a carbonyl carbon atom; that is, they have hydroxy groups capable of functioning as alcohols. Examples of such hydroxy-substituted amines include ethanolamine, di(3-hydroxypropyl)amine, 3-hydroxybutylamine, 4-hydroxybutylamine, diethanolamine, di(2-hydroxypropyl) amine, N-hydroxypropyl propylamine, N-(2-hydroxyethyl)-cyclohexylamine, 3-hydroxycyclopentylamine, parahydroxyaniline, N-hydroxyethyl piperazine, and the like.

The terms hydroxyamine and aminoalcohol describe the same class of compounds and, therefore, can be used interchangeably.

Also suitable as amines are the aminosulfonic acids and derivatives thereof corresponding to the formula: 0 (RcRbN- -4Ra -4S-R) 0 WO89/05848 PCT/US88/04502 -38wherein R is OH, NH 2

ONH

4 etc.; Ra is a polyvalent organic group having a valence equal to x y; Rb and Rc are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl with the proviso that at least one of Rb and Rc is hydrogen per aminosulfonic acid molecule; x and y are each integers equal to or greater than one. Each aminosulfonic reactant is characterized by at least one HN< or H 2 N- group and at least one 0

-S-R

0 group. These sulfonic acids can be aliphatic, cycloaliphatic or aromatic aminosulfonic acids and the corresponding functional derivatives of the sulfo group.

Specifically, the aminosulfonic acids can be aromatic aminosulfonic acids, that is, where Ra is a polyvalent aromatic group such as phenylene where at least one 0

-S-R

0 group is attached directly to a nuclear carbon atom of the aromatic group. The aminosulfonic acid may also be a mono-amino aliphatic sulfonic acid; that is, an acid where x is one and Ra is a polyvalent aliphatic group such as ethylene, propylene, trimethylene, and 2-methylene propylene. Other suitable aminosulfonic acids and derivatives thereof useful as amines in this invention are disclosed in U.S. Patents 3,029,250; 3,367,864; and 3,926,820; which are incorporated herein by reference.

WO 89/05848 PCT/US88/04502 -39- Hydrazine and substituted-hydrazine can also be used as amines in this invention. At least one of the nitrogens in the hydrazine must contain a hydrogen directly bonded thereto. The substituents which may be present on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the substituents are alkyl, especially lower alkyl, phenyl, and substituted phenyl such as lower alkoxy-substituted phenyl or lower alkyl-substituted phenyl. Specific examples of substituted hydrazines are methylhydrazine, N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine, N-(para-tolyl)- N'-(n-butyl)-hydrazine, N-(para-nitrophenyl)-hydrazine, N-(para-itrophenyl)-N-methylhydrazine, N,N'-di-(parachlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine, and the like.

The high molecular weight hydrocarbyl amines, both monoamines and polyamines, which can be used as amines in this invention are generally prepared by reacting a chlorinated polyolefin having a molecular weight of at least about 400 with ammonia or an amine.

The amines that can be used are known in the art and described, for example, in U.S. Patents 3,275,554 and 3,438,757, both of which are incorporated herein by reference. These amines must possess at least one primary or secondary amino group.

Another group of amines suitable for use in Sthis invention are branched polyalkylene polyamines.

The branched polyalkylene polyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene WO 89/05848 PCT/US88/04502, NH2-RN- group per nine amino units present on the main chain; for example, 1-4 of such branched chains per nine units on the main chain, but preferably one side chain unit per nine main chain units. Thus, these polyamines contain at least three primary amino groups and at least one tertiary amino group. These amines may be expressed by the formula:

H

NH

2 RN RNH2 [NH] z

R

NH

2 y wherein R is an alkylene group such as ethylene, propylene, butylene and other homologs (both straight chained and branched), etc., but preferably ethylene; and x, y and z are integers; x is in the range of from about 4 to about 24 or more, preferably from about 6 to about 18; y is in the range of from 1 to about 6 or more, preferably from 1 to about 3; and z is in the range of from zero to about 6, preferably from zero to about 1. The x and y i units may be sequential, alternative, orderly or random- Sly distributed. A useful class of such polyamines includes those of the formula: H H

NH

2 R-N 2H R 2

R

Ij NH •2 n WO 89/05848 PCT/US88/04502 -41wherein n is an integer in the range of from 1 to about or more, preferably in the range of from 1 to about 3, and R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched). Useful embodiments are represented by the formula: H H I NH CH CH2 N-CH CH-N---4CH 2

CK

2 N H

CH

2

CH

2

NH

2 n wherein n is an integer in the range of 1 to about 3.

The groups within the brackets may be joined in a head-to-head or a head-to-tail fashion. U.S. Patents 3,200,106 and 3,259,578 are incorporated herein by reference for their disclosures relative to said polyamines.

Suitable amines also include polyoxyalkylene polyamines, polyoxyalkylene diamines and polyoxyalkylene triamines, having average molecular weights ranging from about 200 to about 4000, preferably from about 400 to 2000. Examples of these polyoxyalkylene polyamines include those amines represented by the formula:

NH

2 -Alkylene-4-O-Alkylene---mNH 2 wherein m has a value of from about 3 to about preferably from about 10 to about 35; and the formula: R-4Alkylene--O-Alkylene-+nNH 2 3-6 I lll WO 89/05848 PCT/US88/04502, -42wherein n is a number in the range of from 1 to about with the proviso that the sum of all of the n's is from about 3 to about 70 and generally from about 6 to about 35, and R is a polyvalent saturated hydrocarbyl group of up to about 10 carbon atoms having a valence of from about 3 to about 6. The alkylene groups may be straight or branched chains and contain from 1 to about 7 carbon atoms, and usually from 1 to about 4 carbon atoms. The various alkylene groups present within the above formulae may be the same or different.

More specific examples of these polyamines include: NH CH-CH--+ OCH 2 CH- xNH 2 2 2 21 X 2

CH

3

CH

3 wherein x has a value of from about 3 to about 70, preferably from about 10 to 35; and CH2----OCH2CHx-NH2

CH

3 3

CH

3

-CH

2

-C-CH

2 -40CH 2

CH-NH

2

CH

3

CH

2

OCH

2 CH+-NH2 CH3 wherein x y z have a total value ranging from about 3 to about 30, preferably from about 5 to about Useful polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the

"'T

WO 89/08 PCT/US88/04502 ,WO 89/05848 -43polyoxypropylene triamines having average molecular weights ranging from about 200 to about 2000. The polyoxyalkylene polyamines are commercially available from the Jefferson Chemical Company, Inc. under the trade name "Jeffamine". U.S. Patents 3,804,763 and 3,948,800 are incorporated herein by reference for their disclosure of such polyoxyalkylene polyamines, Useful amines are the alkylene polyamines, including the polyalkylene polyamines, as described in more detail hereafter. The alkylene polyamines include those conforming to the formula: H-N--Alkylene-N 7

R"

I I R R wherein n is from 1 to about 10; each R" is independently a hydrogen atom, a hydrocarbyl group or a hydroxysubstituted hydrocarbyl group having up to about carbon atoms, and the "Alkylene" group has from about 1 to about 10 carbon atoms with the preferred alkylene being ethylene or propylene. Useful are the alkylene polyamines wherein each R" is hydrogen with the ethylene polyamines, and mixtures of ethylene polyamines being particularly preferred. Usually n will have an average value of from about 2 to about 7. Such alkylene polyamines include methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines, heptylene Spolyamines, etc. The higher homologs of such amines and related aminoalkyl-substituted piperazines are also included.

Alkylene polyamines that are useful include Sethylene diamine, triethylene tetramine, propylene 1- WO 8905848 PCT/US88/04502 wo 89/05848 -44diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine, octamethylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene) triamine, N-(2-aminoethyl) piperazine, 1,4-bis(2-aminoethyl) piperazine, and the like. Higher homologs as are obtained by condensing two or more of the above-illustrated alkylene amines are useful as amines in this invention as are mixtures of two or more of any of the afore-described polyamines.

Ethylene polyamines, such as those mentioned above, are described in detail under the heading "Diamines and Higher Amines" in The Encyclopedia of Chemical Technology, Second Edition, Kirk and Othmer, Volume 7, pages 27-39, Interscience Publishers, Division of John Wiley and Sons, 1965, these pages being incorporated herein by reference. Such compounds are prepared most conveniently by the reaction of an alkylene chloride with ammonia or by reaction of an ethylene imine with a ring-opening reagent such as ammonia, etc. These reactions result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful in preparing compositions of the present invention. Useful hydroxyalkyl-substituted alkylene polyamines include those in which the hydroxyalkyl group is a lower hydroxyalkyl group, having less than eight carbon atoms. Examples of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl) ethylene diamine, 1-(2hydroxyethyl)-piperazine, monohydroxypropyl-substituted WO 89/05848 PCT/US88/04502 diethylene triamine, dihydroxypropyl-substituted tetraethylene pentamine, N-(3-hydroxybutyl) tetramethylene diamine, etc. Higher homologs as are obtained by condensation of the above-illustrated hydroxy alkylene polyamines through amino groups or through hydroxy groups are likewise useful. Condensation through amino groups results in a higher amine accompanied by removal of ammonia and condensation through the hydroxy groups results in products containing ether linkages accompanied by removal of water.

To prepare the hydrocarbyl-substituted carboxylic acid amide derivative one or more of each of the acid or anhydride and one or more of ammonia or the above-described primary or secondary amines are mixed together and heated, optionally in the presence of a normally liquid, substantially inert organic liquid solvent/diluent, at temperatures in the range of from about 50 0 C to about 130 0 C, preferably from about 0 C to about 110 0 C. The acid or anhydride and the amine are reacted in amounts sufficient to provide preferably from about 0.05 to about 0.95 equivalents of amine per equivalent of the acid or anhydride For purposesof this invention an equivalent of amine is that amount of the amine corresponding to the total weight of amine divided by the total number of nitrogens present. Thus, octylamine has an equivalent weight equal to its molecular weight; ethylene diamine has an equivalent weight equal to one-half its molecular weight; and aminoethylpiperazine has an equivalent weight equal to one-third its molecular weight. Also, for example, the equivalent weight of a commercially available mixture of polyalkylene polyamine can be determined by dividing the atomic weight of nitrogen WO89/05848 PCT/US88/04502, -46- (14) by the %N contained in the polyamine. Therefore, a polyamine mixture having a %N of 34 would have an equivalent weight of 41.2. An equivalent of the acid or anhydride is the same as discussed above with respect to reaction with alcohols.

The hydrocarbyl-substituted carboxylic acid or anhydride can be reacted with a hydroxyamine according to conventional ester- and/or amide-forming techniques. This normally involves heating the acid or anhydride with the hydroxyamine, optionally in the presence of a normally liquid, substantially inert, organic liquid solvent/diluent. Temperatures of at least about 30 0 C up to the decomposition temperature of the reaction component and/or product having the lowest such temperature can be used. This temperature is preferably in the range of about 50 0 C to about 130 0

C,

preferably about 80°C to about 100 0 C when the carboxylic reactant is an anhydride. On the other hand, when the carboxylic reactant is an acid, this temperature is preferably in the range of about 100 0 C up to about 300 0

C

with temperatures in the range of about 125 0 C to about 250 0 C often being employed. Usually, about 0.05 to about 0.95, preferably about 0.5 equivalent of hydroxyamine are used for each equivalent of acid or anhydride.

For purposes of this reaction, an equivalent of a hydroxyamine is its molecular weight divided by the total number of -OH, >NH and -NH 2 groups present in the molecule. Thus, diethylethanolamine has an equivalent weight equal to its molecular weight; ethanolamine has an equivalent weight equal to one-half its molecular weight. An equivalent of acid or anhydride is the same as discussed above with respect to reaction with alcohols.

WO 89/05848 PCT/US88/04502 -47-- Component Component includes ammonia, alkali and alkaline earth metals, and/or compounds of such metals.

The alkali and alkaline earth metals that are useful as component can be any alkali or alkaline earth metal. The alkali metals are preferred.

Sodium and potassium are particularly preferred. The alkali and alkaline earth metal compounds that are useful include, for example, the oxides, hydroxides and carbonates. Sodium hydroxide and potassium hydroxide are particularly preferred.

Reaction Between the Hydrocarbyl-Substituted Acid or Anhydride, or Ester or Amide Derivative and Compound The hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derivative and component are reacted together under salt-forming conditions to form the desired salt composition The ratio of reactants utilized in the preparation of the salt composition may be varied over a wide range. Generally, from about 0.1 to about 2 equivalents or more, preferably about 0.5 to about 1.5 equivalents of component is used for each equivalent of component For purposes of this reaction, an equivalent of component in the acid or anhydride form is the same as discussed above with respect to the reaction of the acids and anhydrides with alcohols. The number of equivalents of component in the ester and/or amide derivative form, depends on the total number of carboxy groups present that are capable of reacting as a carboxylic acid acylating agent; that is the number of carboxy groups present- that are capable of forming a WO 89/05848 PCT/US88/04502 -48carboxylic salt with component For example, there would be one equivalent in an acid/amide derived from one mole of a polyisobutylene-substituted succinic anhydride and one mole of ammonia. Similarly, there would be one equivalent in an acid/ester derived from one mole of a polyisobutylene-substituted succinic anhydride and methanol. When component is ammonia, an equivalent weight thereof is its molecular weight. When component is an alkali or alkaline earth metal, an equivalent weight thereof is its molecular weight. When component is an alkali or alkaline earth metal compound, an equivalent weight thereof is its molecular weight divided by the number of alkali or alkaline earth metal atoms present in the molecule.

The product of the reaction between components and must contain at least some carboxylic salt in order for said product to be effective as an emulsifier in accordance with this invention. Thus, this product is typically constituted of compositions containing at least one compound having at least one carboxylic salt linkage 0 O-C-OM _C-O-M wherein M+ is an alkali or alkaline earth metal, or ammonium cation) within its molecular structure. This product can also include other compounds such as amides, esters, and the like. Preferably, these products contain compounds containing such salt linkage at levels of at least about 15% by weight of the product, more preferably at least about 20% by weight, more preferably at O 89/05848 PCT/US88/04502 -49least about 35% by weight, more preferably at least about 50% by weight, and still more preferably at least about 75% by weight.

The reactions between components and is carried out under salt-forming conditions using conventional techniques. Typically, components and are mixed together and heated to a temperature in the range of about 20 0 C up to the decomposition temperature of the reaction component and/or product having the lowest such temperature, preferably about 50 0 C to about 130 0 C, more preferably about 80 0 C to about 110 0 C; optionally, in the presence of a normally liquid, substantially inert organic liquid solvent/diluent, until the desired product has formed.

Unless otherwise indicated, in the entire specification and in the appended claims, all parts and percentages are by weight, and all temperatures are in degrees centigrade.

The Functional Additive The functional additive can be any watersoluble, oil-insoluble functional additive that has utility in the inventive water-in-oil emulsions. Many such additives are known in the art. Typically these additives are organic or inorganic acids or salts. The phosphates, borates and molybdates are useful as such functional additives when the inventive water-in-oil emulsions are, for example, hydraulic fluids. These additives function as rust-inhibiting agents and in some instances as anti-wear agents. Organic salts such as sodium-2-mercaptobenzothiazole are also useful as a rust-inhibiting agent. Non-oxidizing acids such as hydrochloric acid and sulfuric acid are useful as such additives when the inventive water-in-oil emulsions are,

I

s WO 89/05848 PCT/US88/04502.

for example, acidizing fluids for use in enhanced oil recovery. Oxygen supplying salts such as ammonium nitrate are useful as such additives when the inventive water-in-oil emulsions are used as explosives.

Examples of the phosphates include any compound containing the group PO= 4 including the normal or tertiary phosphates (X 3 P0 4 the monoacid, monohydric, dibasic or secondary phosphates (X 2 HP04); the diacid, dihydric, monobasic or primary phosphates

(XH

2

PO

4 the double phosphates ((X,X')P0 4 the triple phosphates 4 and the orthophosphates (X 3

PO

4 as well as the hypophosphates

(X

4

P

2 0 6 and the pyrophosphates (X 4

P

2 0 7 In the above formulae X is a monovalent metal sodium or potassium) or an ammonium group (NH 4 Specific examples of such phosphates include diammonium hydrogen phosphate, monoammonium phosphate, disodium 'phosphate, and monosodium phosphate. Salts formed by the reaction of monoethanolamine with phosphoric acid are useful.

The molybdates include X 2 (Mo 4

X

2 (Mo 2 07) and X 6 Mo70 24 wherein X is an ammonium group or a monovalent metal, alkali metal, especially sodium or potassium). The phosphates, borates and molybdates are useful as such functional additives when the inventive water-in-oil emulsions are, for example, hydraulic fluids. These additives function as rust-inhibiting agents and in some instances as anti-wear agents. Organic salts such as sodium-2-mercaptobenzothiazole are also useful as a rust-inhibiting agent. Non-oxidizing acids such as hydrochloric acid and sulfuric acid are useful as such additives when the inventive water-in-oil emulsions are, for example, WO PCT/US88/04502 -51acidizing fluids for use in enhanced oil recovery.

Oxygen supplying salts suci as ammonium nitrate are useful as such additives when the inventive water-in-oil emulsions are used as explosives.

Examples of the phosphates include any compound containing the group PO= 4 including the normal or tertiary phosphates (X 3 P0 4 the monoacid, monohydric, dibasic or secondary phosphates (X 2 HP0 4 the diacid, dihydric, monobasic or primary phosphates

(XH

2

PO

4 the double phosphates ((X,X')P0 4 the triple phosphates 4 and the orthophosphates (X 3 P04); as well as the hypophosphates

(X

4

P

2 0 6 and the pyrophosphates (X 4

P

2 0 7 In the above formulae X is a monovalent metal sodium or potassium) or an ammonium group (NH 4 Specific examples of such phosphates include diammonium hydrogen phosphate, monoammonium phosphate, disodium phosphate, and monosodium phosphate. Salts formed by the reaction of monoethanolamine with phosphoric acid are useful.

The molybdates include X 2 (MoO 4

X

2 (Mo 2 07) and X 6 Mo70 24 wherein X is an ammonium group (NH 4 or a monovalent metal, alkali metal, especially sodium or potassium). The salts of molybdic acid, H 2 MoO 4 are useful. Similarly, the salts of hydrous molybdic acid, MoO4-4H 2 0, and molybdic anhydride MoO 3 are useful. Sodium molybdate, Na 2 Mo0 4 2H 2 0, is a preferred molybdate.

The borates include XH 2

BO

3 and XH 3

BO,

wherein X is NH 4 or a monovalent metal such as sodium or potassium. The meta-borates, compounds containing the radical -B0 2 the orthoborates, compounds containing the radical -B0 3 and the pyroborates, compounds containing the radical >B 4 0 7 are useful.

Specific examples of useful borates include: sodium metaborate, Na 2

BO

2 sodium borate tetrahydrate, WO 89/05848 PCT/US88/0450 2 -52- Na 2

B

2 04 4H20; borax, Na 2

B

4 07OlOH20; anhydrous borax, Na 2 B40 7 sodium borate pentahydrate Na 2 B40 7 '5H 2 0, and the like.

The non-oxidizing acids include inorganic acids such as hydrochloric acid, sulfuric acid, hydrofluoric acid, sulfamic acid, and the like, as well as organic acids containing from 1 to about 3 carbon atoms such as formic acid, acetic acid, propionic acid, and the like.

Mixtures of two or more of the foregoing acids can be used. Hydrochloric acid is preferred.

The oxygen-supplying salts which are useful as the functional additive include ammonium nitrate, and the alkali or alkaline earth metal nitrates, chlorates, perchlorates and mixtures thereof. Examples include sodium nitrate, sodium perchlorate and ammonium perchlorate. Ammonium nitrate is especially preferred.

Emulsion Stabilizers: Although the inventive emulsions are, in themselves useful, emulsion stabilizers can be used to improve the stability of the emulsion against deterioration due to temperature, pressure, oxidation of the oil, and other harmful environments. Stabilizers include phosphatides, especially those having the structural formula

H

H-C-O-G

H-C-O-G

H-C-O-G

H

wherein G is selected from the class consisting of fatty acyl groups and phosphorus-containing groups having the structural grouping WO 89/05848 PCT/US88/04502 ,wo 89/05848 -53- O R"

-P-O-R'-N-OH

1 I OH R"' wherein R' is a lower alkylene group having from 1 to about 10 carbon atoms and R" and are lower alkyl groups having from 1 to 4 carbon atoms, and at least one but no more than two of the G groups being said phosphorus-containing group. The fatty acyl groups are for the most part those derived from fatty acids having from about 8 to about 30 carbon atoms in the fatty groups such as octanoic acid, stearic acid, oleic acid, palmitic acid, behenic acid, myristic acid, and oleostearic acid. Especially desirable groups are those derived from commercial fatty compounds such as soyabean oil, cotton seed oil, and castor oil. A particularly effective phosphatide is soyabean lecithin which is described in detail in Encyclopedia of Chemical Technology, Kirk and Othmer, Volume 8, pages 309-326 (1952), which is incorporated herein by reference.

The emulsion stabilizer ay be an aliphatic glycol or a mono-aryl ether of an aliphatic glycol. The aliphatic glycol may be a polyalkylene glycol. It is preferably one in which the alkylene group is a lower alkylene group having from 1 to about 10 carbon atoms.

Thus, the aliphatic glycol is illustrated by ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,2-butylene glycol, 2,3-butylene i glycol, tetramethylene glycol, hexamethylene glycol, or the like. Specific examples of the ethers include monophenyl ether of ethylene gly:ol, mono-(heptylphenyl) ether of triethylene glycol, mono-(alpha-octyl-betanaphthyl) ether of tetrapropylene glycol, mono-(poly- I WO 89/05848 PCT/US88/04502- -54isobutene(molecular weight of 1000)-substituted phenyl) ether of octapropylene glycol, and mono-(o,p-dibutylphenyl) ether of polybutylene glycol, mono-(heptylphenyl) ether of trimethylene glycol and dioctylphenyl) ether of tetra-trimethylene glycol, etc.

The mono-aryl ethers are obtained by the condensation of a phenolic compound such as an alkylated phenol or naphthyl with one or more moles of an epoxide such as ethylene oxide, propylene oxide, trimethylene oxide, or 2,3hexalene oxide. The condensation is promoted by a basic catalyst such as an alkali or alkaline earth metal hydroxide, alcoholate, or phenate. The temperature at which the condensation is carried out may be varied within wide ranges such as from room temperature to about 250°C. Ordinarily it is preferably 50-150 0

C.

More than one mole of the epoxide may condense with the phenolic compound so that the product may contain in its molecular structure one or more of the groups derived from the epoxide. A polar-substituted alkylene oxide such as epichlorohydrin or epilbromohydrin likewise is useful to prepare the mono-aryl ether product and such product likewise is useful as the emulsion stabilizer in this invention.

Also useful as the emulsion stabilizers are the mono-alkyl ethers of the aliphatic glycols in which the alkyl group is, octyl, nonyl, dodecyl, behenyl, etc. The fatty acid eshers of the mono-aryl or monoalkyl ethers of aliphatic glycols also are useful. The fatty acids include, acetic acid, formic acid, butanoic acid, hexanoic acid, oleic acid, stearic acid, behenic acid, decanoic acid, iso-stearic acid, linoleic acid, as well as commercial acid mixtures such as are obtained by the hydrolysis of tall oils, sperm oils, -i

A

WO 89/05848 PCT/US88/04502 etc. Specific examples are the oleate of mono-(heptylphenyl)ether of tetraethylene glycol and the acetate of mono-(polypropene(having molecular weight of 1000)-substituted phenyl) ether of tri-propylene glycol.

The alkali metal and ammonium salts of sulfonic acids likewise are useful emulsion stabilizers. The acids are illustrated by decylbenzene sulfonic acid, di-dodecylbenzene sulfonic acid, mahogany sulfonic acid, heptylbenzene sulfonic acid, polyisobutene sulfonic acid (molecular weight of 750), and decylnaphthalene sulfonic acid, and tri-decylbenzene sulfonic acid. The salts are illustrated by the sodium, potassium, or ammonium salts of the above acids.

Also useful as supplementary emulsion stabilizers are the neutral alkali metal salts of fatty acids having at least 12 aliphatic carbon atoms in the fatty group. These fatty acids include, principally, lauric acid, stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, linolenic acid, behenic acid, or a mixture of such acids such as are obtained from the hydrolysis of tall oil, sperm oil, and other commercial fats. The acids should contain at least about 12 aliphatic carbon atoms, preferably from about 16 to about carbon atoms.

Only a small amount of the stabilizer is necessary. It may be as little as 0.01 part and seldom exceeds 2 parts per 100 parts of the emulsion. Prefer- Sably, it is within the range from about 0 1 to about 1 part per 100 parts of the emulsion.

Hydraulic Fluids: When the inventive emulsions are employed as hydraulic fluids, such emulsions typically include other additional E.dditives such as extreme pressure agents, L A WO 89/05848 PCT/US88/04502.

-56rust-inhibiting agents in addition to those discussed above, foam inhibitors, freezing point depressants, bactericides, oxidation-inhibitors, and the like.

Extreme pressure agents are agents which improve the load-carrying properties of the emulsion.

These agents are illustrated by lead or nickel or Group II metal phosphorodithioates in which the metal may be magnesium, calcium, barium, strontium, zinc, or cadmium. Zinc is an especially preferred metal. Specific examples of the metal phosphorodithioates include zinc di(4-methyl-2-pentyl) phosphorodithioate, zinc O-methyl- O'-dodecylphosphorodithioate, barium diheptylphosphorodithioate, barium di(n-butylphenyl) phosphorodithioate, magnesium di-cyclohexylphosphorodithioate, cadmium salt of an equal molar mixture of dimethylphosphorodithioic acid and di-octylphosphorodithioic acid, zinc di-n-nonylphosphorodithioate, zinc di-dodecylphosphorodithioate, lead di-pentyl phosphorodithioate, nickel di-octylphosphorodithioate, and zinc di-(heptylphenyl) phosphorodithioate.

Methods for preparing the phosphorodithioic acids are known in the art, including, for example, the reaction of an alcohol or a phenol with phosphorus pentasulfide. Likewise known are the methods for preparing the Group II metal salts of phosphorodithioic acids.

Such methods are illustrated by the neutralization of phosphorodithioic acids or mixtures of such acids with zinc oxide.

Other extreme pressure agents useful in the emulsions of this invention include the chlorinated waxes; sulfurized or phosphosulfurized fatty acid esters; di- and tri-hydrocarbon phosphites and phosphates; di-hydrocarbon polysulfides; and metal dithiocar- WO 89/05848 PCT/US88/04502 -57bamates. The chlorinated waxes are exemplified by chlorinated eicosane having a chlorine content of 50% or other chlorinated petroleum waxes having a chlorine content of 5-60%. The sulfurized fatty esters are obtained by the treatment of a lower alkyl ester of a fatty acid having at least about 12 carbon atoms with a sulfurizing agent such as sulfur, sulfur mono-chloride, sulfur dichloride, or the like. The fatty acid esters are illustrated by methyl oleate, methyl stearate, isopropyi myristate, cyclohexyl ester of tall oil acid, ethyl palmitate, isooctyl laurate, diester of ethylene glycol with stearic acid, etc. Commercial mixtures of esters likewise are useful. They include, for example, sperm oil, Menhaden oil, glycerol trioleate, etc. The sulfurization is effected most conveniently at temperatures between about 100°C and about 250°C. More than one atom of sulfur can be incorporated into the ester and for the purpose of this invention sulfurized esters having as many as four or five atoms of sulfur per molecule are useful. Examples include sulfurized sperm oil having a sulfur content of sulfurized tall oil having a sulfur content of sulfurized methyl oleate having a sulfur content of and sulfurized stearyl stearate having a sulfur content of The phosphosulfurized fatty acid esters are obtained by the treatment of the esters illustrated above with a phosphorus sulfide such as phosphorus pentasulfide, phosphorus sesquisulfide, or phosphorus heptasulfide. The treatment is illustrated by mixing an ester with from about 0.5% to 25% of a phosphorus sulfide at a temperature within the range from about 100 0

C

to about 250 0 C. The products contain both phosphorus and sulfur but the precise chemical structure of such products is not clearly understood.

.h* i WO 89/05848 PCT/US88/04502 -58- The phosphites and phosphates useful herein are the di- and tri-esters of phosphorus or phosphoric acid in which the ester group is derived from a substantially hydrocarbon group including aryl, alkyl, alkaryl, arylalkyl, or cycloalkyl group as well as a hydrocarbon group having a polar substituent such as chloro, nitro, bromo, ether, or the like. Particularly desirable phosphites and phosphates are those in which the ester groups are phenyl, alkylphenyl or alkyl groups containing from about 6 to about 30 carbon atoms. Examples are dibutyl phosphite, diheptyl phosphite, dicylohexyl phosphite, di-(pentylphenyl) phosphite, bis-(dipentylphenyl) phosphite, tridecyl phosphite, di-stearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, triphenyl phosphite, bis-(hexapropylene-substituted phenyl) phosphite, tri(n-chloro-3-heptylphenyl) phosphite, triphenyl phosphate, tricresyl phosphate, tri(p-chlorophenyl) phosphate, and triheptylphenyl) phosphate.

The metal dithiocarbamates include principally those of zinc, lead, strontium, nickel, cadmium, and palladium with N,N-dialkyldithiocarbamic acids in which the alkyl group contains from 3 to about 30 carbon atoms. Examples are zinc N,N-dioctyl dithiocarbamate, lead N,N-dicyclohexyl dithiocarbamate, cadmium N,N-dibehenyl dithiocarbamate, lead N,N-didodecyl dithiocarbamate, and mixtures thereof.

SThe concentration of the extreme pressure agent is usually within the range from about 0.05 to about parts, although it is seldom necessary to employ more than 2 parts of this agent per 100 parts of the emulsion.

7 SWO 89/05848 PCT/US88/04502 -59- Another type of additive which finds use in the emulsion is a rust-inhibiting agent. The most effective rust-inhibiting agents in the emulsions of this invention are aliphatic amines, especially aliphatic primary amines having at least 8 carbon atoms in the molecule.

The aliphatic amines are preferably tertiaryalkyl primary amines having from about 12 to about 30 carbon atoms. The amines include stearyl amine, oleyl amine, myristyl amine, palmityl amine, n-octyl amine, dodecyl amine, octadecyl amine, and other commercial primary amine mixtures such as the mixture in which the aliphatic group is a mixture of tertiary-alkyl group having from 11 to 14 carbon atoms and an average of 12 carbon atoms, and the mixture in which the aliphatic group is a mixture of tertiary-alkyl groups having from 18 to 24 carbon atoms.

Also effective as rust-inhibiting agents are the salts of an aromatic acid such as benzoic acid, toluic acid, naphthoic acid, phthalic acid, or terephthalic acid with any of the aliphatic amines listed above. Salts derived from other acids such as p-aminobenzoic acid and o-chlorobenzoic acid likewise are useful.

The salts of amines with the aromatic acids are prepared simply by mixing the reactants at a temperature below the dehydration temperature, below about 0 C. In most instances the reaction is exothermic and heating is not necessary. A solvent such as benzene, toluene, naphtha, and chlorobenzene may be used.

Still another class of rust-inhibiting agents are the hydroxy-alkyl amines, especially the long chain C8- 30 aliphatic amines containing one or two hydroxy-alkyl substituents on the amine nitrogen atom.

71 WO 89/05848 PCT/US88/04502 Examples are N-(2-hydroxyethyl) octylamine, N,N-di-(2hydroxy-l-propyl) dodecylamine, N-(3-hydroxy-l-pentyl) octadecylamine, and N,N-di-(2-hydroxy-3-butyl) decylamine.

Also useful as the rust-inhibiting agents are the nitrous acid salts of the long chain aliphatic amines illustrated above. Such salts are obtained simply by mixing at ordinary temperatures such as room temperature an amine with nitrous acid. Specific examples include the nitrous acid salt of the tertiaryalkyl (Cl-1 4 primary amine and the nitrous acid salt of octadecylamine.

The concentration of rust-inhibiting agent in the emulsion depends to some extent upon the relative concentration of water in the emulsion. Ordinarily from about 0.01 part to about 2 parts of a rust-inhibiting Sagent per 100 parts of the emulsion is sufficient.

Still another type of additive which finds use in these emulsions is a foam-inhibitor which may be a commercial dialkyl siloxane polymer or a polymer of an alkyl methacrylate. Freezing point depressants, i.e., water-soluble polyhydric alcohols such as glycerol or other polar substances such as Cellosolve are also useful. The concentration of these additives usually is less than 5 parts per 100 parts of the emulsion.

Bactericides are also useful in the emulsions of this invention. They are illustrated by nitro-bromoalkanes (such as 3-nitro-l-propyl bromide), nitro-hydroxy-alkanes (such as tri-(hydroxymethyl) nitro-methane, 2-nitro-2-ethyl-l,3-propane-diol, and 2-nitro-lbutanol), and boric acid esters (such as glycerol borate). The concentration of the bactericide may be from about 0.001 to about 1 part per 100 parts of the emulsion.

I

S :i WO 89/05848 PCT/US88/04502 -61-- Oxidation-inhibitors useful in the emulsions of this invention include the hindered phenols such as 2,4di-tert-butyl-6-methylphenol, 4,4'-methylene-(2,6-ditert-pentylphenol), and 2,6-di-tert-octyl-4-sec-butylphenol. The concentration of the oxidation-inhibitors is usually 0.01 to 2 parts per 100 parts of the emulsion.

The emulsions can be prepared simply by mixing the oil the water the emulsifying salt the functional additive and any other ingredient which may be desirable, in a. homogenizer or any other efficient blending device. Heating the emulsion during or after it is prepared is not necessary. The order of mixing of the ingredients is not critical, although it is convenient first to prepare an oil concentrate containing from about 50 to about 95% of the oil-soluble ingredients and from about 5 to about 50% of the oil and then to emulsify the concentrate with a water solution containing the functional additive in appropriate proportions.

Acidizing Fluids: When the inventive emulsions are employed as acidizing fluids, such emulsions can optionally contain one or more oil-soluble surfactants. These surfactants include anionic, cationic and nonionic surfactants.

Suitable anionic surfactants include fatty acid soaps which are the salts of long chain fatty acids derived from naturally occurring fats and oils and salts of alkylbenzene sulfonic acids. A useful anionic surfactant is the morpholinium salt of tetracosanylbenzene sulfonic acid. The ammonium and alkali metal salts are also suitable. Cationic surfactants include amine salts such as polyoxyethylene amine as well as quaternary

I

F '1,f ~oflrAQ PCT/US8/045 ;02 vY F 07uVJO-o -62- 1 i f .^1 ammonium compounds. Useful cationic surfactants include high molecular weight alkyl imides and amides of polybasic amines. Suitable nonionic surfactants include derivatives of glycerides, glucosides, polyoxyethylene and polyoxypropylene. Typical nonionic surfactants include ethoxylated linear alcohols and ethoxylated alkyl phenols. Mixtures of surfactants can also be used. The acidizing fluids of the invention generally contain up to about 10% by weight, preferably from about 0.1% to about 2% by weight of the foregoing surfactants.

The acidizing fluids can be prepared simply by mixing the oil the water the emulsifying salt the functional additive and any other ingredient which may be desirable, in a homogenizer or any other efficient blending device. Heating the emulsion during or after it is prepared is not necessary. The order of mixing of the ingredients is not critical, although it is convenient first to prepare an oil concentrate containing from about 50 to about 95% of the oilsoluble ingredients and from about 5 to about 50% of the oil and then to emulsify the concentrate with a water solution containing the functional additive in appropriate proportions.

Reference is herein made to U.S. Patents 4,140,640 and 4,233,165 which disclose the preparation and use of water-in-oil acidizing fluids. These patents are incorporated herein by reference.

Explosive Emulsions: When the inventive emulsions are employed as explosive emulsions, such emulsions typically contain other additional additives such as sensitizing components, oxygen-supplying salts, particulate light metals, particulate solid explosives, soluble and partly soluble I II I WO 89/05848 PCT/US88/04502 -63self-explosives, explosive oils and the like for purposes of augmenting the strength and sensitivity ox decreasing the cost of the emulsion.

The sensitizing components are distributed substantially homogeneously throughout the emulsions. These sensitizing components are preferably occluded gas bubbles which may be introduced in the form of glass or resin microspheres or other gas-containing particulate materials. Alternatively, gas bubbles may be generated in-situ by adding to the composition and distributing therein a gas-generating material such as, for example, an aqueous solution of sodium nitrite. Other suitable sensitizing components which may be employed alone or in addition to the occluded or in-situ generated gas bubbles include insoluble particulate solid self-explosives such as, for example, grained or flaked TNT, DNT, RDX and the like and water-soluble and/or hydrocarbon-soluble organic sensitizers suTh as, for example, amine nitrates, alkanolamine nitrates, hydroxyalkyl nitrates, and the like. The explosive emulsions of the present invention may be formulated for a wide range of applications. Any combination of sensitizing components may be selected in order to provide an explosive composition of virtually any desired density, weight-strength or critical diameter.

The quantity of solid self-explosive ingredients and of water-soluble and/or hydrocarbon-soluble organic sensitizers may comprise up to about 40% by weight of the total emulsion. The volume of the occluded gas component may comprise up to about 50% of the volume of the total explosive emulsion.

Optional additional materials may be incorporated in the explosive emulsions of the invention in WO 89/05848 PCT/US89/04502, -64order to further improve sensitivity, density, strength, rheology and cost of the final explosive. Typical of materials found useful as optional additives include, for example, emulsion promotion agents such as highly chlorinated paraffinic hydrocarbons, particulate oxygensupplying salts such As prilled ammonium nitrate, calcium nitrate, perchlorates, and the like, particulate metal fuels such as aluminum, silicon and the like, particulate non-metal fuels such as sulfur, gilsonite and the like, particulate inert materials such as sodium chloride, barium sulphate and the like, water phase or hydrocarbon phase thickeners such as guar gum, polyacrylamide, carboxymethyl or ethyl cellulose, biopolymers, starches, elastomeric materials, and the like, crosslinkers for the thickeners such as potassium pyroantimonate and the like, buffers or pH controllers such as sodium borate, zinc nitrate and the like, crystals habit modifiers such as alkyl naphthalene sodium sulphonate and the like, liquid phase extenders such as formamide, ethylene glycol and the like and bulking agents and additives of common use in the explosives art.

The quantities of optional additional materials used may comprise up to about 50% by weight of the total explosive composition, the actual quantities employed depending upon their nature and function.

A preferred method for making the water-in-oil explosive emulsions of the invention comprise the steps of mixing the water, inorganic oxidizer salts and, in certain cases, some of the optional water-soluble compounds, in a first premix, mixing the oil, emulsifying salt and any other optional oil-soluble compounds, in a second premix and adding the first premix to the second premix in a suitable mixing appara- 'WO 89/05848 PCT/US88/04502 tus, to form a water-in-oil emulsion. The first premix is heated until all the salts are completely dissolved and the solution may be filtered if needed in order to remove any insoluble residue. The second premix is also heated to liquefy the ingredients. Any type of apparatus capable of either low or high shear mixing can be used to prepare the explosive emulsions of the invention. Glass microspheres, solid self-explosive ingredients such as particulate TNT, solid fuels such as aluminum or sulfur, inert materials such as barytes or sodium chloride, undissolved solid oxidizer salts and other optional materials, if employed, are added to the emulsion and simply blended until homogeneously dispersed throughout the composition.

The explosive emulsions of the invention can also be prepared by adding the second premix liquefied oil solution phase to the first premix hot aqueous solution phase with sufficient stirring to invert the phases. However, this method usually requires substantially more energy to obtain the desired dispersion than does the preferred reverse procedure. Alternatively, the explosive emulsion is particularly adaptable to preparation by a continuous mixing process where the two separately prepared liquid phases are pumped through a mixing device wherein they are combined and emulsified.

While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading this specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims (10)

1. A water-in-oil emulsion comprising: a continuous oil phase; a discontinuous aqueous phase; a minor emulsifying amount of at least one salt made by reacting component with component under salt-forming conditions, component comprising at least one hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derived from said acid or anhydride, the hydrocarbyl substituent of having an average of from 20 to 500 carbon atoms, and component (C)(II) comprising at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; and a functional amount of at least one water-soluble, oil-insoluble functional additive dissolved in said aqueous piase; said functional additive being one or more oxygen-supplying salts, one or more non-oxidizing acids, or one or more borates, phosphates and/or molybdates.

2. The composition of claim 1, wherein component is present in said emulsion at a level in the range of from 2% to 70% by weight of said emulsion; component is present in said emulsion at a level in the range of from 1% to 98% by weight of said emulsion; component is present in said emulsion at a level in the range of from 0.05% to 30% by weight of said emulsion; and component is present in said emulsion at a level in the range of from 0.05% to 95% by weight of said emulsion. S• 3. The composition of claim 1 or claim 2, wherein is an acid or anhydride represented by the formulae 0 hyd-CHCOOH or hyd-CH-C CH2COOH O CH 2 -C wherein "hyd" is the hydrocarbyl substituent of or is an ester or an amide derived from said acid or anhydride. 0 ,7 iI IIi-r -67- 0 00.0 *000 S 0* I S. 0 0 0*S* 0* 9 0

4. The composition of any one of claims 1 to 3, wherein said hydrocarbyl substituent of has an average of from 30 to 500 carbon atoms. The composition of any one of claims 1 to 3, wherein said hydrocarbyl substituent of has an average of from 50 to 500 carbon atoms.

6. The composition of any one of claims 1 to 5, wherein said hydrocarbyl substituent of is a poly(isobutenyl) group.

7. The composition of claim 1 or claim 2, wherein component comprises at least one amide derived from at least one alkylene polyamine of the formula H- N---Alkylene-N-)R" R" R" wherein n is a number of from 1 to 10, each R" is independently a hydrogen atom or a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having up to carbon atoms, and the Alkylene group has from 1 to 10 carbon atoms.

8. The composition of claim 1, wherein component comprises at least one ester and/or amide derived from the group consisting of primary, secondary and tertiary alkanol amines which can be represented correspondingly by the formulae H N-R'-OH HX N-R'-OH R RN-R-OH N-R'-OH RI -68 hydroxyl-substituted oxyalkylene analogs of said alkanol amines represented by the formulae H II H 15 -H H N-(R'-O)2-15-H R R N-(R'-O)2.15-H R Sg" wherein each R is independently a hydrocarbyl group of one to 8 carbon atoms or a hydroxyl-substituted hydrocarbyl group of 2 to 8 carbon atoms and R' is a S divalent hydrocarbyl group of 2 to 18 carbon atoms, and mixtures of two or more thereof.

9. The composition of claim 1 or claim 2, wherein component is polyisobutenyl succinic acid and/or poly-isobutenyl succinic anhydride reacted with diethylethanolamine.

10. The composition of any one of claims 1 to 9, wherein component (D) comprises ammonium nitrate.

11. A water-in-oil emulsion of claim 1, substantially as herein described with reference to any one of the Examples. DATED this 11th day of October 1991. THE LUBRIZOL CORPORATION By their Patent Attorneys: CALLINAN LAWRIE l u *JYOY' INTERNATIONAL SEARCH REPORT International Application No PCT/US 88 0 4502 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC IPC4 C 10 M 173/00; E 21 B 43/27; C 06 B 47/14;//(C 10 M 173/00 S129:93. 133:52) C 10 N 40:08 II, FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols 4 I PC C 10 M; E 21 B; C 06 B; B 01 F Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched III. DOCUMENTS CONSIDERED TO BE RELEVANT' Category I Citation of Document, with indication, where appropriate, of the relevant passages 12 Relevant to Claim No. "1 X WO, A, 8703613 (LUBRIZOL) 18 June 1987, 1-31,37-47 see claims 1-51; page 45, paragraph 2 Y Y

32-36 Y US, A, 3269946 WIESE) 30 August 1966, 32-36 see claim 1; column 2, lines 46-65 X US, A, 4225447 LAW) 30 September 1980, 1-6,8,9, see column 1, lines 1-34; column 2, 11-15,32-36 line 16 column 3, line X EP, A, 0156572 (ICI) 2 October 1985, 1-6,8-22, see claims 1-10; page 5, line 23 31-36 page 6, line.9 i SSpecial categories of cited documents: 1o later document published after the international filing date document defining the general state of the art which is not or priority date and not in conflict with the application but cited to understand tie principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the International document of particular relevance: the claimed invention filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the International filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Data of the Actual Completion of the International Search Date of Mailing of this International Search Report 4th April 1989 24. 0 89 International Searching Authority Signature of c Tr EUROPEAN PATENT OFFICE DER PUTTEN Form PCT/ISA/210 (second sheet) (January 1965) I 0' ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8804502 SA 26169 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 13/04/89 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date WO-A- 8703613 18-06-87 AU-A- 6738287 30-06-87 US-A- 4708753 24-11-87 JP-T- 63502254 01-09-88 EP-A- 0285608 12-10-88 US-A- 3269946 FR-A- 1337544 DE-B-. 1270723 GB-A- 1009197 US-A- 4225447 30-09-80 None EP-A- 0156572 02-10-85 GB-A- 2157700 30-10-85 JP-A- 60212214 24-10-85 AU-A- 4006285 26-09-85 AU-B- 575922 11-08-88 CA-A- 1244463 08-11-88 Formore dtai about nnex see Official Joual of the European Patent Office, No. w For more details about this annex see Official Journal of the European Patent Office, No. 12/82