AU617425B2 - Salt compositions and explosives using same - Google Patents

Description

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DATE 19/07/89 P DATE 17/08/89 APPLN. ID 30311 89 PCT NUMBER PCT/US88/04501 INTERNATIONAL APPLICATI (51) International Patent Classification 4 (11) International Publication Number: WO 89/ 05786 C06B 47/14 Al (43) International Publication Date: 29 June 1989 (29.06.89) (21) International Application Number: PCT/US88/04501 (81) Designated States: AT (European patent), AU, BE (European patent), CH (European patent), DE (Euro- (22) International Filing Date: 16 December 1988 (16.12.88) pean patent), FR (European patent), GB (European patent), IT (European patent), LU (European patent), NL (European patent), SE (European patent).

(31) Priority Application Number: 137,301 (32) Priority Date: 23 December 1987 (23.12.87) Published With international search report.

(33) Priority Country: US Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of amendments.

(71) Applicant: THE LUBRIZOL CORPORATION [US/ US]; 29400 Lakeland Boulevard, Wickliffe, OH 44092

(US),

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

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

(54) Title: SALT COMPOSITIONS AND EXPLOSIVES USING SAME (57) Abstract Salt compositions are disclosed which comprise; at least one salt moiety derived from at least one highmolecular weight polycarboxylic acylating agent, said acylating agent having at least one hydrocarbyl substituent having an average of from about 20 to about 500 carbon atoms, and (II) ammonia, at least one amine, at hast one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; at least one salt moiety derived from at least one low-molecular weight polycarboxylic acylating agent, said acylating agent optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms, and (11) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; said components and being coupled together by at least one compound having two or more primary amino groups, (ii) two or more secondary amino groups, (iii) at least one primary amino group and at least one secondary amir!o group, (iv) at least two hydroxyl groups or at least one primary or secondary amino group and at least one hydroxyl group, These salt compositions are useful as emulsifiers in water-in-oil explosive emulsions, particularly cap-sensitive explosive emulsions, i WO 89/05786 PCT/US88/04501 -1- SALT COMPOSITIONS AND EXPLOSIVES USING SAME Technical Field This invention relates to novel salt compositions and to explosive compositions comprising said salt compositions. The salt compositions are useful as emulsifiers in the explosive compositions. The explosive compositions are water-in-oil explosive emulsions which, in one embodiment, are cap-sensitive explosive emulsions.

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

II) C WO 89/05786 PCT/US88/04501 -2- U.S. Patent 3,216,936 describes nitrogen-containing dispersants for use in lubricants which are obtained by the reaction of an alkylene amine with an acidic mixture consisting of a hydrocarbon-substituted succinic acid having at least about 50 aliphatic carbon atoms in the hydrocarbon substituent and an aliphatic monocarboxylic acid. The aliphatic monocarboxylic acids are described as including saturated and unsaturated acids such as acetic acid, dodecanoic acid, oleic acid, naphthenic acid, formic acid, etc. Acids having 12 or more aliphatic carbon atoms, particularly stearic acid and oleic acid, are described as being especially useful.

U.S. Patents 3,639,242 and 3,708,522 describe compositions prepared by post-treating mono- and polycarboxylic acid esters with mono- or polycarboxylic acid acylating agents. The compositions thus obtained are reported to be useful as dispersants in lubricants and fuels.

U.S. Patent 4,642,330 discloses dispersant salt compositions made by reacting phosphorus-free carboxylic solubilizers with iulfonic acid-free organic acids or mineral acids. The carboxylic solubilizer is the reaction product of a polycarboxylic acid acylating agent having at least one hydrocarbon-based substituent of at least 8 to 500 carbon atoms with at least one poly(alkyleneamine). The reference indicates that these dispersant salt compositions have good thermal stability when mixed with a surfactant or a hydrophilic organic solvent, and that they can be used with aqueous solutions to disperse various fillers including carbon black and to solubilize various fluids.

WO 89/05786 PCTIUS88/04501 -3- Nitrogen-containing, phosphorus-free carooxylic solubilizers useful in water based functional fluids are disclosed in U.S. Patents 4,329,249; 4,368,133; 4,435,297; 4,447,348; and 4,448,703. These solubilizers are made by reacting at least one carboxylic acid acylating agent having at least one hydrocarbyl substituent of from about 12 to about 500 carbon atoms with (II) at least one N-(hydroxyl-substituted hydrocarbyl) amine, hydroxyl-substituted poly(hydrocarbyloxy) analog of said amine or mixtures of (a) and These patents indicate that preferred acylating agents include the substituted succinic acids or anhydrides, such as polyisobutenyl-substituted succinic anhydride, and that the amines that are useful include the primary, secondary and tertiary alkanol amines, such as diethylethanolamine and mixtures of diethylethanolamine and ethanolamine. These solubilizers are useful in dispersing oil-soluble, water-insoluble functional additives in water-based functional fluids.

Water-in-oil explosive emulsions typically comprise a continuous organic phase and a discontinuous oxidizer phase containing water and an oxygen-supplying source such as ammonium nitrate, the oxidizer phase being dispersed throughout the continuous organic phase.

Examples of such water-in-oil explosive emulsions are disclosed, 'nter alia, in U.S. Patents 3,447,978; 3,765,964; 3,985,593; 4,008,110; 4,097,316; 4,104,092; 4,218,272; 4,259,977; 4,357,184; 4,371,408; 4,391,659; 4,404,050; 4,409,044; 4,448,619; 4,453,989; and 4,534,809; U.K. Patent Application GB 2,050,340A; and European Application Publication No. 0,156,572.

European Application 0,155,800 discloses an explosive emulsion composition comprising a discontini: WO 89/05786 PCT/US88/04501 -4uous phase containing an oxygen-supplying component and an organic medium forming a continuous phase wherein the oxygen-supplying component and organic medium are capable of forming an emulsion which, in the absence of a supplementary adjuvant, exhibits an electrical conductivity measured at 60 0 C, not exceeding 60,000 picomhos/ meter. The reference indicates that the conductivity may be achieved by the inclusion of a modifier which also functions as an emulsifier. The modifier is comprised of a hydrophilic moiety and a lipophilic moiety.

The lipophilic moiety can be derived from a poly[alk- (en)yl] succinic anhydride. Poly(isobutylene) succinic anhydride having a number average molecular weight in the range of 400 to 5000 is specifically identified as being useful. The hydrophilic moiety is described as being polar in character, having a molecular weight not exceeding 450 and can be derived from polyols, amines, amides, alkanol amines and heterocyclics. Example 14 of this reference discloses the use of a 1:1 condensate polyisobutenyl succinic anhydride (number average molecular weight 1200) and N, N-dimethylamino ethanol as the modifier.

Cap-sensitive explosive emulsions are water-inoil explosive emulsions which can be detonated without the use of a booster. Examples of such cap-sensitive explosive emulsions are disclosed, inter alia, in U.S.

Patents 3,715,247; 4,110,134; 4,149,916; 4,149,917; 4,231,821; 3,383,873; 4,394,198; and 4,490,195.

Summary of the Invention The present invention provides for a novel salt composition comprising: at least one salt moiety derived from at least one hig.h-molecular weight polycarboxylic acylating agent, said acylating agent WO 89/05786 PCT/US88/04501 having at least one hydrocarbyl substituent having an average of from about 20 to about 500 carbon atoms, and (II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; at least one salt moiety derived from at least one lowmolecular weight polycarboxylic acylating agent, said acylating agent optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms, and ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; said components and being coupled together by at least one compound having two or more primary amino groups, (ii) two or more secondary amino groups, (iii) at least one primary amino group and at least one secondary amino group, (iv) at least two hydroxyl groups or at least one primary or secondary amino group and at least one hydroxyl group. These salt compositions are useful as emulsifiers in water-in-oil explosive emulsions, particularly cap-sensitive water-in-oil explosive emulsions.

Description of the Preferred Embodiments The term "emulsion" as used in this specification and in the appended claims is intended to cover not only water-in-oil emulsions, but also compositions derived from such emulsions wherein at temperatures below that at which the emulsion is formed the discontinuous phase is solid or in the form of droplets of super-cooled liquid. This term also covers compositions derived from or forx41ated as such water-in-oil emulsions that are in the form of gelatinous cr semi-gelatinous compositions.

I I_ i lario O 89/05786 PCT/US88/04501 -6i Y&e. cescfYoi The term "hydrocarbyl" is used herein/ to include: hydrocarbyl groups, that is, aliphatic alkyl or alkenyl), alicyclic cycloalkyl, cycloalkenyl), aromatic, aliphatic- and alicyclicsubstituted aromatic groups and the like as well as cyclic groups wherein the ring is completed through another portion of the molecule (that is, any two indicated groups may together form an alicyclic group); substituted hydrocarbyl groups, that is, those groups containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbyl nature of the hydrocarbyl group; those skilled in the art will be aware of such groups, examples of which include ether, oxo, halo chloro and fluoro), alkoxyl, mercapto, alkylmer pto, nitro, nitroso, sulfoxy, etc.; hetero groups, that is, groups which, while having predominantly hydrocarbyl character within the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.

Suitable heteroatoms will be apparent to those of skill in the ar': and include, for example, sulfur, oxygen, nitrogen and such slibstituents as pyridyl, furanyl, thiophenyl, imidazolyl, etc.

In general, no more than about three nonhydrocarbon groups or heteroatoms and preferably no more than one, will be present for each ten carbon atoms in a hydrocarbyl group. Typically, there will be no such groups or heteroatoms in a hydrocarbyl group and it will, therefore, be purely hydrocarbyl.

The hydrocarbyl groups are preferably free from acetylenic unsaturation; ethylenic unsaturation, when

K>,

WO 89/05786 PCT/US88/04501 -7present will generally be such that there is no more than one ethylenic linkage present for every ten carbonto-carbon bonds. The hydrocarbyl groups are often completely saturated and therefore contain no ethylenic unsaturation.

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

Components and The carboxylic acylating agents and are aliphatic or aromatic, polycarboxylic acids or acid-producing compounds. Throughout this specification and in the appended claims, the term "carboxylic acylating agent" is intended to include carboxylic acids as well as acid-producing derivatives thereof such as anhydrides, esters, acyl halides and mixtures thereof, unless otherwise specifically stated.

The acylating agents and may contain polar substituents provided that the polar substituents are not present in portions sufficiently large to alter significantly the hydrocarbon character of the acylating agent. Typical suitable polar substituents include halo, 4uch as chloro and bromo, oxo, oxy, formyl, sulfenyl, sulfinyl, thio, nitro, etc. Such polar substituents, if present, preferably do not exceed about by weight of the total weight of the hydrocarbon portion of the acylating agent, exclusive of the carboxyl groups.

Examples of low molecular weight polycarboxylic acids include dicarboxylic acids and derivatives such as maleic acid, maleic anhydride, chloromaleic anhydride, malonic acid, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, WO 89/ 05786 PCIUS88/04501 pimelic acid, azelaic acid, sebacic aiguaoi acid, citraconic acid, itaconic acid, allyl succinic acid, cetyl malonic acid, tetrapropylene-substituted succinic anhydride, etc. Lower alkyl esters of these acids can also be used.

Low molecular weight hydrocarbyl-substituted succinic acid and anhydrides can also be used. These succinic acids and anhydrides can be represented by the formulae 0 R-CHCOOH and R- CH -C C2COOH 0 0 wherein R is a C1. to about a CIB hydrocarbyl group.

Piceferably, R is an aliphatic or alicyclic hydrocarby].

group with less than about 10% of its carbon-to-carbon bonds being unsaturated. R can be derived from olefins of from 2 to about l8 carbon atoms with aipha-olefins being particularly useful. E4xaniples of such olefins include ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-l-butenet 3-methyl-l-butene, 1-hexene, 1-heptene, 1-octene, styrene, 1-nonenet 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene? 1-octadecene, etc.

Comecially available alpha olefin fractions such as C15-18 alpha-olef ins, C12-16 aipha-olef ins, C14-16 alpha-olefins, C14-18 ailpha-olefins, C16-1c alphaolefins, etc., are particularly useful; these commercial alpha-olefin fractions also usually include minor amounts of alpha-olefins outside the given ranges. The WO 89/05786 PCI/US88/04501 -9production of such substituted succinic acids and their derivatives is well known to those of skill in the art and need not be discussed in detail herein.

Acid halides of the afore-described low-molecular weight polycarboxylic acids can be used as the low-molecular weight acylating agents of this invention. These can be prepared by the reaction of such acids or their anhydrides with halogenating agents such as phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride. Esters of such acids can be prepared simply by the reaction of the acid, acid halide or anhydride with an alcohol or phenolic compound. Particularly useful are the lower alkyl and alkenyl alcohols such as methanol, ethanol, allyl alcohol, propanol, cyclohexanol, etc.

Esterification reactions are usually promoted by the use of alkaline catalysts such as sodium hydroxide or alkoxide, or an acidic catalyst such as sulfuric acid or toluene sulfonic acid.

Although it is preferred that the acylating agent is an aliphatic polycarboxylic acid, and more preferably a dicarboxylic acid, the carboxylic acylating agent may also be an aromatic polycarboxylic acid or acid-producing compound. The aromatic acids are preferably dicarboxy-substituted benzene, naphthalene anthracene, phenanthrene or like aromatic hydrocarbons. They include also the alkyl-substituted derivatives, and the alkyi groups may contain up to about 12 carbon atoms. The aromatic acid may also contain other substituents such as halo, hydroxy, lower alkoxy, etc. Specific examples of aromatic polycarboxylic acids and acid-producing compounds useful as acylating agent include phthalic acid, isophthalic ii WO 89/05786 PCT/US88/04501 acid, terephthalic acid, 4-methyl-benzene-L,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, anthracene dicarboxylic acid, 3-dodecyl-benzene-l,4-dicarboxylic acid, 2,5-dibutylbenzene-1,4-dicarboxylic acid, etc.

The anhydrides of these dicarboxylic acids also are useful as the carboxylic acylating agent The high-molecular weight polycarboxylic acylating agents are well known in the art and have been described in detail, for example, in the following British and Canadian patents: U.S. Patents 3,024,237; 3,087,936; 3,163,603; 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; 3,306,907; 3,307,928; 3,312,619; 3,341,542; 3,346,354; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179; 3,454,607; 3t346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169; 3j868,330; 3,912,764; 4,234,435; and 4,368,133; British Patents 944,136; 1,085,903; 1,162,436; and 1,440,219; and Canadian Patent 956,397. These patents are incorporated herein by reference.

As disclosed in the foregoing patents, there are several processes for preparing these high-molecular weight acylating agents Generally, these processes involve the reaction of an ethylenically unsaturated carboxylic acid, acid halide, anhydride or ester reactant with an ethylenically unsaturated hydrocarbon containing at least about 20 aliphatic carbon atoms or a chlorinated hydrocarbon containing at least about aliphatic carbon atoms at a temperature within the range of about 100-300OC. The chlorinated hydrocarbon or ethylenically unsaturated hydrocarbon reactant prefErably contains at least about 30 carbon atoms, more preferably at least about 40 carbon atoms, more preferably WO 89/05786 PCT/US88/04501 -11at least about 50 carbon atoms, and may contain polar substituents, oil-solubilizing pendant groups, and be unsaturated withir the general limitations explained hereinabove.

When preparing the carboxylic acid acylating agent, the carboxylic acid reactant usually corresponds to the formula Ro-(COOH)n, where Ro is characterized by tne presence of at least one ethylenically unsaturated carbon-to-carbon covalent bond and n is an integer from 2 to about 6 and preferably is 2. The acidic reactant can also be the corresponding carboxylic acid halide, anhydride, ester, or other equivalent acylating agent and mixtures of two or more of these. Ordinarily, the total number of carbon atoms in the acidic reactant will not exceed about 20, preferably this number will not exceed about 10 and generally will not exceed about 6, exclusive of the carboxyl-based groups, Preferably the acidic reactant will have at least one ethylenic linkage in an alpha, beta-position with respect to at least one carboxyl function. Exemplary acidic reactants are maleic acid, maleic anhyl le fumaric acid, itconic acid itaconic anhyd re-,t citraconic acid, citraconic anhydride, mesaconic acid, chloroioaleic acid, aconitic acid, and the like.

Preferred acid reactants include maleic acid and maleic anhydride.

The ethylenically unsaturated hydrocarbon reactant and the chlorinated hydrocarbon reactant used in the preparation of these high-molecular weight carboxylic acylating agents are preferably high molecular weight, substantially saturated petroleum fractions and svbstantially saturated olefin polymers and the corresr. nding chlorinated products, Polymers and chle tinated I r WO 89/05786 WO 89/05786PCT/US88/04501 -12polymers derived from iono-olefins having from 2 to about 30 carbon atoms are preferred. Especially useful polymers are the polymers of 1-mono-olef ins such as ethylene, propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl- 1-heptene, 3-cyclohexyl-l-butene, and Polymers of medial olefins, olefin5 in which the olefinic linkage is not at tna terminal position, likewise are useful. These are exem~plified by 2-butener 3-pentene-, and 4-octene.

tnterpolymers of 1-mono-olefins such as illustrated above with each other and with other interpolymerizable olefinic substances such as aromatic olefins, cyclic olefins,. and polyolefins, are also useful sources of the ethylenically un! aturated reactant. Such interpolymers include for example, those prepared by polymerizing isobutene with styrene, isoihutene with butadiene, propene with isoprenet propene with isobutene, ethylene with piperylene, isobutene with chloroprene, isobutene ,with p-inef*hy -styrene f 1-hexene with 1,3-hexadiene, 1-cctene with 1-hexene, 1-heptene with 1-pentene, 3-methyl- 1-butene with 1-octener 3t3-dimethyl-l-pentene with l-hexeneo isobutene with styren-z and piperylene, etc.

For reasons of hydrocarbon solubiJlityt the interpolymers contemplated for use in preparing the acylating agents of this invention are prefEerably substantially al~iphatic and substantially saturated, that is, they should contain at least about 80% and preferably about 95%f on a weight basis, of units derived from aliphatic mono-olef ins. Preferably, they will contain no more than abkoUt 53% olefinic linkages based on the total number of the carbon-to-carbon covalent linkages present, WO 89/05786 PCT/US88/04501 -13- In one embodiment of the invention, the polymers and chlorinated polymers are obtained by the polymerization of a C4 refinery stream having a butene content of about 35% to about 75% by weight and an isobutene content of about 30% to about 60% by weight in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. These polyisobutenes preferably contain predominantly (that is, greater than about 80% of the total repeat units) isobutene repeat units of the configuration.

CH3 CH2 C CH3 The chlorinated hydrocarbons and ethylenically unsaturated hydrocarbons used in the preparation of the higher molecular weight carboxylic acylating agents preferably have up to about 500 carbon atoms per molecule. Preferred acylating agents are those containing hydrocarbyl groups of from about 20 to about 500 carbon atoms, more preferably from about 30 to about 500 carbon atoms, more preferably from about 40 to about 500 carbon atoms, more preferably from about 50 to about 500 carbon atoms.

The high-molecular weight polycarboxylic acylating agents may also be prepared by halogenating a high molecular weight hydrocarbon such as the abovedescribed olefin polymers to produce a polyhalogenated product, converting the polyhalogenated product to a polynitrile, and then hydrolyzing the polynitrile. They may be prepared by oxidation of a high molecular weight polyhydric alcohol with potassium permanganate, nitric L Iillli~li~ WO 89/05786 PCT/US88/04501 -14acid, or a similar oxidizing agent. Another method involves the reaction of an olefin or a polar-substituted hydrocarbon such as a chloropolyisobutene with an unsaturated polycarboxylic acid such as 2-pentene-l,3,5tricarboxylic acid prepared by dehydration of citric acid.

The polycarboxylic acid acylating agents (I) can also be obtained by reacting chlorinated polycarboxylic acids, anhydrides, acyl halides, and the like with ethylenically unsaturated hydrocarbons or ethylenically unsaturated substituted hydrocarbons such as the polyolefins and substituted polyolefins described hereinbefore in the manner described in U.S. Patent 3,340,281, this patent being incorporated herein by reference.

The high-molecular weight polycarboxylic acid anhydrides can be obtained by dehydrating the corresponding acids. Dehydration is readily accomplished by heating the acid to a temperature above about 0 preferably in the presence of a dehydration agent, e.g, acetic anhydride. Cyclic anhydrides are usually obtained from polycarboxylic acids having acid groups separated by no more than three carbon atoms such as substituted succinic or glutaric acid, whereas linear anhydrides are usually obtained from polycarboxylic acids having the acid groups separated by four or more carbon atoms.

The acid halides of the polycarboxylic acids can be prepared by the reaction of the acids or their anhydrides with a halcgenating agent such as phosphorus tribromide, phosphorus pentachloride, or thionyl chloride.

Hydrocarbyl-substituted succinic acids and the anhydride, acid halide and ,ster derivatives thereof are VVO 89/05786 PCTIUS88/04501 particularly preferred acylating agents These acylating agents are preferably prepared by reacting maleic anhydride with a high molecular weight olefin or a chlorinated hydrocarbon such as a chlorinated polyolefin. The reaction involves merely heating the two reactants at a temperature in the range of about 100 0

C

to about 300 0 C, preferably, about 100°C to about 200 0

C.

The product from this reaction is a hydrocarbyl-substituted succinic anhydride wherein the substituent is derived from the olefin or chlorinated hydrocarbon. The product may be hydrogenated to remove all or a portion of any ethylenically unsaturated covalent linkages by standard hydrogenation procedures, if desired. The hydrocarbyl-substituted succinic anhydrides may be hydrolyzed by treatment with water or steam to the corresponding acid and either the anhydride or the acid may be converted to the corresponding acid halide or ester by reacting with a phosphorus halide, phenol or alcohol. The hydrocarbyl-substituted succinic acids and anhydrides can be represented by the formulae R CH COOH

I

CH2 COOH or R CHC CH2C\ wherein R is the hydrocarbyl substituent. Preferably R contains from about 20 to about 500 carbon atoms, more preferably from about 30 to about 500 carbon atomsr more preferably from about 40 to about 500 carbon atoms,, iiore preferably from about 50 to about 500 carbon atoms.

A L r 11;1 l~ WO 89/05786 PCT/US88/04501 16- Although it is preferred that tne acylacing agent is an aliphatic polycarboxylic acid, and more preferably a dicarboxylic acid, the carboxylic acylating agent may also be an aromatic polycarboxylic acid or acid-producing compound. The aromatic acids are preferably alkyl-substituted, dJicarboxysubstituted benzene, naphthalene, anthracene, phenanthrene or like aromatic hydrocarbons. The alkyl groups may contain up to about 30 carbon atoms. The aromatic acid may also contain other substituents such as halo, hydroxy, lower alkoxy, etc.

Component Component can be any compound having (i) two or more primary amino groups, (ii) two or more secondary amino groups, (iii) at least one primary amino group and at least one secondary amino group, (iv) at least two hydroxyl groups, or at least one primary or secondary amino group and at least one hydroxyl group. These incude polyamines, polyols and hydroxyamines.

Polvamines Useful as Component The polyamines useful as component are characterized by the presence within their structure of at least two -NH2 groups, at least two >NH groups, or at least one -NH2 group and at least one >NH group.

These polyamines 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 heterocyelic, heterocyclic-substi- WO 89/05786 PCT/US88/04501 -17tuted aliphacic, heterocyclic-substituted cycloaliphatic and heterocyclic-substituted aromatic amines. These amines may be saturated or unsaturated. If unsaturated, the amine is preferably free from acetylenic unsaturation. These amines may also contain non-hydrocarbon substituents or groups as long as these groups do not significantly interfere with the reaction of such amines with reactants and Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl; mercapto, nitro, and interrupting groups such as and as in such groups as -CH2CH2-X-CH2CH2where X is or The polyamines include aliphatic, cycloaliphatic and aromatic polyamines analogous to the aliphatic, cycloaliphatic and aromatic monoamines described below except for the presence within their structure of at least one additional >NH or -NH2 group.

Aliphatic monoamines include mono-aliphatic and di-aliphatic-subs tituted amines wherein the aliphatic groups can be saturated or unsaturated and straight or branched chain. Thus, they are primary or secondary aliphatic amines. Such amines include, for example, mono- and di-alkyl-substituted amines, mono- and dialkenyl-substituted amines, And amines having one N-alkenyl substituent and one N-alkyl substituent, and the like. The total number of carbon atoms in these aliphatic monoamines preferably does not exceed about 40 and usually does not exceed about 20 carbon atoms. Specific examples of such monoamines include ethylamine, di-ethylamine, n-butylamine, di-n-butylamine, allylamine, isobut- WO 89/05786 PCT/US88/04501 -18ylamine, 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, include 2-(cyclohexyl)-ethylamine, benzylamine, phenylethylamine, and 3-(furylpropyl) amine.

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

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

WO 89/05786 PCT/US88/04501 -19deterocyclic polyamines can also be used. As used herein, the terminology "heterocyclic polyamine" is intended to describe those heterocyclic amines containing at least two primary amino groups, at least two secondary amino groups, or at least one of each, and at least one nitrogen as a heteroatom in the heterocyclic ring. As long as there is present in the heterocyclic polyamines at least two primary amino croups, at least two secondary amino groups, or at least one of each, the hetero-N atom in the ring can be a tertiary amino nitrogen; that is, one that does not have hydrogen attached directly to the ring nitrogen. The hetero-N atom can be one of the secondary amino groups; that is, it can be a ring nitrogen with hydrogen directly attached to it.

Heterocyclic amines can be saturated or unsaturated and can contain various substituents such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the total number of carbon atoms in the substituents will not exceed about Heterocyclic amines can contain heteroatoms other than nitrogen, especially oxygen and sulfur. Obviously they can contain more than one nitrogen heteroatom. The and 6-membered heterocyclic rings are preferred.

Among the suitable heterocyclic polyamines are the aziridines, azetidines, azoli[dines tetra- and di-hydro pyridines, pyrroles, indoles, piperadines, imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, NN'-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. Useful heterocyc- S- I The hydrocarbyl groups are preferably free from acetylenic unsaturation; ethylenic unsaturation, when WO 89/05786 PCTJIJS88/04501 lic polyamines are tfle saturated 5- and 6-membered heterocyclic poliyaiines containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines, and the like. Usually the aminoalkyl substituents are substituted on a nitrog~en atom forming part of the hetero ring. Spticiic examples of such heterocyclic amines include N-aminoethylpiperazine and N,N'adiIinoethylpiperazine.

Hydrazine and substituted-hydrazines can also be used. The substituents which may be present on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the substituents are alkyl, especially lower alkyl, phenyl, and substituted phenyl such as lower alkoxy-substituted phenyl or lower alkyl-substituted phenyl. Specific examples of substituted hydrazines are rethylhydrazine, NfN-dimethylhydrazine, N, N I-dime thylhyd razine, phenylhydrazine, N-phenyl- N'-ethylhydrazine, N-(para-tolyl)-N'-(n-butyl)-hydrazinee. N-(para-nit, ophenyl)-hydrazine, N-(para-nitrophenyl) -N-methylhydrazine, N,N'-di-(para-chlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine, and the like.

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

The branched polyalkylene poJlyamines are polyalkylene polyamines wherein the branched group is a side chain containing on the average at least one nitrogen-bonded aminoalkylene group per nine amino units present on the main chain, for example, 1-4 of such branched chains per nine units -IS1 i WO 89/05786 PCT/US88/04501 -21on the main chain, but preferably one side chain unit per nine main chain units. Thus, these polyamines contain at least three primary amino groups and at least one tertiary amino group. These amines may be expressed by the formula:

H

NH2-(R -N)x RN RNH2

R

RI

NH2 y wherein R is an aliylene group such as ethylene, propylene, butylene and other homologs (both straight chained and branched), etc., but preferably ethylene; and x, y and z are integers; x is in the range of from about 4 to about 24 or more, preferably from about 6 to about 18; y is in the range of from 1 to about 6 or more, preferably from 1 to about 3; and z is in the range of from zero to about 6, preferably from zero to about 1. The x and y units may be sequential, alternative, orderly or randomly distributed. A useful class of such polyamines includes those of the formula: NH fR-N)gRN-JR-N H

R

NH

n wherein n is an integer in the range of from 1 to about or more, preferably in the range of from 1 to about 3, and R is preferably ethylene, but may be propylene, ib WO 89/05786 PCT/US88/04501 -22butylene, etc. (straight chained or branched). Useful embodiments are represented by the formula: -H H

NH

2

C

2

CH

2

N)-CH

2

CH

2 -N CHCH 2 N -2 H CH2 CH2 NH2 n wherein n is an integer in the range of I to about 3.

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

Suitable polyamines also include polyoxyalkylene polyamines, polyoxyalkylene diamines and polyoxyalkylene triamines, having average molecular weights ranging from about 200 to about 4000, preferably from about 400 to 2000, Examples of these polyoxyalkylene polyamines include those amines represented by the formula: NH2-Alkylene---O-Alkylene-mNH2 wherein m has a value of from about 3 to about preferably from about 10 to about R-Alkylene- -O-Alkylene-nNH2]3-6 wherein n is a number in the range of from A to about with the proviso that the sum of all of tha n's is from, about 3 to about 70 and generally from about 6 to

L~

wo 89/05786 PCT/US88/04501 -23about 35, and R is a poiyvalent saturated bydrocarbyl group of up to about 10 caroon atoms having a valence of from about 3 to about 6. The alkylene groups may be straight or branched chains and contain from 1 to about 7 carbon atoms, and usually from 1 to about 4 carbon atoms. The various alkylene groups present within the above formulae may be the same or different.

More specific examples of these polyairnes include:

NH

2 CH-C-(

OCH

2 C HNH 2 I; 1 CH 3

C

3 herein x has a value of from about 3 to about 70, preferably from about 10 to 35; and C CCU 2 C* UNH

CU

3

CU

3

-CU

2

CU

2 -oC2 1 H 2

CH

3 3 U 2

OC

2 CU'21 y 2

CH

3 wherein x y z have a total value ranging from abouc 3 to about 30, preferably from about 5 to about Useful polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropyiene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to about 2000. The polyoxyalkylene polyamines are commerially available from the Jefferson Chemical Company, Ina. under the trade name "Jeffamine". U.SI. Patents 3,804,763 and 3,948,800 he ;i WO 89/05786 PCT/US88/04501 -24are incorporated herein by reference for tneir disclosure of such polyoxyalkylene polyainines.

Useful polyamines are the alkylene polyainines, including the polyalkylene polyamines, as described in more detail hereafter, The al~ylene poJlyainines include those conforming to the formula: R-N- (Alkylene-Nthfl'

RR

wherein n is from I to about 10, preferably from 1 to about 7; each P, and RO is independently a hydrogen atomf a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having up to about 700 carbon atoms, preferably up to about 100 carbon atoms, more preferably up to about carbon atoms, more preferably up to about 30 carbon atoms, with the proviso that At least one of R and at least one of are hydrogen; and the "Alkylene" group has from about I to about 18 carbon atoms, preferably from I to about 4 carbon atoms, with the preferred Alkylene being ethylene or pr~pylene. Useful alkylene polyamines are those wherein each R and eaich RI is hydrogen with the ethylene polyamines, and niixtu4ies of ethylene poJlyamines being particularly pref'erred, Such alkylene polyamines include methylene polyam3inese ethylene. polyamines, butylene polyaminest propylene polyamines, pentylene polyamines, hexy2.ene polyaminea, heptylene polyamines, etc. The higher homologs of such amInes and related atinoalkyl-subatituted piperazines are also included.

Alkyilen* polyamine8 that are useful include ethylene 6 iamiiie, diethylene, trliaminef triethylene tetraminet tetraethylene pentaimine, penta&&thylene hex- MIN07 zzaa WO 89/05786 WO 8905786PCT/US88/04501 amine, propylene diamine, tr.-metnylene diandine, hexamethylene diamine, decainethylene diamine, octametbylene diamine, di(heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, di(trimethylene) triamine, N-(2aminoethyl) piperazine, l,4-bls(2-aminoethyl) piperazine, and the lik~e. Higher homologs as are obtained by condensing two or more of the above-illustrated alkylene amines are useful as amines in this invention as are mixtures of two or more of any of the afore-described polyainines.

Ethylene polyamines, such as those mentioned above, are described in detail under the heading "Diamines and Higher Axninest A3.1phatic" in The Encyclopedia of Chemical Technology, Third Edition, Kirk-Othnerr Volume 7, pp. 580-602, a Wiley -IntersCience Publication, John Wiley and Sons, 1979, these pages being incorporated herein by reference. Suich compounds are prepared, most conveniently by the reaction of an alkylene chloride with ammnonia or by reaction of an ethylene imine with a ring-opening reagent Such As ammonia, etc, These reactions result in the production of the somewhat complex mixtures of alkylene polyamines, including cyclic condensation products such as plperazines.

Alkoxylated alkylene polyamines NrtW- (diethanol)-ethylene diamine) can be used. Such polyamines can be made by reactlnq a4.kylene amines ethylenediamine) with one or more alkkylene oxides ethylene oxidef octadecene oxide) of two to about carbons. similar alky2lene oXide-alkanol, amine reaction products can also be used such as, the products made by reacting the afore-described primary, seaondary or tertiary alkanol amines With 1ethylene, propylene or higher 9 1 ell- W'O 89/05786 PC.7/US88/04501 -26epoxides in a 1:j or 1.-2 no.iar ratio. RB'-actant ratios and temnreratures for carrying oot such reactions are known to those skilled in the art.

Specific examples of aJlkoxylated alkylene polyaminez include N-(2-hydroxyethyl) ethylene dianiine, N,N- L-s(2-hydc~cyethy.)-ethylene-di-ainer. 1-(2"hydroxiyethyl) piperazinef mono(hydroxypropyl)-substituted diethylene triamine, di (hy.droxypropyl) -substituted tetraethylene pentamine, (3-hydroxybutyl) -tetramethylene diam'ine, etc. Higher homologs obtained by condensation of the above-illustrated hydroxy alkylene polyamines through amino groups or through hydroxy groups are likewise useful. Condensation through amino groups results in a higher amine accompanied by removal of ammonia while condensation thL)t,1qh the hydroxy groups results in products containing ether linkages accompanied by removal of w ater. Mixtures of two or more of any of the afore-aid polyamines are also useful.

Polvols Useful as mponent (C: The polyolz or polyhydric alcohcs useful as compojvept Include those compounds of the general formulaz: Rl(OH%/m wherein RI is a monovalent or po'lyvalent organic group joined to the -OH groups through carbon-to-oxygen bonds (that is, -CQU wherein the caroon is rtot part of a carbonyl group) and m, is an integer of from 2 to abovc pref'erably 2 to about 6. These alcohols can be aiipha- 1-1c, cycloalipiiatice aromatico and heterocyclic, includi) aliphatio-substituted cycloaliphatic 71cohol-. al phatic-st~batituted aromatic alcohols, aliphatic-suibstii WO 89/05786 PCT/US88/04501 -27tuted heterocyclic alcohols, cycloalipnatic-substituted aliphatic alcohols, cycloaliphatic-substituted heterocyclic alcohols, heterocyclic-substituted aliphatic alcohols, heterocyclic-substituted cycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols. Except for the polyoxyalkylene alcohols, the polyhydric alcohols corresponding to the formula Rl(OH)m preferably contain not more than about 40 carbon atoms, more preferably not more than about 20 carbon atoms. The alcohols may contain non-hydrocarbon substituents or groups which do not interfere with the reaction of the alcohols with the hydrocarbyl-substituted carboxylic acids or anhydrides of this invention. Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as and as in such groups as -'CH2CH2-X-CH2CH2 where X is or Useful polyoxyalkylene alcohols and derivatives thereof include the hydrocarbyl ethers and the carboxylic acid esters obtained by reacting the alcohols with various carboxylic acids. Illustrative hydrocarbyl groups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkyla'yl alkyl, etc., containing up to about 40 carbon atoms. Specific hydrocarbyl groups include methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, p-octylphenyl ethyl, cyclohexyl, and the like. Carboxylic acids useful in preparing the ester derivatives are mono- or polycarboxylic acids such as acetic acid, valeric acid, lauric acid, stearic acid, succinic acid, and alkyl or alkenyl-substituted succinic acids wherein the alkyl or alkenyl group contains up to about 20 carbon atoms. Members of this class of alcohols are commercially available from various sources; PLUR- L WO 89/05786 PCTIS8804501 -28- ONICS, polyols available from Wyandotte Chemicals Corporation; POLYGLYCOL 112-2, a liquid triol derived from ethyleneoxide and propylene-oxide available from Dow Chemical Co.; and TERGITOLS, dodecylphenyl or nonylphenyl polyethylene glycol ethers, and UCONS, polyalkylene glycols and various derivatives thereof, both available from Union Carbide Corporation. However, the alcohols used must have an average of at least one free alcoholic hydroxyl group per molecule of polyoxyalkylene alcohol. For purposes of describing these polyoxyalkylene alcohols, an alcoholic hydroxyl group is one attached to a carbon atom that does not form part of an aromatic nucleus.

Alcohols useful in this invention also include alkylene glycols and polyoxyalkylene alcohols such as polyoxyethylene alcohols, polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. These polyoxyalkylene alcohols (sometimes called polyglycols) can contain up to about 150 oxyalkylene groups, with the alkylene group containing from about 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols are generally dihydric alcohols. That is, each end of the molecule terminates with an OH group. In order for such polyoxyalkylene alcohols to be useful, there must be at least two OH groups.

The polyhydric alcohols use:.ul in this invention include polyhydroxy aromatic compounds. Polyhydric phenols and naphthols are useful hydroxyaromatic compounds. These hydroxy-substituted aromatic compounds may contain other substituents in addition to the hydroxy substituents such as halo, alkyl, alkenyl, alkoxy, alkylmercapto, nitro and like. Usually, the hydroxy aromatic compound will ooti~in from 2 to about 4 WO 89/05786 PCT/US88/04501 -29hydroxy groups. The aromatic hydroxy compounds are illustrated by the following specific examples: resorcinol, catechol, p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol, phloroglucinol, hexylresorcinol, orcinol, etc.

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

Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methyl ester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritolt arabitol, sorbitol, mannitol, 1,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugars, starches, celluloses, and so forth likewise can be used. The carbohydrates may be exemplified by glucose, fructose, sucrose, rhamose, mannose, glyceraldehyde, and galactose.

Polyhydric alcohols having at least 3 hydroxyl groups, some, but not all of which have been esterified with an aliphatic monocarboxylic acid having from about 8 to about 30 carbon atoms such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oil acid are useful. Further specific examples of such partially esterified polyhydric alcohols are the monooleate of sorbito', distearate of sorbitol, monoolearomatic-substituted heterocyclic, heterocyclic-substi- I WO 89/05786 PCT/US88/04501 ate of glycerol, monostearate of glycerol, di-dodecanoate of erythritol, and the like.

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

Useful polyhydric alcohols are the polyhydric alkanols containing from about 3 to about 10 carbon atoms and particularly, those containing about 3 to about 6 carbon atoms and having at least three hydroxyl groups. Such alcohols are exemplified by glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl-1,3-propanediol-(trimethylolethane), 2-hydroxymethyl-2-ethyl-l,3-propanediol(trimethylopropane), 1,2,4-hexanetriol, and the like.

Hydroxyamines Useful as Component The hydroxyamines can be primary or secondary amines. They can also be tertiary amines provided said tertiary amines also contain at least two hydroxyl groups. These hydroxyamines contain at least two >NH groups, at least two -NH2 groups, at least one -OH group and at least one >NH or -NH2 group, or at least two -OH groups. The terms "hydroxyamine" and "aminoalcohol" describe the same class of compounds and, therefore, can be used interchangeably.

WO 89/05786 PCT/US88/04501 -31- The hydroxyamines can be primary or secondary alkanol amines or mixtures thereof. Such amines can be represented, respectfully, by the formulae: H2N-R'-OH and

H

N-R'-OH

R

wherein R is a hydrocarbyl group of one to about eight carbon atoms or hydroxyl-substituted hydrocarbyl group of two to about eight carbon atoms and R' is a divalent hydrocarbyl group of about two to about 18 carbon atoms.

The group -R'-OH in such formulae represents the hydroxyl-substituted hydrocarbyl group. R' can be an acyclic, alicyclic or aromatic group. Typically, R' is an acyclic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc.

group. Typically, R is a lower alkyl group of up to seven carbon atoms.

The hydroxyamines can also be ether N-(hydroxy-substituted hydrocarbyl)amines. These are hydroxyl-substituted poly (hydrocarbyloxy) analogs of the above-described primary and secondary alkanol amines (these analogs also include hydroxyl-substituted oxyalkylene analogs). Such N-(hydroxyl-substituted hydrocarbyl) amines can be conveniently prepared by reaction of epoxides with afore-described amines and can be represented by the formulae:

LI

WO 89/05786 PCT/US88/04501 -32- H2N-(R'O) x-H and

H

N-(R'O)x-H

R

wherein x is a number from about 2 to about 15 and R and R' are as described above.

Polyamine analogs of these hydroxy amines, particularly alkoxylated alkylene polyamines N,N-(diethanol)-ethylene diamine) can also be used. Such polyamines can be made by reacting alkylene amines ethylenediamine) with one or more alkylene oxides ethylene oxide, octadecene oxide) of two to about carbons. Similar alkylene oxide-alkanol amine reaction products can also be used such as the products made by reacting the afore-described primary or secondary alkanol amines 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 those skilled in the art.

Specific examples of alkoxylated alkylene polyamines include N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl) piperazine, mono(hydroxypropyl)-substituted diethylene triamine, di(hydroxypropyl)-substituted tetraethylene pentamine, N-(3-hydroxybutyl)-tetrameThylene diamine, etc. Higher homologs obtained by condensation of the above-illustrated hydroxy alkylene polyamines through amino groups or through hydroxy groups are likewise useful. Condensation through amino groups results i WO 89/05786 PCT/US88/04501 -33in a higher amine accompanied by removal of ammonia while condensation through the hydroxy groups results in products containing ether linkages accompanied by removal of water. Mixtures of two or more of any of the aforesaid mono- or polyamines are also useful.

Examples of the N-(hydroxyl-substituted hydrocarbyl) amines include mono-, di-, and triethanol amine, diethylethanol amine, di-(3-hydroxyl propyl) amine, N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine, N,N-di-(2-hydroxyl propyl) amine, N-(2-hydroxyl ethyl) morpholine and its thio analog, N-(2-hydroxyl ethyl) cyclohexyl amine, N-3-hydroxyl cyclopentyl amine, mand p-aminophenol, N-(hydroxyl ethyl) piperazine, N,N'di(hydroxyl ethyl) piperazine, and the like.

Further hydroxyamines are the hydroxy-substituted primary amines described in U.S. Patent 3,576,743 by the general formula Ra-NH2 wherein 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 about Hydroxy-substituted aliphatic primary amines containing a total of up to about 10 carbon atoms are useful. The polyhydroxy-substituted alkanol primary amines wherein there is only one amino group present a primary amino group) having one alkyl substituent containing up to about 10 carbon atoms and up to about 6 hydroxyl groups are useful. These alkanol primary amines correspond to Ra-NH2 wherein Ra is a monoor polyhydroxy-substituted alkyl group. Specific examples of the hydroxy-substituted primary amines include WO 89/05786 WO 8905786PCT/US88/04501 -34- 2-amino-i-butanoll 2-amino-2-methyl-1--propanoi p- kbetahydroxyetyl)-aniline, 2-amino-l-propanol, 3-amino-i-propanol, 2-amino-2-methyl- 3-propanediol, 2-aiino-2-ethyl-l,3-propanediol, N-(beta-hydroxypropyl)-N'-(betaaminoethyl)-piperazine, tris-(hydroxymethyl) amino methane (also known as trismethylolamino methane), 2-amino- 1-butanol, ethanolamine, beta- (beta-hydroxyethoxy) -ethyl amine, glucamine, glusoamine, 4-amino--3-hydroxy-3-methyl-l-buten (which can be prepared according to procedures known in the art by reacting isopreneoxide with ammonia) N-3-(aminopropyl)-4-(2-hydroxyethyl)-piperadiner 2-amino-6-methyl-6-heptanol, N-(beta-hydroxyethyl)-l,3-diamino propane, 1,3-diamino- 2-hydroxypropane, N- (beta-hydroxy ethoxyethyl) -ethylenediamine, trismethylolaminomethane and the like. U.S.

Patent 3,576,743 is incorporated herein by reference.

Eydroxyalkyl alkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atoms, are also useful. Useful hydroxyalkyl-substituted alkylene polyamines include those in which the hydroxyalkyl group is a lower hydroxyalkyl group, having less than eight carbon atoms. Examples of such hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl) ethylene diamine, l-(2-hydroxyethyl) -piperazine, monohydroxypropyl-substituted diethylene triamine, dihydroxy'propylsubstituted tetraethylene pentamine, N-(3-hydroxybutyl) Letramethylene diamine, c. Higher homologs as are obtained by condensation of the above-illustrated hydroxy alkylerie polyamines through amino groups or through hydroxy groups are likewise useful. Condensation through amir'o groups results in a higher amine accompanied by removal of ammonia and condensation WO 89/05786 PCT/US88/04501 througn the hydroxy groups results in products containing ether linkages accompanied by removal of water.

Components (II) and (II): Components (II) and (II) can be the same or different, but preferably are the same. The amines useful as component and in preparing the salt compositions of the invention include ammonia, and the primary amines, secondary amines and hydroxyamines discussed above as being useful as component In addition to ammonia, the primary amines, secondary amines and hydroxyamines discussed above, the emines useful as components (II) and (II) also intcude primary and secondary monoamines, and tertiary mono- and polyamines. The primary and secondary monoamines that are useful as components and are described above under the sub-title Polyamines Useful as Component as being analogues of the polyamines described above. These primary and secondary monoamines include the aliphatic, cycloaliphatic and aromatic monoamines discussed above. The tertiary amines are analogous to the primary amines, secondary amines and hydroxyamines discussed above with the exception that they can be either monoamines or polyamines and the hydrogen atoms in the H-N< or -N.2 groups are replaced by hydrocarbyl groups.

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-sub tituted cycloaliphatic, aromatic-substituted heterocyclic, heter- WO 89/ 05736 7/U Pcr/u"; -36ocyci-c-substituted aiiphatic, heterocyclirc-suostituted cycloaliphatic and heterocyclic-substituted aromatic amines. These tertiary amines may be saturated or unsaturated. If unsaturated, the amine is preferably free from acetylenic unsaturation. The tertiary amines may also contain non-hydrocarbon substituents or groups as long as these groups do not significantly interfere with the reaction of component with component Such non-hydrocarbon substituents or groups include lower alkoxy, lower alkylr mercapto, nitrof and interrupting groups such as and as in such groups as -CH2CH2-X--CH2CH2- where X is or The monoaniines can be represented by the formula RI-N-R2 wherein RW, R2 and R~3 are the same or different hydrocarby. groups. Preferably, R11 R 2 and R 3 are independently hydrocarbyl groups of f ror 1, Ito atbout carbon atoms.

Examples of useful tertiary amines include trimethyl amine, triethyl amine, tripropyl amine, tributyl aminet monomethyldiethylamine, monoethyldimethyl amine, dimethylpropyl amine, dimethylbutyl amine, dimethylpentyl amine, dimethylhexyl, amine, dimethylheptyl aminef dimethylocty. amine, dimethylnonyl amno, dimethyldecyl amine, dixmethylphenyl am~ine, NN-dioctyl-1-octanamine, NN-didodecyl-l-dodecanamine tricoco amino, trihydtogenated-tallow amine, 1-mothyl-dihydrogenated tallow amine, NdI-dimethyl-l-dodecangminer NsN-dimothyl- 1-tetradecanaminee NN-cl~mthyl-l-hexadecarlamineI WN- WO 89/05786 PTU8/40 PCT/US88/04501 -37dimethvl-l-octladecanamine, N,N-dimethylcocoamine, NNdirnethylsoyaamine, N,N-dimethylhydrogenated tallow amine, etc.

Useful tertiary alkanol amnines are represented by the formula

N-RI-'

wherein each Rl is independently a hydrocarbyl group of one to about eight carbon atoms or hydroxyl-substituted hydrocarby2, group of two to about eight carbon atoms and R' is a divalent hydrocarbyl group of about two to about 18 carbon atoms. The group -RI-OI4 in such formula represents the hydroxyl-substituted hydrocarby. group. RI can be an acyclicp alicyclic or aromatic group. Typical,lyj RI is an acycl~ic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc, group. Where two R groups are present in the same molecule they can be joined by a direct carbon-to-carbon bond or through a heteroatom oxygen, nitrogen or sulfur) to form a 7- or 8-inembered ring structure. Exampl~es of such heterocyclic amines include N-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidiries, -oxatolidines, -thiazolidines and the lik~e. Typically, however, each R~ is a lower alkyl group Of up to seven 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 hydroxy amines (these analogs also include hydroxyl-substituted oxyalkyleno analogs) Such 14-(hydroxyl-substituted WO 89/(S786 PCr/JS88/04501 -38hydrocarbyl) amines can b e conveniently prepared by reaction of epoxides with afore-described amines and can be represented by the formpula: N- (R 1O) x-H wherein x is a number f rom about 2 to about 15 and R and RI are as described above.

Useful polyamines include the alkylene pol~yamines discussed above as well as alkylene polyamines with only one or no hydrogens attached to the nitrogen atomso Thus, the alkylene polyamines useful as components (11) and (11) include those conforming to the formula; IR-N--AJlkyl ene-Ntfl wherei~n n is f rom 1 to about 10, preferably from 1 to about 7 each R iA' independently a hydrogen atom, a hydrocarbyl group or a hydroxy-substituted hydrocArbyl, group having up to about 700 carbon atoms, preferably up to about 100 carbon atoms, more preferabl.y up to about carbon atoms, more preferably up to about 30 carbon at)ms; and the "Alkylene", group has from about I to about 18 carbon atoms, preferably from 1 to about 4 carbon atoms, with the preferred Alkyleno being ethylene or propylene.

The, alkali and Alkaline earth metals that are useful as COrnponentS (IIt) and aan be any alkali or alkaline earth metal. Tlkhe alkali metals are ;i~ WO 89/05786 PCT/US88/04501 preferred. Sodium and potassium are p&tticularly preferred. The alkali and alkaline earth metal compounds that are useful include, for example, the oxides, hydroxides and carbonates. Sodium hydroxide and potassium hydroxide are particularly preferred.

Formation of the Salt Compositions: The salt compositions of the invention can be prepared by initially reacting the acylating agents and with component to form an intermediate, and thereafter reacting said intermediate with components (II) and (II) to form the desired salt.

An alternative method of preparing these salt colipositions involves reacting components and (II) with each other to form a first salt moiety, separately reacting components and (II) with each otherto form a second salt moiety, then reacting a mixture of these two salt moieties with component The ratio of reactants utilized in the preparation of the inventive salt compositions may be varied over a wide range. Generally, for each equivalent of each of the acylating agents and at least about one equivalent of component is used. From about 0.1 to about 2 equivalents or mtore of components (I1) and are used for each equivalent of components and respectively. The upper limit of component is about 2 equivalents of component for each equivalent of component and about two equivalents of component for each equivalent of component Generally the ratio of equivalents of components to is about 0.5 to about 2, with about 1:1 being preferred. Preferred amounts of the reactants are about 2 equivalents of the component and from about 0.1 to about 2 equivalents r ii*l.

WO 89/05786 P('1/US88/04501 of eacii of components (II) and (II) for each equivalent of each of components and The number of equivalents of the acylating agents A) ,nd depends on the total number of carboxylic functions present in each. In determining the number of equivalents for each of the acylating agents and those carboxyl functions which are not capable of reacting as a carboxylic acid acylating agent are excluded. In general, however, there is one equivalent of acylating agent and for each carboxy group in these acylating agents. For exampie, there would be two equivalents in an anhydride derived from the reaction of one mole of olefin polymer and one mole of maleic anhydride. Conventional techniques are readily available for determining the number of carboxyl functions acid number, saponification number) and, thus, the number of equivalents of each of the acvlating agents and can be readily determined by one skilled in the art.

An equivalent weight of a polyamine is the molecular weight of the polyamine divided by the total number of nitrogens present in the molecule. If the poly- ,mine is to be used as component tertir:y amino groups are not counted. On the other handr if the polyamine is to be used as component (II) or 01), teti ry amino groups are counted. Thus, ethylene d~.amine has an equivalent weight equal to one-half of its molecular weight; diethylene triamine has an equivalent weight equal to one-third its molecular weight. The equivalenit weight of a commercially available mixture of polyalkylene polyamine can be determined by dividing the atortc weight of nitrogen (14) by the %1 contained in the polyamine; thus, a polyamine tixture having a %N of WO 89/05786 PCT/US88/14501 -41- 34 would have an equivalent weight of 41.2. An equivalent weight of ammonia or a monoamine is its molecular weight.

An equivalent weight of polyhydric alcohol is its molecular weight divided by the total number of hydroxyl groups present in the molecule. Thus, an equivalent weight of ethylene glycol is one-half its molecular weight.

An equivalent weight of a hydroxyamine which is to be used as component is its molecular weight divided by the total number of -OH, >NH and -NH2 groups present in the molecule. Thus, dimethylethanolamine when used as component has an equivalent weight equal to its molecular weight; ethanolamine ha.

an equivalent weight equal to one-half its molecular weight, On the other hand, if the hydroxyamine is to be used as components (II) or an equivalent weight thereof would be its molecular weight divided by the total number of nitrogen groups present in the molecule. Thus, dimethylethanolamine, when used as component (II) or would have an equivalent weight equal to its molecular weight; ethanolamine would also have an equivalent weight equal to its molecular weight.

An equivalent weight of an alkali or alkaline carth metal is its molecular weight. An equivalent weight of an alkali or alkaline earth metal compound is its molecular weight divided by the number of alkali or alkaline earth metal atoms present in the molecule.

The acylating agents and can be reacted with component according to conventional ester- and/or amide-forming techniques. This normally involves heating acylatirtg agents and with component optionally in tne presence of a normally WO 89/05786 PCT/US88/04501 -42liquid, substantially inert, organic liquid solvent/diluent. Temperatures of at least about 30°C up to the decomposition temperature of the reaction component and/or product having the lowest such temperature can be used. This temperature is preferably in the range of about 50°C to about 130°C, more preferably about 80°C to about 100°C when the acylating agents and are anhydrides. On the other hand, when the acylating agents and are acids, this temperature is preferably in the range of about 100°C to about 300°C with temperatures in the range of abo&,t 125°C to about 250°C often being employed.

The react ons between components and and (II) and (II) are carried out under salt forming conditions using conventional techniques.

Typically, components and and and are mixed together and heated to a temperature in the range of about 20°C up to the decomposition temperature of the reaction component and/or product having the lowest such temperature, preferably about 50°C to about 130°C, more preferably about 80°C to about 110°C; optionally, in the presence of a normally liquid, substantially inert organic liquid solvent/diluent, until the desired product has formed.

The product of the reaction between components and and (II) and (II) respectively, must contain at least some salt linkage to permit said product to be effective as an emulsifier in accordance with the invention. Preferably at least about more preferably at least about 30%, more preferably at least about 50%, more preferably at lr about 70%, and advantageously up to about 100% of components (A)(It) and that react with the acylating agents and respectively, form a salt linkage.

i; 1 WO 89105786 PCT/US88/04501 -43- The following examples illustrate the preparation of the salt compositions of this invention. Unless otherwise indicated, in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, and all temperatures are in degrees centigrade.

Example 1 1120 parts of polyisobutylene (number average molecular weight 950) substituted succinic anhydride and 325 parts of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C16 alpha-olefin and one mole of maleic anhydride are heated to a temperature of 93 0 C with stirring and maintained at that temperature for one hour. 62 parts of ethylene glycol are added to the mixture. The mixture is maintained at a temperature of 93-105 0 C for 2 hours.

178 parts of dimethylethanolamine are added to the mixture over a period of 0.5 hour. The mixture is maintained at 93-104 0 C for 2.5 hours then cooled to 70 0 C to provide the desired product.

Example 2 1370 parts of polyisobutylene (number average molecular weight 1200), substituted succinic anhydride, 260 parts of a low molecular weight hydrocarbylsubstituted succinic anhydride derived from one mole of a C12 alpha-olefin and one mole of maleic anhydride, and 104 parts of neopentyl glycol are reacted under ester-forming conditions to form an intermediate product. 234 parts of diethylethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 3 1120 parts o, the polyisobutylene substituted succinic anhydride identified in Example 1, 260 parts of cohol" describe the same class of compounds and, therefore, can be used interchangeably.

WO 89/05786 PCT/US88/04501 -44a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C12 alpha.-olefin and one mole of maleic anhydride, and 104 parts of neopentyl glycol are reacted under ester-forming conditions to form an intermediate product. 234 parts of diethylethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 4 1370 parts of the polyisobutylene substituted succinic anhydride identified in Example 2, 325 parts of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C16 alpha-olefin and one mole of maleic anhydride, and 104 parts of neopentyl glycol are reacted under ester-forming conditions to form an intermediate product. 234 parts of diethylethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 1120 parts of the polyisobutylene substituted Puccinic anhydride identified in Example 1, 325 parts of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C16 alpha-olefin and one mole of maleic anhydride, and 75 parts of N-methylethanolamine are reacted under ester-amide-forming conditions to form an intermediate product. 298 parts of triethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composit'on.

Example 6 1120 parts of the polyisobutylene-substituted succinic anhydride identified in Example 1, 325 parts of WO 89/05786 PCT/US88/04501 a low-molecular weight hydrocarbyl-substituted succinic anhydride derived from a C16 .alpha-olefin and maleic anhydride, and 75 parts of N-methylethanolamine are reacted under ester-amide forming conditions to form an intermediate product. 179 parts of triethylamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 7 1120 parts of the polyisobutylene-substituted succinic anhydride identified in Example 1, 325 parts of a low-molecular weight hydrocarbyl-substituted succinic anhydride derived from a C16 alpha-olefin and maleic anhydride, and 106 parts of diethylene glycol are reacted under ester-forming conditions to form an intermediate product. 234 parts of diethylethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 8 1120 parts of the polyisobutylene-substituted succinic anhydride identified in Example 1, 325 parts of a low-molecular weight hydrocarbyl-substituted succinic anhydride derived from a Cl6 alpha-oJ'fin and maleic anhydride, and 75 parts of propylene glycol are reacted under ester-forming conditions to form an intermediate product. 210 parts of diethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 9 1370 parts of the polyisobutylene-substituted succinic anhydride identified in Example 2, 325 parts of a low-molecular weight hydrocarbyl-substituted succinic anhydride derived from a C16 alpha-olefin and maleic anhydride, and 118 parts of hexylene glycol are reacted WO 89/05786 PCr/US88/04501 -46under ester-forming conditions to form an intermediate product. 179 parts of triethylamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 1120 parts of the polyisobutylene-substituted succinic anhydride identified in Example 1, 260 parts of a low-molecular weight hydrocarbyl-substituted succinic anhydride derived from a C12 alpha-olefin and maleic anhydride, and 104 parts of pentanediol are reacted under ester-forming conditions to form an intermediate product. 298 parts of triethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 11 Two equivalents of the polyisobutylene-substituted succinic anhydride identified in Example 1, two equivalents of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a, C16-18 alpha-olefin fraction and one mole of maleic anhydride, and two equivalents of ethylene diamine are reacted under amide-forming conditions to form an intermediate product. Two equivalents of NaOH are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 12 Two equivalents of the polyisobutylene-substituted succinic anhydride identified in Example 1, two equivalents of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C12 alpha-olefin and one mole of maleic anhydride, and two equivalents of N-methylethanolaminr are reacted under ester-amide-forming conditions to form an intermed- WO 89/05786 PCT/US88/04501 -47iate product. Two equivalents of calcium hydroxide are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 13 Two equivalents of the polyisobutylene-substituted succinic anhydride identified in Example 1, two equivalents of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C8 alpha-olefin and one mole .f maleic anhydride, and two equivalents of ethylene diamine are reacted under amideforming conditions to form an intermediate product. Two equivalents of ammonia are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 14 Two equivalents of the polyisobutylene-substituted succinic anhydride identified in Example Il two equivalents of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C12-16 alpha-olefin fraction and one mole of maleic anhydride, and two equivalents of ethylene glycol are reacted under ester-forming conditions to form an intermediate product. Two equivalents of potassium carbonate are reacted with the intermediate product under saltforming conditions to form a desired salt composition.

Example Two equivalents of a C20 hydrocarbyl-substituted succinic anhydride, two equivalents of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C18 alpha-olefin and one mole of maleic anhydride, and two equivalents of ethylene diamine are reacted under amide-forming conditions to form an intermediate product. Two equivalents of WO 89/05786 PCT/US88/04501 -48dimethylethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 16 Two equivalents of a C500-hydrocarbyi-substituted succinic anhydride, two equivalents of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C8 alpha-olefin and one mole of maleic anhydride, and two equivalents of ethylene glycol are reacted under ester-forming conditions to form an intermediate product. Two equivalents of ammonia are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 17 Two equivalents of the polyisobutylene-substituted succinic anhydride identified in Example 1, two equivalents of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C16 alpha-olefin and one mole of maleic anhydride, and two equivalents of ethylene glycol are reacted under ester-forming conditions to form an intermediate product. Two equialents of sodium hydroxide are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 18 Two equivalents of the polyisobutylene-substituted succinic anhydride identified in Example 1, two equivalents of a low molecular weight hydrocarbyl-substituted succinic anhydride derived from one mole of a C16-18 alpha-olefin fraction and one mole of maleic anhydride, and two equivalents of ethylern diamine are reacted under amide-forming conditions to form an inter- WO 89/05786 PCT/US88/04501 -49mediate product. Two equivalents of morpholine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Example 19 Two equivalents of the polyisobutylene-substituted succinic anhydride identified in Example 1, two equivalents of maleic anhydride, and two equivalents of ethylene glycol are reacted under ester.-forming conditions to form an intermediate product. Two equivalents of dimethylethanolamine are reacted with the intermediate product under salt-forming conditions to form a desired salt composition.

Explosive Compositions: The explosive compositions of the invention are water-in-oil emulsions which, in one embodiment, are cap-sensitive water-in-oil explosive emulsions. These explosive emulsions employ the salt compositions of the invention as emulsifiers. The inventive explosive emulsions comprise a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifying amount of at least one of the salt compositions of the invention.

The continuous organic phase is preferably present at a level of at least about 2% by weight, more preferably in the range of from about 2% to about 15% by weight, more preferably in the range of from about to about 8% by weight based on the total weight of explosive emulsion. The discontinuous oxidizer phase is preferably present at a level of at least about 85% by weight, more preferably at a level in the range of from about 85% to about 98% by weignt, more preferably from about 92% to about 96.5% by t-.ignt based on the total i

II

PCT/US88/04501 WO 89/05786 weight of said explosive emulsion. Tihe salt compositions of the invention are preferably present at a level in the range of from about 4% to about 40% by weight, more preferably from about 12% to about 20% by weight based on the total weight of the organic phase. The oxygen-supplying component is preferably present at a level in the range of from about 70% to about 95% by weight, more preferably from about 85% to about 92% by weight, more preferably from about 87% to about 90% by weight based on the total weight of the oxidizer phase.

The water is preferably present at a level in the range of about 5% to about 30% by weight, more preferably about 8% to about 15% by weight, more preferably about to about 13% by weight based on the weight of the oxidizer phase.

The carbonaceous fuel that is useful in the explosive emulsions of the invention can include most hydrocarbons, for examiple, paraffinic, olefinic, naphthenic, aromatic, saturated or unsaturated hydrocarbons, and is typically in the form of an oil or a wax or a mixture thereof. In general, the carbonaceous fuel is a water-immiscible, emulsifiable hydrocarbon that is either liquid or liquefiable at a temperature of up to about 95OC, and preferably between about 40 0 C and about 0 C. Oils from a variety of sources, including natural and synthetic oils and mixtures thereof can be used as the carbonaceous fuel.

Natural oils include animal oils and vegetable oils castor oil, lard oil) as well as solventrefined or acid-refined mineral oils of the paraffinic, naphthenic, or mixed pa affin-naphthenic types. Oils derived from coal or shale are also useful. Synthetic oils include hydrocarbon oils and halo-substituted WO 89/05786 WO 8905786PCr/US88/04501 -51hydrocarbon oils such as polymerized and interpolymerized olefins polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.) alkyl benzenes dodecylbenzenes, tetradecylbenzenesf dinonylbenzenes, di-(2-ethyihexyl) benzenes, etc.); polyphenyls biphenyls, terphenyls, alkylated polyphenyls, etc.); and the like.

Another suitable class of synthetic oils that can be used comprises the esters of dicarboxylic acids phthalic acid, succinic acid, alKyl succinic acid,0 maleic acid, azelaic acid, suberic acid, sebacic acid, furnaric acid, adipic acid, linoleic acid diuier, ma1lonic, acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols butyl al1cohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, pentaerythritoll etc.) Specific examples of these esters include dibutyl adipate, di(2ethyihexyl) -sebacate, di-n--hexyl fumarate, dioctyl sebacate, diisooctyl azelate, disodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyi. sebacatef the 2-ethylhexyl, diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexano~c acid, and the like.

Esters useful ets synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, trlpentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyairyloXy-ailoxane oils and silicate oils comprise another class oL' useful oils.

These include tetraethyl-silicatef tetraisopropylsili- WO 89/05786 PCr/US88/04501 -52cate, tetra- (2-ethyihexyl) -silicate, tetra- (4-methylhexyl) -silicate, tetr (p-tert-butylphenyl) -silicate, hexyl- (4-methyl-2-pentoxy) -di-siloxale, poly(methyl)siloxanes, poly- (methylpheny.)-siloxanes, etc. Other useful synthetic oils include liquid esters of phosphorus-containing acid tricresyl phosphate, trioctyl phosphate, diethyl. ester of decane phosphonic acidf polymeric tetrahydrof uransr and the like.- Unref ined refined and rerefined 1s (and mixtures of each with each other) of the type disclosed hereinabove can be used. Unrefined oils are those obtained directly from a natural or synthetic soutce without further purification treatmenit. For example, a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. PRefinod oils are similar to the unrefined oila except that they have been further treated in one or more purification &teps to improve onte or more Ptoperties. Many Ouch purification techniques are known t4, those of skill in the art such (as solvent extraction, acid or base Pxtraction, filtration, perco- 1aiont etc. Reretined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which nave been already used in service, Such rerefined oils are also known as reclaimied or reprocessed oils and often are additionally processed by technicjuez directed toward removal of spent additives and oil breakdown prod,'ets, Examnp.les. of useful oils include a white mineral oil available from Witco Chemical Company under the trade deisignation 1XAYDObJ a white mineral oil availab:le

I

WO 89/05786 PCT/US88/04501 -53from Shell under the trade designation ONDINA; and a mineral oil available from Pennzoil under the trade designation N-750-HT.

The carbonaceous fuel can b~ any wax having melting point of at least about 25C, such as petrolatum wax, microcrystalline wax, and paraffin wax, mineral waxes such as ozocerite and montan wax, animal waxes such as spermacetic wax, and insect waxes such as beeswax and Chinese wax. Useful waxes include waxes identified by the trade designation MOBILWAX 57 which is available from Mobil Oil Corporation; D02764 which is a blended wax available from Astor Chemical Ltd.; and VYBAR which is available from Petrolite Corporation.

Preferred waxes are blends of microcrystalline waxes and paraffin.

In one embodiment, the carbonaceous fuel includes a combination of a wax and an oil. In this embodiment, the wax content is 4t least about 25% and preferably ranges from about 25% to about 90% by weight of the organic phase, and the oil content is at least about 10% and preferably ranges from about 10% to about by weight of the organic phase. These mixtures are particularly suitable for use in cap-sensitive explosive emulsions.

While its presence is not necessary, the explosive emulsions can also contain up to about 15% by weight of an auxiliary fuel, such as aluminum, aluminum alloys, magnesium, and the like. Particulate aluminum is a preferred auxiliary fuel.

The oxygen-supplying component is preferably at least one inorganic oxidizer salt such as ammonium, alkali or alkaline earth metal 4trate, chlorate or perchlorate. Examples inlcude ammonJow nitrate, sodium WO 89/05786 PCT/US88/04501 -54nitrate,, calcium nitrate, ammonium chlorate, sodium perchlcrate and ammonium perchlorate. Ammonium nitrate is especially preferred. Mixtures of ammonium nitrate and sodium or calcium nitrate are also preferred. In one embodiment, inorganic oxidizer salt comprises principally ammonium nitrate, although up to about 25% by weight of the oxidizer phase can comprise either another inorganic nitrate alkali or alkaline earth metal nitrate) or an inorganic perchlorate ammonium perchlorate or an alkali or alkaline earth metal perchlorate) or a mixture thereof.

In one embodiment of The invention, closedcell, void-containing materials are used as sensitizing components. The term "closed-cell, void-containing material" is used herein to mean any particulate material which comprises closed cell, hollow cavities. Each particle of the material can contain one or more closed cells, and the cells can contain a gas, such as air, or can be evacuated or partially evacuated. In one embodiment of the invention, sufficient closed cell void containing material is used to yield a density in the resulting emulsion of from about 0.8 to about 1.35 g/cc, more preferably about 0.9 to about 1.3 g/cc, more preferably about 1.1 to about 1.3 g/cc. In general, the emulsions of the subject invention can contain up to about by weight, preferably from about 0.25% to about by weight of the closed cell void contatning material.

Preferred closed cell void containing materials are discrete glass spheres having a particle size within the range of about 10 to about 175 microns. In general, the bulk density of such particles can be within the range of about 0.1 to about 0.4 g/cc. Useful glass microbubbles which can be used are the microbubbles sold by 3M

A

WO 89/0578 PCT/US88/ 0r WO 89/05786 PCT/US88/04501 Company and which have a particle size distribution in the range of from about 10 to about 160 microns and a nominal size in the range of about 60 to 70 microns, and densities in the range of from about 0.1 to about 0.4 g/cc.; these include microbubbles distributed under the trade designation Bl /250. Other useful glass microbubbles are sold under the trade designation of ECCOSPHERES by Emerson Cumming, Inc., and generally have a particle size range from about 44 to about 175 microns and a bulk density of about 0.15 to about 0.4 g/cc. Other suitable microbubbles include the inorganic microspheres sold under the trade designation of Q-CEL by Philadelphia Quartz Company. The closed cell void containing material can be made of inert or reducing materials.

For example, phenol-formaldehyde microbubbles can be utilied within the scope of this invention. If the phenol-furmaldehyde microbubbles are utilized, the microbubbles themselves are a fuel component for the explosive and their fuel value should be taken into consideration when designing a water-in-oil emulsion explosive composition. Another closed cell void containing material which Nan be used thin the scope of the subject invention is the saran m ospheres sold by Dow C'hemical Company. The saran mici.o pheres have a diameter of about 30 microns and a particle density of about 0.032 g/cc. Because of the low bulk density of the saran microspheres, it is preferred that only from about 0.25 to about 1% by weight thereof be used in the waterin-oil emulsions of the subject invention.

Gas bubbles which are generated in-situ by adding to the composition and distributing therein a gasgenerating material such as, for example, an aqueous solution of sodium nitrite, can also be used can be used advantageously up to about 100% of components (II) and that react with the acylating agents (I) and respectively, form a salt linkage.

WO 89/05786 PCT/US88/04501 -56to sensitize the explosive emulsions. Other suitable sensitizing components which may be employed alone or in addition to the foregoing include insoluble particulate solid self-explosives such as, for example, grained or flaked TNT, DNT, RDX and the like and water-soluble and/or hydrocarbon-soluble organic sensitizers such as, for example, amine nitrates, alkanolamine nitrates, hydroxyalkyl nitrates, and the like. The explosive emulsions of the present invention may be formulated for a wide range of applications. Any combination of sensitizing components may be selected in order to provide an explosive composition of virtually any desired density, weight-strength or critical diameter. The quantity of solid self-explosive ingredients and of water-soluble and/or hydrocarbon-soluble organic sensitizers may comprise up to about 40% by weight of the total explosive composition. The volume of the occluded gas component may comprise up to about 50% of the volume of the total explosive composition.

Optional additional materials may be incorporated in the explosive emulsions of the invention in order to further improve sensitivity, density, strength, rheology and cost of the final explosive. Typical of materials found useful as optional additives include, for example, particulate non-metal fuels such as sulfur, gilsonite and the like, particulate inert materials such as sodium chloride, barium sulphate and the like, water phase or hydrocarbon phase thickeners such as guar gum, polyacrylamide, carboxymethyl or ethyl cellulose, biopolymers, starches, elastomeric materials, and the like, crosslinkers for the thickeners such as potassium pyroantimonate and the like, buffers or pH controllers such as sodium borate, zinc nitrate and the like, crystals WO 89/05786 PCT/US88/04501 -57habit modifiers such as alkyl naphthalene sodium sulpnonate and the like, liquid phase extenders such as formamide, ethylene glycol and the like and bulking agents and additives of common use in the explosives art. The quantities of optional additional materials used may comprise up to about 50% by weight of the total explosive emulsion.

The general criteria for cap-sensitivity is that the explosive be sensitive to a No. 8 blasting cap at a cartridge diameter of 1.25 inch under normal temperature conditions. The cap-sensitive explosive emulsions of the present invention are shelf stable, which means they exhibit shelf stability of at least six months and typically one year or more.

A preferred method for making the explosive emulsions of the invention comprises the steps of (1) mixing water, inorganic oxidizer salts ammonium nitrate) and, in certain cases, some of the supplemental water-soluble compounds, in a first premix, mixing the carbonaceous fuel, the emulsifying salt compositions of the invention and any other optional oil-soluble compounds, in a second premix and adding :he first premix to the second premix in a suitable mixing apparatus, to form a water-in-oil emulsion. The first premix is heated until all the salts are completely dissolved and the solution may be filtered if needed in order to remove any insoluble residue. The second premix is also heated to liquefy the ingredients, Any type of apparatus capable of either low or high shear mixing can be used to prTpare these water-in-oil emulsions. Closedcell void containing materials, gas-generating materials, solid self-explosive ingredients such as particulate TNT, solid fuels such as aluminum or sulfur, WO 89/05786 PCT/US88/04501 -58inert materials such as barytes or sodium chloride, undissolved solid oxidizer salts and other optional materials, if employed, are added to the emulsion and simply blended until homogeneously dispersed throughout the composition.

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

The salt compositions of this invention can be added directly to the inventive explosive emulsions.

They can also be diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concentrates usually contain from about 10% to about 90% by weight of the salt composition of this invention and may contain, in addition, one or more other additives known in the art or described hereinabove.

An advantage of the present invention is that by using the salt compositions of the present invention as emulsifiers, explosive emulsions can be provided in gelatinous or semi-gelatinous forms that are dry to the touch and cuttable. These are important characteristics when using these explosive emulsions in the preparation WO 89/05786 PCT/US83/04501 -59of cap-sensitive explosive emulsions, particularly when such cap-sensitive explosive emulsions are used in the manufacture of explosive cartridges, especially small diameter diameters of about 1.25 inches or smaller) cartridges.

Explosive cartridges within the scope of this invention can be made using techniques well known in the art. The cap-sensitive explosive emulsions of the invention are particularly suitable for making cartridges on cartridging machines such as the type available from Niepmann under the trade designation ROLLEX.

The following Examples A-G are illustrative of cap-sensitive water-in-oil explosive emulsions within the scope of the invention. Examples A-E, which are identified in Table I below, are prepared as follows.

The organic phase is prepared using the wax and oil indicated in Table I and the product of Example 1. The oxidizer phase contains 78.5% NH4NO3, 10.7% NaNO3, and 10.8% H20. The weight ratio of the oxidizer phase to the organic phase is 95/5. The organic phase is melted at 90°C. The oxidizer phase is heated to 1040C.

The oxidizer phase is added to the organic phase with stirring using a Sunbeam Mixmaster mixer at 50-100% on the variac for one minute, The emulsions are mixed or "worked" an additional six minutes in the Sunbeam Mixmaster mixer at 100% on the variac. The viscosity of each emulsion and initial emulsion temperatures are indicated in Table I. A sample of each emulsion is stored at 49 0 C for 4 days and then at 700C for 2 days.

After that time the emulsions are removed and stored at room temperature. The stability of each emulsion is observed overtime and reported in Table I. The penetration of the samples is measured using a 159 gram cone and apparatus.

WO 89/05786 PC/US88/04501 TABLE I A C D E Product of Ex. 1, of organic phase) Mineral oil, of organic phase) 50:50 blend of microcrystalline wax and paraffin wax, of organic phase) Initial Viscosity (cPs x 10 3

/OF)

Avg. Penetration at Room Temp. (mm) Storage Stability Room Temp.

(Appearance/Days) Storage Stability 120°F (Appearance/Days) Storage Stability 158 0

F

(Appearance/Days) 20 20 20 20 32 40 20 60 48 40 65 115/ 170 125/ 162 120/ 166 95/ 170 160/ 166 8.8 8.95 10.7 11.5 8.4 OK/37 OK/37 OK/42 OK/33 OK/33 OK/37 OK/37 OK/42 OK/33 OK/33 OK/37 OK/37 OK/42 OK/33 OK/33 SI WO 8905786 PCT/US88/04501 wo 89/05786 -61- Each of the emulsions identified in Table I are dry to the touch and cuttable.

Examples F and G which are identified in Table II below are prepared as follows, The oxidizer phase contains 78.5% NH4N03, 10.7% NaNO3, and 10.8% The organic phase is prepared using the wax and oil indicated in Table II and the product of Example 1.

The organic phase is melted at 90°C. The oxidizer is heated to 104 0 C. The oxidizer is added to the organic phase with stirring usiing a Sunbeam Mixmaster mixer at 50-100% on the variac for one minute. The ratio of oxidizer to organic phase, viscosity, and the amount of additional mixing or working in the Sunbeam Mixmaster mixer at 100% on the variac are indicated in Table II.

Glass microbubbles (68-82 microns) are added to the hot emulsion at a level of 42.5 grams of beads per 100 grams of emulsion.

TABLE II F G Product of Ex. 1, of organic phase) 20.4 20.0 Mineral oil, of organic phase) 20.4 20.0 50:50 blend of microcrystalline wax and paraffin wax, of organic phase) 59.2 60.0 Oxidizer/Organic phase ratio 95.2/4.9 95.0/5.0 Work, (min.) 6.0 Initial Viscosity, (cPs/ F) 142,000/ 77,000/ 166 180 WO 89/05786 PCT/US88/04501 -62- Examples F and G are dry to the touch, cuttable, and stable at room temperature and after one hour at 900C.

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

Claims (45)

1. A composition comprising: at least one salt moiety derived from 1) at least one high-molecular weight polycarboxylic acylating agent, said acylating agent having at least one hydrocarbyl substituent having an average of from -abeu-t- 20 to -abou-t- 500 carbon atoms, and (II) ammonia, at least one amine, at least one alkali or alkaline eatth metal, and/or at least one alkali or alkaline earth metal compound; at least one salt moiety derived from at least one low-molecular weight polycarboxylic acylating agent, said acylating agent optionally having at least one hydrocarbyl substituent having an average of up to -abWet 18 carbon atoms, and (II) ammonia, at least one amine, at least one alkali o.' alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; said components and being coupled together by at least one compound having two or more primary amino groups, (ii) two or more secondary amino groups, (iii) at least one primary amino group and at least one secondary amino group, (iv) at least two hydroxyl groups or at least one primary or secondary amino group and at least one hydroxyl group.

2. The composition of claim 1 wherein is derived from at least one alpha-beta olefinically unsaturated carboxylic acid or acid-producing compound, said acid or acid-producing compound containing up to .abut- 20 carbon atoms exclusive of the carboxyl-based groups.

3. The composition of claim I wherein is represented by the formulae L I WO 89/05786 PCT/JUS88/04501 -64- R- CH-COOH R--CH-C CH2-COOH or 0 CH2--C wherein R is said hydrocarbyl substituent of (1)

4. The composition of claim 1 wherein said hydrocarbyl substituent of has an average of frow .at-bu 30 to abu 500 carbon atoms. The composition of claim 1 wherein said hydrocarbyl substituent of has an average of from 40 to 500 carbon atoms.

6. The composition of claim 1 wherein said hydrocarbyl substituent of has an average of from -aet 50 to ab-u4- 500 carbon atoms.

7. The composition of claim 1 wherein said hydrocarbyl substituent of is an alkyl or an Alkenyl group.

8. The composition o- claim 1 wherein said hydrocarby substituent of is a poly(isobutylene) group.

9. The composition of claim 1 wherein compon- ent comprises at least one monoamine. The composition of claim I wherein compon- ent (II) comprises at least one polyamine.

11. The composition of claim 1 wherein compon- ent (11) comprises at least one primary, secondary and/or tertiary amine.

12. The composition of claim 1 wherein compon- ent comprises at least one aliphatiat cycloali- phatic and/or aromatic amine 17 WO 89/05786 PCT/US8810450 I .13. The composition of claim i wherein compon- Lnt (II) comprises at least one alkylene polyamine of the formula R- N-(-Alkylene-N 1-nR RR wherein n is a number of from 1 to-abe-b-l0, each R is independently a hydrogen atom or a hydrocarbyl group or a hydroxy-substituted hycirocarbyl group having up to 700 carbon atoms, and the Alkylene group has from 1 to-abut 1 carbon atoms. 14, The composition of claim 1 wherein compon- eaf, (II) comprises at least one N-(hydroxyl-sub- s t itiC- Qe hydroca--byl) amine, at least one hydroxyl- substituted poly(bydroca~blov alo of or a mixture of and The composition of claim 1 wherein compon- ent (11) comprises at least one alkanol amine contain- ing up to ab.&.4i 40 carbon atoms.

16. The composition of claim 1 wherein compon- ent (I1) is selected from tke group consisting of (a) primary, secondary and tertiary alkanol amines which can be represented correspondingly by the formulae P, II L: IM u PCT/US88/04501 WO 89/05786 -66- R SN-R'-OH R" hydroxyl-substituted oxyalkylene analogs of said alkanol amines represented by the formulae H N-(R'0)2-15-H H H H 2-15-H R 2-15-H SR wherein each R is independently a hydrocarbyl group of i one to about- 8 carbon atoms or a hydroxyl-substituted hydrocarbyl group of 2 to abeut 8 carbon atoms and R' is a divalent hydrocarbyl group of 2 to abeut 18 carbon atoms, and mixtures of two of more of any of the above.

17. The composition of claim 1 wherein compon- ent (II) comprises dimethylethanolamine.

18. The composition of claim 1 wherein compon- ent comprises ammonia.

19. The composition of claim 1 wherein compon- ent comprises at least one alkali metal. The composition of claim 1 wherein compon- ent comprises sodium or potassium. 4 *a j vl I I WO 89/05786 PCT/US88/04501 -67-

21. The composition of claim 1 wherein compon- ent comprises at least one alkaline earth metal.

22. The composition of claim 1 wherein compon- ent comprises at least one alkali metal oxide, hydroxide or carbonate.

23. The composition of claim 1 wherein compon- ent comprises at least one alkaline earth metal oxide, hydroxide or carbonate.

24. The composition of claim 1 wherein compon- ent is at least one compound selected from the group consisting of maleic acid, maleic anhydride, chlor- omaleic anhydride, malonic acid, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, azelaic acid, sebacic acid, glu<._con- ic acid, citraconic acid, itaconic acid, allyl succinic acid, cetyl malonic acid and tetrapropylene-substituted succinic anhydride. The composition of claim 1 wherein is represented by the formulae 0 R CH--COOH R-CH C CH 2-COOH or CH2 -C wherein R is said hydrocarbyl substituent of (I)

26. The composition of claim 1 wherein said hydrocarbyl substituent of is derived from at least one compound selected from the group consisting of ethylene, propylene, 1-butene, isobutene, 1-pentene, 2-methyl-l-butene, 3-methyl-l-butene, 1-hexene, 1-heptene, 1-octene, styrene, 1-nonene, 1-decene, WO 89/05786 PCT/US88/04501 wo 89/05786 -68- 1-undecene, 1-dodecene, l-tridecene, l-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene and 1-octadec- ene.

27. The composition of claim 1 wherein said hydrocarbyl substituent of is derived from at least one member within alpha-olefin fraction selected from the group consisting of C15-18 alpha-olefins, C12-16 alpha-olefins, C14-16 alpha-olefins, C14-18 alpha-olefins and C16-18 alpha-olefins.

28. The composition of claim 1 wherein said hydrocarbyl substituent of has an average of from about 8 to about 18 carbon atoms.

29. The composition of claim 1 wherein said hydrocarbyl substituent of has an average of from -abet 12 to ab t- 18 carbon atoms. The composition of claim 1 wherein said hydrocarbyl substituent of is an alkyl or an alkenyl group.

31. The composition of claim 1 wherein compon- ent comprises at least one monoamine.

32. The composition of claim 1 wherein compon- ent comprises at least one polyamine.

33. The composition of claim 1 wheri"in compon- ent comprises at least one primary, secondary and/or tertiary amine.

34. The composition of claim 1 wherein compon- ent (II) comprises at least one aliphatic, cycloali- phatic and/or aromatic amine. The composition of claim 1 wherein compon- ent comprises at least one alkylene polyamine of the formula i WO 89/05786 PCT/US88/04501 -69- N--Alkylene-N-T-IR R wherein n is a number of from 1 to-about ,l each R is independently a hydrogen atom or a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having up to 'abut 700 carbon atoms, and the Alkylene group has from 1 to about 10 carbon atoms.

36. The composition of claim 1 wherein compon- ent comprises at least one N-(hydroxyl-sub- stituted hydrocarbyl) amine, at least one hydroxyl- substituted poly(hydrocarbyloxy) analog of or a mixture of and

37. The composition of claim 1 wherein compon- ent comprises at least one alkanol amine contain- ing up to ab4ut 40 carbon atoms.

38. The composition of claim 1 wherein compon- ent (II) is selected from the group consisting of (a) primary, secondary and tertiary alkanol amines which can be represented correspondingly by the formulae H |N-R'-OH H N-R 'OH RV N-R'-OH l V WO 89/05786 PCT/US88/04501 hydroxyl-substituted oxyalkylene analogs of said alkanol amines represented by the formulae H\ N-(R'O)2-15-H H- H 2- 1 5 -H R- R 2-15-H RI wherein each R is ind~endently a hydrocarbyl group of one to abut- 8 carbon atoms or a hydroxyl-substituted hydrocarbyl group of 2 to abe-t 8 carbon atoms and R' is a divalent hydrocarbyl group of 2 to abeut 18 carbon atoms, and mixtures of two or more thereof.

39. The co.position of claim 1 wherein compon- ent (II) comprises dimethylethanolamine. The composition of claim 1 wherein compon- ent comprises ammonia.

41. The composition of claim 1 wherein compon- ent (SI) comprises at least one alkali metal.

42. The composition of claim 1 wherein compon- ent comprises sodium or potassium.

43. The composition of claim 1 wherein compon- ent (II) comprises at least one alkaline earth metal.

44. The composition of claim 1 wherein compon- ent comprises at least one alkali metal oxide, hydroxide or carbonata. i WO 89/05786 PCT/US88/04501

51. The composition of claim 1 wherein compon- ent comprises at least one polyhydroxy aromatic compound.

52. The composition of claim 1 wherein compon- ent comprises ethylene glycol.

53. The composition of claim 1 wherein compon- ent comprises at least one primary or secondary hydroxyamine.

54. The composition of claim 1 wherein compon- ent comprises at least one N-(hydroxyl-substi- tuted hydrocarbyl) primary or secondary amine, at least one hydroxyl-substituted poly(hydrocarbyloxy) analog of or a mixture of and The composition of claim 1 wherein compon- ent comprises at least one primary or secondary alkanol amine containing up to abeut 40 carbon atoms.

56. The composition of claim 1 wherein compon- ent is selected from the group consisting of (a) primary and secondary alkanol amines which can be repre- sented correspondingly by the formulae H N-R'-OH H H N-R'-OH R hydroxyl-substituted oxyalkylene analogs of said alkanol amines represented by the formulae 1 1 1 I i-i ~~cl. r- C WO 89/05786 PCT/US88/04501 -71- The composition of claim 1 wherein compon- ent comprises at least one alkaline earth metal oxide, hydroxide or carbonate. 46. The composition of claim 1 wherein compon- ent comprises at least one polyamine. 47. The composition of claim I wherein compon- ent comprises at least one aliphatic, cycloaliphatic or aromatic polyamine. 48. The composition of claim 1 wherein compon- ent comprises at least one alkylene polyamine of the formula N--Alkylene-N-rnR' R wherein n is a number in the range of from 1 to about each R and R' is independently hydrogen or a hydro- carbyl group or a hydroxy-substituted hydrocarbyl group having up to -abe4 700 carbon atoms, with the proviso that at least one of R and at least one of R' are hydrogen, and the Alkylene group has from 1 to abeout-1 carbon atoms, 49. The composition of claim 1 wherein compon- ent comprises at least one polyol. The composition of claim 1 wherein compon- ent comprises at least one compound represented by the formula R(OH)m wherein R is a monovalent or polyvalent organic group joined to the OH groups through carbon-to-oxygen bonds and m is an integer of from 2 to about t WO 89/05786 PCT/US88/04501 -73- N-(R'O)2-15-H H N-(R'O)2-15-H R wherein R is a hydrocarbyl group of one to about 8 car- bon atoms or a hydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms and R' is a divalent hydrocar- byl group of 2 to -abe-ft-18 carbon atoms, and mix tures of two of more thereof.

57. A composition comprising; at least one salt moiety derived from at l.east one high molecular weight polycarboxylic acylating agent, said acylating agent having at least one hydrocarbyl substituent having an average of from about 50 to about 500 carbon atoms, and (II) dimethylethanolamine; at least one salt moiety derived from at least one low molecular weight polycarboxylic acylating agent, said acylating agent having at least one hydrocarbyl substituent having an average of about 8 to-abouat18 carbon atoms, and (II) dimethyl- ethanolamine; said components and being coupled together by ethylene glycol. i8. A concentrate comprising from eabhe 10% to about 90% by weight of che composition of claim 1, and a diluent.

59. A concentrate made by combining the compo- sition of claim 1 with a diluent, said concentrate com- *;^Jg i i WO 89/05786 PCT/US88/04501 -74- prising from -abe- 10% to about 90% by weight of said diluent. An explosive composition comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emul- sifying amount of the composition of claim 1.

61. An explosive composition made by combining an oxidizer phase comprising at least one oxygen-supply- ing component with an organic phase comprising at least one carbonaceous fuel and the composition of claim 1.

62. A cap-sensitive explosive emulsion comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifying amount of a composition comprising: at least one salt moiety derived from at least one high-molecular weight polycarboxylic acylating agent, said acylating agent having at least one hydrocarbyl substituent having an average of from -about 20 to -abut 500 carbon atoms, and (II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; at least one salt moiety derived from at least one low-molecular weight polycarboxylic acylating agent, said acylating agent optionally having at least one hydrocarbyl substituent having an average of up to -abut- 18 carbon atoms, and (II) ammonia, at least one .aine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; 4 dVL~" 1v~" WO 89/05786 PCT/US88/04501 said components and being coupled together by at least one compound having two or more primary amino groups, (ii) two or more secondary amino groups, (iii) at least one primary amino group and at least one secondary amino group, (iv) at least two hydroxyl groups or at least one primary or secondary amino group and at least one hydroxyl group.

63. A cartridge comprising at least one cap- sensitive explosive emulsion, said emulsion comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsi- fying amount of a composition comprising: at least one salt moiety derived from I at least one high-molecular weight polycarboxylic acylating agent, said acylating agent having at least one hydrocarbyl substituent having an average of from -abut 20 to abou-t 500 carbon atoms, and (II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; at least one salt moiety derived from at least one low-molecular weight polycarboxylic acylating agent, said acylating agent optionally having at least one hydrocarbyl substituent having an i average of up to -abut- 18 carbon atoms, and (II) n ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; said components and being coupled together by at least one compound having two or more primary amino groups, (ii) two or more secondary amino groups, (iii) at least one primary amino group and WO 89/05786 PCT/US88/04501 -76- at least one secondary amino group, (iv) at least two hydroxyl groups or at least one primary or secondary amino group and at least one hydroxyl group.

64. A cartridge having a diameter of abeot 1.25 inches or less comprising at least one cap-sensi- tive explosive emulsion, said emulsion comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least one carbonaceous fuel, and an emulsifying amount of a composition comprising: at least one salt moiety derived from at least one high-molecular weight polycarboxylic acylating agent, said acylating agent having at least one hydrocarbyl substituent having an average of from -abfot- 20 to abe-t 500 carbon atoms, and (II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; at least one salt moiety derived from at least one low-molecular weight polycarboxylic acylating agent, said acylating agent optionally having at least one hydrocarbyl substituent having an average of up to about 18 carbon atoms, and (II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; said components and being coupled together by at least one compound having two or more primary amino groups, (ii) two or more secondary amino groups, (iii) at least one primary amino group and at least one secondary amino group, (iv) at least two hydroxyl groups or at least one primary or secondary amino group and at least one hydroxyl group. v INTERNATIONAL SEARCH REPORT International Avoicniion N~o CT /US 88 /04501 1. CLASSIFICA~TION OF SUBJECT MATTER (it several classincotion &Ymoois 4poly, indicaite ail) According to injernalaon&'i Patent Classification JIPC) or to both National Classification and IRC IPC4* C 06 3 47/14 11, ;-IELOS SEARCHED Minimum Documentation SearcheaI Ciasslification System Classification Symbols IPC 4 C 06 B; B 01 F Documentation Searched other than Minimum Documentation to the Extent that auch Documents are Included In the Filds Searched 1i1, DOCUMENTS CONSIDAR90 TO BE RELE91.11VANT' Catgor itaionof Document, 11 witl', indication, where sp~roprlato, of the relevant pssages 12 Relevant to Claim No."1 A EP, At 0155800 25 September 1985, 1-64 see claims 1-17 (cited in the application) A WO, A, 87/03613 (LUBRIZOL) 18 Ju~ne 1987, 1-64 see qlA3-ms 50-51 A US, A, 4357184 BINET) 2 November' 1982, 1-64 ge claims 1-48 (cited in the application) A EP, A, 0004426 3 October 197 9, 1 see claim 1 A US, A, 4447348, FORSBERG) 8 May 1984, 1 see claim 1 i(cited in the application) 0 pecial Categories of cited documenisi tOi later document published @her the International filing dJate clofumnrt deflnlgv he general sltle of the ert which Is not or Priority a4te and not in conflict with the appication b c4iiee tob0fpriua elec cited to understand the principle or theory unaerlying thue As etiri omn but on. patcl r re haan he ntranlInvent ion "114ealig docenbu published ona ta h ntrainl "I document of Particular reloeanca: the claimed invention Oil n datecannot be constidered novei at cannot be considered to ILI' document which may throw doubts on Priority claim~a) or Involve an Inventive step whl^.h Is illd to estabishn the publication date of another document of PertiClia releVenCoal the Claimed Invention citation Or )ther Special leason las specified) cannot be considered to Involve an Inventive step when the N" document tllering !a an oral disciosure, use, exhibition or document is combined with one or rioove other Such docu- other mains mont. such combination being obvious to a person skilled 0101 document oubliehed prior to the rins'national ftirg date but In the an, later than theo Priority date Claimed &ik document member of the same Patent family Date ot the Actual Completion of the International Search Oate of Mailing of thin~ International Search Report 4th kril 1989 '~6APR 1989" 11nte(slitionol Searchintg Authority 31 utlra o EUROPEAN PATENT O~tICE MDRFTE fPerm PCTIIIAi21O seconid ahieet) lJonuery ill$), ANNEX TO THE INTERNATIONAL SE -CH REPORT QN INTERNATIONAL PATENT APPLIC-,, ON NO- US 8804501 SA 26387 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The memners are as contained in the Furopeaii Patenlt office EDP file on 13/04/89 The European patent Office is in~ no way liable for these particulars which are merdh' given for the purpose of information. Patent document Publication Patent family PubliC21ion cited in search report date member(s) date GB-A, B 2156799 16-10-85 AU-A- 4000685 26-09-85 574140 3-06-88 WO-A- 8703613 18-06-87 AU-A- 6738287 3-68 US-A- 4708753 24-11-87 JP-T- 63502254 01-09-88 EP-A- 0285608 12-10-88 U-A- 4357184 0-11-82 E-A,B 0018085 29-10-80 GB-A,B 2050340 07-01-81 AU-A- 5624380 09-10-80 JP-A- 55136196 23-10-80 OA-A- 6502 31-08-81 CA-A- 1139106 11-01-83 AU,-B- 528656 05-05-83 CA-A- 1140765 08-02-83 EP-A- 0004426 03-10-79 GB-AB 2017719 10-10-79 JP-A- 54132492 15-10-79 AU-A- 4523379 27-09-79 US-A-- 4256605 17-03-81 CA-A- 1126123 22-06-82 US-A- 4447348 08-05-84 US-A- 4368133 11-01-83 US-A- 4448703 15-05-84 t o e il w.ti annex i see Official Jo~lof the Curopean Patent Offce, No. 12/82