RU2127239C1 - Type water-in-oil emulsion, explosive composition - Google Patents

Abstract

FIELD: type water-in-oil emulsions and explosive compositions on their basis. SUBSTANCE: emulsions are substantially mixed with granules of ammonium nitrate, and modified explosive compositions are obtained. These emulsions comprise: discontinuous aqueous phase containing at least single oxygen-supplying component; continuous organic phase, including, at least one carbon fuel; and a small amount, at least of one emulsifier. Emulsifier represent a product obtained as a result of interaction between component A (at least one substituted succinic acylating agent, containing on the average, at least 1.3 of succinic groups per equivalent weight of substituting groups, which come from polyalkene) and component B (ammonia and/or at least one amine). EFFECT: enhanced efficiency. 38 cl, 3 tbl, 19 ex

Description

 The invention relates to water-in-oil emulsions that are useful as explosives. These emulsions contain at least one emulsifier produced from at least one substituted succinic acylating agent. A substituted amber acylating agent consists of substituent groups / substituent groups / and succinic groups in which the substituent groups are derived from polyalkylene (for example, polybutenes), said acylating agents are characterized by the presence in their structure of an average of at least 1.3 succinic groups per equivalent weight of substituent groups.

 Hydrocarbyl substituted carboxyl acylating agents are known having at least about 30 aliphatic carbon atoms in the substituent. Examples of such acylating agents include polyisobutenyl substituted succinic acids and anhydrides. The use of such carboxylic acylating agents as additives in conventional fuels and lubricants is described in US Pat. ; 3087936; 3,163,603; 3,172,892; 3,198,544; 3,215,707; 9219666; 3231587; 3,235,503; 3272746; 3,306,907; 3,306,908; 3,331,776; 3,341,542; 3,346,354; 3,374,174; 3,397,515; 3,381,022; 3,413,104; 3,450,715; 3,454,607; 3,455,728; 3,476,686; 3513095; 3,523,768; 3,630,904; 3,632,511; 3,697,428; 3,755,169; 3804763; 3,836,470; 3,862,981; 3,936,480; 3,948,909; 3,950,341; and 4,471,091; and French patent 2223415.

 US Pat. No. 4,234,435 discloses carboxylic acid acylating agents derived from polyalkenes, such as polybutenes, and dibasic carboxylic agents, such as maleic or fumaric acid or some derivatives thereof. These acylating agents are characterized in that the polyalkenes from which they are obtained have a Mn value of from about 1300 to 5000 and a Mw / Mn value of from about 1.5 to 4. The acylating agents are further characterized by the presence of at least 1, 3 groups derived from a dibasic carboxyl reagent for each equivalent weight of groups derived from polyalkene. Acylating agents can be reacted with an amine to give derivatives useful as additives for lubricating oils or as intermediates that are subsequently treated with various other chemical compounds and compositions, such as epoxides, to produce other derivatives useful as lubricant additives oils.

 Explosive water-in-oil type emulsions typically include a continuous organic phase (for example, carbonaceous fuel) and a discontinuous aqueous phase containing an oxygen-containing component (for example, ammonium nitrate). Examples of such water-in-oil explosive emulsions typically include a continuous organic phase (for example, carbonaceous fuel) and a discontinuous aqueous phase containing an oxygen-containing component (for example, ammonium nitrate). Examples of such water-in-oil explosive emulsions are disclosed in US Pat. Nos. 3,447,978; 3,765,964; 3,985,593; 4,008,110; 4,097,316; 4,104,092; 4,218,272; 4,259,977; 5,357,184; 4,371,408; 4,391,659; 4404050; 4409044; 4,448,619; 4,453,989; and 4,534,809 and UK patent application GB 2050340A.

 US Pat. No. 4,216,040 discloses water-in-oil emulsion explosives having a discontinuous aqueous phase, a continuous oily or water-immiscible liquid organic phase, and an organic cationic emulsifier having a lipophilic moiety and a hydrophilic moiety, the lipophilic moiety being an unsaturated hydrocarbon chain.

 US patent 4708753 and 4644756 disclose emulsions of the type water-in-oil, which include / A / continuous oil phase; / B discontinuous aqueous phase; (C) a small emulsifying amount of at least one salt originating or produced from / C / / I / at least one salt, a hydrocarbid-substituted carboxylic acid or anhydride, an ester or amide derivative of the specified acid or anhydride, the hydrocarbyl substituent / C / / I / has an average of about 20 to 500 carbon atoms, and / C / / II / ammonia or at least one amine; and / D / a functional amount of at least one water-soluble, oil-insoluble functional additive dissolved in said aqueous phase.

 Patent 4844756 also discloses that the component / C / / II / may also be an alkali or alkaline earth metal. These emulsions are useful as explosive emulsions when the functional additive / D / is an oxygen supply component / for example, ammonium nitrate /.

 US patent 4710248 discloses an explosive emulsion composition comprising a discontinuous oxidizing phase dispersed in a continuous fuel phase, with a modifier, hydrophilic and lipophilic moieties. The hydrophilic moiety includes a carboxylic acid or a group capable of hydrolyzing into a carboxylic acid. The lipophilic moiety is a saturated or unsaturated hydrocarbon chain. The pH of the explosive emulsion composition is higher than 4.5.

US patent 4822433 discloses an explosive emulsion composition comprising an intermittent phase containing an oxygen-containing component and an organic medium forming a continuous phase, in which the oxygen-containing component and the organic medium are able to form an emulsion, which in the absence of an additional additive / or activating agent / detects conductivity when measured at 60 ^o C, not exceeding 60,000 / meter. The reference indicates that conductivity can be achieved by introducing a modifier that also functions as an emulsifier. The modifier includes a hydrophilic part / fragment / and a lipophilic part. The lipophilic moiety can be obtained from poly / alk / en / yl / succinic anhydride. As being useful, it is identified, in particular, poly / isobutylene / succinic anhydride having a number average molecular weight in the range of 400 to 5000. The hydrophilic moiety is described as being polar in nature, having a molecular weight not exceeding 450 and can be obtained from polyols, amines , amides, alkanolamines and heterocyclic compounds. Reference Example 14 discloses the use of a 1: 1 condensate of polyisobutenyl succinic anhydride (average molecular weight = 1200) and dimethylethanolamine as a modifier / emulsifier.

 US Pat. No. 4,828,633 discloses salt compositions which comprise / A / at least one salt portion derived from / A / / I / of at least one high molecular weight polycarboxyl acylating agent, said acylating agent / A / / I / having at least one hydrocarbyl / hydrocarbon / substituent having an average of about 20 to 500 carbon atoms and / A / / A / ammonia of at least one amine, at least one alkaline or alkaline earth metal, and / or at least one alkaline compound or alkaline earth metal ceiling elements; / B / at least one salt portion derived from / B / / I / at least one low molecular weight polycarboxyl acylating agent, said acylating agent / B / / I / not necessarily having at least one hydrocarbon substituent having an average up to about 18 carbon atoms, and / B / / II / ammonia of at least one amine, at least one alkaline or alkaline earth metal, and / or at least one alkali or alkaline earth metal compound; moreover, these components / A / and / B / bind / bind / together using / C / at least one compound having / I / two or more primary amino groups / II / two or more secondary amino groups / III / at least at least one primary amino group, / IV / at least two hydroxyl groups or / V / 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.

 US patents 4840487 and 4956028 disclose an explosive composition comprising an intermittent oxidizing phase comprising at least one oxygen-containing component, a continuous organic phase comprising at least one water-immiscible organic liquid, and an emulsifying amount of at least one nitrogen-containing emulsifier obtained from / A / at least one carboxyl acylating agent, / B / at least one polyamine and / C / at least one acid or acid-giving compound, capable of x to form at least one salt with said polyamine. Examples / A / include alkylene polyamines. Examples (C) include phosphorus acids (for example, 0.9-dialkylphosphoric acid). These explosive compositions may be water-in-oil or melt-in-oil emulsions, one oxygen-supplying component, a continuous organic phase including at least carbon fuel, and an emulsifying amount (A) of at least one salt composition obtained from / A / / I / of at least one high molecular weight hydrocarbid-substituted carboxylic acid or anhydride, or an ester or amide derivative of said acid or anhydride, the hydrocarbyl substituent of the compound / A / / I / having, on average, from about 20 to 500 carbon atoms and / A / / 2 / ammonia of at least one amine of at least one alkali or alkaline earth metal compound; and / B / at least one salt composition obtainable from / B / / I / at least one low molecular weight hydrocarbyl substituted carboxylic acid or anhydride or ester or amide derivative of said acid or anhydride, wherein the hydrocarbyl substituent / B / / I /, has an average of about 8 to 18 carbon atoms, and / B / / 2 / ammonia of at least one amine of at least one alkaline or alkaline earth metal, and / or at least one alkali or alkaline earth metal compound.

US patent 4,919,178 discloses emulsifiers that include the reaction product of component / I / t with component / II /. Component / I / includes the reaction product of certain carboxylic acids or anhydrides, or their ester or amide derivatives with ammonia, at least one amine, at least one alkaline and / or at least one alkaline earth metal. Component / II / includes some phosphorus-containing acids; or metal salts of said phosphorus-containing acids, the metals being selected from the group consisting of magnesium, calcium, strontium, chromium, manganese, iron, molybdenum, cobalt, nickel, copper, silver, zinc, cadmium, aluminum, tin, lead and mixtures of two or more of them. These emulsifiers are useful in water-in-oil explosive emulsions.
US Pat. No. 4,956,028 discloses explosive compositions that include an intermittent phase of an oxidizing agent comprising at least one oxygen-containing component, a continuous organic phase comprising at least one water-immiscible organic liquid, and an emulsifying amount of at least one nitrogen-containing emulsifier selected from / A / at least one craboxyl acylating agent, / B / at least one polyamine and / C / at least one acid or an acid-producing compound, sp sobnogo form at least one salt with said poliamnom. These explosive compositions may be water-in-oil emulsions or melt-in-oil emulsions.

 US 4,999,062 discloses an emulsion explosive composition comprising an intermittent phase comprising an oxygen releasing salt, a continuous water-immiscible organic phase and an emulsifier component comprising a condensation product of a primary amine and poly alk (en) yl succinic acid or anhydride, and where the condensation product includes at least 70% by weight of a succinimide product.

 US Pat. No. 4,820,361 discloses an explosive emulsion composition comprising a water-in-oil emulsion comprising an intermittent aqueous phase including at least one oxygen-containing component and a continuous organic phase including hydrocarbon fuel and an emulsifier.

 Explosive water-in-oil emulsions are often mixed with granules of ammonium nitrate or ANFO in order to increase the explosive energy of such emulsions. Among industrially available ammonium nitrate granules, granules are used which are made using one or more crystalline habit modifiers to control crystal growth and one or more surfactants to reduce sintering. A problem with the use of these processed granules is that they tend to destabilize emulsions. Therefore, it would be very favorable to develop explosive emulsions that remain stable when mixed with such treated granules of ammonium nitrate.

 The present invention is directed to water-in-oil emulsions that are useful as explosives. These emulsions include an intermittent aqueous phase comprising at least one oxygen-containing component, a continuous organic phase comprising at least one carbonaceous fuel, and a minor emulsifying amount of at least one emulsifier. An emulsifier is a product obtained by the reaction of component / A / and component / B /: wherein component / A / is at least one substituted amber acylating agent, wherein said substituted amber acylating agent consists of substituent groups and amber (succinic) groups, in which substituent groups or substituent groups are derived from polyalkene, said acylating agents are characterized by the presence in their structure of an average of at least 1.3 amber groups for each weight equivalent of substituent groups; and component / B / is ammonia and / or at least one amine. According to one embodiment, these emulsions are stably mixed with ammonium nitrate granules that have been prepared using one or more crystalline habit modifiers to control crystal growth and one or more surfactants to reduce sintering.

 The term "emulsion", as used in this description and in the attached claims, is intended to cover not only water-in-oil emulsions, but also compositions obtained from such emulsions in which, at temperatures lower than that at which the emulsion is formed, the intermittent phase is solid or in the form of droplets of supercooled liquid. The term also encompasses compositions prepared from or formed in the form of such water-in-oil emulsions that are in the form of gelatin or semi-gelatin compositions.

The term "hydrocarbide or hydrocarbon radical" is used here in the sense to include:
(1) hydrocarbon groups, i.e. aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic and alicylic substituted aromatic groups and the like, as well as cyclic groups in which the ring terminates with using another part of the molecule (that is, any two of these groups can together form an alicyclic group);
(2) substituted hydrocarbon groups, that is, groups containing non-hydrocarbon groups which, in the context of the present invention, do not predominantly alter the hydrocarbon nature of the hydrocarbyl group; those skilled in the art are aware of such groups, examples of which include an ether group, oxo, halogen (for example, chlorine or fluorine), alkoxyl, mercapto, alkyl mercapto, nitro, nitroso, sulfoxy, etc .;
(3) hetero groups, that is, groups which, having a predominantly hydrocarbon nature in the context of the present invention, contain in the ring or chain composed of carbon atoms and other atoms other than carbon. Suitable heteroatoms are known to those skilled in the art and include, for example, sulfur, oxygen, nitrogen, and substituents such as pipridyl, furanyl, thiophenyl, imidazolyl, etc.

 Typically, for every ten carbon atoms in a hydrocarbon group, no more than about three non-hydrocarbon groups or heteroatoms are present, and preferably no more than one group or heteroatoms. Typically, there are no such groups or heteroatoms in a hydrocarbon group, and therefore, in this case, they are purely hydrocarbon.

 The hydrocarbon groups are preferably free of acetylene unsaturation; the ethylenically unsaturated, when present, is usually such that for every ten carbon-carbon bonds no more than one ethylene bond is present. Hydrocarbon groups are often completely saturated and therefore do not contain ethylene unsaturation.

 The term “lower”, used here in combination with terms such as alkyl, alkenyl, alkoxy and the like, covers groups that contain a total of up to 7 carbon atoms.

 The water-in-oil emulsions according to the invention, which are useful as explosives, include an intermittent aqueous phase comprising at least one oxygen-containing component, a continuous organic phase comprising at least one carbonaceous fuel, and a minor emulsifying amount of at least one emulsifier . According to one embodiment, these emulsions are stably mixed with ammonium nitrate granules that are treated with surfactants and crystal growth modifiers.

 The continuous organic phase is preferably present in an amount of at least about 2% by weight, more preferably in the range of about 3.5% to 10%, more preferably about 5% to 8% by weight, based on the total weight of the water-in-emulsion oil. The discontinuous aqueous phase is preferably present in an amount of at least about 85% by weight, more preferably in an amount in the range of from about 85% to 98% by weight, and more preferably from about 92% to 95% by weight, based on the total weight of the emulsion. The emulsifier is preferably present in an amount in the range of from about 5% to 95%, more preferably about 5% to 50%, even more preferably about 5% to 20%, and even more preferably about 10% to 20% by weight based on the total the weight of the organic phase. The oxygen-containing component is preferably present in an amount in the range of about 70% to 95% by weight, more preferably about 75% to 92% by weight, even more preferably about 78% to 90% by weight, based on the total weight of the aqueous phase. Water is preferably present in an amount in the range of from about 5% to 30% by weight, more preferably from about 8% to 25% by weight, and even more preferably from about 10% to 22% by weight, based on the weight of the aqueous phase.

Carbon fuel
The carbon fuel that is useful in the emulsions of this invention may include most hydrocarbons, for example, paraffinic, olefinic, naphthenic, aromatic, saturated or unsaturated hydrocarbons, and typically is in the form of an oil or wax or a mixture thereof. Typically, the carbonaceous fuel is a water-immiscible, emulsifiable hydrocarbon that is either liquid or capable of being expected to be at a temperature of up to about 95 ^° C, and preferably at a temperature between about 40 ^° C and 75 ^° C. Oil from a wide variety of sources, including natural and synthetic oils and mixtures thereof.

 Natural oils include animal oils and vegetable oils (for example, castor oil, lard), as well as solvent-free or acid-free mineral oils of the paraffinic, naphthenic or mixed paraffin-naphthenic types. Oils derived from coal or hot shale are also useful. Synthetic oils include hydrocarbon oils and halogenated hydrocarbon oils, such as polymerized and copolymerized / with regular alternating units / olefins / e.g. polybutylene, polypropylene, propylene-isobutyl copolymers, chlorinated polybutylene and the like. /; alkylbenosols / for example, dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di- / 2-ethylhexyl / benzenes, etc. /; polyphenyls / for example biphenyls, terphenyls, alkylated polyphenyls, etc. /; and similar.

 Another suitable class of synthetic oils that can be used includes esters of dicarboxylic acids / e.g. phthalic acid, succinic acid, alkyl succinic acid, maleic, azelaic, suberinic, sebacic, fumaric, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids , alkenyl malonic acids, etc. / with various alcohols / for example, butyl alcohol, hexyl, dodecyl, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoester, propylene glycol, ne taerythritol and others. Specific examples of these esters include dibutylacitate, di- (2-ethylhexyl) -sebacinate, di-n-hexyl fumarate, dioctyl sebacinate, diisooctylazelaate, diisodecylvelainate, dioctyl phthalate, didecyl oxydilene acid 2-diacyloxydyl acid-2-diacyloxydyl acid reactions of one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid and the like.

 Esters useful as synthetic oils also include those derived from (5-12C) monocarboxylic acids and polyols or polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.

 Silicon-based oils such as polyalkyl, polyaryl, polyalkoxy or polyaryloxy siloxane oils and silicate oils are another class of healthy oils. These oils include tetraethyl silicate, tetraisopropyl silicate, tetra- / 2-ethylhexyl / silicate, tetra- / 4-methyl-hexyl / silicate, tetra / p-tert-butylphenyl / silicate, hexyl / 4-methyl-2-pentoxy / -di -siloxane, poly / methyl / -siloxanes, poly- / methylphenyl / -siloxanes, and others. Other useful synthetic oils include liquid phosphate esters / for example tricresyl phosphate, trioctyl phosphate, decanphosphonic acid diethyl ester, etc. /, polymer tetrahydrofurans and the like .

 Unrefined (unrefined), refined and refined oils (and mixtures of each other) can be used, such as those disclosed hereinabove. Crude oils are obtained directly from natural or synthetic sources without further purification. For example, shale oil obtained directly by distillation in a retort, petroleum oil obtained directly by distillation, or ester oil obtained directly by a complex esterification process and used without further treatment will be unrefined oil. Refined oils are similar to unrefined oils except that they have been subjected to further processing at one or more refining steps to improve one or more properties. Many of these purification techniques are known to those skilled in the art, such as solvent extraction, distillation, acid or base extraction, filtration, filtration through an adsorbent bed / percolation / etc. Refined oils are obtained using processes similar to the processes used to produce refined oils and applied to refined oils that are already used in practice. Such refined oils are also known as regenerated or recycled oils and are often further refined using technology designed to remove spent additives and oil breakdown products.

 Examples of useful oils include white mineral oil, supplied by Vitko Chemical Company under the trademark KAIDOL; white mineral oil supplied by Shell under the trade name ONDINA; and mineral oil, supplied by Pennzoil under the trade name N-750-HT. The oil can be used diesel fuel / for example, grades N 2-D, according to the specification in ASTM D-975 /.

The carbonaceous fuel may be any paraffin or wax having a melting point of at least about 25 ^° C., such as petrolatum wax, microcrystalline wax and paraffin, mineral waxes such as ozokerite and montan wax, animal waxes such as spermaceti wax, and insect waxes such as beeswax and Chinese wax. Useful waxes include waxes identified by the trade name MOBILVOSK 57, which is supplied by Mobile Oil Corporation; D02764, which is a mixed wax supplied by Astor Chemical Ltd; and VIBAR, which is supplied by Petrolight Corporation. Preferred waxes are mixtures of microcrystalline waxes and paraffin.

 In one embodiment, the carbonaceous fuel comprises a combination of wax and oil. The wax content can be at least about 25% and preferably is in the range of about 25% to 90% by weight of the organic phase, and the oil content can be at least about 10%, and is preferably in the range of about 10% to 75 % by weight of the organic phase.

 Oxygen-containing component.

 The oxygen-containing component is preferably at least one inorganic oxidizing role, such as ammonium nitrate, an alkali or alkaline earth metal, ammonium chlorate or perchlorate, an alkali or alkaline earth metal. Examples thereof include ammonium nitrate, sodium nitrate, calcium nitrate, ammonium chlorate, sodium perchlorate and ammonium perchlorate. Ammonium nitrate is preferred. Mixtures of ammonium nitrate and sodium or calcium nitrate are also suitable. According to one embodiment, the inorganic oxidizing salt mainly comprises ammonium nitrate, although up to about 25% by weight of the oxidizing phase may comprise either some other inorganic nitrate (e.g. alkaline or alkaline earth metal nitrate) or inorganic perchlorate (e.g. ammonium perchlorate or alkali metal or alkaline earth metal perchlorate), or a mixture thereof.

Emulsifier
The terms “substituent” and “acylating agent” or “substituted amber acylating agent” are given in their nominal values. For example, substituents are an atom or group of atoms that has another substituted atom or group in the molecule as a result of the reaction. The term “acylating agent” or “substituted acylating amber agent” refers to the compound per se and does not include unreacted reagents used to form the acylating agent or substituted amber acylating agent.

 The substituted amber acylating agent / A / used in the preparation of the emulsifier may be characterized by the presence of two groups or fragments in its structure. For convenience, the first group or fragment is hereinafter referred to as a substituent group (s) and this group or fragment originates from a polyalkene. The polyalkene from which the substituted groups originate is characterized by a Mn / number average molecular weight of at least about 500, more preferably at least about 1000, even more preferably at least about 1300, and even more preferably at least about 1500. In an advantageous manner the case of polyalkene has an Mn in the range of from about 500 to 10,000, more preferably from about 1000 to 7000, even more preferably from about 1300 to 5000, even more preferably from about 1500 to about 5000, even more preferably from about about 1500 to about 3000, even more preferably from about 1500 to about 2400, even more preferably from about 1500 to about 2000, even more preferably from about 1600 to about 1900. The polyalkene preferably has an Mw / Mn of at least about 1.5 preferably from about 1.5 to 5, more preferably from about 2 to 5, even more preferably from 2.8 to 5, more preferably from 2.8 to 4.5, and even more preferably from 3.3 to 3, nine. The abbreviation Mw is a common symbol representing the weight average molecular weight.

 Gel permeation chromatography / GPC / is a method that gives both weight average and number average molecular weights, as well as a complete distribution of the molecular weight of the polymers. For the purposes of this invention, as a calibration standard for GPC, a standard for GPC is used, a number of fractionated polymers of isobutene, polyisobutene are used. Methods for determining the values of Mn and Mw polymers are well known and described in numerous books and articles. For example, methods for determining Mn and molecular weight distribution of polymers are described in W.W. Join J.J. Kirkland and D. D. Bly, "Modern Siac Exelusion Liguid Chromatograths", J. Wilny & Sons, Jni. 1979.

 Polyalkenes having the Mn and Mw values discussed above are known in the art and can be prepared in accordance with conventional procedures. For example, some of these polyalkenes are described and examples thereof in US Pat. No. 4,234,435. The contents of this patent regarding such polyalkenes are incorporated herein by reference. Several of these polyalkenes, especially polybutenes, are commercially available.

где
X и X' являются одинаковыми или различными при условии, что по крайней мере один из X и X' является таким, что замещенный янтарный ацилирующий агент может функционировать как карбоксильный ацилирующий агент. То есть по крайней мере один из X и X'должен быть таким, чтобы замещенный ацилирующий агент мог образовывать, например, амиды, имиды, или аминные соли с аминосоединениями, и сложные эфиры, сложноэфирные соли, амиды, имиды и др. с гидроксиламинами, и в остальных отношениях функционировать как обычный карбоновокислотный ацилирующий агент. Для целей данного изобретения реакции переэтерификации и трансамидирования рассматриваются как обычные реакции ацилирования.The second group or fragment in the acylating agent is referred to herein as an “amber group (s)". Amber or succinic groups are groups characterized by structure

Where
X and X 'are the same or different, provided that at least one of X and X' is such that the substituted succinic acylating agent can function as a carboxyl acylating agent. That is, at least one of X and X ’must be such that the substituted acylating agent can form, for example, amides, imides, or amine salts with amino compounds, and esters, ester salts, amides, imides, etc. with hydroxylamines, and in other respects, function as a normal carboxylic acid acylating agent. For the purposes of this invention, transesterification and transamidation reactions are considered as normal acylation reactions.

So, X and / or X 'is usually -OH, -O-hydrocarbyl, -OM ⁺ , where M ⁺ is one equivalent of a metal, ammonium or amine cation, NH ₂ , Cl, -Br, and together X and X' can represent -O- so that they form an anhydride. The specific nature of any of the X and X ′ groups, which is not one of the above, is not essential until its presence prevents the remaining group from entering the acylation reaction. Preferably, however, X and X ′ are each such that both carboxyl functions of the amber group / i.e. both -C / O / X and -C / O / X 'could undergo an acylation reaction.

формулы I образует углерод-углеродную связь с атомом углерода в замещающей группе. Хотя другая такая незанятая валентность может быть занята аналогичной связью с той же самой или иной замещающей группой, все, кроме указанной одной такой валентности, обычно заняты водородом; т.е. -H.However, from unoccupied valencies in the grouping

Formula I forms a carbon-carbon bond with a carbon atom in a substituent group. Although another such unoccupied valency may be occupied by a similar bond with the same or another substituent group, all but the indicated one such valency are usually occupied by hydrogen; those. -H.

 Substituted succinic or succinic acylating agents are characterized by the presence in their structure of an average of at least 1.3 succinic groups (i.e., groups corresponding to formula I) for each weight equivalent of substituent groups. These acylating agents may have from about 1.5 to 2.5, preferably from about 1.7 to 2.1, more preferably from about 1.8 to 2.0, succinic groups for each weight equivalent of the substituent group. For the purposes of this invention, the weight equivalent of substituted groups is understood to mean the number obtained by dividing the Mn value of the polyalkene from which the substituent is derived by the total weight of the substituent groups present in the substituted succinic acylating agents. Thus, if a substituted amber acylating agent is characterized by a total weight of substituent groups of 40,000, and the Mn value for the polyalkene from which the substituent groups originate is 2000, then this substituted amber acylating agent is characterized by a total number of weight equivalent of substituting groups of 20/4000: 2000 = 20 /. Therefore, this particular amber acylating agent should also be characterized by the presence in their structure of at least 26 /1.3 • 20 = 26 / amber groups.

 The ratio of amber groups to the equivalent number of substituent groups present in the acylating agent can be determined by specialists in this field using conventional methods / for example, using an acid number, a saponification number /.

где R и R' каждый независимо выбран из группы, состоящей из -OH, -Cl, -O-низшего алкила, а взятые вместе R и R' представляют -O-.In one embodiment, the amber groups correspond to the formula

where R and R ′ are each independently selected from the group consisting of —OH, —Cl, —O — lower alkyl, and taken together R and R ′ are —O—.

и смесям III/a/ и III/b/.In the latter case, the amber group is succinic anhydride group. All amber groups in a particular amber acylating agent need not be the same, but they can be the same. Preferably, amber groups correspond to groups of formulas

and mixtures III / a / and III / b /.

 The preparation of substituted succinic acylating agents in which the amber groups are the same or different is within the knowledge of those skilled in the art and can be achieved using generally accepted procedures, such as treating the substituted succinic acylating agents themselves / for example, hydrolysis of anhydride into a free acid or conversion of free acid to acid chloride using thionyl chloride / and / or selection of appropriate maleic or fumaric reagents.

 Preferred characteristics of amber acylating agents are to be understood as dependent as well as independent. They are considered independent in the sense that, for example, the presence of at least 1.4 or 1.5 amber groups per weight equivalent of substituent groups is not related to the more preferred value of Mn or Mw / Mn. They are considered dependent in the sense that, for example, when at least 1.4 or 1.5 amber groups are preferably combined with more preferred Mn and / or Mw / Mn values, the combination or combination of preferred values actually describes or characterizes even more preferred embodiments of the invention. Thus, in relation to the particular parameters being served, the various parameters are intended to be considered separately, but they can also be combined with other parameters to identify additional preferred features. This same concept is intended to be used throughout this description to describe preferred values, ranges, ratios, reagents and the like, unless the opposite intention is demonstrated or clearly apparent.

 The polyalkenes from which substituted groups originate are homopolymers or copolymers of polymerizable olefin monomers with carbon numbers from 2 to about 16; typically 2 to about 6 carbon atoms. Copolymers are those in which two or more olefin monomers are polymerized in accordance with well-known generally accepted procedures to form polyalkenes having in their structure units derived from each of the two or more olefin monomers. Thus, “Copolymers or interpolymer (s)” as used herein include copolymers, terpolymers, tetrapolymers similar. As will be appreciated by those skilled in the art, the polyalkenes from which substituted groups are derived or derived are often commonly referred to as "polyolefin (s)".

 The olefin monomers from which the polyalkenes are derived are polymerizable olefin monomers characterized by the presence of one or more ethylenically unsaturated groups / i.e. > C = C </; that is, they are monodiphene monomers, such as ethylene, propylene, butene-1, isobutene, and octene-1, or polyolefin monomers / usually diolefin monomers / such as butadiene-1,3 and isoprene.

Когда применяются внутренние олефиновые мономеры, они обычно применяются с концевыми олефинами, давая полиалкены, которые являются сополимерами. Для целей данного изобретения, когда какой-либо конкретный полимеризуемый олефиновый мономер может классифицироваться как в качестве концевого олефина, так и в качестве внутреннего олефина, он будет считаться концевым олефином. Так, например, для целей данного изобретения пентадиен-1,3 /т.е. пиперилен/ считается концевым олефином.These olefin monomers are typically polymerizable terminal olefins; i.e., olefins characterized by the presence of> C = CH ₂ in their structure. However, polymerizable internal olefin monomers (sometimes referred to in the literature as middle olefins), characterized by the presence of a group in their structure, can also be used to form polyalkenes.

When internal olefin monomers are used, they are usually used with terminal olefins to give polyalkenes, which are copolymers. For the purposes of this invention, when a particular polymerizable olefin monomer can be classified as both a terminal olefin and an internal olefin, it will be considered a terminal olefin. So, for example, for the purposes of the present invention, pentadiene-1.3 / i.e. piperylene / is considered a terminal olefin.

 Some of the substituted succinic acylating agents (A) useful in preparing the emulsifiers of the invention are known in the art and are described, for example, in US Pat. No. 4,234,435, the contents of which are incorporated herein by reference. The acylating agents described in US Pat. No. 4,234,435 are characterized as containing substituent groups derived from polyalkenes having a Mn value of from about 1300 to 5000 and a Mw / Mn value of from about 1.5 to 4.

 Generally, aliphatic polyalkene hydrocarbons free of aromatic and cycloaliphatic groups are preferred. Within this preferred feature, additional preference is given to polyalkenes that originate from the group consisting of terminal olefinic hydrocarbon homopolymers and copolymers having from 2 to about 16 atoms. This preferred feature is further determined by the fact that although copolymers are also usually preferred, optionally containing up to about 40% polymer units derived from internal olefins with up to about 16 carbon atoms. More preferred the class of polyalkenes is comprised of polyalkenes selected from the group consisting of terminal olefin homopolymers and copolymers with carbon atoms from 2 to about 6, more preferably from 2 to 4 carbon atoms. However, another preferred class of polyalkenes is the latter more preferred polyalkenes, optionally containing up to about 25:% polymer units made from internal olefins with up to about 6 carbon atoms. Polybutenes and polyisobutenes are particularly preferred. In one embodiment, the polyalkene is polybutene, in which at least about 50% of the total units derived from butenes are derived from isobutene. In one embodiment, the polyalkene is an interpolymer or copolymer of ethylene and propylene, or an interpolymer or copolymer of styrene and at least one diene (for example, butadiene, pentadiene, isoprene, etc.).

 Obtaining polyalkenes described above, which meet different criteria with respect to the values of Mn and Mw / Mn, are within the competence of specialists in this field and does not form part of the present invention. Examples that are readily apparent to those skilled in the art include adjusting the polymerization temperatures, controlling the amount and type of polymerization initiators and / or catalyst, using chain-terminating groups in the polymerization, and the like. Other conventional techniques may also be used, such as distillation / including vacuum distillation / of very light fractions and / or oxidative or mechanical degradation of high molecular weight polyalkenes to produce lower molecular weight polyalkenes.

 Upon receipt of the substituted succinic acylating agents of the present invention, one or more of the polyalkenes described above is reacted with one or more acidic reagents selected from the group consisting of maleic or fumaric reagents of the general formula.

X / O / C-CH = CH-C / O / X '(IV)
where X and X 'have the meanings previously defined for formula I. Preferably, the maleic and fumar reactants are one or more compounds of the formula
RC / O / -CH = CH-C / O / R '(V)
where R and R 'have the meanings previously defined here for formula II. Typically, maleic or fumaric regents are maleic acid, fumaric acid, maleic anhydride, or a mixture of two or more of them. Maleic reagents are usually preferred over fumaric reagents because the former are more readily available and usually more freely interact with the polyalkenes / or their derivatives / to produce the substituted succinic acylating agents of the present invention. Particularly preferred reagents are maleic acid, maleic anhydride, and mixtures thereof. Due to the availability and ease of reaction, maleic anhydride is usually used.

 For convenience and brevity, the term “maleic reagent” is sometimes used to refer to acidic reagents used to produce succinic acylating agents. It should be understood that when used, this term is common to acidic reagents selected from maleic and fumaric reagents corresponding to the formula / IV / and / V / above, including mixtures of such reagents.

 Examples of patents describing various procedures for preparing beneficial acylating agents include US patents 3215707, 3219668, 3231587, 3912764, 4110349, 4234435 and 5041662; and UK patents 1440219 and 1492337. The contents of these patents are provided here for information in connection with the information contained therein regarding the preparation of substituted succinic acylating agents.

 The acylating agents described above are intermediates in the process of preparing an emulsifier for an emulsion according to the invention, the process comprising reacting / A / one or more acylating agents with / B / ammonia and / or at least one amine.

 Amines (B) useful in the manufacture of emulsifiers include primary amines, secondary amines and tertiary amines, with secondary and tertiary amines being preferred, and tertiary amines are particularly useful. These amines can be monoamines or polyamines. Hydroxyamines, especially tertiary alkanol monoamines, are useful. Mixtures of two or more amines may be used.

Amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic, including aliphatic substituted aromatic, aliphatic substituted cycloaliphatic, aliphatic substituted heterocyclic, cyaloaliphatic substituted, aromatic, substituted cycloaliphatic, aromatic substituted cycloaliphatic, cycloaliphatic aliphatic substituted hetero iklami cycloaliphatic and heterocyclic-substituted aromatic amines. These amines may be saturated or unsaturated. If it is unsaturated, the amines are preferably free of acetylene unsaturation. Amines may also contain non-hydrocarbon substituents or groups, unless these groups significantly interfere with the reaction of amines with acylating agents / A /. Such non-carbon substituents or groups include lower alkoxy, lower alkyl, mercapto, nitro and such superior groups as —O— and —S— / for example in groups such as —CH ₂ CH ₂ —X — CH ₂ CH ₂ -, where X is —O— or —S— /.

 With the exception of the branched polyalkylene polyamines, polyoxyalkylene polyamines and high molecular weight hydrocarbyl substituted amines described more fully hereinafter, the amines used in this invention typically contain less than about 40 carbon atoms, in total, and usually not more than about 20 carbon atoms.

 Aliphatic monoamines include mono-aliphatic, dialiphatic and tri-aliphatic-substituted amines in which the aliphatic groups may be saturated or unsaturated and straight or branched chain. Such amines include, for example, mono-, di- and tri-alkyl-substituted amines; mono-, di and tri-alkenyl-substituted amines; amines having one or more N-alkenyl substituents and one or more N-alkyl substituents 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, tri-ethylamine, n-butylamine, di-n-butylamine, allylamide, isobutylamine, cocoamine, stearylamine, laurylamine, metallurylamine, oleylamine, N-methyl-octidamine, dodecylamine, octadecylamine similar. Examples of substituted cycloaliphatic radicals of aliphatic amines, substituted aromatic groups of aliphatic amines, and substituted heterocyclic radicals of aliphatic amines include 2- / cyclohexyl / ethylamine, benzylamine, phenylethylamine, and 3- / furylpropyl / amine.

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

 Suitable aromatic amines include those monoamines in which the carbon atom of the aromatic ring structure is attached directly to the amino nitrogen. The aromatic ring is usually a mononuclear aromatic ring / i.e. a benzene derivative ring /, but it may include fused aromatic rings, especially rings derived from naphthalene. Examples of aromatic monoamines include aniline, di / para-methylphenyl / amine, naphthylamine, N- / n-thuli / aniline and the like. Examples of substituted aliphatic, substituted cycloaliphatic and heterocycle-substituted aromatic monoamines include para-ethoxyaniline, paradecyl-amine, cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.

 Suitable polyamines include aliphatic, cycloaliphatic and aromatic polyamines similar to those described above monoamines, except for the presence in their structure another amino nitrogen. The other nitrogen of the amino group may be a primary, secondary or third amino nitrogen. Examples of such polyamines include N-aminopropylcyclohexylamine, N, N'-di-n-butyl-para-phenylenediamine, bis- / para-aminophenyl / methyl, 1,4-diaminocyclohexene and the like.

 Heterocyclic mono and polyamines may also be used. As used herein, the term “heterocyclic or heterocyclic mono- and polyamine (s)” is intended to describe heterocyclic amines containing at least one primary, secondary or tertiary amino group and at least one as a hetero atom in the heterocyclic ring. Heterocyclic amines may be saturated or unsaturated and may contain various substituents, such as nitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl or aralkyl substituents. Typically, the total number of carbon atoms in the substituents does not exceed about 20. Heterocyclic amines may contain heteroatoms other than nitrogen, especially oxygen and sulfur. They can, of course, contain more than one nitrogen heteroatom. 5- and 6-membered heterocyclic rings are preferred.

 Among the suitable heterocyclic compounds are aziridines, azetidines, azolidines, tetra- and di-hydro-pyridines, pyrroles, indoles, piperidines, imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, n-amino , N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N, N'-di-aminoalkylpiperazines, azepines, azocins, azonins, acetins and tetra-, di- and perhydro derivatives of each of the above and mixtures of two or more of these heterocyclic amines. Preferred heterocyclic amines are saturated 5- and 6-membered heterocyclic amines containing only nitrogen, oxygen and / or sulfur in the hetero ring, especially piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines and the like. Suitable and useful are piperidine, aminoalkyl substituted piperidines, piperazine, aminoalkyl substituted piperazines, morpholine, aminoalkyl substituted morpholines, pyrrolidine and aminoalkyl substituted pyrrolidines. Typically, aminoalkyl substituents are substituted at the nitrogen atom forming part of the hetero ring. Control examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine and N, N'-di-aminoethylpiperazine.

 Tertiary amines include monoamines and polyamines. Monoamines can be represented by the formula.

где R¹, R² и R³ представляют собой одинаковые или различные углеводородные группы. Предпочтительно, R¹, R² и R³ независимо представляют собой углеводородные группы, содержащие от 1 до примерно 20 атомов углерода. Примеры полезных третичных аминов включают триметиламин, триэтиламин, трипропиламин, трибутиламин, монометилдиэтиламин, моноэтилдиметиламин, диметилпропиламин, диметилбутиламин, диметилпентиламин, диметилгексиламин, диметилгептиламин, диметилоктиламин, диметилнониламин, диметилдециламин, диметилдикоданиламин, диметилфениламин, N, N-диоктил-1-октанамин, N, N-дидодецил-1-додеканамин, трикокоамин (кокосовой пальмы), тригидрированный талловый (говяжьего сала) амин, N-метил-дигидрированный талловый амин, N,N-диметил-1-додеканамин, N, N-диметил-1-тетрадеканамин, N,N-диметил-1-гексадеканамин, N,N-диметил-1-октадеканамин, N,N-диметилкокоамин, N,N-диметилсоевый амин, N,N-диметилгидрированный талловый амин и др.

where R ¹ , R ² and R ³ represent the same or different hydrocarbon groups. Preferably, R ¹ , R ² and R ³ independently represent hydrocarbon groups containing from 1 to about 20 carbon atoms. Examples of useful tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, monometildietilamin, monoetildimetilamin, dimethylpropylamine, dimethylbutylamine, dimethylpentylamine, dimetilgeksilamin, dimetilgeptilamin, dimetiloktilamin, dimetilnonilamin, dimetildetsilamin, dimetildikodanilamin, dimethylphenylamino, N, N-dioctyl-1-octanamine, N, N -didodecyl-1-dodecanamine, tricocoamine (coconut palm), trihydrated tall (beef tallow) amine, N-methyl-dihydrogenated tall amine, N, N-dimethyl-1-dodecanamine, N, N-dimethyl-1- etradekanamin, N, N-dimethyl-1-geksadekanamin, N, N-dimethyl-1-oktadekanamin, N, N-dimetilkokoamin, N, N-dimetilsoevy amine, N, N-tallow amine dimetilgidrirovanny et al.

 Hydroxyamines, such as mono- and polyamines similar to the mono- and polyamines described herein, are also suitable. Hydroxy substituted amines encompass amines having hydroxy substituents directly bonded to a carbon atom other than a carbonyl carbon atom; those. they have hydroxy groups capable of functioning as alcohols. Hydroxyamines may be primary, secondary or tertiary amines, with secondary and tertiary amines being preferred, and tertiary amines are particularly preferred. The terms "hydroxyamine" and "amine alcohol" describe the same class of compounds, and therefore can be used interchangeably.

где каждый R независимо представляет углеводородную или гидрокарбильную группу с числом атомов углерода от одного до примерно восьми, или гидроксилзамещенную углеводородную группу примерно с двумя-восемью атомами углерода, и R' представляет собой двухвалентную углеводородную группу примерно с 2 - 18 атомами углерода. Группа -R'-OH в этих формулах представляет гидроксизамещенную углеводородную группу. R' может быть ациклической, алициклической или ароматической группой. В типичном случае R' представляет ациклическую прямую или разветвленную алкиленовую группу, такую как этиленовая, 1,2-пропиленоновая, 1,2-бутиленовая, 1,2-октадециленовая и др. группа. Когда в одной и той же молекуле присутствуют две R группы, они могут быть связаны прямой углерод-углеродной связью или через гетероатом /например, кислород, азот или серу/, образуя 5-, 6-, 7- или 8-членную кольцевую структуру. Примеры таких гетероциклических аминов включают N-/гидроксил-низший-алкил/-морфолины, -тиоморфолины, -пиперидины, -оксазолидины, -тиазолидины и аналогичные. Типично, однако, каждый R представляет низшую алкильную группу, содержащую до семи атомов углерода.Hydroxyamines include N- / hydroxy substituted hydrocarbyl / amines, hydroxyl substituted poly / hydrocarbyloxy / analogs thereof, and mixtures thereof. They include secondary and tertiary alkanolamines, respectively represented by the formulas:

wherein each R independently represents a hydrocarbon or hydrocarbyl group with one to about eight carbon atoms, or a hydroxyl substituted hydrocarbon group with about two to eight carbon atoms, and R 'is a divalent hydrocarbon group with about 2 to 18 carbon atoms. The group —R′ — OH in these formulas represents a hydroxy-substituted hydrocarbon group. R 'may be an acyclic, alicyclic or aromatic group. Typically, R ′ represents an acyclic straight or branched alkylene group, such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene and other group. When two R groups are present in the same molecule, they can be connected by a direct carbon-carbon bond or through a heteroatom (for example, oxygen, nitrogen or sulfur), forming a 5-, 6-, 7- or 8-membered ring structure. Examples of such heterocyclic amines include N- (hydroxyl lower alkyl) morpholines, thiomorpholines, piperidines, oxazolidines, thiazolidines and the like. Typically, however, each R represents a lower alkyl group containing up to seven carbon atoms.

 Examples of N- / hydroxyl-substituted hydrocarbyl / amines include both li- and tri-ethanolamines, dimethylethanolamine, diethylethanolamine, di / 3-hydroxypropyl / amine, N- / 3-hydroxybutyl / amine, N- / 4-hydroxybutyl / amine, N, N -di- / 2-hydroxypropyl / amine, N- / 2-hydroxyethyl / morpholine and its thio-analog, N- / 2-hydroxyethyl / cyclohexylamine, N-3-hydroxycyclopentylamine, o-, m-, and p-aminophenol, N- / hydroxyethyl / piperazine; N, N'-di / hydroxyethyl / piperazine and the like.

где каждый R представляет независимо алкильную группу примерно с 1 - 4 атомами углерода, предпочтительно с 1 или 2 атомами углерода, и R' представляет алкиленовую группу с примерно 2 - 4 углеродными атомами, предпочтительно примерно с 2 или 3 атомами углерода. Согласно особенно полезному воплощению гидроксиламином является диметилэтаноламин.In a particularly advantageous embodiment, the hydroxyamine is a compound represented by the formula

where each R independently represents an alkyl group with about 1 to 4 carbon atoms, preferably with 1 or 2 carbon atoms, and R 'represents an alkylene group with about 2 to 4 carbon atoms, preferably with about 2 or 3 carbon atoms. According to a particularly useful embodiment, the hydroxylamine is dimethylethanolamine.

где x - число примерно от 2 до 15, и R и R' имеют значения, описанные выше в отношении формул /VI/ и /VII/.Hydroxyamines may also be ether N- / hydroxy-substituted hydrocarbyl / amines. They are hydroxyl substituted poly (hydrocarbyloxy) / analogues of the hydroxy amines described above / these analogues also include hydroxyl substituted oxyalkylene analogues /. Such N- / hydroxyl-substituted hydrocarbyl / amines can conveniently be obtained by the reaction of epoxides with the amines described above and can be represented by the formulas:

where x is a number from about 2 to 15, and R and R 'have the meanings described above in relation to the formulas / VI / and / VII /.

 Polyamine analogs of these hydroxyamines, including alkoxylated alkylene polyamines / for example N, N- / diethanol / ethylene diamine /, can also be used. Such polyamines can be prepared by the reaction of alkyleneamines (for example, ethylene diamine) with one or more alkylene oxides (for example, ethylene oxide, octadecene oxide) with about 2 to 20 carbon atoms. The reaction products of a similar alkylene oxide and alkanolamine oxide, such as those obtained by reacting the above secondary or tertiary alkanolamines with ethylene, propylene, or higher epoxies in molar ratios of 1: 1 or 1: 2, can also be used. The ratio of reagents and temperature for the implementation of such reactions are known to specialists in this field of technology.

 Specific examples of alkoxylated alkylene polyamines include N / 2-hydroxyethyl / ethylenediamine, N, N-bis / 2-hydroxyethyl / ethylenediamine, 1/2-hydroxyethyl / piperazine, mono- (hydroxypropyl) -substituted diethylenetriamine, di (hydroxypropyl) -substituted tetramine , N- / 3-hydroxybutyl / tetramethylenediamine and the like. Higher homologues are likewise suitable, obtained by condensation of the hydroxyalkylene-polyamines illustrated above through amino groups or through amino groups as a result to a higher amine, and is accompanied by the removal of ammonia, while condensation through hydroxy groups results in products containing ether bonds , and is accompanied by the removal of water. Mixtures of two or more of any of the above mono- or polyamines are also suitable.

 Hydroxyalkyl-alkylene polyamines having one or more hydroxyalkyl substituents on nitrogen atoms are also useful. Useful hydroxyalkyl substituted alkylene polyamines include compounds in which the hydroxyalkyl group is a lower hydroxyalkyl group, i.e. having less than eight carbon atoms. Examples of such hydroxyalkyl substituted polyamines include N- / 2-hydroxyethyl / ethylenediamine, N, N-bis / 2-hydroxyethyl / ethylenediamine, 1- / 2-hydroxyethyl / piperazine, mono-hydroxypropyl substituted diethylene triamine, dihydroxypropyl substituted 3-tetra-ethylenediamine 3-tetra-ethylenediamine / tetramethylenediamine, etc. Similarly useful homologues are obtained by condensation of the hydroxyalkylene polyamines illustrated above through amino groups or via hydroxy groups. Condensation through amino groups results in a higher amine followed by removal of ammonia, and condensation through hydroxy groups results in products containing ether bonds followed by removal of water.

в которой n представляет число от 1 до примерно 10, предпочтительно примерно 2-10; каждый R независимо представляет атом водорода, углеводородную или -гидроксизамещенную углеводородную группу, имеющую примерно до 700 атомов углерода, предпочтительно примерно до 100 атомов углерода, более предпочтительно до примерно 50 атомов углерода, еще более предпочтительно примерно до 30 атомов углерода; и "алкиленовая" группа имеет примерно от 1 до 18 атомов углерода, предпочтительно примерно 2-18 углеродных атомов: более предпочтительно 2-4 атома углерода, причем предпочтительной алкиленовой группой является этиленовая или пропиленовая. Пригодные алкиленполиамины включают полиамины, в которых каждый R представляет водород, причем особенно предпочтительными являются этиленполиамины и смеси этиленполиаминов.Useful polyamines include alkylene polyamines represented by the formula

in which n represents a number from 1 to about 10, preferably about 2-10; each R independently represents a hydrogen atom, a hydrocarbon or hydroxy-substituted hydrocarbon group having up to about 700 carbon atoms, preferably up to about 100 carbon atoms, more preferably up to about 50 carbon atoms, even more preferably up to about 30 carbon atoms; and the "alkylene" group has from about 1 to 18 carbon atoms, preferably about 2-18 carbon atoms: more preferably 2-4 carbon atoms, with the preferred alkylene group being ethylene or propylene. Suitable alkylene polyamines include polyamines in which each R represents hydrogen, with ethylene polyamines and mixtures of ethylene polyamines being particularly preferred.

 Alkylene polyamines that are useful include methylene polyamines, ethylene polyamines, butylene polyamines ,pilepylene polyamines, pentylene polyamines, hexylene polyamines, heptylene polyamines, hephenylenediamine diamine diamine diamine diamine diamine diamine diamine diamine diamine diamine diamine diamine tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine di / trimethylene / triamine, N- / 2-aminoethyl / piperazine, 1,4-bis-2-aminoethyl / piperazine, and the like. Higher homologues are also useful as amines in this invention, such as those obtained by condensation of two or more alkyleneamines illustrated above, as well as a mixture of two or more of any of the polyamines described.

 Ethylene polyamines, such as those mentioned above, are described in detail in the section entitled "Diamines and Higher Amines" in the Encyclopedia of Chemical Technology, second edition. Kirk and Otmer, Volume 7, pp. 27-39, Int. Science Publishers, John Wiley & Sons, 1965 / Eng. language /, and these pages are mentioned here for information. Such compounds are most conveniently prepared by reacting alkylene chloride with ammonia or by reacting ethyleneimine with a ring opening reagent such as ammonia and others. These reactions result in several complex mixtures of alkylene polyamines, including cyclic condensation products such as piperazines.

где R представляет OH, NH₂, ONH₄, и др.; R_a представляет поливалентную органическую группу, имеющую валентность равную x + y; R_b и R_c каждый независимо представляет водород, гидрокарбил или замещенный гидрокарбил, при условии, что по крайней мере один из R_b и R_c представляет водород на молекулу аминосульфоновой кислоты; x и y каждый представляет целое число равное или большее, чем один. Каждый аминосульфоновый реагент характеризуется по крайней мере одной HN< или H₂N-группой, и по крайней мере одной группой

Этими сульфоновыми кислотами могут быть алифатические, циклоалифатические или ароматические аминосульфокислоты и соответствующие функциональные производные сульфогруппы. В частности, аминосульфоновыми кислотами могут быть ароматические аминосульфоновые кислоты, то есть в которых R_a представляет многовалентную ароматическую группу, такую как фенилен, где по крайней мере одна группа

присоединена непосредственно к ядерному атому углерода ароматической группы. Аминосульфоновой кислотой может быть также моноаминоалифатическая сульфоновая кислота; то есть кислота, в которой x = 1, и R_a представляет собой поливалентную алифатическую группу, такую как этилен, пропилен, триметилен, и 2-метилен-пропилен. Другими подходящими аминосульфоновыми кислотами и их производными, полезными в качестве аминов в данном изобретении, являются соединения, описанные в патентах США 3029250, 3367864 и 3926820; которые включены в данное описание для сведения.Aminosulfonic acids and their derivatives corresponding to the formula are also suitable as amines:

where R represents OH, NH ₂ , ONH ₄ , and others; R _a represents a polyvalent organic group having a valency equal to x + y; R _b and R _c each independently represents hydrogen, hydrocarbyl or substituted hydrocarbyl, provided that at least one of R _b and R _c represents hydrogen per amino sulfonic acid molecule; x and y each represents an integer equal to or greater than one. Each aminosulfone reagent is characterized by at least one HN <or H ₂ N group, and at least one group

These sulfonic acids can be aliphatic, cycloaliphatic or aromatic amino sulfonic acids and the corresponding functional derivatives of the sulfo group. In particular, the amino sulfonic acids can be aromatic amino sulfonic acids, that is, in which R _a represents a multivalent aromatic group, such as phenylene, where at least one group

attached directly to the nuclear carbon atom of the aromatic group. Aminosulfonic acid may also be monoaminoaliphatic sulfonic acid; that is, an acid in which x = 1 and R _a represents a polyvalent aliphatic group, such as ethylene, propylene, trimethylene, and 2-methylene-propylene. Other suitable aminosulfonic acids and their derivatives useful as amines in this invention are the compounds described in US Pat. Nos. 3,029,250, 3,367,864 and 3,926,820; which are included in this description for information.

 Hydrazine and substituted hydrazine may also be used as amines in this invention. At least one of the nitrogen in hydrazine must contain directly bonded hydrogen. Substituents that may be present in hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Typically, substituents are alkyl, especially lower alkyl, phenyl, and substituted phenyl, such as lower alkoxy substituted phenyl or lower alkyl substituted phenyl. Specific examples of substituted hydrazines are methylhydrazine, N, N-dimethylhydrazine, N, N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine, N- / paro-tolyl / -N '- / n-butyl / -hydrazine, N- (para-nitrophenyl) -hydrazine, N- (paranitrophenyl) -N-methylhydrazine, N, N'-di- (para-chlorophenol) -hydrazine, N-phenyl-N'-cyclohexyhydrazine and the like.

 High molecular weight hydrocarbylamines, both monoamines and polyamines that can be used as amines in this invention, are usually prepared by reacting a chlorinated polyolefin having a molecular weight of at least about 400 with ammonia or amine. Amines that can be used are known in the art and are described, for example, in US Pat. Nos. 3,275,554 and 3,438,757, both of which are incorporated herein by reference. These amines must have at least one primary or secondary amino group.

группу на девять аминозвеньев, присутствующих в главной цепи; например, 1-4 таких разветвленных цепи на девять звеньев в главной цепи, но предпочтительно одну боковую цепь на девять звеньев главной цепи. Таким образом, эти полиамины содержат по крайней мере три первичные аминогруппы и по крайней мере одну третичную аминогруппу. Эти амины могут быть выражены формулой:

где R представляет алкиленовую группу, такую как этиленовая, пропиленовая, бутиленовая и другие гомологи /как с прямой, так и с разветвленной цепью/, и др. , но предпочтительно этиленовую; а x, y и z являются целыми числами; x находится в интервале примерно от 4 до 24 или более, предпочтительно примерно от 6 до 18; y находится в интервале от 1 до примерно 6 или более, предпочтительно от 1 до примерно 3; и z находится в интервале от нуля до примерно 6, предпочтительно от 0 до 1. Звенья x и y могут быть последовательными, чередующимися, упорядоченно или беспорядочно распределенными. Пригодный класс таких полиаминов включает полиамины формулы:

где n - целое число в интервале от 1 до примерно 20, или более, предпочтительно в интервале от 1 до 3, и R представляет предпочтительно этилен, но может быть пропиленом, бутиленом и др. /с прямой или разветвленной цепью/. Полезные воплощения представлены формулой:

где n - целое число в интервале от 1 до 3. Группы в скобках могут быть соединены таким образом, как голова-к-голове или голова-к-хвосту. Патенты США NN 3200106 и 3259578 включены для сведения в связи с информацией, приведенной в них и касающейся указанных полиаминов.Another group of amines suitable for use in this invention are branched polyalkylene polyamines. branched polyalkylene polyamines are polyalkylene polyamines in which a branched group is a side chain containing on average at least one nitrogen-linked aminoalkylene

a group of nine amino links present in the main chain; for example, 1-4 of such branched chains of nine links in the main chain, but preferably one side chain of nine links of the main chain. Thus, these polyamines contain at least three primary amino groups and at least one tertiary amino group. These amines can be expressed by the formula:

where R represents an alkylene group, such as ethylene, propylene, butylene and other homologs / as a straight or branched chain /, etc., but preferably ethylene; and x, y and z are integers; x is in the range of from about 4 to 24 or more, preferably from about 6 to 18; y is in the range from 1 to about 6 or more, preferably from 1 to about 3; and z is in the range from zero to about 6, preferably from 0 to 1. The units x and y can be sequential, alternating, orderly or randomly distributed. A suitable class of such polyamines includes polyamines of the formula:

where n is an integer in the range from 1 to about 20, or more, preferably in the range from 1 to 3, and R is preferably ethylene, but may be propylene, butylene, etc. / with a straight or branched chain /. Useful embodiments are represented by the formula:

where n is an integer in the range from 1 to 3. The groups in brackets can be connected in such a way as head-to-head or head-to-tail. US patents NN 3200106 and 3259578 are included for information in connection with the information provided therein regarding these polyamines.

Suitable amines also include polyoxyalkylene polyamines, for example polyoxyalkylene diamines and polyoxyalkylene triamines having an average molecular weight of from about 200 to 400, preferably from about 400 to 2000. Examples of these polyoxyalkylene polyamines include amines represented by the formula:
NH ₂ -alkylene - / - O-alkylene- / _m NH ₂ ,
where m has a value of from about 3 to 70, preferably from 10 to 35; and the formula:
R- [Alkylene- (O-Alkylene-) _n NH ₂ ] _3-6 ,
where n is a number in the range from 1 to 40, provided that the sum of all n is from about 3 to 70, and usually from about 6 to 35, and P represents a polyvalent saturated hydrocarbyl group with about 10 carbon atoms having a valency from about 3 to 6. Alkylene groups can be straight or branched chain groups and contain from 1 to about 7 carbon atoms, and usually from 1 to 4 carbon atoms. The various alkylene groups present in the above formulas may be the same or different.

где x имеет значение примерно от 3 до 70, предпочтительно примерно от 10 до 35; и

где X+Y+Z имеет общее значение в интервале примерно от 3 до 30, предпочтительно примерно от 5 до 10.More specific examples of ethyl polyamines include:

where x has a value of from about 3 to 70, preferably from about 10 to 35; and

where X + Y + Z has a total value in the range of from about 3 to 30, preferably from about 5 to 10.

 Suitable polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene diamines and polyoxypropylene triamines having an average molecular weight in the range of about 200 to 2000. Polyoxyalkylene polyamines are commercially available from the Jefferson Chemical Company under the Jeffamine brand name. US patents 3804763 and 3948800 are mentioned here for information in connection with the description in them of such polyoxyalkylene polyamines.

где R представляет собой полиалкиленовую / например полибутеновую группу/.Compositions of carboxy derivatives derived from acylating agents / A / and ammonia or amines / B / described herein previously include acylated amines, which typically include one or more of the salts of amines, amides, imides and / or imidazolines, as well as two or more of them. When the amine (B) is hydroxyamine, the carboxyl derivative compositions usually include esters and / or ester salts (for example, a half ester and a half salt). The amine salt may be an external salt in which an ionic salt bond is formed between the acylating agent / A / and the nitrogen atom from the amine / B /; otherwise, the amine is not bound to an acylating agent. The amine salt may also be an internal salt in which the acylating agent / A / and the amine / B / are linked to each other via a non-salt bond (for example, an ester bond), and the nitrogen atom from the bound amine forms a salt bond with the acylating agent. Examples of these salts are the following:

where R represents a polyalkylene / for example polybutene group /.

To obtain compositions of carboxylic acid derivatives from acylating agents / A / ammonia or amines / B /, one or more acylating agents and one or more ammonia and / or amines are heated optionally in the presence of a usually liquid, mainly inert organic liquid solvent / diluent, at temperatures in the range of from about 30 ^o C to the decomposition point of a reactant or product having the lowest such temperature, but normally at temperatures in the range from about 50 "to 300", provided that 300 ^o C does not exceed the point decomp zheniya. Temperatures from about 50 ^° C to 200 ^° C can be used.

 Due to the fact that the acylating agents / A / can be reacted with ammonia and amines / B / in the same manner as the high molecular weight acylating agents of the prior art, US Pat. connection with the information available in them regarding the procedures used for the interaction of acylating agents / A / with ammonia and amines / B /.

 In one embodiment, the acylating agent (A) is reacted with about 0.5-3, preferably about 0.5-2, more preferably 0.5-1.5, and even more preferably 0.8-1.2 equivalents of ammonia or amine (B) per equivalent acylating agent / A /. In other embodiments, increasing amounts of ammonia or amine (B) may be used.

 The number of equivalents of the acylating agent / A / depends on the total number of carboxyl functions present. When determining the number of equivalents of acylating agents, those carboxylic functions that are not able to react as a carboxylic acid acylating agent are excluded. Usually, however, there is one equivalent of an acylating agent per carboxy group in these acylating agents. For example, there are two equivalents in the anhydride resulting from the reaction of one mole of oleic polymer and one mole of maleic anhydride. Conventional techniques are freely available to determine the number of carboxyl functions (e.g., acid number, saponification number), and thus, the number of equivalents of the acylating agent can be easily determined by one skilled in the art.

 The equivalent weight of an amine or polyamine is the molecular weight of an amine or polyamine divided by the total number of nitrogen atoms present in the molecule. So, ethylenediamine has an equivalent weight equal to half its molecular weight; diethylenetriamine has an equimolar weight equal to one third of its molecular weight. The equivalent weight of an industrially available mixture of polyalkylene polyamine can be determined by dividing the atomic weight of nitrogen / 14 / by% N contained in the polyamine, multiplying by 100; thus, a polyamine mixture containing 34% N will have an equivalent weight of 41.2. The equivalent weight of ammonia or monoamine is its molecular weight.

 The equivalent weight of hydroxyamine reacted with an acylating agent under amide or imide formation conditions is its molecular weight divided by the total number of nitrogen atoms present in the molecule. Under such conditions, hydroxyl groups are not taken into account when calculating the equivalent weight. Thus, ethanolamine has an equivalent weight equal to its molecular weight, and diethanolamine has an equivalent weight (based on nitrogen) equal to its molecular weight when such amines undergo reaction under the conditions of formation of an amide or imide.

 The equivalent weight of a hydroxyamine reacted with an acylating agent under ester formation conditions is its molecular weight divided by the number of hydroxyl groups present, and the nitrogen atoms present are ignored. Thus, in the preparation of esters from diethanolamine, the equivalent weight of diethanolamine is equal to half its molecular weight.

The amount of ammonia or amine / B / which is reacted with the acylating agent / A / may also partially depend on the number and type of nitrogen atoms present. For example, a reaction with an acylating agent requires a smaller amount of a polyamine containing one or more —NH ₂ groups than a polyamine having the same number of nitrogen atoms, but fewer or not containing at all —NH ₂ groups. To form an imide, one —NH ₂ group can react with two —COOH groups. If only secondary nitrogen atoms are present in the amine compound, each> NH group can interact with only one —COOH group. Accordingly, the amount of polyamine reacted with an acylating agent to form carboxylic derivatives of the invention can be easily determined based on the number and types of nitrogen atoms in the polyamine (e.g., —NH ₂ ,> NH and> N—).

 In addition to the relative amounts of the acylating agent / A / and ammonia or amine / B / used to form the carboxyl derivative composition, other important features of the carboxyl derivative compositions used in this invention are the Mn and Mw / Mn values of the polyalkene, as well as the presence of acylating agents on average at least 1.3 amber groups for each equivalent weight of the substituent groups.

 The preparation of acylating agents / A / is illustrated in the following Examples 1-10, and the preparation of carboxylic acid derivative compositions useful as emulsifiers in the emulsions of the invention is illustrated in Examples A-C. In the following examples, and throughout the description and claims, all temperatures are given in degrees C, and all percentages and parts are given by weight, unless otherwise indicated.

 Example 1

A mixture of 1000 parts of polyisobutene / Mn = 1750; Mn = 6300 / and 106 parts of maleic anhydride was heated to 138 ^° C. This mixture was heated to 190 ^° C for 9-14 hours, during which 90 parts of liquid chlorine was added. The reaction mixture was adjusted by the addition of chlorine, the addition of maleic anhydride or a purge of nitrogen, as necessary to obtain a composition of a polyisobutene-substituted succinic acylating agent with a total acid number of 95, with a content of free maleic anhydride of not more than 0.6% by weight and with a chlorine content of about 0.8 % by weight. The composition had a flash point of 180 ^° C, a viscosity at 150 ^° C of 530 cst and a viscosity at 100 ^° C of 5,400 ct. The ratio of amber groups to the equivalent weights of polyisobutene in the acylating agent was x 1.91.

Example 2
A mixture of 510 parts of polyisobutene / Mn = 1845; Mw = 5325 / and 59 parts of maleic anhydride was heated to 110 ^° C. The mixture was heated to 190 ^° C. after 7 hours, during which 43 parts of chlorine gas were added below the surface of the mixture. At 190-192 ^° C., an additional 11 parts of chlorine were added over 3.5 hours. The reaction mixture was distilled off by heating at 190-193 ^o C with a nitrogen purge for 10 hours. The residue is the desired polyisobutene-substituted succinic acylating agent having an equivalent saponification number of 87, as determined by ASTM D-94. (ASTM - American Society for Testing Materials).

Example 3
A mixture of 1000 parts of polyisobutene / Mn = 2020; Mw = 6049 / and 115 parts /1.17 moles / of maleic anhydride was heated to 110 ^° C. The mixture was heated to 184 ^° C after 6 hours, during which 85 parts of chlorine gas were added below the surface of the mixture. At 184-189 ^° C., an additional 59 parts of chlorine were added over 4 hours. The reaction mixture was distilled off by heating at 186-190 ^o C with a nitrogen purge for 26 hours. The residue is the desired polyisobutene-substituted succinic acylating agent having an equivalent saponification number of 87, as determined by ASTM (Procedure D-94).

Example 4
A mixture of polyisobutene chloride, obtained by adding 251 parts of gaseous chlorine to 3000 parts of polyisobutene (Mn = 1696, Mw = 6594) at 80 ^° C. for 4.66 hours, and 345 parts of maleic anhydride was heated to 200 ^° C. for 0.5 hour . The reaction mixture was left to stand for 6.33 hours at 200-224 ^° C, distilled off at 210 ^° C under vacuum, and filtered. The filtrate is the desired polyisobutene-substituted succinic acylating agent having an equivalent saponification number of 94, as determined by ASTM D-94.

Example 5
A mixture of 3000 parts of polyisobutene / Mn = 1845; Mw = 5325 / and 344 parts of maleic anhydride is heated to 140 ^° C. This mixture is heated to 201 ^° C. after 5.5 hours, during which 312 parts of chlorine gas are added below the surface. The reaction mixture is heated at 201-236 ^° C. under nitrogen purging for 2 hours and evaporated in vacuo at 203 ^° C. The reaction mixture is filtered to give the filtrate as the desired polyisobutene-substituted succinic acylating agent having an equivalent saponification number of 92 as determined by ASTM / American Society for Testing Materials / D-94.

Example 6
A mixture of 3000 parts of polyisobutene / Mn = 2020; Mw = 6049 / and 364 parts of maleic anhydride is heated at 220 ^° C. for 8 hours. The reaction mixture is cooled to 170 ^° C. At 170-190 ^° C. below the surface after 8 hours, 105 parts of chlorine gas are added. The reaction mixture is heated at 190 ^° C. under nitrogen purging for 2 hours and then evaporated in vacuo at 190 ^° C. The reaction mixture is filtered to give the filtrate as the desired polyisobutene-substituted succinic acylating agent.

Example 7
A mixture of 800 parts of polyisobutene falling within the scope of the claims of the present invention and having a Mn of about 2000, 646 parts of mineral oil and 87 parts of maleic anhydride is heated at 179 ^° C. for 2.3 hours. 100 parts of gaseous chlorine at 176-180 ^o C are added below the surface of the mixture over a period of 19 hours. The reaction mixture is evaporated by nitrogen purging for 0.5 hours at 180 ^° C. The residue is an oil-containing solution of the desired polyisobutene-substituted succinic acylating agent.

Example 8
The procedure of example 2 is repeated except that polyisobutene / Mn = 1845; Mw = 5808 / is replaced on an equimolar basis with polyisobutene / Mn = 1457; Mw = 5808 /.

Example 9
The procedure of example 2 is repeated except that polyisobutene / Mn = 1845; Mw = 5325 / is replaced on an equivalent basis with polyisobutene / Mn = 251; Mw = 5793 /.

Example 10
The procedure of example 2 is repeated except that polyisobutene / Mn = 1845; Mw = 5325 / is replaced on an equivalent basis with polyisobutene / Mn = 3220; Mw = 5660 /.

Example A
A mixture of 4920 parts /8.32 equivalent / of a polyisobutene-substituted succinic acylating agent obtained in accordance with the procedure of Example 1 and 2752 parts of 40 Neutral oil is heated to 50-55 ^° C. with stirring. Over a period of 6 minutes, 742 parts of /8.32 equivalents / dimethylethanolamine are added. The reaction mixture exotherms to 59 ^° C. The reaction mixture is heated to 115 ^° C. over a period of 3 hours. The nitrogen product begins at a speed of 1.5 standard cubic feet per hour / 0.042 m ³ / hour /, and the reaction mixture is heated to 135 ^° C. over a period of 0.5 hours. The mixture is heated to and maintained at 140-160 ^o C for 14 hours, then cooled to room temperature, giving the desired product. The product has a nitrogen content of 1.35% by weight, total acid number 13.4, total base number 54.8, viscosity at 100 ^° C 125 cst, viscosity at 40 ^° C 2945 ct, specific gravity at 15.6 ^° C 0 , 94, and flash point 82 ^o C.

Example B
A mixture of 1773 parts / 3 equivalents / of a polyisobutene-substituted succinic acylating agent prepared in accordance with the procedure of Example 1 and 992 parts of a neutral oil 40 was heated at 80 ^° C. with stirring. To it was added 267 parts / 3 equivalents / dimethylethanolamine over a period of 6 minutes. The reaction mixture was heated to 132 ^° C. over a period of 2.75 hours. The mixture was heated to and maintained at a temperature of 150-174 ^o C for 12 hours, then cooled to room temperature, giving the desired product. The product had a nitrogen content of 0.73% by weight, a total acid number of 12.3, a total base number of 29.4, viscosity at 100 ^° C. 135 cst. viscosity at 40 ^o C 2835 cst, specific gravity at 15.6 ^o C 0.933, flash point 97 ^o C.

Example C
The procedure of Example B is repeated except that after cooling the product to room temperature, 106 parts of dimethylethanolamine are added with stirring. The resulting product has a nitrogen content of 1.21% by weight, total acid number 11.3, total base number 48.9, viscosity at 100 ^° C 110 sst, viscosity at 40 ^° C 2730 sst, specific gravity at 15.6 ^° C 0.933 and inflammation point 90 ^° C.

Example D
The mixture is prepared by adding 10.2 parts of /0.25 equivalent / industrial mixture of ethylene polyamines having from about 3 to 10 nitrogen atoms in the molecule to 113 parts of mineral oil and 161 parts of /0.25 equivalent / substituted succinic acylating agent obtained in example 2, at 138 ^o C. The reaction mixture is heated to 150 ^o C after 2 hours and evaporated by blowing nitrogen. The reaction mixture is filtered to give the filtrate as a solution of the desired solution of the desired product.

Sensitizers
In one embodiment of the invention, closed-cell materials containing voids are used as sensitizing components. The term "closed cell, void-containing material" is used here to mean any material in the form of particles, which includes closed cells, cavities. Each material particle may contain one or more closed cells, the cells may contain a gas, such as air, or may be evacuated or partially evacuated / with evacuated gas /. In one embodiment of the invention, a sufficiently closed cellular material containing voids is used to obtain a density in the resulting emulsion of about 0.8 to 1.35 g / cm3, more preferably about 0.9-1.3 g / cm3, even more preferably about 1.1-1.3 g / cc. Typically, the emulsions that are the subject of this invention may contain up to about 15% by weight, preferably from about 0.25% to 15% by weight of the closed cell containing void material. Preferred enclosed cellular, void containing materials are discrete glass spherical particles having a size in the range of about 10-175 microns. Typically, the bulk density of such particles can be in the range of about 0.1 to 0.4 g / cc. Useful glass microbubbles or microspheres that can be used are microbubbles sold by 3M, which have a particle size distribution in the range of about 10 and 160 microns and a nominal size in the range of about 60-70 microns, and a density in the range of about 0.1 to 0.4 g / cube see. Microbeads identified by the industrial designation C15 / 250, which have a particle density of 0.15 g / cc, can be used. cm, and 10% of such beads break at a static pressure of 250 lbs. / sq. inch /17.63 kg / sq.cm /. Balls identified by B37 / 2000, which have a particle density of 0.37 g / cc, can also be used. cm, and 10% of such beads are crushed at a static pressure of 2000 psi. inch /140.6 kg / sq.cm /. Other suitable glass beads are sold under the ECOSPHERE trademark by Emerson & Cumming, Inc. and typically have a particle size of about 44 to 175 microns and a bulk density of about 0.15-0.4 g / cc. Other suitable beads include inorganic microspheres sold under the trade name Q-CEL by the Philadelphia Quartz Company.

 Closed cellular materials containing voids may be made from inert or reducing materials. For example, phenol-formaldehyde beads may be used within the scope of this invention. If phenol-formaldehyde microbubbles or microspheres are used, the microbubbles themselves are the fuel component for the explosive, and their fuel number should be taken into account when designing the explosive composition in the form of a water-in-oil emulsion. Another closed cellular, void-containing material that can be used within the scope of this invention are saran microspheres sold by the Dow Chemical Company. Saran microspheres have a diameter of about 30 microns and a particle density of about 0.032 g / cc. Due to the low bulk density of sarana microspheres, it is preferred that only about 0.25 to 1% by weight of these particles are used in the emulsions of the present water-in-oil type emulsions.

 Gas bubbles can also be used to sensitize explosive emulsions, which are generated in situ when a gas-generating material is added to or distributed in the composition, such as, for example, an aqueous solution of sodium nitrite. Other suitable sensitizing components, which can be used singly or in addition to those listed, include insoluble solid self-explosive substances in the form of particles or fuels, such as, for example, granular or flaky or flake-like TNT, DNT, RDX and the like, aluminum, aluminum alloys, silicon and ferrosilicon; and water soluble and / or hydrocarbon soluble organic desensitizers, such as, for example, amine natrates, alkanolamine, hydroxyalkyl nitrates and the like. Explosive emulsions of the present invention can be formed for a wide variety of applications. Any combination of sensitizing components can be selected in order to provide the explosive composition with virtually any desired density, tensile strength under the influence of weight or critical diameter. The amount of solid self-explosive substances or fuels and water-soluble and / or hydrocarbon-soluble organic sensitizers can be up to about 50% by weight of the entire explosive composition. The volume of the occluded gas component can be up to about 50% of the volume of the entire explosive composition.

 Oxygen-containing salts from solid particles.

 In one embodiment of the invention, oxygen-containing salts and solid particles may be included in the emulsions or mixed in the emulsions of the invention to increase the explosive strength of such emulsions. These salts may be ammonium nitrate, sodium nitrate, calcium nitrate, or a mixture of two or more of these salts. Ammonium nitrate is particularly useful. These particulate solids may be in the form of granules, crystals or flakes. Ammonium nitrate granules are especially useful. In one embodiment of the invention, the Kaltenbach-Thoring / KT / process is used to prepare ammonium nitrate granules. This process includes the use of one or more crystal growth modifiers to help control crystal growth. It also includes the use of one or more surfactants to reduce sintering. An example of a commercially available material prepared by this process are Columbia KT ammonium nitrate granules sold by Columbia Nitrogen. The habitus crystal modifier and surface active agent used in the preparation of Columbia CT granules are each sold under the trade name Galoril.

 Particulate ammonium nitrate solids (for example, ammonium nitrate granules), which are available in the form of pre-prepared mixtures of ammonium nitrate and fuel oil / ANFO / Normally ANFO contains about 94% by weight of ammonium nitrate and about 6% fuel oil / for example diesel fuel /, although these proportions may vary.

 The amounts of these particulate solid oxygen-supplying salts or ANFOs that are used can be up to about 80% by weight of the total explosive composition. In one embodiment of the invention, explosive compositions are used comprising about 25% to 35% by weight of the emulsion according to the invention and about 65% to 75% of solid particulate oxygen-supplying salts or ANFOs. In one embodiment, explosive compositions are used comprising about 45% to 65% by weight of the emulsion of the invention and about 45% to 55% of solid oxygen-containing particulate salts or ANFOs. In another embodiment, explosive compositions are used comprising about 70% to 80% by weight of the emulsion of the invention and about 20% to 30% of solid oxygen-containing particulate salts or ANFOs.

Additional additives
Additional additives may be included in the emulsions of the invention in order to improve the sensitivity, density, strength, rheological properties and cost of the final explosive. Typical materials that are found useful as optional additives include, for example, particulate non-metallic fuels such as sulfur, gilsonite and the like; particulate inert materials such as sodium chloride, barium sulfate and the like; thickeners such as kieselguhr resin, polyacrylamide, carboxymethyl or ethyl cellulose, biopolymers, starch, elastomeric materials and the like; crosslinking agents for thickeners such as potassium pyroantimonate and the like; buffers or pH adjusters such as sodium borate, zinc nitrate and the like; crystal habit modifiers such as alkalnaphthalene sodium sulfonate and the like; liquid phase extenders such as formamide, ethylene glycol and the like; and bulk agents and additives commonly used in explosive technology. Used in explosive technology. The amounts of additional additives used may be up to about 50% by weight of the total explosive composition.

The method of obtaining emulsions
A useful method for preparing the emulsions of the invention includes the steps of [1] mixing water, inorganic oxidizing salts / for example ammonium nitrate /, and, in some cases, some of the additional water-soluble compounds, in the first premix, / 2 / mixing carbonaceous fuel, an emulsifier of the invention and or other optional oil soluble compounds, in another premix, and / 3 / adding the first premix to the second premix in a suitable mixing device to form a water-in-oil emulsion. The first premix is heated until all salts are completely dissolved, and the solution can be filtered, if necessary, to remove any insoluble residue. The second premix is also heated to fluidize the ingredients. Any type of device capable of mixing with either low or high shear can be used to prepare these water-in-oil emulsions. Closed cellular, void-containing materials, gas-generating materials, solid self-exploding ingredients, such as particulate TNT, particulate oxygen-containing solid salts, such as ammonium nitrate and ANFO granules, solid fuels, such as aluminum or sulfur, inert materials are added to the emulsion such as barites or sodium chloride, undissolved solid oxidizing salts and other optional materials, if applicable, and simply mix until homogeneously dispersed throughout the composition .

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

 The emulsifiers of this invention can be added directly to the emulsions of the invention. They can also be diluted with a substantially inert, usually liquid, organic diluent, such as mineral oils, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concentrates typically contain from about 10% to about 90% by weight of the emulsifier composition of the present invention and may contain, in addition to it, one or more other additives known in the art or described herein above.

Examples I-IX are directed to explosive emulsions using an emulsifier prepared in accordance with the description of Example A. The preparations of these explosive emulsions are shown below in table 1 / and all numerical quantities are given in grams /. The procedure for creating these emulsions includes the following steps. Ammonium nitrate is mixed with water at a temperature of 82 ^o C. The emulsifier is mixed with mineral oil at a temperature of 52 ^o C. A mixture of ammonium nitrate and water is added to the mixture of oil and emulsifier to form a water-in-oil emulsion. Then glass microbubbles are added. Each of these explosive emulsions is useful as an explosive / nitroglycerin / agent.

Example X
The following emulsion is obtained using the Kolumbai CT ammonium nitrate granules / Columbia Nitrogen product, identified as ammonium nitrate granules made using the Kaltenbach-Toring process using a crystal growth modifier and a surface active agent, each of which is available under the trade name Galoril. Below is the preparation of this emulsion / all numerical quantities are presented in grams /.

Ammonium nitrate - 534.52
Granules Columbio CT - 229.08
Water - 156.40
40 Neutral oil - 65.00
The product of example A - 15.00
An emulsion is prepared by mixing ammonium nitrate with water, and then melting the Columbia CT granules in ammonium nitrate and water. The emulsifier of Example A is mixed with a neutral oil 40. A mixture of ammonium nitrate, water and Columbia CT granules is added to the mixture of oil and emulsifier. The resulting emulsion has a cream consistency (no graininess) for three months after its manufacture.

 Examples XI-XIX are directed to explosive compositions consisting of mixtures of emulsions from Examples I-III and ANFO. ANFO is a mixture of solid particles of ammonium nitrate / 94% by weight / and diesel fuel oil / 6% by weight /. preparations are presented in table 2 / all numerical quantities are presented in grams /.

 Although the invention has been explained in relation to its preferred embodiments, it should be understood that various modifications are apparent to those skilled in the art after reading the description. Therefore, it should be understood that the invention disclosed in the description is intended to cover such modifications as are included in the scope of the attached claims.

Claims (38)

 1. A water-in-oil emulsion comprising a discontinuous aqueous phase containing at least one oxygen — a supply component and a continuous organic phase comprising at least one carbonaceous fuel, as well as a small amount of at least one emulsifier, characterized in that an emulsifier is obtained by the reaction of component (A) with component (B), wherein component (A) is at least one substituted amber acylating agent, said substituted amber acylating agent consisting of groups and succinic groups in which the substituent groups are derived from polyalkene, said acylating agents are characterized by the presence in their structure of an average of at least 1.3 succinic groups for each equivalent weight of the substituent groups, and component (B) is ammonia and / or at least one amine.  2. The emulsion according to claim 1, characterized in that said acylating agents are characterized by the presence in their structure of from about 1.5 to about 2.5 succinic groups for each equivalent weight of the replacement groups.  3. The emulsion according to claim 1, characterized in that said polyalkene has an Mn of at least about 500.  4. The emulsion according to claim 1, characterized in that the Mw / Mn value for the specified polyalkene is from about 1.5 to about 5.  5. The emulsion according to claim 1, characterized in that said polyalkene has a Mn value from about 1300 to about 5000 and an Mw / Mn value from about 2.8 to about 5.  6. The emulsion according to claim 1, characterized in that the substituent groups in component (A) are derived from one or more polyalkenes selected from the group consisting of terminal olefin homopolymers and copolymers with carbon numbers from 2 to about 16, provided that that these copolymers may optionally contain up to about 25% of polymer units derived from internal olefins with up to about 6 carbon atoms.  7. The emulsion according to claim 1, characterized in that the substituent groups in component (A) come from a compound selected from the group consisting of polybutene, polypropylene-RWT, ethylene-propylene copolymer, styrene-diene copolymer and mixtures of any two or more of them.  8. The emulsion according to claim 1, characterized in that the substituents in component (A) come from polybutene, in which at least about 50% of all units derived from butenes come from isobutene.  9. The emulsion according to claim 1, characterized in that component (B) is at least one monoamine, one hydroxyamine, one tertiary amine, one alkanol-tertiary monoamine.  10. The emulsion according to claim 1, characterized in that component (B) is (a) at least one N- (hydroxyl substituted hydrocarbyl) amine, (b) at least one hydroxyl substituted poly (hydrocarbyloxy) analog of compound (a) ) or (c) a mixture of (a) and (b).  11. The emulsion according to claim 1, characterized in that component (B) is at least one alkanolamine containing up to about 40 carbon atoms. 12. The emulsion according to claim 1, characterized in that component (B) is selected from the group consisting of (a) secondary and tertiary alkanolamines represented by the formulas, respectively

(b) hydroxyl substituted oxyalkylene analogs of said alkanolamines represented by the formulas

where X is from about 2 to 15;
each R independently represents a hydrocarbon group with the number of carbon atoms from 1 to about 8 or a hydroxyl substituted hydrocarbon group with 2 to about 8 carbon atoms;
R 'represents a divalent hydrocarbon group with a carbon number of from 2 to about 18,
and (c) mixtures of two or more of them. 13. The emulsion according to claim 1, characterized in that the component (B) is represented by the formula

where each R independently represents an alkyl group containing from 1 to about 4 carbon atoms;
R 'represents an alkylene group containing from 2 to about 4 carbon atoms.  14. The emulsion according to claim 1, characterized in that the component (B) is dimethylethanolamine. 15. The emulsion according to claim 1, characterized in that component (B) is at least one alkylene polyamine of the formula

where n represents a number from 1 to about 10;
each R independently represents a hydrogen atom, or a hydrocarbon group, or a hydroxy-substituted hydrocarbon group having up to about 700 carbon atoms, and the alkylene group has from 1 to about 18 carbon atoms.  16. The emulsion according to claim 1, characterized in that the equivalent ratio of component (A) to component (B) is in the range from about 1: 0.5 to about 1: 3.  17. The emulsion according to claim 1, characterized in that the oxygen-containing component is ammonium nitrate and / or one or more nitrates of alkali or alkaline earth metals, chlorates or perchlorates. 18. The emulsion according to claim 1, characterized in that said carbon fuel is a water-immiscible emulsifiable hydrocarbon that is either liquid or capable of liquefying at a temperature of up to about 95 ^° C.  19. The emulsion according to claim 1, characterized in that said discontinuous aqueous phase is present in an amount of from about 85% to about 98% by weight based on the weight of said emulsion, and said continuous organic phase is present in an amount of from about 2% to about 15% by weight based on the weight of the specified emulsion, the specified oxygen-containing component is present in an amount in the range of from about 70% to about 95% by weight based on the weight of the specified aqueous phase, and the emulsifier is present in an amount in the range of from about 5% to approx. angles 95% by weight based on the weight of the organic phase.  20. The emulsion according to claim 1, characterized in that said emulsion contains a sensitizing amount of at least one closed cell material containing voids, or a sensitizing amount of gas bubbles, or a sensitizing amount of micro bubbles.  21. The emulsion according to claim 1, characterized in that it contains up to about 80% by weight of solid oxygen-containing salts in the form of particles dispersed in it.  22. The emulsion according to claim 17, wherein said particulate solids are selected from the group consisting of ammonium nitrate, sodium nitrate, calcium nitrate and a mixture of two or more of them.  23. The emulsion according to claim 1, characterized in that the emulsion contains up to about 80% by weight of solid ammonium nitrate in the form of particles.  24. The emulsion according to claim 1, characterized in that component (B) is dimethylethanolamine, and said emulsion contains up to about 80% by weight of solid particles of ammonium nitrate, wherein the ammonium nitrate particulate matter is obtained using at least one habit modifier crystals and at least one surfactant.  25. The emulsion according to claim 1, characterized in that it contains up to about 80% by weight of a pre-mixed mixture of ammonium nitrate and fuel oil.  26. The emulsion according to claim 1, characterized in that it contains up to about 80% by weight a mixture of ammonium nitrate - fuel oil.  27. The emulsion according to claim 1, characterized in that it contains up to about 50% by weight of metallic fuel in the form of particles selected from the group consisting of aluminum, aluminum alloys, silicon and ferrosilicon.  28. The emulsion according to claim 1, characterized in that it contains up to about 50% by weight of solid fuel in the form of particles.  29. The emulsion according to claim 1, characterized in that said emulsion contains up to about 50% by weight of a solid inert material in the form of particles.  30. The emulsion according to claim 1, characterized in that it contains at least one thickener.  31. The emulsion according to claim 1, characterized in that it contains at least one habit modifier of crystals.  32. The emulsion according to claim 1, characterized in that the substituent groups in component (A) are derived from polyalkene, said substitution groups having an Mn of at least about 1300 and an Mw / Mn of from about 2.8 to about 5.  33. The emulsion according to claim 1, characterized in that the substituent groups in component (A) come from polybutene, in which at least about 50% of all units derived from butenes come from isobutene, and the polybutene is characterized by a value of Mn of at least about 1000, and component (B) is at least one secondary and / or tertiary hydroxyamine.  34. The emulsion according to claim 1, characterized in that the substituent groups in component (A) come from polybutene, in which at least about 50% of all units derived from butenes come from isobutene, and the polybutene is characterized by a value of Mn of at least about 1300, and component (B) is at least one alkanol-tertiary monoamine. 35. The emulsion according to claim 1, characterized in that the reaction of component (A) with component (B) is carried out under ester formation conditions, the substituent groups in component (A) come from polybutene, in which at least about 50% of all units derived from butenes originate from isobutene, wherein said polybutene is characterized by a Mn value of at least about 1500 to about 2000, and a Mw / Mn value of from about 2.8 to about 4.5, said acylating agents are characterized by the presence of structure on average from about 1.7 to about 2.1 succino output groups for each equivalent weight of the substituent groups, and component (B) is a compound represented by the formula:

in which each R independently represents an alkyl group containing from 1 to about 4 carbon atoms;
R 'represents an alkylene group containing from 2 to about 4 carbon atoms,
moreover, the equivalent ratio of component (A) to component (B) is from about 1: 0.8 to about 1: 1.2.  36. The emulsion according to claim 1, characterized in that the reaction of component (A) with component (B) is carried out under ester formation conditions, the substituent groups in component (A) come from polybutene, in which at least about 50% of all units originating from butenes originates from isobutene, said polybutene having a Mn value of from about 1600 to about 1900 and a Mw / Mn value of from about 3.3 to about 3.9; said acylating agents are characterized by an average of about 1 in their structure , 8 to about 2.0 succinic groups for each equivalent weight of substituent groups, and component (B) is dimethylethanolamine, wherein the equivalent ratio of component (A) to component (B) is from about 1: 0.8 to about 1: 1.2.  37. An explosive composition containing a water-in-oil emulsion comprising an intermittent aqueous phase containing at least one oxygen-containing component, a continuous organic phase comprising at least one carbonaceous fuel and a minor amount of at least one emulsifier, characterized in that the emulsifier is obtained by the reaction of component (A) with component (B), and the explosive composition includes up to about 80% by weight of a pre-prepared mixture of ammonium nitrate - fuel oil, while component (A) is at least one substituted succinic acylating agent, which consists of substituent and succinic groups, where the substituent groups come from polybutene, in which at least about 50% of all units derived from butenes come from isobutene, while said polybutene is characterized by a Mn of at least about 1300, said acylating agents are characterized by the presence in their structure, on average, of at least about 1.3 succinic groups for each equivalent weight of the substituent groups, and onentom (B) is at least one tertiary alkanolmonoamin.  38. An explosive composition containing a water-in-oil emulsion comprising an intermittent aqueous phase containing at least one oxygen-containing component, a continuous organic phase comprising at least one carbonaceous fuel and a minor amount of at least one emulsifier, characterized in that the emulsifier is obtained by the reaction of component (A) with component (B), carried out under the conditions of formation of ester, and the explosive composition includes up to about 80% by weight of solid particles of ammonium nitrate obtained using at least one habit crystal modifier and at least one surfactant, component (A) being at least one substituted amber acylating agent, which consists of substituent and succinic groups, where substituent groups come from polybutene, in which at least about 50% of all units derived from butenes come from isobutene, said polybutene having a Mn value of from about 1600 to about 1900 and a value of Mw / Mn about t is about 3.3 to about 3.9, these acylating agents are characterized by the presence in their structure on average from about 1.7 to about 2.1 succinic groups for each equivalent weight of the substituent groups, and component (B) is dimethylethanolamine, the equivalent ratio component (A) to component (B) is from about 1: 0.8 to about 1: 1.2.

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