NO169723B - WATER-IN-OIL-EMULSIONS. - Google Patents

Description

The present invention relates to water-in-oil emulsions and more particularly water-in-oil emulsions containing nitrogen-containing salt emulsifiers and water-soluble, oil-insoluble functional additives. The area of use for these emulsions depends on the specific functional additives used and includes hydraulic fluids, explosives and acidizing fluids.

Water-in-oil emulsions have found wide application as flame-resistant hydraulic fluids in general industry, coal mines and rolling mills where there is a risk of fire. These hydraulic fluids are generally used where the fluid can generally be sprayed or dripped out from a break or a leak on an ignition source, for example on molten metal or a gas flame. This condition often exists in casting machines or in presses near furnaces. Characteristically, these hydraulic fluids consist of a continuous oil phase, a discontinuous aqueous phase, at least one emulsifier and one or more functional additives such as rust inhibitors, extreme pressure agents, foam inhibitors, freezing point lowering agents, bactericides, oxidation inhibitors and the like. Examples of such fluids are described in US-PS 3,255,108, 3,269,946, 3,281,356, 3,311,4561, 3,378,494, 3,629,119 and 4,225,447.

A problem with water-in-oil hydraulic fluids is that they tend to cause wear on metal pump parts and other equipment with which they come into contact. The water phase, even if it is dispersed in the oil phase, causes wear problems that do not occur in connection with pure petroleum oil mixtures. Another problem is that the water phase tends to corrode the metallic parts with which they come into contact. The water phase additives that have previously been used to reduce wear and/or corrosion have had the shortcoming that they tend to precipitate out of the emulsion, especially when the water content is reduced during use. Omission of the water phase additives is, on the other hand, undesirable because it is often impossible to achieve satisfactory wear and/or corrosion resistance when using additives that dissolve only in the oil phase.

Explosive emulsions characteristically consist of a continuous organic fuel or oil phase in which discrete droplets of an aqueous solution of an oxygen-releasing source are dispersed as a discontinuous phase. Such mixtures are conventionally described as water-in-oil explosive emulsion mixtures and examples are described for example in TJS-PS 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; EP-A1 155,800. Formation of these explosive emulsions is generally carried out in the presence of an emulsifier which is chosen 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 prior art are favorable, none have provided emulsion stability characteristics that are entirely satisfactory. In addition, for most emulsifiers used in the known technique, the choice of fuel or oil for the continuous phase is generally limited to highly refined and highly paraffinic oils such as "white oils".

Acid treatment or acidification of porous underground formations penetrated by a borehole is frequently used to increase the production of fluids, for example crude oil, natural gas and so on, from these formations. The usual technique for acidizing a formation involves introducing a non-oxidizing acid into the well under sufficient pressure to force the acid out and into the formation where the acid reacts with the acid-soluble components of the formation. The technique is applicable in formations with high acid solubility such as lime, dolomite and so on, as well as other types of formations such as sandstone-bearing strings or striations of acid-soluble components such as the various carbonates. During the acid treatment step, passages for fluid flow are formed in the formation, possibly existing passages are enlarged, which stimulates the production of fluids from the formation. This acid action on the formation is often called etching. Acid treatment or acidification where the acid is injected into the formation at a pressure the amount of which is not sufficient to form cracks or fracturing in the formation is called frequent matrix acidification. Various acidification mixtures are described in the prior art and examples of these are, for example, US-PS 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, 4,163,727, 4,167,214, 4,169,797, 4,169,798, 4,169,819, 4,169,816 945, 4172041, 4172055, 4174283, 4191657, 4200151, 4200539, 4200540, 4202795, 4203492, 4205724, 42062015, 4,210,206, 4,215,001, 4,217,231, 4,219,429, 4,225,445, 4,244,826 and 4,246,124. Examples of water-in-oil emulsions used in acidification are described in US-PS 4,140,640 and 4,233,165.

Hydrocarbyl-substituted carboxylic acid acylating agents having at least 30 aliphatic carbon atoms in the substituent are known. The use of such carboxylic acid acylating agents as additives in conventional liquid fuels and lubricants is described in US-PS 3,288,714 and 3,346,354. These acylating agents are also useful as intermediates for the production of additives for use in generally liquid fuels and lubricants as described in US-PS 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, 3,450,345,345,345 607. 3,948,909, 3,950,341, 4,234,435 and 4,471,091 as well as FR-PS 2,223,415. Nitrogen-containing, phosphorus-free carboxylic acid solubilizers that can be used as high water-based functional fluids are described in US-PS 4,329,249, 4,368,133, 4,435,297, 4,447,348 and 4,448,703. These solubilizers are produced by reacting

(I) -at least one carboxylic acid acylating agent with at least one hydrocarbyl-based substituent with at least 12 to 500

carbon atoms with

(II) at least one (a) N-(hydroxyl-substituted hydrocarbyl)amine,

(b) a hydroxyl-substituted poly(hydrocarbyloxy) analog

of the amine (a), or

(c) mixtures of (a) and (b).

These patents indicate that the preferred acylating agents include substituted succinic acids or succinic anhydrides and that the amines useful include primary, secondary and tertiary alkanolamines. 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 solubilizing agent is the reaction product of a polyisobutenyl-substituted succinic anhydride with diethylethanolamine or a mixture of diethylethanolamine and ethanolamine.

An advantage of the present invention is that stable water-in-oil emulsions are provided and which can be used 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 rust inhibition and anti-wear characteristics of such fluids. A particular advantage with regard to explosives is an increased flexibility when it comes to the choice of oils or fuels for the continuous phase.

According to the present invention, a water-in-oil emulsion is characterized in that it comprises: (A) a continuous oil phase; (B) a discontinuous aqueous phase; (C) a smaller emulsifying amount of at least one salt produced -by reacting component (C)(I) with component (C)(II) under salt-forming conditions, component (C)(I) being at least one hydrocarbyl-substituted carboxylic acid or an anhydride thereof, or ester or amide derivative of the acid or anhydride, the hydrocarbyl substituent of (C)(I) having on average from 20 to 500 carbon atoms, and component (C)(II) is ammonia and/or at least one

amine; and

(D) a functional amount of at least one water-soluble, oil-insoluble functional additive, dissolved in the

aqueous phase; the functional additive being one or more oxygen-carrying salts, one or more non-oxidising acids or one or more borates, phosphates and/or molybdates; provided that when component (D) is ammonium nitrate, component (C) is different from an ester/salt formed by reacting polyisobutenyl (Mn=950) substituted succinic anhydride with diethylethanolamine in a ratio of one equivalent anhydride per equivalent amine.

Preferably, the invention relates to an emulsion characterized by component (A) being present in the emulsion in an amount within the range of 2 to 70% by weight of the emulsion; component

(B) is present in the emulsion in an amount within the range of 1 to 97.9% by weight of the emulsion; component (C) is present in

the emulsion in an amount within the range of 0.05 to 30 wt-# of the emulsion; and

component (D) is present in the emulsion in an amount within the range of 0.05 to 95% by weight of the emulsion.

The term "hydrocarbyl" is used herein to include essentially hydrocarbyl groups as well as pure hydrocarbyl groups. The description of these groups as essentially hydrocarbyl groups means that they do not contain non-hydrocarbyl substituents or non-carbon atoms which significantly affect the hydrocarbyl properties of such groups in connection with their use as described here. Non-limiting examples of substituents which do not significantly change the hydrocarbyl properties of the general nature of the hydrocarbyl groups according to the invention are: Ether groups (especially hydrocarbyloxy such as phenoxy, benzyloxy, methoxy, n-butoxy and so on, and especially alkoxy groups of up to about 10 carbon atoms); oxo groups (for example -0 bonds in the main carbon chain); nitro groups; thioether groups (especially C 1-6 alkylthioethers); thia groups (eg -S bonds in the main carbon chain); carbohydrocarbyloxy groups (eg sulfonyl groups (eg sulfinyl groups (eg

This list is only illustrative and not exhaustive and the omission of a certain class of substituents is not intended to mean that it outside the scope of the invention. Generally, if such substituents are present, they will not be more than 2 per 10 carbon atoms in the essentially hydrocarbyl group and preferably no more than 1 per 10 carbon atoms because this number of substituents will not usually affect the hydrocarbyl properties and properties of the group. Nevertheless, the hydrocarbyl groups are preferably free of non-hydrocarbon groups; that is to say, they are preferably hydrocarbyl groups consisting only of carbon and hydrogen atoms.

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

The term "water-soluble" refers to substances that are soluble in water in an amount of at least 1 g per 100 ml of water at 25"C.

The term "oil-insoluble" refers to substances that are not soluble in mineral oil above a level of approx. 1 g per 100 ml of oil at 25°C.

The term "functional amount" refers to a sufficient amount of an additive to provide desired properties, intended by the addition of said additive. If, for example, an additive is a rust inhibitor, a functional amount of the rust inhibitor will be an amount sufficient to increase the rust-inhibiting characteristics of the emulsion to which the additive is added. If the corresponding additive is an anti-wear agent, a functional amount of the anti-wear agent will be a sufficient amount of this agent which improves the anti-wear properties of the emulsion to which the agent is added.

The oil phase (A) in the water-in-oil emulsions according to the invention is a continuous oil phase, while the aqueous phase (B) is a discontinuous aqueous phase that is dispersed in the oil phase

(A). The functional additive (D) is dissolved in the dispersed aqueous phase (B). The emulsifying salt (C) stabilizes

the emulsion. The emulsions of the invention preferably comprise: from 2 to 70% by weight, from 4 to 60% by weight, calculated on the total weight of the emulsion, of component (A), from 1 to 98% by weight, and preferably from 3 to 96 weight-* of component (B); and from 0.05 to 30 wt-*, more preferably from 0.2 to 15 wt-*, preferably from 0.2 to 10 wt-*, most preferably from 0.2 to 5 wt-* and most preferably from 0 .5 to 2 wt-* of component (C). The level of addition of component (D) is within the general range of 0.05 to 95 wt-*, calculated on the total weight of the emulsion. The addition level for component (D) depends on the intended use of the emulsion of the invention as described in more detail below.

These emulsions have a spectrum of applications which, among other things, depends on the special functional additives (D) used. For example, these emulsions can be used as hydraulic fluids. For such fluids, the functional additive (D) is preferably a rust-inhibiting and/or anti-wear agent such as a phosphate, borate or molybdate. In such fluids, the oil phase (A) is preferably present in an amount within the range from 40 to 70 weight-*, preferably 50 to 65 weight-*, calculated on the total weight of the emulsion. The aqueous phase (B) is preferably present at a level within the range of 30 to 60 weight-* and preferably from 35 to 50 weight-*, calculated on the total weight of the emulsion. Component (C) is preferably present at a level within the range 2.5 to 25 weight-* and most preferably from 5 to 15 weight-*, calculated on the total weight of the oil phase (A). The functional additive (D) is preferably present within a range from 0.2 to 20 weight-*, preferably from 0.5 to 10 weight-*, calculated on the total weight of the aqueous phase (B).

These emulsions can also be used in enhanced oil recovery processes as acidification fluids. For such acidifying fluids, the functional additive is preferably a non-oxidizing acid. In such acidification fluids, the oil phase (A) is preferably present at a level within the range from 20 to 70 weight-*, and more particularly from 40 to 60 weight-*, calculated on the total weight of the emulsion. The aqueous phase

(B) is preferably present at a level within the range of 30

to 80 weight-* and more particularly from 40 to 60 weight-*, calculated on the total weight of the emulsion. Component (C) is preferably present in an amount within the range of 4 to 40 weight-*, and more particularly from 10 to 20 weight-*, calculated on the total weight of the oil phase (A). The functional additive (D) is preferably present in an amount within the range of 10 to 90 weight-* and more particularly from 30 to 80 weight-* of the total weight of the aqueous phase (B).

These emulsions can also be used as explosive emulsions. For such explosive emulsions, it is a functional additive

(D) preferably an oxygen-adding salt. In such explosive emulsions, the oil phase (A) is preferably present in a

amount within the range 2 to 15 weight-* and more preferably from 4 to 8 weight-*, calculated on the total weight of the emulsion. The aqueous (B) is preferably present in an amount within the range of 85 to 98 wt-*, and more particularly from 92 to 96 wt-*, calculated on the total weight of the emulsion. Component

(C) is preferably present in an amount within the range of 4 to 40 wt-* and more particularly from 12 to 20 wt-*, calculated on

the total weight of the oil phase (A). The functional additive

(D) is preferably present in an amount within the range of 70 to 95 wt-*, more particularly from 85 to 92 wt-*, and preferably

from 87 to 90 weight-*, calculated on the total weight of the aqueous phase (D).

These emulsions may contain further additives to improve the properties of the emulsions, these further additives which depend on the intended area of use for the emulsion, are discussed in more detail below.

The oil phase ( A);

The oil which is usable in the emulsions of the invention can be a hydrocarbon oil with viscosity values of 20 SUS (Saybolt Universal Seconds) at 40° C to 2500 SUS at 40" C. Mineral oils with lubricant viscosities, for example SAE 5-90 grade, can be used Oils from a number of sources including natural and synthetic oils and mixtures thereof can be used.

Natural oils are animal oils and vegetable oils (for example, castor oil, lard oil) as well as solvent-refined or acid-refined mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic type. Oils of lubricant viscosity, derived from coal or shale are also usable.

Synthetic lubricating oils are hydrocarbon oils and halogen-substituted hydrocarbons such as polymerized and inter-polymerized olefins (for example, polybutylenes, polypropylenes, polypropylene-isobutylene copolymers, chlorinated polybutylenes, and so on); alkylbenzenes (for example dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)benzenes and so on); polyphenols (eg biphenyls, terphenyls and so on); and such. Alkylene oxide polymers and interpolymers and derivatives thereof in which the terminal hydroxyl groups have been modified by esterification, etherification and so on, constitute another class of known synthetic lubricating oils. These are exemplified by the oils produced by polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (for example methyl polyisopropylene glycol ether with an average molecular weight of about 1000, diphenyl ether of polyethylene glycol with a molecular weight of 500-1000, diethyl ether of polypropylene glycol with a molecular weight of 1000-1500, and so on) or mono- and polycarboxylic acid esters thereof, for example the acetic acid esters, mixed C 8 -g fatty acid esters or the C 8 -oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (for example, phthalic, succinic, maleic, azelaic, suberinic, sebacic, fumaric and adipic acids as well as linoleic acid dimer, and so on) with a number of alcohols (for example butyl, hexyl, dodecyl, 2-ethylhexyl alcohol or pentaerythritol and so on). Specific examples of these esters are dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of the linoleic acid dimer, the complex ester formed by reaction of one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid and the like. Silicone-based oils such as polyalkyl, polyaryl, polyalkyloxy, or polyaryloxysiloxane oils and silicate oils are another useful class of synthetic lubricants (for example, tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-( 4-methyl-2-tetraethyl)-silicate, tetra-(p-tert-butylphenyl)-silicate, hexyl-(4-methyl-2-pentoxy)-di-siloxane, poly(methyl)-siloxanes, poly(methyl- phenyl) siloxanes and so on).

Other synthetic oils are liquid esters of phosphorus-containing acids (for example, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, and so on), polymeric tetrahydrofurans, and the like.

Unrefined, refined and re-refined oils (and mixtures of these with each other) of the type described above can be used in the emulsions according to the invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification. For example, a shale oil obtained directly from retort operation, a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process and used without further treatment will be an unrefined oil. In the case where the emulsions of the invention are used as acidification fluids in enhanced oil recovery processes, the oil can be unrefined oil obtained directly from the underground oil reservoir which is treated with such fluids. Refined oils are similar to unrefined oils except that they are further processed in one or more purification steps to improve one or more properties. Many such purification techniques are known to those skilled in the art such as solvent extraction, acid or base extraction, filtration, percolation and so on. Re-refined oils are obtained by processes similar to those used to obtain refined oils, but applied to refined oils that have already been used. Such re-refined oils are also known as reprocess oils and are often further processed by techniques aimed at removing used additives and oil degradation products.

Hydrocarbyl-substituted carboxylic acid or anhydride. or ester or amide derivative thereof ( CUP;

The hydrocarbyl-substituted carboxylic acid or anhydride, or its ester or amide derivatives, is prepared by reacting one or more cx,p-olefinic unsaturated carboxylic acid reagents containing 2 to 20 carbon atoms, excluding the carboxyl-based groups, with one or more olefin polymers containing at least 20 carbon atoms, as described in more detail below.

The oc,P-olefinically unsaturated carboxylic acids can be either mono- or polybasic in type. Examples of monobasic cx,<p->olefinically unsaturated carboxylic acids are the carboxylic acids according to the formula:

where 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 hydrogen or a lower alkyl group. The total number of carbon atoms in R and R^ should not exceed 18 carbon atoms. Specific examples of useful monobasic α,β-olefinically unsaturated carboxylic acids are acrylic acid; methacrylic acid; cinnamic acid; crotonic acid; 3-phenylpropenoic acid; a,p-decenoic acid and so on. The polybasic acids are preferably dicarboxylic,

although tri- and tetracarboxylic acids can be used. Examples of polybasic acids are maleic, fumaric, mesaconic, itaconic and citraconic acids.

The cx,p-olefinically unsaturated carboxylic acid reagents can also be anhydride, ester or amide functional derivatives of the above stated acids. A preferred α,3-olefinic unsaturated carboxylic acid reagent is maleic anhydride. Methods for the production of such functional derivatives are well known to those skilled in the art and can be satisfactorily described by noting the reactants used in the production. Thus, for example, derivative esters for use as described here can be prepared by esterification of monohydroxy or polyhydroxy alcohols or epoxides with any of the above stated acids or anhydrides with ammonia, primary amines and secondary amines. The amines and alcohols described below 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, will be free of acetylenic unsaturation; ethylenic unsaturation, when present will generally be such that there is no more than one ethylenic bond per 10 carbon-carbon bonds in the substituent. The substituents are often completely saturated and therefore contain no ethylenic unsaturation. These hydrocarbyl substituents preferably have from 20 to 500, preferably from 30 to 500, most preferably from 40 to 500 and very particularly preferred from 50 to 500 carbon 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 which are characterized by having one or more ethylenically unsaturated groups. They can be monoolefinic monomers such as ethylene, propylene, butene-1, isobutene and octene-1 or polyolefinic monomers (usually diolefinic monomers such as butadiene-1,3 and isoprene). Usually these monomers are terminal olefins, that is, olefins characterized by the presence of the group >C-CH2« However, certain internal olefins can also serve as monomers (these are sometimes called medial olefins). When such medial olefin monomers are used, they are usually used in combination with terminal olefins to thereby give 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(tert-butyl)phenyl groups) and alicyclic groups as obtained from polymerizable cyclic olefins or alicyclic-substituted polymerizable cyclic olefins. The olefin polymers are usually free of such groups. Nevertheless, polymers derived from such interpolymers of both 1,3-dienes and styrenes such as butadiene-1,3 and styrene or para(tert-butyl)styrene are exceptions to this general rule.

In general, the olefin polymers are homo- or interpolymers of terminal hydrocarbyl olefins having 2 to 16 carbon atoms. A more typical class of olefin polymers is selected from the group consisting of homo- and interpolymers of terminal olefins having 2 to 6 carbon atoms and especially those having 2 to 4 carbon atoms.

Specific examples of terminal and medial olefin monomers that can be used to prepare the olefin polymers from which the hydrocarbyl substituents are derived are ethylene, propylene, butene-1, butene-2, isobutene, pentene-1, hexene-1, heptene-1, octene-1 , nonene-1, docene-1, pentene-2, propylene tetramer, diisobutylene, isobutylene trimer, butadiene-1,2, butadiene-1,3, pentadiene-1,2, pentadiene-1,3, isoprene, hexadiene-1,5 . Among these, the pure hydrocarbyl monomers are preferred and the terminal olefin monomers are particularly preferred.

A particularly advantageous embodiment of the invention is the polymers poly(isobutenes) as they are obtained by polymerizing a C4 refining stream with a butene content of 35 to 75 wt-*, and an isobutene content of 30 to 60 wt-* in the presence of a Lewis acid -catalyst such as aluminum chloride or boron trifluoride. These polyisobutenes preferably contain predominantly (that is, more than 80* of the total repeating units) isobutene repeating units of the configuration.

Preferred acids and anhydrides are the hydrocarbyl-substituted succinic acids and anhydrides represented by the formulas:

where "hyd" is the hydrocarbyl substituent.

The hydrocarbyl-substituted carboxylic acids and anhydrides as well as their ester and amide derivatives can be prepared by a large number of known processes which are described, for example, in the following US, GB and CA patents: US-PS 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, 3,17,3,3,17,3,3,37 174, 3,381,022, 3,394,179, 3,454,607, 3,446,354, 3,470,098, 3,630,902, 3,652,616, 3,755,169, 3,868,330, 3,912,764 and 4,368,133; GB-PS 944,136, 1,085,903, 1,162,436 and 1,440,219;

CA-PS 956,397.

A procedure for preparing the hydrocarbyl-substituted carboxylic acids and anhydrides as well as the ester and amide derivatives is partially illustrated in US-PS 3,219,666. This procedure is often called the "two-step procedure". It entails a first chlorination of an olefin polymer until there is on average at least one chlorine group per molecular weight olefin polymer. (For the purposes of the invention, the molecular weight of the olefin polymer is the weight corresponding to the Mn value.) The chlorination only involves contact between the olefin polymer and chlorine gas until the desired amount of chlorine is incorporated into the chlorinated polyolefin. The chlorination is usually carried out at a temperature of 75 to 125"C. If a diluent is used in the chlorination procedure, this should be one that cannot itself be easily further chlorinated. Poly- and perchlorinated and/or fluorinated alkanes and benzenes are examples of suitable for - thinners.

The second step in the two-step chlorination procedure is to react the chlorinated polyolefin with the α,β-olefinically unsaturated carboxylic acid reagent at a temperature generally in the range of 100°C to 200°C. The molar ratio of chlorinated polyolefin: carboxylic acid reagent is usually approx. 1:1. (For the purposes of the invention, one mole of a chlorinated polyolefin has the molecular weight of a chlorinated polyolefin corresponding to the Mn value for the non-chlorinated polyolefin.) However, a stoichiometric excess of carboxylic acid reagent can be used, for example in a molar ratio of 1:2. If the average more than approx. one chlorine group per molecule of polyolefin is introduced during the chlorination step, more than one mole of carboxylic acid reagent can react per moles of chlorinated polyalkene. Because of such situations, it is better to describe the ratio of chlorinated polyolefin:carboxylic acid reagent expressed as equivalents. (For the purposes of the invention, an equivalent weight of chlorinated polyolefin is the weight corresponding to the Mn value divided by the average number of chlorine groups per molecule of chlorinated polyolefin. An equivalent weight of a carboxylic acid reagent is the molecular weight.)

Thus, the ratio between chlorinated polyolefin and carboxylic acid reagent will usually be such that approx. one equivalent carboxylic acid reagent per moles of chlorinated polyolefin up to approx. one equivalent carboxylic acid reagent per equivalent chlorinated polyolefin provided that it is usually desirable to provide an excess of carboxylic acid reagent; for example a surplus of 5-25 weight-*. Unreacted excess carboxylic acid reagent can be stripped from the reaction product, usually under vacuum, or reacted during a further processing step as explained below.

The resulting polyolefin-substituted carboxylic acid or anhydride, or ester or amide derivative, is optionally chlorinated again, if the desired number of carboxylic groups is not present in the product. If at the time of this subsequent chlorination any excess carboxylic acid reagent from the other steps is present, the excess will react as further chlorine is added during the subsequent chlorination. Otherwise, further carboxylic acid reagent will be introduced during and/or after the further chlorination step. This technique can be repeated until the total number of carboxylic acid groups per equivalent weight of substituent groups reaches the desired level.

Another procedure for preparing hydrocarbyl-substituted carboxylic acids and derivatives according to the invention uses a process as described in US-PS 3,912,764 and GB-PS 1,440,219. According to this procedure, the polyolefin and the carboxylic acid reagent are first reacted by heating together in a direct alkylation procedure. When the direct alkylation step is complete, chlorine is added to the reaction mixture to thereby provide conversion 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 per moles of olefin polymer. The direct alkylation step is carried out at temperatures of 180°C to 250°C. During the chlorine introduction step, a temperature of 160°C to 225°C is used.

A preferred method for preparing the hydrocarbyl-substituted carboxylic acids and derivatives is the so-called "one-step" process. This process is described in US-PS 3,215,707 and 3,231,587. In principle, the one-step process entails the preparation of a mixture of the polyolefin and the carboxylic acid reagent containing the necessary amounts of both to give the desired hydrocarbyl-substituted carboxylic acids or derivatives. Chlorine is then introduced into the mixture, usually by passing chlorine gas through the mixture while stirring, while maintaining the mixture at a temperature of at least 140°C. A variation of this process involves adding additional carboxylic acid reagent during or after the chlorine introduction. Generally, where the polyolefin is sufficiently fluid at 140°C and above, there is no need to employ any additional, substantially inert, usually liquid solvent/diluent mixture in the one-step process. However, as explained above, if a solvent/diluent diluent is used, preferably that it is resistant to chlorination.Also here, poly- and perchlorinated and/or -fluorinated alkanes, cycloalkanes and benzenes can be used for this purpose.

Chlorine can be introduced continuously or intermittently during the one-stage process. The rate of introduction of chlorine is not essential, although the rate of maximum utilization of chlorine should be the same as the rate of consumption of chlorine during the reaction. When the rate of introduction 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 to prevent chlorine loss for maximum chlorine utilization.

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

In the one-step process, the molar ratio between carboxylic acid reagent and chlorine is such that there is at least 1 mol of chlorine per moles of carboxylic acid reagent to be incorporated into the product. For practical reasons, a slight excess, usually in the vicinity of 5 to 30 weight-* of chlorine, is also used to supplement any chlorine losses from the reaction mixture. Larger amounts of excess chlorine can be used, but do not seem to give any favorable results.

Alcohol consumption in the production of hydrocarbyl-substituted carboxylic acid ester derivatives (C)(I): Alcohols that can be used in the production of hydrocarbyl-substituted carboxylic acid ester derivatives (C)(I) include the compounds with the general formula: where Ri is a monovalent or polyvalent organic group bound to the -OH groups via carbon-oxygen bonds (that is, -COH is carbon not part of a carbonyl group) and m is an integer from 1 to 10 and preferably 2 to 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. Apart from the polyoxy-alkylene alcohols, the mono- and polyhydroxy alcohols corresponding to the formula R 1 -(OH) m preferably contain no more than 40 carbon atoms and preferably no more than 20 carbon atoms. The alcohols may contain non-hydrocarbon substituents or groups which do not affect the reaction of the alcohols with the hydrocarbyl-substituted carboxylic acids or anhydrides. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl, mercapto, nitro and terminating groups such as -O- and -S- (that is, in such groups as -CB^CEtø-X-CEtøCEtø- X is -0- or -S-).

Among the polyoxyalkylene alcohols suitable for use in the preparation of the ester derivatives are the commercially available polyoxyalkylene alcohols which include the polyoxyethylated amines, amides and quaternary ammonium salts of the commercially available type "ETH0DU0MEEN" polyoxyethylated high molecular weight aliphatic diamines; "ETHOMEEN" polyethoxylated aliphatic amines containing alkyl groups in the range of 8 to 18 carbon atoms; "ETH0MID" 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 carboxylic acid esters obtained by reacting the alcohols with various carboxylic acids. Illustrative hydrocarbyl groups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkylarylalkyl and so on containing up to 40 carbon atoms. Specific hydrocarbyl groups are methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenylethyl, cyclohexyl and the like. Carboxylic acids that can be used in the preparation of the ester derivatives are mono- and polycarboxylic acids such as acetic acid, valeric acid, lauric acid, stearic acid, succinic acid and alkyl- or alkenyl-substituted succinic acids where the alkyl or alkenyl group contains up to 20 carbon atoms. Belonging to this class of alcohols are those commercially available from various sources, such as the polyols "PLURONICS"; a liquid triol derived from ethylene oxide and propylene oxide with the designation "POLYGLYCOL 112-2"; dodecylphenyl or nonylphenyl polyethylene glycol ethers under the designation "TERGITOLS" and polyalkylene glycols and various derivatives under the designation "UCONS". However, the alcohols used must have an average of at least one free alcoholic hydroxyl group per molecule polyoxyalkylene alcohol. To describe these polyoxyalkylene alcohols, an alcoholic hydroxyl group is one that is attached to a carbon atom that does not form part of an aromatic nucleus.

Alcohols that can be used according to the invention are also 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 150 oxyalkylene groups where the alkylene group contains from 2 to 8 carbon atoms. Such polyoxyalkylene alcohols are generally dlhydroxyalcohols. This means that each end of the molecule ends with an OH group. For such polyoxyalkylene alcohols to be usable, there must be at least one such OH group. However, the remaining OH group may be esterified with a monobasic, aliphatic or aromatic carboxylic acid of up to 20 carbon atoms such as acetic, propionic, oleic, stearic, benzoic and the like. The monoethers of these alkylene glycols and polyoxyalkylene glycols are also useful. These include the monoaryl, monoalkyl and monoaralkyl ethers of these alkylene glycols and polyoxyalkylene glycols. These groups of alcohols can be represented by the formula:

wherein R^°2 RB are independently alkylene groups having from 2 to 8 carbon atoms and Rq is aryl such as phenyl, lower alkoxyphenyl, or lower alkylphenyl, or lower alkyl such as ethyl, propyl, tert-butyl, pentyl and so on; or aralkyl such as benzyl, phenylethyl, phenylpropyl, p-ethylphenylethyl and so on; p is from 0 to 8, preferably from 2 to 4. Polyoxyalkylene glycols in which the alkylene groups are ethylene or propylene and p is at least 2, as well as the monoethers thereof as described above, are useful.

The monohydroxy and polyhydroxy alcohols that can be used are monohydroxy and polyhydroxy aromatic compounds. Monohydroxy and polyhydroxyphenols and naphthols are preferred hydroxyaromatic compounds. These hydroxy-substituted aromatic compounds may contain other substituents in addition to hydroxy substituents such as halogen, alkyl, alkenyl, alkoxy, alkyl mercapto, nitro and the like. Generally, the hydroxyaromatic compound will contain from 1 to 4 hydroxy groups. The aromatic hydroxy compounds are illustrated by the following specific examples: phenol, p-chlorophenol, p-nitrophenol, p-naphthol, a-naphthol, cresols, resorcinol, catechol, carvacrol, thymol, eugenol, p,p'-dihydroxy-biphenyl, hydroquinone , pyrogallol, phloroglucinol, hexylresorcinol, orquine, quaiacol, 2—chloro-phenol, 2,4-dibutylphenol, propene-tetramer-substituted phenol, didodecylphenol, 4,4'-methylene-bis-methylene-bis-phenol, a—decyl -P-naphthol, polyisobutenyl-(molecular weight approx. 1000)-substituted phenol, the condensation product of heptylphenol with approx. 0.5 mol of formaldehyde, the condensation product of octylphenol with acetone, di(hydroxyphenyl)oxide, di-(hydroxyphenyl)sulfide, di(hydroxyphenyl)disulfide and 4-cyclohexylphenol. Phenol itself and aliphatic hydrocarbon-substituted phenols, such as alkylated phenols with up to 3 aliphatic hydrocarbon substituents, are useful. Each of the aliphatic hydrocarbon substituents may contain 100 or more carbon atoms, but will usually have from 1 to 20 carbon atoms. Alkyl and alkenyl groups are the preferred aliphatic hydrocarbon substituents.

Further specific examples of monohydroxy alcohols that can be used are monohydroxy alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, p<->phenylethyl alcohol, 2-methyl-cyclohexanol, p<->chloroethanol , the monomethyl ether of ethylene glycol, the monobutyl ether of ethylene glycol, the monopropyl ether of diethylene glycol, the monododecyl ether of triethylene glycol, the monooleate of ethylene glycol, the monostearate of diethylene glycol, sec-pentyl alcohol, tert-butyl alcohol, 5-bromo-dodecanol, nitro-octadecanol and the dioleate of glycerol. Alcohols that can be used according to the invention can be unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, 1-cyclohexen-3-ol and oleyl alcohol.

Other specific alcohols that can be used in this regard are the ether alcohols and the amino alcohols which, for example, comprise oxyalkylene-, oxyarylene-, amino-alkylene- and amino-arylene-substituted alcohols with one or more oxyalkylene-, aminoalkylene- or aminoaryleneoxy-arylene groups. These alcohols are exemplified by the commercially available "Cellosolves" which are identified as mono- and dialkyl ethers of ethylene glycol and their derivatives, "Carbitols" which are identified as mono- and dialkyl ethers of diethylene glycol and their derivatives, phenoxyethanol, heptylphenyl-(oxypropylene OH, octyl -(oxyethylene)3Q-0H, phenyl-(oxyoctylene)2~0H, mono-(heptylphenyloxypropylene)-substituted glycerol, poly(styrene oxide), aminoethanol, 3-aminoethylpentanol, di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine, N-hydroxyethylethylenediamine, N,N,N',N'-tetrahydroxytrimethylenediamine and the like.

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

Other useful polyhydroxy alcohols are glycerol, glycerol monooleate, glycerol monostearate, the monomethyl ether of glycerol, pentaerythritol, the n-butyl ester of 9,10-dihydroxystearic acid, the methyl ester of 9,10-dihydroxystearic acid, 1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2-cyclohexanediol and xylene glycol. Carbohydrates such as sugars, starches, celluloses and so on can also be used. The carbohydrates can be exemplified by glucose, fructose, sucrose, rhamose, mannose, glyceraldehyde and galactose.

Polyhydroxyalcohols having at least 3 hydroxyl groups some but not all of which are esterified with an aliphatic monocarboxylic acid having from 8 to 30 carbon atoms such as octanoic, oleic, stearic, linoleic, dodecanoic or talloleic acid or usable. Further specified examples of such partially esterified polyhydroxy alcohols are the monooleate of sorbitol, the distearate of sorbitol, the monooleate of glycerol, the monostearate of glycerol, the didodecanoate of erythritol and the like.

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

Useful polyhydroxyalcohols are those polyhydroxyalkanols containing from 3 to 10 carbon atoms and especially those containing 3 to 6 carbon atoms and having at least 3 hydroxyl groups. Such alcohols are exemplified by glycerol, erythritol, penerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl-1,3-propanediol-(trimethylolethane), 2-hydroxymethyl-2-ethyl-1,3-propanediol (trimethylpropane ), 1,2,4-hexanetriol and the like.

Many issued patents describe procedures for reacting carboxylic acid acylating agents with alcohols to produce acidic esters and neutral esters. These same techniques can be used in the preparation of esters from hydrocarbyl-substituted carboxylic acids and/or the anhydride thereof as described here, and the alcohols described above. All that is required is that the acid and/or anhydride be used in place of the carboxylic acid acylating agents described in these patents, usually on an equivalent weight basis. The following US patents should be specifically mentioned with regard to the description of suitable methods for reacting the acids and/or anhydrides with the alcohols described above: US-PS 3,331,776, 3,381,022, 3,522,179, 3,542,680, 3,697,428 and 3,755,169.

The amines for use in the preparation of the amide derivatives (C)(I): The amines that can be used in the preparation of the hydrocarbyl-substituted acid amide derivatives (C)(I) include ammonia and primary and secondary amines where the secondary amines are preferred. These amines are characterized by the presence of at least one H-N< group and/or at least one -NHg group. These amines can be monoamines or polyamines. Hydrazine and substituted hydrazines containing up to three substituents are included as amines suitable for the preparation of the derivatives

(C)(I). 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 can be saturated or unsaturated. If unsaturated, the amine is preferably free of acetylenic unsaturation. The amines may also contain non-hydrocarbon substituents or groups as long as these groups do not significantly affect the reaction between the amine and the hydrocarbyl-substituted carboxylic acids and derivatives thereof according to the invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl, mercapto, nitro and terminating groups such as -O- and -S- (for example as in groups such as -CH2CH2-X- CH2CH2- where X is -0- or -S-).

Except for the branched polyalkylene polyamines, polyoxyalkylene polyamines and high molecular weight carbyl substituted amines described in more detail below, the amines used herein generally contain less than 40 carbon atoms in total, and usually no more than 20 carbon atoms in total.

Aliphatic monoamines are mono-aliphatic- and di-aliphatic-substituted amines where the aliphatic groups can be saturated or unsaturated and straight or branched. Thus, they are primary or secondary aliphatic amines. Such amines are, for example, mono- and dialkyl-substituted amines, mono- and dialkenyl-substituted amines and amines with an N-alkenyl substituent and an N-alkyl substituent, and the like. The total number of carbon atoms in these aliphatic monoamines preferably does not exceed 40 and usually does not exceed 20 carbon atoms. Specific examples of such monoamines are ethylamine, diethylamine, 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 heterocyclic-substituted aliphatic amines are 2-(cyclohexyl)ethylamine, benzylamine, phenylethylamine and 3-(furylpropyl)amine.

Cycloaliphatic monoamines are those monoamines in which there is a cycloaliphatic substituent attached directly to the amino nitrogen via a carbon atom in the cyclic ring structure. Examples of cycloaliphatic monoamines are cyclohexylamines, cyclopentylamines, cyclohexenylamines, cyclopentenylamines, N-ethylcyclohexylamines, dicyclohexylamines and the like. Examples of aliphatic-substituted, aromatic-substituted and heterocyclic-substituted cycloaliphatic monoamines are propyl-substituted cyclohexylamines, phenyl-substituted cyclopentylamines and pyranyl-substituted cyclohexylamine.

Suitable aromatic amines are those monoamines in which a carbon atom in the aromatic ring structure is bound directly to the amino nitrogen. The aromatic ring will usually be a mononuclear aromatic ring (ie one derived from benzene) but may include fused aromatic rings, particularly those derived from naphthyl. Examples of aromatic monoamines are aniline, di(para-methylphenyl)amine, naphthylamine, N-(n-butyl)-anllin and the like. Examples of aliphatic-substituted, cycloaliphatic-substituted and heterocyclic-substituted aromatic monoamines are para-ethoxyaniline, paradodecylamine, cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.

Suitable polyamines are aliphatic, cycloaliphatic and aromatic polyamines analogous to the monoamines described above except for the presence in the structure of an additional amino nitrogen. The second amino nitrogen can be a primary, secondary or tertiary amino nitrogen. Examples of such polyamines are N-aminopropyl-cyclohexylamine, N,N'-di-n-butyl-para-phenylenediamine, bis-(para-aminophenyl)-methane, 1,4-diamino-cyclohexane and the like.

Heterocyclic mono- and polyamines can also be used in the preparation of the hydrocarbyl-substituted carboxylic acid amide derivatives (C)(I). As used herein, the term "heterocyclic mono- and polyamines" is intended to describe those heterocyclic amines which contain at least one primary or secondary amino group and at least one nitrogen as a heteroatom in the heterocyclic ring. As long as, however, in the heterocyclic mono- and polyamines at least one primary or secondary amino group is present, the hetero-N atom in the ring can be a tertiary amino nitrogen; that is, one that does not have hydrogen bonded directly to the ring nitrogen. Heterocyclic amines may be saturated or unsaturated and may contain various substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl or aralkyl substituents. In general, the total number of carbon atoms in the substituents will not exceed approx. 20. Heterocyclic amines may contain heteroatoms other than nitrogen, especially oxygen and sulfur. Of course, they may contain more than one nitrogen heteroatom. The 5- and 6-membered heterocyclic rings are preferred.

Among the suitable heterocyclic compounds are aziridines, azetidines, azolidines, tetra- and dihydropyridines, pyrroles, indoles, piperadines, imidazoles, di- and tetrahydroimidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N- amlnoalkyl-thiomorpholines, 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 heterocyclic amines are the saturated 5- and 6-membered heterocyclic amines containing only nitrogen, oxygen and/or sulfur in the heteroring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines and the like. Piperidine, aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substituted piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine and aminoalkyl-substituted pyrrolidines are useful. Usually the aminoalkyl substituents are substituted on a nitrogen atom which forms part of the heteroring. Specific examples of such heterocyclic amines are N-aminopropylmorpholine, N-aminoethylpiperazine and N,N'-diaminoethylpiperazine.

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 with only tertiary amino nitrogen atoms such as in trihydroxyethylamine are thus excluded as amines, but can be used as alcohols as described above. The hydroxy-substituted amines intended are those which have hydroxy substituents attached directly to a carbon atom other than a carbonyl carbonate atom, that is to say they have hydroxy groups capable of acting as alcohols. Examples of such hydroxy-substituted amines are ethanolamine, di(3-hydroxypropyl)amine, 3-hydroxybutylamine, 4-hydroxybutylamine, diethanolamine, di(2-hydroxypropyl)amine, N-hydroxypropylpropylamine, N-(2-hydroxyethyl)cyclohexylamine , 3-hydroxycyclopentylamine, parahydroxyaniline, N-hydroxyethylpiperazine and the like.

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

Also suitable as amines are the aminosulfonic acids and their derivatives which correspond to the formula:

where R is OH, NHg, ONH4 and so on; Ra is a polyvalent organic group with a value equal to x 0 y; Rjj and Rc are both independently hydrogen, hydrocarbyl or substituted hydrocarbyl provided that at least one of RD and Rc is hydrogen per aminosulfonic acid molecule; x and y are each whole numbers equal to or greater than one. Each aminosulfone reactant is characterized by at least HN< or ^N group and at least one group. These sulfonic acids can be aliphatic, cycloaliphatic or aromatic aminosulfonic acids and the corresponding functional derivatives of the sulfo group. In particular, the amino-sulfonic acids can be aromatic aminosulfonic acids, that is, where Ra is a polyvalent aromatic group such as phenyl where at least one

group is bonded directly to a core carbon atom of the aromatic group. The aminosulfonic acid can also be a mono-amino-aliphatic sulfonic acid, i.e. an acid where x is 1 and Ra is a polyvalent aliphatic group such as ethylene, propylene, trimethylene and 2-methylenepropylene. Other suitable aminosulfone-

acids and derivatives thereof which can be used as amines are described in US-PS 3,029,250, 3,367,864 and 3,926,820.

Hydrazine and substituted hydrazine can also be used as amines. At least one of the nitrogens in the hydrazine must contain a hydrogen directly bonded to it. Substituents which may be present on the hydrazine are alkyl, alkenyl, aryl, aralkyl, alkaryl and the like. Generally, the substituents are alkyl, and especially lower alkyl, phenyl and substituted phenyl such as lower alkoxy-substituted phenyl and 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-nitrophenyl)-N-methylhydrazine, N,N'-di-(parachlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine and the like.

High molecular weight hydrocarbylamines, both monoamines and polyamines, which can be used as amines, are generally prepared by reacting a chlorinated polyolefin having a molecular weight of at least 400 with ammonia or an amine. The amines that can be used are known in this technique and are, for example, described in US-PS 3,275,554 and 3,438,757. These amines must have at least one primary or secondary amino group.

Other groups of amines suitable for use are branched polyalkylene polyamines. The branched polyalkylene polyamines are polyalkylene polyamines in which the branched group is a side chain containing on average at least one nitrogen-bonded aminoalkylene

group per 9 amino units present in the main chain, for example 1-4 such branched chains per 9 units of the main chain, but preferably one side chain unit per 9 main chain units. Thus, these polyamines contain at least three primary amino groups and at least one tertiary amino group. These amines can be expressed by the formula: where R is an alkylene group such as ethylene, propylene, butylene and other homologues (both straight and branched), and so on, but preferably ethylene; and x, y, and z are integers; x within the range of 4 to 24 or more, preferably from 6 to 18; y within the range of 1 to 6 or more, preferably from 1 to 3; and z within the range from 0 to 6 and preferably from 0 to 1. The x and y units may be sequential, alternate, regularly or randomly distributed. A useful class of such polyamines are those of the formula:

where n is an integer in the range of 1 to 20 or more and preferably in the range of 1 to 3, and R is preferably ethylene but may be propylene, butylene and so on, straight

or branched. Usable embodiments are represented by the formula:

where n is an integer in the range 1 to 3. The group within the parenthesis can be connected in a head-head or head-talk pattern. US-PS 3,200,106 and 3,259,578 describe such.

Suitable amines also include polyoxyalkylene polyamines, for example polyoxyalkylene diamines and polyoxyalkylene triamines with average molecular weights within the range of 200 to 4000 and preferably from 400 to 2000. Examples of these polyoxyalkylene polyamines are the amines represented by the formula: where m has a value from 3 to 70, and preferably from 10 to 35; and the formula:

wherein n is an integer in the range of 1 to 40, provided that the sum of all n's is from 3 to 70 and generally from 6 to 35, and R is a polyvalent saturated hydrocarbyl group of up to 10 carbon atoms having a valency of from 3 to 6 The alkylene groups may be straight or branched and contain from 1 to 7 carbon atoms and usually from 1 to 4 carbon atoms. The

different alkylene groups present in the formulas may be the same or different.

More specific examples of these polyamines are:

wherein x has a value from 3 to 70, preferably from approx. 10 to 35; and

where x + y + z together lie within the range 3 to 30, and preferably from 5 to 10.

Useful polyoxyalkylene polyamines are the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines with average molecular weights in the range of 200 to 2000. The polyoxyalkylene polyamines are commercially available under the trademark "Jeffamine". US-PS 3,804,763 and 3,948,800 describe such.

Useful amines are the alkylene polyamines including the polyalkylene polyamines as described below. The alkylene polyamines include those corresponding to the formula:

where n is from 1 to 10; each R" independently is a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group of up to 30 carbon atoms, and the "alkylene" group has from 1 to 10 carbon atoms where the preferred alkylenes are ethylene or propylene. Useful are alkylene polyamines where each R" is hydrogen, the ethylene polyamines and mixtures of ethylene polyamines being particularly preferred. Generally, n will have an average value of from 2 to 7. Such alkylene polyamines include methylene, ethylene, butylene, propylene, pentylene, hexylene and heptylene polyamines and so on. The higher homologues of such amines and related aminoalkyl-substituted piperazines also belong thereto.

Alkylene polyamines which may be used include ethylenediamine, triethylenetetramine, propylenediamine, trimethylenediamine, hexamethylenediamine, decamethylenediamine, octamethylenediamine, di(heptamethylene)triamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, di(trimethylene)triamine, N-(2-aminoethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and the like. Higher homologues as obtained by condensing two or more of the above-mentioned alkylene amines are useful as amines in the same way as mixtures of two or more of the above-described polyamines.

Ethylene polyamines such as those mentioned above are described in detail in the article "Diamines and Higher Amines" in The Encyclopedia of Chemical Technology, 2nd Ed., Kirk and Othmer, vol. 7, p. 27-39, Interscience Publishers, Division of John Wiley and Sons, 1965. Such compounds are most conveniently prepared by reacting an alkylene chloride with ammonia or by reacting an ethylene imine with a ring-opening agent such as ammonia and so on. These reactions result in the production of a somewhat complex mixture of alkylene polyamines, including cyclic condensation products such as piperazines.

Hydroxyalkylalkylene polyamines with one or more hydroxyalkyl substituents on the nitrogen atoms are also usable in the preparation of the emulsions of the invention. Useful hydroxyalkyl-substituted alkylene polyamines are those in which the hydroxyalkyl group is a lower hydroxyalkyl group, for example, with fewer than 8 carbon atoms. Examples of such hydroxy-alkyl-substituted polyamines are N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, l-(2-hydroxyethyl)-piperazine, monohydroxypropyl-substituted diethylenetriamine, dihydroxypropyl- substituted tetraethylenepentamine, N-(3-hydroxybutyl)tetramethylenediamine and so on. Higher homologues obtained by condensation of the hydroxyalkylene polyamines illustrated above via amino groups or via hydroxy groups can also be used. Condensation via amino groups results in a higher amine accompanied by removal of ammonia and condensation via the hydroxy groups results in products containing ether linkages accompanied by removal of water.

To prepare the hydrocarbyl-substituted carboxylic acid amide derivatives (C)(I), one or more of each of the acids or anhydrides (C)(I) or one or more of the above-described primary or secondary amines are mixed and heated, optionally in the presence of a usually liquid, essentially inert organic liquid solvent/diluent, at temperatures within the range from 50 to 130°C and preferably from 80 to 110°C. The acid or anhydride (C)(I) and the amine are reacted in amounts sufficient to give from 0.5 to 3 equivalents of amine per equivalent acid or anhydride (C)(I). For the purposes of the invention, an equivalent amine is the amount of the amine which corresponds to the total weight of the amine divided by the total weight of nitrogen atoms present. Thus, octylamine has an equivalent weight equal to its molecular weight, ethylenediamine has an equivalent weight equal to half its molecular weight, and aminoethylpiperazine has an equivalent weight equal to one-third its molecular weight. For example, the equivalent weight of a commercially available mixture of polyalkylene polyamine can also be determined by dividing the atomic weight of nitrogen, 14, by the #N contained in the polyamine. Therefore, a polyamine mixture with a percentage of N of 34 will have an equivalent weight of 41.2. The number of equivalents of the acid or anhydride (C)(I) depends on the total number of carboxylic acid functions (for example, carboxylic acid or carboxylic anhydride groups), present in the acid or anhydride (C)(I). Thus, the number of equivalents of component (C)(I) will vary with the number of carboxy groups present. To determine the number of equivalents of acid or anhydride (C)(I), those carboxyl functions that are not capable of reacting as a carboxylic acid acylating agent are excluded. In general, however, there is one equivalent of the acid or anhydride (C)(I) per carboxy group in component (C)(I). For example, there will 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 to determine the number of carboxyl functions (eg, acid number, saponification number) and therefore the number of equivalents of acid or anhydride (C)(I) available for reaction with the amine can be readily determined by one skilled in the art.

The amines (CUlI):

The amines (C)(II) that can be used in the preparation of the salts (C) are ammonia and all the primary and secondary amines described above as usable in the preparation of the amide derivatives (C)(I). In addition to ammonia and the amines described above, the amines (C)(II) also include tertiary amines. The tertiary amines are analogous to the primary and secondary amines discussed above except that the hydrogen atoms in the H-N< or -NB^ groups are replaced by the hydrocarbyl groups. These tertiary amines can be monoamines or polyamines. The monoamines are represented by the formula:

where R<1>, R<2> and R<3> are the same or different hydrocarbyl groups. Preferably, R<1>, R<2> and R<3> are independent hydrocarbyl groups having from 1 to 20 carbon atoms. The tertiary amines can be symmetrical amines, dimethylalkylamines or those derived from the reaction of a primary amine or a secondary amine with ethylene oxide. The tertiary 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 tertiary amines can be saturated or unsaturated. If they are unsaturated, the amine is preferably free of acetylenic unsaturation, that is

-C=C-. The tertiary amines may also contain non-hydrocarbon substituents or groups as long as these groups do not significantly affect the reaction of the amines with the hydrocarbyl-substituted carboxylic acids and their derivatives

(C)(I). Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl, mercapto, nitro and

interrupting groups such as -0- and -S- (for example such as in groups such as -CH2CH2-X- CH2CH2- where X is -0- or -S-). Examples of such tertiary amines are trimethyl-, triethyl-, tripropyl-, tributyl-, monomethyldiethyl-, monoethyldimethyl-, dimethylpropyl-, dimethylbutyl-, dimethylpentyl-, dimethylhexyl-, dimethylheptyl-, dimethyloctyl-, dimethylnonyl-, dimethyldecyl-, dimethyldicodanyl-, dimethylphenyl-, N,N-dioctyl-1-octane-, N,N-didodecyl-l-dodecane tricoco-, trihydro-generated-tal-, N-methyldihydrogenated-tal—, N,N-dimethyl-l-dodecane -, N,N-dimethyl-l-tetradecane-, N,N-dimethyl-l-hexa-

decane—, N,N-dimethyl-1-octadecane—, N,N-dimethylcoco—, N,N-dimethylsoy— and N,N-dimethyl hydrogenated tallamine and so on.

In a particularly advantageous embodiment, the amines (C)(II) are hydroxyamines. These hydroxyamines can be primary, secondary or tertiary amines. Characteristically, the hydroxyamines are primary, secondary or tertiary alkanolamines or mixtures thereof. Such amines can be exemplified by the formulas:

wherein each R is independently a hydrocarbyl group of 1 to 8 carbon atoms or hydroxyl-substituted hydrocarbyl group of 2 to 8 carbon atoms and R' is a divalent hydrocarbyl group of 2 to 18 carbon atoms. The group R'-OH in these formulas represents the hydroxyl-substituted hydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group. Characteristically, R' is an acyclic residue or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene group and so on. Where two R groups are present in the same molecule, they may be linked via a direct carbon-carbon bond or via a heteroatom such as oxygen, nitrogen or sulphur, to give a 5-, 6-, 7- or 8 -joint ring structure. Examples of such

heterocyclic amines are N-(hydroxyl-lower alkyl)-morpholines, -trimorpholines, -piperidines, -oxazolidines, -thiazolidines and the like. Characteristically, however, each R is a lower alkyl group with up to 7 carbon atoms.

The hydroxyamines can also be an ether-N-(hydroxy-substituted hydrocarbyl)amine. These are hydroxyl-substituted poly(hydrocarbyloxy) analogs of the above-described hydroxyamines (these analogs also include hydroxyl-substituted oxyalkylene analogs). Such N-(hydroxyl-substituted hydrocarbyl)amines can conveniently be prepared by reacting epoxides with the amines described above and can be represented by the formulas:

where x is an integer from 2 to 15 and R and R' are as described above.

Polyamine analogues of these hydroxyamines, especially alkoxylated alkylene polyamines, for example N,N-(diethanol)-ethylenediamine) can also be used.

Such polyamines can be produced by reacting alkylene amines, for example ethylenediamine, with one or more alkylene oxides such as ethylene oxide or octadecene oxide with from 2 to 20 carbon atoms. Corresponding alkylene oxide-alkanolamine reaction products can also be used in the same way as products prepared by reacting the above-described primary, secondary or tertiary alkanolamines with ethylene, propylene or higher epoxides in a 1:1 or 1:2 molar ratio. Reactant ratios and temperatures for carrying out such reactions are known to the person skilled in the art.

Specific examples of alkoxylated alkylene polyamines are N-(2-hydroxyethyl)ethylenediamine, N,N-bis(2-hydroxyethyl)ethylenediamine, l-(2-hydroxyethyl)piperazine, mono(hydroxypropyl)-substituted diethylenetriamine, di(hydroxypropyl)- substituted tetraethylenepentamine, N-(3-hydroxybutyl)-tetramethylenediamine and so on. Higher homologues obtained by condensation of the hydroxyalkylene polyamines illustrated above via amino groups or via hydroxy groups can also be used. Condensation via amino groups results in a higher amine with simultaneous removal of ammonia, while condensation via hydroxy groups results in products containing ether linkages accompanied by removal of water. Mixtures and two or more of any of these mono- or polyamines are also useful.

Examples of the N-(hydroxyl-substituted hydrocarbyl)amines are mono-, di- and triethanol-, diethylethanol-, di-(3-hydroxyl-propyl)-, N-(3-hydroxylbutyl)-, N-(4- hydroxylbutyl)- and N,N-di-(2-hydroxylpropyl)amine, N-(2-hydroxylethyl)morpholine and its thio analog, N-(2-hydroxylethyl)cyclohexylamine, N-3-hydroxylcyclopentylamine, o-, m - and p-aminophenol, N-(hydroxylethyl)piperazine, N,N'-di-(hydroxylethyl)piperazine and the like.

Further amino alcohols are the hydroxy-substituted primary amines described in US-PS 3,576,743 with the general formula where Ra is a monovalent organic group containing at least one alcoholic hydroxy group. The total number of carbon atoms in Ra preferably does not exceed 20. Hydroxy-substituted aliphatic primary amines containing a total of up to 10 carbon atoms are usable. The polyhydroxy-substituted alkanol primary amines in which at least one amino group is present (for example, a primary amino group) with an alkyl substituent containing up to 10 carbon atoms and up to 6 hydroxyl groups are useful. These alkanol primary amines correspond to Ra-NH2 where Ra is a mono-O- or polyhydroxy-substituted alkyl group. It is desirable that at least one of the hydroxyl groups is a primary alcoholic hydroxyl group. Specific examples of the hydroxy-substituted primary amines are 2-amino-l-butanol, 2-amino-2-methyl-l-propanol, p-(<p->hydroxyethyl)aniline, 2-amino-l-propanol, 3 -amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N-(p<->hydroxypropyl)-N'-(p <->aminoethyl)piperazine, tris-(hydroxymethyl)aminomethane (also known as trismethylolaminomethane), 2-amino-l-butanol, ethanolamine, p-(p-hydroxy-ethoxy)-ethylamine, glucamine, glucoamine, 4-amino- 3-Hydroxy-3-methyl-1-butene (which can be prepared according to known procedures by reacting isoprene oxide with ammonia), N-3-(aminopropyl)-4-(2-hydroxyethyl)piperadine, 2-amino -6-methyl-6-heptanol, 5-amino-l-pentanol, N-(p<->hydroxyethyl)-l,3-diaminopropane, 1,3-diamino-2-hydroxypropane, N-(p-hydroxy- ethoxyethyl )-ethylenediamine, trismethylolaminomethane and the like. Reference should be made here to US-PS 3,576,743.

Reaction between hydrocarbyl-substituted acid or anhydride. or an ester or amide derivative (C)(I) and amine (C)(II): The product of the reaction between a hydrocarbyl-substituted carboxylic acid or anhydride, or the ester or amide derivative (C)(I), and the amine (C) (II), comprises at least one salt

(C). This salt may be an inner salt comprising residues of a molecule of the hydrocarbyl-substituted carboxylic acid

or the anhydride, or the ester or amide derivative (C)(I), and the amine (C)(II), in which one of the carboxyl groups is ionic

bonded to a nitrogen atom within the same group; or it can be an external salt where the ionic salt group is formed with a nitrogen atom that is not part of the same molecule. The reaction product between components (C)(I) and (C)(II) may also include other compounds such as imides, amides, esters and the like, but at least some salt must be present for component (C) to be used according to the invention. In a preferred embodiment, the amine (C)(II) is a hydroxyamine and the product of the reaction between the components (C)(I) and (C)(II) is the half-ester and the half-salt, i.e. an ester/salt.

The reaction between the components (C)(I) and (C)(II) is carried out under conditions which result in the formation of the desired salt. Characteristically, one or more components (C)(I) and one or more components (C)(II) are mixed together and heated to a temperature within the range from 50 to 130°C and preferably from 80 to 110°C, optionally in the presence of a usually liquid, substantially inert organic liquid solvent/diluent, until the desired product is formed Components (C)(I) and (C)(II) are reacted in amounts sufficient to give from 0.5 to 3 equivalents component (C)(II) per equivalent component (C)(I).

The following examples describe examples of preparations of nitrogen-containing salt emulsifiers (C) which can be used in water-in-oil emulsions according to the invention. Unless otherwise stated, in the following examples as well as throughout the specification and in the accompanying claims, all parts and percentages are by weight and all temperatures are in °C.

EXAMPLE 1

2240 parts of polyisobutylene (Mn=950) substituted succinic anhydride are heated to a temperature in the range 110-116°C. 174 parts of morpholine are then added dropwise to the anhydride. After the addition of morpholine, the reaction mixture is kept at a temperature of 116-126°C for 2 hours. 234 parts diethyl-

ethanolamine is then added dropwise, while the temperature is maintained at 116-126°C. After completion of the addition of diethylethanolamine, the resulting mixture is held at 116-126°C for 50 minutes with stirring. The resulting product is an amide/salt.

EXAMPLE 2

A mixture of 110 parts polyisobutylene-substituted succinic anhydride as used in Example 1 and 100 parts "Carbowax 200" (a polyethylene glycol with a molecular weight of 200) is heated to and then held at a temperature of 123-134°C, held at this temperature for 2 hours and then cooled to 100°C. 117 parts of diethylethanolamine are added to the resulting product over a 0.2 hour period while maintaining the temperature at 100°C. The mixture is then cooled to room temperature. The product is an ester/salt.

EXAMPLE 3

A mixture of 1100 parts of polyisobutylene-substituted succinic anhydride as used in example 1 and 34 parts of pentaerythritol is heated to a temperature of 125-160°C, kept at this for 4 hours, then adjusted to 130°C. 117 parts of diethylethanolamine are added to the mixture. The temperature is kept at 100-130°C for 1 hour. The resulting product is then cooled to room temperature. The product is an ester/salt.

EXAMPLE 4

A mixture of 2240 parts of polyisobutylene-substituted succinic anhydride as used in example 1 and 300 parts of a 40 SUS mineral packing oil is heated to 50°C with continuous stirring for a period of Vt hours. 54 parts of tap water are added and the resulting mixture is heated from 50°C to 92°C over the course of one hour and then held at 92-98°C for 5 hours. 244 parts of monoethanolamine are added and the resulting mixture is kept at 92-98°C. The product is a di-salt.

EXAMPLE 5

A mixture of 2240 parts of polyisobutylene-substituted succinic anhydride as used in example 1 and 62 parts of ethylene glycol is heated to a temperature within the range of 116-120°C and then held at this temperature for 5 hours. The temperature in the mixture is then increased to the range 138-146°C and maintained at this increased temperature for a further 4.5 hours. The temperature in the mixture is then reduced to 115°C over the course of one hour. 122 parts of monoethanolamine are added to the mixture over the course of a Vi hour, while maintaining the temperature at 115-120°C. The mixture is then stirred for a further V hour, while maintaining the temperature at 115-120°C. The resulting product is an ester/salt.

EXAMPLE 6

2895 parts of polyisobutylene (Mn=1700) substituted succinic anhydride are heated to 121°C for 1 hour. 605 parts of diethylethanolamine are added dropwise over the course of 2 hours, while maintaining the temperature of the mixture at 121-128°C. The mixture is kept at 121-123°C for a further hour, and then cooled to 50°C to thereby obtain the desired product. The product is an ester/salt.

EXAMPLE 7

A mixture of 1000 parts of polyisobutylene-substituted succinic anhydride as used in example 1 and 337 parts of a mixture oil is heated to 85°C. 26 parts of tap water are added. The mixture is heated to 102°C within 0.25 hours. The mixture is kept at a temperature of 102-105°C for 4 hours and then cooled to 70°C. 209 parts of diethylethanolamine are added to the mixture over 0.2 hours, and the mixture gives an exothermic reaction to 79°C. The mixture is then held at a temperature of 78-79°C for 15 hours and then cooled to give the desired product. The product is a disalt.

EXAMPLE 8

1120 parts of polyisobutylene-substituted succinic anhydride as used in example 1 is heated to 85-90°C during one hour. 117 parts of diethylethanolamine are added dropwise over the course of one hour. The resulting mixture is held at a temperature of 85-90°C for 4 hours and then cooled to room temperature to give the desired product. The product is an internal salt.

EXAMPLE 9

A mixture of 917 parts diluent oil, 40 parts diatomaceous earth filter aid, 10 parts caustic soda, 0.2 parts of a silicone-based antifoam agent, 135 parts 3-amino-1,2,4-triazole and 6.67 parts commercial polyethylene polyamine mixture containing 33.5% nitrogen and substantially equivalent tetraethylenepentamine was heated to a temperature of 121°C with stirring. 1000 parts of the polyisobutylene-substituted succinic anhydride that was used in example 1 is slowly added to the mixture over approx. an hour and during this addition the temperature in the mixture is increased from 121 to 154°C. The mixture is then kept at a temperature of 154-160°C under nitrogen blowing for 12 hours. The mixture is then cooled to 138-149°C and filtered. A final oil adjustment is carried out to adjust the product to 45 weight* dilution oil. The product contains a small amount of salt.

EXAMPLE 10

6720 parts of polyisobutenyl succinic anhydride as used in example 1 is heated to 90° C with stirring. 702 parts of diethylethanolamine are added over a 16-hour period. This intermediate mixture is then heated for a further 15 hours to 90°C. Then slowly add 366 parts of monoethanolamine. The mixture is held at 90°C for one hour and then cooled to give a clear brown, viscous liquid product. The product is a mixture of imide and salt, with minor amounts of amide and ester present.

EXAMPLE 11

2240 parts of polyisobutenyl-substituted succinic anhydride used in example 1 is heated to a temperature of approx. 90° C. 468 parts of diethylethanolamine are added over the course of 2 hours. The mixture is heated for a further hour to 90°C in order to obtain the desired product. The product is an ester/salt.

The functional additive (Dl:

The functional additive (D) can be any water-soluble, oil-insoluble functional additive that can be used in the water-in-oil emulsions of the invention. Many such additives are known. Typical such additives are organic or inorganic acids or salts. Phosphates, borates and molybdates can be used as such functional additives (D) when the water-in-oil emulsions of the invention are, for example, hydraulic fluids. These additives act as rust inhibitors and in some cases as anti-wear agents. Organic salts such as sodium 2-mercapto-benzothiazole are also useful as rust inhibitors. Non-oxidizing acids such as hydrochloric acid and sulfuric acid can be used as such additives when the invention's water-in-oil emulsions, for example, acidifying liquids, when used in improved oil recovery. Oxygen-adding salts such as ammonium nitrate are usable as such additives when the water-in-oil emulsions of the invention are used as explosives.

Examples of phosphates are any compound containing the group <E>PO4 including normal and tertiary phosphates (X3PO4); monoacid, monohydroxy, dibasic or secondary phosphates (X2HPO4); diacid, dihydroxy, monobasic or primary phosphates (XH 2 PO 4 ); the double phosphates ((X,X')PO 4 ); the triple phosphates ((X,X',X")P04 ); and the orthophosphates (X3PO4); as well as the hypophosphates (X4P2O6); and the <pyr>rophosphates (X4P2O7). In the above formulas, X is a monovalent metal, for example, sodium or potassium, or the amino group, NH4<+>. Particular examples of such phosphates are diammonium hydrogen phosphate, monoammonium phosphate, disodium phosphate and monosodium phosphate. Salts formed by reacting monoethanolamine with phosphoric acid are useful.

The molybdates include X2(MoC4), X2(Mo2O7) and X5M07O24, where X is an ammonium group, NH4<+>, or a monovalent metal such as an alkali metal, such as sodium or potassium. The salts of molybdic acid, H2M0O4, can be used. Similarly, salts of aqueous molybdic acid, M0O4^B^O, and molybdic anhydride, M0O3, can be used. Sodium molybdate, Na2MoC<4 • 2H2O, is a preferred molybdate.

The borates include XH2BO3 and XH3B0, where X is NH4<+> or a monovalent metal such as sodium or potassium. Meta-borates, compounds containing the residues -BO2; orthoborates, compounds containing the residue -BO3; and pyroborates, compounds containing the residue B4O7, can be used. Specific examples of useful borates are: sodium etaborate, Na 2 B0 2 , sodium borate tetrahydrate, Na 2 B 2 O 4•4H 2 O; borax, ^26407 *IOH2O; anhydrous borax, ^28407; sodium borate pentahydrate, Na2B407<*>5H20 and the like.

The non-oxidizing acids are inorganic acids such as hydrochloric acid, sulfuric acid, hydrofluoric acid, sulfamic acid and the like, as well as organic acids containing from 1 to 3 carbon atoms such as formic acid, acetic acid, propionic acid and the like. Mixtures of two or more of these acids can be used. Hydrochloric acid is preferred.

The oxygen-adding salts that can be used as functional additive (D) include ammonium nitrate and alkali or alkaline earth metal nitrates, chlorates, perchlorates and mixtures thereof. Examples are sodium nitrate, sodium perchlorate and ammonium perchlorate. Ammonium nitrate is particularly preferred.

Emulsion stabilizers:

Although the emulsions of the invention are in themselves usable, emulsion stabilizers can be used to improve the stability of the emulsion against deterioration due to temperature, pressure, oxidation of the oil or other unfavorable environments. Stabilizers include phosphatides, especially those having the structural formula where G is selected from fatty acyl groups and phosphorus-containing groups having the structural scheme where R' is a lower alkylene group having from 1 to 10 carbon atoms and R" and R"' are lower alkyl groups having from 1 to 4 carbon atoms and at least one, but not more than 2 of the G groups are said phosphorus-containing groups. The fatty acyl groups are mostly those derived from fatty acids with 8 to 30 carbon atoms in the fatty groups such as octanoic, stearic, oleic, palmitic, behenic, myristic and oleostearic. Particularly desirable groups are those derived from commercial fatty compounds such as soybean oil, cottonseed oil and castor oil. A particularly effective phosphatide is soybean lecithin which is described in detail in the "Encyclopedia of Chemical Technology", Kirk and Othmer, vol. 8, pp. 309-326 (1952). The emulsion stabilizers can be an aliphatic glycol or a monoaryl 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 10 carbon atoms. Thus, the aliphatic glycol is illustrated by ethylene, trimethylene, propylene, tetramethylene, 1,2-butylene, 2,3-butylene, tetramethylene and hexamethylene glycol or the like. Specific examples of the ethers are the monophenyl ether of ethylene glycol, the mono-(heptylphenyl)ether of triethylene glycol, the mono-(cx-octyl-p-naphthyl)ether of tetrapropylene glycol, the mono-(polyisobutene (molecular weight 1000)-substituted phenyl)ether of octapropylene glycol, and the mono-(o,p-dibutylphenyl)ether of polybutylene glycol, the mono-(heptylphenyl)ether of trimethylene glycol and the mono-(3,5-dioctylphenyl)ether of tetratrimethylene glycol and so on. The mono-aryl ethers are obtained by condensation of a phenolic compound such as an alkylated phenol or a naphthyl with one or more moles of an epoxide such as ethylene oxide, propylene, trimethylene oxide or 2,3-hexalene oxide. The condensation is promoted by means of a basic catalyst such as an alkali or alkaline earth metal hydroxide, -alcoholate or -phenate. The temperature at which the condensation is carried out can be varied within wide limits such as from room temperature to 250°C. Usually it is preferably 50-150°C. More than one mole of epoxide can condense with the phenolic compound so that the product in its structure can contain one or more of the groups derived from the epoxide. A polar-substituted alkylene oxide such as epichlorohydrin or epibromohydrin can likewise be used to prepare the monoaryl ether product and such a product is likewise usable as an emulsion stabilizer according to the invention.

Also useful as an emulsion stabilizer are the monoalkyl ethers of the aliphatic glycols where the alkyl group is, for example, octyl, nonyl, dodecyl, behenyl and so on. The fatty acid esters of the monoaryl or monoalkyl ethers of aliphatic glycols are also useful. The fatty acids are, for example, acetic, formic, butane, hexane, oleic, stearic, behenic, decanic, isostearic and linoleic acids as well as commercial acid mixtures as obtained by hydrolysis of tall oils, sperm oils and so on. Specific examples are the oleate of mono-(heptylphenyl)ether of tetraethylene glycol and the acetate of mono-(propylene (molecular weight 1000)-substituted phenyl)ether of tripropylene glycol.

The alkali metal and ammonium salts of sulfonic acids are likewise useful as emulsion stabilizers. The acids are illustrated by decylbenzene, didodecylbenzene, mahogany, heptene, polyisobutene (molecular weight 750) and decylnaphthalenesulfonic acid as well as tridecylbenzenesulfonic acid. The salts are illustrated by the sodium, potassium or ammonium salts of these acids.

Also usable as supplementary emulsion stabilizers are the neutral alkali metal salts of fatty acids with at least 12 aliphatic carbon atoms in the fatty group. These fatty acids are mainly lauric, stearic, oleic, myristic, palmitic, linoleic, linolenic and behenic acids or a mixture of such acids obtained from the hydrolysis of tall oil, sperm oil and other commercial fats. The acids should contain at least 12 aliphatic carbon atoms, preferably from 16 to 30 carbon atoms.

Only a small amount of stabilizers is needed. It can be as low as 0.01 part and rarely exceeds 2 parts per 100 parts emulsion. Preferably, it is within the range of 0.1 to 1 part per 100 parts emulsion.

Hydraulic fluids:

When the emulsions of the invention are used as hydraulic fluids, the emulsion characteristically includes other additional additives such as extreme pressure agents, rust inhibitors in addition to those described above, foam inhibitors, freezing point lowering agents, bactericides, oxidation inhibitors and the like.

Extreme pressure agents are agents that improve the loading properties of the emulsion. These agents are exemplified by lead or nickel or group II metal phosphorodithioates where the metal may be magnesium, calcium, barium, strontium, zinc or cadmium. Zinc is a particularly preferred metal. Particular examples of metal phosphorodithioates are zinc di(4-methyl-2-pentyl) phosphordithioate, zinc O-methyl-0'-dodecyl phosphordithioate, barium diheptyl phosphordithioate, barium di(n-butyl-phenyl) phosphordithioate, magnesium dicyclohexyl phosphordithioate, the cadmium salt of an equal molar mixture of dimethylphosphodithioate and di-octylphosphodithioate, zinc-di-n-nonylphosphodithioate, zinc-di-dodecylphosphodithioate, lead-di-pentylphosphodithioate, nickel-di-octylphosphodithioate and zinc-di-( heptylphenyl) phosphorodithioate.

Methods for preparing phosphorodithioic acids are well known in the art and include, for example, reacting an alcohol or a phenol with phosphorus pentasulfide. In the same way, methods for the production of group II metal salts of phosphorodithioic acids are known. Such methods are illustrated by the neutralization of phosphorodithioic acids or mixtures of such acids with zinc oxide.

Other extreme pressure agents that can be used in the emulsions according to the invention are chlorinated waxes; sulfurized or phosphosulfurized fatty acid esters; di- and trihydrogen carbon phosphites and phosphates; dihydrogen polysulfides; and metal dithiocarbamates. The chlorinated waxes are exemplified by chlorinated eicosane with a chlorine content of 50* or other chlorinated petroleum waxes with a chlorine content of 5-60*. The sulfurized fatty esters are obtained by treating a lower alkyl ester of a fatty acid with at least 12 carbon atoms with a sulfurizing agent such as sulfur, sulfur monochloride, sulfur dichloride or the like. The fatty acid esters are illustrated by methyl oleate, methyl stearate, isopropyl myristate, the cyclohexyl ester of talloleic acid, ethyl palmitate, isooctyl laurate, the diester of ethylene glycol with stearic acid, and so on. Commercial mixtures of esters can also be used. These include, for example, sperm oil, menhaden oil, glycerol trioleate and so on. Sulfurization is most conveniently carried out at temperatures between 100°C and 250°C. More than one sulfur atom can be incorporated into the ester, and for the purposes of the invention, esters with up to 4 or 5 sulfur atoms per molecule usable. Examples are sulfurized sperm oil with a sulfur content of 5*, sulfurized tallow oil with a sulfur content of 9*, sulfurized methyl oleate with a sulfur content of 3* and sulfurized stearyl stearate with a sulfur content of 15*.

The phosphosulfurized fatty acid esters are obtained by treating esters as illustrated above with a phosphorus sulfide such as phosphorus pentasulfide, phosphorus sesquisulfide or phosphorus hepta-sulfide. The treatment is illustrated by mixing an ester with from 0.5 to 25% of a phosphorus sulphide at a temperature within the range of 100°C to 250°C. The products contain both phosphorus and sulphur, but the exact chemical structure of such products is not fully understood.

The phosphites and phosphates that can be used here are the di- and tri-esters of phosphoric acid or phosphoric acid where the ester groups are derived from an essentially hydrocarbon group such as, for example, aryl, alkyl, alkaryl, arylalkyl or cycloalkyl, as well as a hydrocarbon group with a polar substituent such as chlorine, nitro, bromine, ether and the like. Particularly desirable phosphites and phosphates are those in which the ester groups are phenyl, alkylphenyl or alkyl groups containing from 6 to 30 carbon atoms. Examples are dibutyl-, diheptyl-, cyclohexyl-, di-(pentylphenyl)-, bis-(dipentylphenyl)-, tridecyl-, distearyl-, dimethylnaphthyl-, oleyl-4-pentylphenyl-, triphenyl-, bis-(hexapropylene-substituted phenyl) and tri(n-chloro-3-heptylphenyl)phosphite, triphenyl, tricresyl, tri(p-chlorophenyl) and tri(heptylphenyl)phosphate.

The metal dithiocarbamates are mainly those of zinc, lead, strontium, nickel, cadmium and palladium with N,N-dialkyl dithiocarbamic acids in which the alkyl groups contain from 3 to 30 carbon atoms. Examples are zinc-N,N-dioctyldithiocarbamate, lead-N,N-dicyclohexyldithiocarbamate, cadmium-N,N-dibehenyl-dithiocarbamate, lead-N,N-didodecyldithiocarbamate and mixtures thereof.

The concentration of these extreme pressure agents is usually within the range of 0.05 to 5 parts, although it is rarely necessary to use more than 2 parts of this agent per 100 parts emulsion.

Another type of additive that finds use in the emulsion is a rust inhibitor. The most effective rust-inhibiting agents in the emulsions according to the invention are aliphatic amines, especially aliphatic primary amines with at least 8 carbon atoms in the molecule. The aliphatic amines are preferably tertiary alkyl primary amines with from 12 to 30 carbon atoms. The amines include stearyl, oleyl, myristyl, palmityl, n-octyl, dodecyl, octadecylamine as well as other commercial primary amine mixtures such as mixtures where the aliphatic group is a mixture of the tert-alkyl group with from 11- 14 carbon atoms and an average of 12 carbon atoms, and mixtures where the aliphatic group is a mixture of tert-alkyl groups with 18-24 carbon atoms.

Also effective as rust inhibitors are the salts of an aromatic acid such as benzo, toluene, naphtho, phthalic 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 can also be used.

The salts of the amines with the aromatic acids are simply prepared by mixing the reactants at a temperature below the dehydration temperature, i.e. below approx. 90°C. In most cases, the reaction is exothermic and heating is not necessary. A solvent such as benzene, toluene, naphtha and chlorobenzene can be used.

Another class of rust inhibitors are the hydroxy-alkylamines, especially the long-chain (that is, Cg_3ø) long-chain amines containing 1 or 2 hydroxy-alkyl substituents on the amine nitrogen atom. Examples are N-(2-hydroxyethyl)octylamine, N,N-di-(2-hydroxy-1-propyl)dodecylamine, N-(3-hydroxy-1-pentyl)octadecylamine and N,N-di-(2- hydroxy-3-butyl)decylamine.

Also usable as rust-inhibiting agents are nitric acid salts of the above-mentioned long-chain aliphatic amines. Such salts are easily obtained by mixing an amine with a nitric acid at ordinary temperatures such as room temperature. Specific examples are the nitric acid salt of tert-alkyl (Cn_i4) primary amine and the nitric acid salt of bctadecylamine.

The concentration of rust inhibitor in the emulsion depends to a certain extent on the relative concentration of water in the emulsion. Usually from 0.01 to 2 parts of rust inhibitor per 100 parts emulsion will be sufficient.

Another type of additive that finds use in these emulsions is a foam inhibitor which can be a commercial dialkyl siloxane polymer or a polymer of an alkyl methacrylate. Freezing point depressants, for example water-soluble polyhydroxy alcohols such as glycerol or other polar substances such as "Cellosolve" are also useful. The concentration of these additives is usually less than 5 parts per 100 parts emulsion.

Bactericides are also usable in the emulsions according to the invention. These are illustrated by nitro-bromoalkanes such as 3-nitro-l-propyl bromide, nitro-hydroxyalkanes such as tri-(hydroxymethyl)-nitromethane, 2-nitro-2-ethyl-1,3-propanediol and 2-nitro-l-butanol, and boric acid esters such as glycerol borate. The concentration of the bactericide can be from 0.001 to 1 part per 100 parts emulsion.

Oxidation inhibitors that can be used in the emulsions according to the invention include the hindered phenols such as 2,4-di-tert-butyl-6-methylphenol, 4,4'-methylene-(2,6-di-tert-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 emulsion.

The emulsions can be prepared by simple mixing of the oil (A), water (B), the emulsifying salt (C), the functional additive (D) and any other component that is desired, in a homogenizer or any other efficient mixing device. device. Heating the emulsion during or after it is produced is not necessary. The order of mixing the ingredients is not critical, although it is convenient to first prepare an oil concentrate containing from 50 to 95* of the oil-soluble ingredients and from 5 to 50* of the oil and then to emulsify the concentrate with a water solution containing the functional additive ( D) in suitable proportions.

Illustrative water-in-oil hydraulic fluids within the framework of the invention are described in Table I in parts by weight.

Sorrow. learning fluids:

When the emulsions of the invention are used as acidifying fluids, such emulsions may optionally contain one or more oil-soluble surfactants. These include anionic, cationic and non-ionic surfactants. Suitable anionic ones include fatty acid soaps which are salts of long chain fatty acids derived from naturally occurring fats and oils and salts of alkylbenzenesulfonic acids. A useful anionic surfactant is the morpholinium salt of tetracosanylbenzenesulfonic acid. Ammonium and alkali metal salts are also suitable. Cationic surfactants include the amine salts such as polyoxyethyleneamine as well as quaternary ammonium compounds. Useful cationic surfactants include high molecular weight alkylimides 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 alkylphenols. Mixtures of surfactants can also be used. The acidification fluids generally contain up to 10 and preferably from 0.1 to 2 weight-* of the aforementioned surfactants.

The pickling fluids can be prepared simply by mixing the oil (A), the water (B), the emulsifying salt (C) and the functional additive (D) and any other ingredient that may be appropriate, in a homogenizer or any other efficient mixing device. Heating the emulsion during or after it is produced is not necessary. The order of mixing the ingredients is not critical, although it is convenient to first prepare an oil concentrate with from 50 to 95* of the oil-soluble ingredients and from 5 to 50* of the oil and then to emulsify the concentrate with a water solution containing the functional additive ( D) in suitable proportions. Reference should be made here to US-PS 4,140,640 and 4,233,165 which describe the production and use of water-in-oil acidification fluids.

Illustrative fluids of this type within the framework of the invention are shown in table II. The numerical values in table II are on a part-by-weight basis.

Sprengs toffemuls. 1 oner:

When the emulsions of the invention are used as explosive emulsions, these characteristically contain other additional additives such as sensitizing components, oxygen-supplying salts, particulate light metals, particulate solid explosives, soluble and partially soluble auto-explosives, explosive oils and the like in order to thereby increase strength and sensitivity or to reduce costs at the emulsion.

The sensitizing components are distributed essentially homogeneously in the emulsions. These sensitizing components are preferably occluded gas bubbles which can be introduced in the form of glass or resin microspheres or other gaseous particulate substances. Alternatively, the gas bubbles can be formed in situ by adding to the mixture and distributing in it a gas-forming agent such as an aqueous solution of sodium nitrite. Other suitable sensitizing components that can be used alone or in addition to the occluded or in situ formed gas bubbles are insoluble particulate auto-explosives such as grain or flake TNT, DNT, RDX and the like as well as water-soluble and/or hydrocarbon-soluble organic sensitizing agents such as amine nitrates, alkanolamine nitrates, hydroxyalkyl nitrates and the like. The explosive emulsions according to the invention can be formulated for a wide range of application areas. Any combination of sensing components may be selected to provide an explosive mixture of substantially any desired density and of any desired weight, strength or critical diameter.

The amount of solid auto-exploding components and of water-soluble and/or hydrocarbon-soluble organic sensitizing agents can comprise up to 40 weight-* of the total emulsion. The volume of the occluded gas component can comprise up to 50* of the volume of the total explosive emulsion.

Any additional substances can be incorporated into the explosive emulsions according to the invention to further improve sensitivity, density, strength, rheology or cost estimates for the finished explosives. Typical materials which are usable as possible additives are, for example, emulsion promoters such as highly chlorinated paraffinic hydrocarbons, particulate oxygen supply salts such as prilled ammonium nitrate, calcium nitrate, perchlorates and the like, particulate metal fuels such as aluminium, silicon and the like, particulate non-metallic fuels such as sulphur, gilsonite and the like , particulate Inert substances such as sodium chloride, barium sulfate and the like, water-phase or hydrocarbon-phase thickeners such as guar gum, polyacrylamide, carboxymethyl or ethyl cellulose, biopolymers, starches, elastomer materials and the like, cross-linkers for the thickeners such as potassium pyroantimonate and the like, buffers or pH controlling agents such as sodium borate, zinc nitrate and the like, crystal formation modifying agents such as alkylnaphthalene sodium sulphonate and the like, liquid phase retarding agents such as formamide, ethylene glycol and the like as well as bulking agents and additives tives of the usual type for use in this technique.

The quantities of any additional substances used can amount to up to 50 weight-* of the total explosive mixture, the actual quantities used depend on the nature and function.

A preferred method of preparing water-in-oil explosive emulsions according to the invention comprises the steps: (1) mixing water, inorganic oxidation salt and, in certain cases, some of the possible water-soluble compounds in a first premix; (2) mixing oil, emulsifying salt (C) and any oil-soluble compound, if any, in a second premix; and (3) adding the first premix to the second premix in a suitable mixing apparatus to thereby obtain a

water-in-oil emulsion.

The first premix is heated until all salts are completely dissolved and the solution can be filtered if necessary to remove soluble residues. 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 emulsion according to the invention. Glass microspheres, solid auto-explosive components such as particulate TNT, solid fuels such as aluminum or sulphur, inert substances such as barytes or sodium chloride, undissolved solid oxidizing salts and other possible substances are, if used, added to the emulsion and simply mixed until a homogeneous dispersion is achieved in the mixture.

The explosive emulsions according to the invention can also be prepared by adding the second premix fluidized solution phase to the first premix heated aqueous solution phase with sufficient stirring to invert the phases. However, this method requires significantly more energy to achieve the desired dispersion than the preferred reverse procedure. Alternatively, the explosive emulsions are particularly suitable for production by continuous mixing processes where two separately produced liquid phases are pumped through a mixing device where they are combined and emulsified.

Claims (10)

1. Water-in-oil emulsion, characterized in that it comprises: (A) a continuous oil phase; (B) a discontinuous aqueous phase; (C) a minor emulsifying amount of at least one salt prepared by reacting component (C)(I) with component (C)(II) under salt-forming conditions, wherein component (C)(I) is at least one hydrocarbyl-substituted carboxylic acid or a anhydride thereof, or ester or amide derivative of the acid or anhydride, the hydrocarbyl substituent of (C)(I) having on average from 20 to 500 carbon atoms, and component (C)(II) is ammonia and/or at least one amine; and (D) a functional amount of at least one water-soluble, oil-insoluble functional additive, dissolved in the aqueous phase; the functional additive being one or more oxygen-carrying salts, one or more non-oxidising acids or one or more borates, phosphates and/or molybdates; provided that when component (D) is ammonium nitrate, component (C) is different from an ester/salt formed by reacting polyisobutenyl (Mn=950) substituted succinic anhydride with diethylethanolamine in a ratio of one equivalent anhydride per equivalent amine. 2. Emulsion according to claim 1, characterized in that component (A) is present in the emulsion in an amount within the range of 2 to 70 weight-* of the emulsion; component (B) is present in the emulsion in an amount within the range of 1 to 97.9% by weight of the emulsion; component (C) is present in the emulsion in an amount within the range of 0.05 to 30 wt-* of the emulsion; and component (D) is present in the emulsion in an amount within the range of 0.05 to 95% by weight of the emulsion. 3. Emulsion according to claim 1, characterized in that fC)(I) is an acid or an anhydride represented by the formula wherein hyd is the hydrocarbyl substituent of (C)(I), or is an ester or an amide derived from the acid or anhydride. 4. Emulsion according to claim 1, characterized in that the hydrocarbyl substituent of (C)(I) has an average of 50 to 500 carbon atoms. 5. Emulsion according to claim 1, characterized in that the hydrocarbyl substituent of (C)(I) is a polyisobutylene group. 6. Emulsion according to claim 1, characterized in that component (C)(I) comprises at least one ester and/or an amide derived from at least one hydroxyamine. 7. Emulsion according to claim 1, characterized in that component (C)(II) comprises at least one alkylene polyamine with the formula where n is an integer from 1 to 10, each R" independently is a hydrogen atom or a hydrocarbyl group of up to 30 carbon atoms, and the alkylene group has from 1 to 10 carbon atoms. 8 Emulsion according to claim 1, characterized in that component (C)(II) comprises (a) at least one N-(hydroxyl-substituted hydrocarbyl)amine, (b) at least one hydroxyl-substituted poly(hydrocarbyloxy) analogue of (a), or (c) a mixture of (a) and (b). 9. Emulsion according to claim 1, characterized in that component (C)(II) is selected from the group comprising (a) primary, secondary and tertiary alkanolamines which can be represented respectively by the formulas (b) hydroxyl-substituted oxyalkylene analogues of alkanol- the amines represented by the formulas wherein each R is independently a hydrocarbyl group of 1 to 8 carbon atoms or a hydroxyl-substituted hydrocarbyl group of 2 to 8 carbon atoms and R<*> is a divalent hydrocarbyl group of 2 to 18 carbon atoms, and (c) mixtures of two or more thereof. 10. Emulsion according to claim 1, characterized in that component (D) comprises ammonium nitrate.