CN103079689B

CN103079689B - Salt compositions and explosives using the same

Info

Publication number: CN103079689B
Application number: CN201180040655.6A
Authority: CN
Inventors: T·J·沃拉克; C·J·科尔普; A·马斯特兰杰洛; B·洛夫
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2010-06-25
Filing date: 2011-06-22
Publication date: 2015-04-08
Anticipated expiration: 2031-06-22
Also published as: EP2585205A2; AU2011312846A1; WO2012047333A3; CN103079689A; CA2803576A1; US20130139716A1; WO2012047333A2

Abstract

This invention relates to novel salt compositions and to explosive compositions comprising said salt compositions. The salt compositions are useful as emulsifiers in the explosive compositions. The explosive compositions are water-in-oil emulsion explosives.

Description

The explosive of salt composite and this salt composite of use

Invention field

The present invention relates to new salts composition and the explosive compositions comprising described salt composite.Described salt composite can be used as the emulsifying agent in described explosive compositions.Described explosive compositions is water-in-oil emulsion explosive.

Background of invention

Water-in-oil emulsion explosive usually comprises continuous organic phase and contains the discontinuous oxidant phase of water and oxygen source of supply such as ammonium nitrate, and described oxidant is dispersed in whole continuous organic phase mutually.The example of this kind of water-in-oil emulsion explosive is especially disclosed in U.S. Patent No. 3,447,978; 3,765,964; 3,985,593; 4,008,110; 4,097,316; 4,104,092; 4,218,272; 4,259,977; 4,357,184; 4,371,408; 4,391,659; 4,404,050; 4,409,044; 4,448,619; 4,453,989 and 4,534,809; UK Patent Application GB2,050,340A; With European application numbers 0,156,572 and 0,155, in 800.

The class surfactant used in conventional emulsions explosive and/or emulsifier package containing middle-molecular-weihydroxyethyl (as below limit) carboxylic acylating agent that replaces of alkyl; the i.e. salt of polyisobutylene succinic anhydride (PIBSA); with the carboxylic acylating agent that salinization low-molecular-weight alkyl replaces, i.e. salinization alkenyl succinic anhydride.Together with these two structure divisions are coupled at by making them react with connectivity compound.The connectivity compound be applicable to comprises the compound containing following group: (i) two or more primary amino radicals, (ii) two or more secondary amino groups, (iii) at least one primary amino radical and at least one secondary amino group, (iv) at least two hydroxyls, (v) at least one uncle or secondary amino group and at least one hydroxyl, or their combination.For other background relevant with these materials, see United States Patent (USP) 5047175.

Usually by the surfactant of these couplings and HMW (as below limit) emulsifying agent, such as HMW PIBSA and alkanolamine, the product of such as dimethylethanolamine combines.Then the mixture of gained is used as the surfactant formulations in emulsion explosive compositions.For other background relevant with these materials, see United States Patent (USP) 5920031.

Although the performance of these blends is good, surfactant bag is expensive and requirement blended with additional high molecular weight surface activating agent for the surfactant of coupling is added complexity and the spending of composition.

Still need to be provided to the surfactant being equivalent to the performance that above-mentioned surfactant bag provides less, and one or more additional surfactants need not be added to described bag.

In addition, being used for the reaction of the surfactant preparing above-mentioned coupling may slow down and be difficult to be driven into.This causes the low and extra cost of refuse, efficiency.Still need to develop preparation and be effective to the reaction of the surfactant of emulsion explosive compositions, this reaction more promptly completes and without the need to the process modification of costliness, such as, adds expensive catalyst, increase reaction temperature and/or reaction time etc.

Another problem of conventional surfactants bag is the carboxylic acylating agent that the surfactant of above-mentioned coupling must replace with middle-molecular-weihydroxyethyl alkyl; the i.e. carboxylic acylating agent of polyisobutylene succinic anhydride (PIBSA) and the replacement of salinization low-molecular-weight alkyl, i.e. the mixture preparation of salinization alkenyl succinic anhydride.This needs middle-molecular-weihydroxyethyl and low-molecular-weight acylating agent simultaneously, and adds cost and the complexity of technique.Still need to show the surfactant well and not using additional high molecular weight surface activating agent but still provide even without improving also at least suitable performance.

Another problem of emulsion explosive is their stability, especially during transportation.If surfactant and its emulsion of providing have poor handling property, then described emulsion may during transportation crystallization and be not suitable for using.Some the fine surface activating agents done very well in other fields all wrap in this field and have problem.Still need to show good and provide more firmly and avoid during transportation may the surfactant of produced problem.If can handling property be improved, especially when it is to when storing relevant with the stability of In transit, suitable performance, or even worse a little in some fields performance will be enough.Still need the emulsion explosive that the surfactant addressed these problems will provide with them.

Summary of the invention

The invention provides new salts composition, it comprises: (A) is derived from the salt structure division of following material: (A) (I) at least one has at least one containing on average about 20 to the polybasic carboxylic acid acylating agent (such as at least one have at least one containing on average about 20 to the middle-molecular-weihydroxyethyl polybasic carboxylic acid acylating agent of the hydrocarbyl substituent of about 500 carbon atoms) of the hydrocarbyl substituent of about 500 carbon atoms; (A) (II) is selected from one or more in ammonia, at least one amine, at least one alkali metal or alkaline-earth metal and at least one alkali metal or alkaline earth metal compound; Two in wherein said structure division (A) to be coupled at the compound of at least one tertiary amino containing at least two hydroxyls by (B) at least one together with.

(A) (I) polybasic carboxylic acid acylating agent can by with in following formula any one or multiplely to represent:

Each R wherein in each formula ¹the described hydrocarbyl substituent of (A) (I) and each R wherein in each formula independently ²hydrogen or methyl independently.In some embodiments, hydrocarbyl substituent is poly-(isobutene) base.

The compound and the component (B) that contain at least two hydroxyls and at least one tertiary amino can represent by with following formula:

Wherein each a, b and c are 0 or 1 independently, as long as a+b+c sum is at least 2, and wherein each R ³, R ⁴and R ⁵the alkyl containing 1-50 carbon atom or-(-R independently ⁶-O-) n-group, wherein R ⁶that in some embodiments, the thiazolinyl of 2 carbon atoms, n is the integer of 1-50 or 1-20 containing 1-6 carbon atom.

(A) (II) can represent by with following formula:

Wherein n is the number of 0 to about 10 or the number of 1-10, each R ⁷hydrogen atom or containing the alkyl of about 700 carbon atoms or the alkyl of hydroxyl-replacements at the most, described alkylidene contains 1 to about 10 carbon atoms independently.

The present invention also provides detonator sensitiveness or detonator sensitive emulsion explosive, comprises containing the discontinuous oxidant phase of at least one oxygen-supplying component, the continuous organic phase containing at least one carbonaceous fuel.Described carbonaceous fuel can comprise at least one wax, and the surface activator composition described herein of emulsifying amount.

The present invention further provides cartridge sleeve pipe, described cartridge sleeve pipe contains at least one detonator sensitive emulsion explosive or detonator sensitiveness explosive compositions, and described emulsion comprises containing the discontinuous oxidant phase of at least one oxygen-supplying component, containing the continuous organic phase of at least one carbonaceous fuel and the surface activator composition described herein of emulsifying amount.

The present invention further provides surfactant as herein described, wherein component (A) (I) is substantially free of, or not even containing such acylating agent, namely in their alkyl containing being less than 50,40,20 or the acylating agent of even 15 carbon atoms.

Detailed Description Of The Invention

By non-limitative illustration, various characteristic sum embodiment of the present invention will be described below.

The term " low-molecular-weight " used in this specification and the appended claims, " middle-molecular-weihydroxyethyl " and " HMW " aim to provide the relative description when discussing the acylating agent for the preparation of the acylating agent of the surfactant of coupling described herein and the surfactant of non-coupled that is combined for the preparation of the surfactant of coupling conventional with some sometimes.In some embodiments, low-molecular-weight refers to the half of the molecular weight being less than described middle-molecular-weihydroxyethyl material, and HMW refers at least twice of the molecular weight of described middle-molecular-weihydroxyethyl material.In some embodiments, low-molecular-weight refers to that involved material contains and is less than 50 carbon atoms, or is less than 40,20 or even 15 carbon atoms.In some embodiments, middle-molecular-weihydroxyethyl refers to that involved material contains 20-500 carbon atom, or 30,40 or even 50 to 500,250,150,120 or even 100 carbon atoms.In some embodiments, HMW refers to that involved material contains at least 120 carbon atoms, or 100,120 or 140 to 500,400 or even 300 carbon atoms.Above-named carbon atom number can be applied as the minimum accordingly of the material of the mixture of the hydrocarbon containing different size or maximum, or is applied as the scope that the average that limits the carbon atom existed in the mixture of the hydrocarbon of different size falls into.In some embodiments, low-molecular-weight refers to that involved material has and is less than 700 or be even less than 500, or the number-average molecular weight (Mn) of 100 or 120 to 700 or 500 or even 450.In some embodiments, middle-molecular-weihydroxyethyl refer to involved material have 500-1600 or 800 or 900 to 1500,1300 or even 1200 Mn.In some embodiments, HMW refers to that involved material has 1300-5000, or the Mn of 1300,1500 or even 1600 to 5000,3000 or even 2000.

The term " emulsion " used in this specification and the appended claims is intended to not only contain water-in-oil emulsion, and contain the composition being derived from such emulsion, wherein at the temperature being less than emulsion formation temperature, discontinuous phase is solid or the drops in supercooled liquid.This term also contain be derived from or prepare into this kind of plastic or the composition of water-in-oil emulsion of composition forms of half plastic.

Term " alkyl " is used for comprising in this article: (1) alkyl, namely, aliphatic series (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group), cyclic group (that is, any two groups pointed out can form alicyclic group together) that the aromatic group of aromatics, aliphatic series and alicyclic replacement and analog and ring have come via another part of molecule; (2) alkyl replaced, namely contains those groups of the non-hydrocarbon of the main hydrocarbon nature not changing alkyl in the scope of the invention; Those skilled in the art will understand such group, and their example comprises ether, oxo (oxo), halogen (such as chlorine and fluorine), alkoxyl, sulfydryl, alkyl thiol, nitro, nitroso, sulphur oxygen base etc.; (3) assorted group, namely still mainly has the group also containing non-carbon in the original ring that is made up of carbon or chain of hydrocarbon nature within the scope of this invention.The hetero atom be applicable to will be apparent for those skilled in the art and comprise such as sulphur, oxygen, nitrogen, and substituting group such as pyridine radicals, furyl, thienyl, imidazole radicals etc.

Generally speaking, for the carbon atom of every ten in alkyl, about three non-hydrocarbon or hetero atom at the most will be there is, preferably at the most one.Usually, will not have such group or hetero atom in alkyl, therefore, it will be pure alkyl.

In some embodiments, alkyl is not containing the unsaturated part of acetylene series; The unsaturated part of olefinic, when it is present, generally will meet and there is an olefinic connection at the most for every ten carbon-carbon bonds.

The term " rudimentary " used together with term such as alkyl, thiazolinyl, alkoxyl etc. herein can be intended to describe this type of group and contain altogether at the most 30,24 or even 16 or 8 or 7 carbon atoms.

Term as used herein " is substantially free of " and is intended to mean to be less than and will affect the composition and/or the character of compound or the significant quantity of characteristic that are described.This term can also refer to that involved material is less than 10 % by weight, 5 % by weight, 2 % by weight, 1 % by weight by what account for the composition that is described and/or component, and 0.5 % by weight or even 0.1 % by weight exists.In other other embodiment, it can refer to that existence is less than 1,000ppm, 500ppm or the material even described in 100ppm.In other embodiments, this term can mean be no more than because use may contain the industrial materials of accessory substance and/or impurity and be not intended to and/or the inevitable amount existed.

component (A) (I)

The carboxylic acylating agent of component (A) (I) can be aliphatic series or aromatic polycarboxylic acid or acidic compound.In whole description and appended claims, term " carboxylic acylating agent " is intended to comprise carboxylic acid and its acidic derivative such as acid anhydrides, ester, acyl halide and their mixture, unless stated otherwise.

Acylating agent (A) (I) can contain polar substituent, as long as described polar substituent exists not according to the ratio being large enough to significantly change the hydrocarbon characteristic of described acylating agent.The typical polar substituent be applicable to comprises halogen, such as chlorine and bromine, oxo, oxygen base, formoxyl, sulfinyl, sulfinyl, sulphur, nitro etc.If exist, this type of polar substituent preferably more than the hydrocarbon part of acylating agent gross weight about 10 % by weight, do not include carboxyl interior.

Polybasic carboxylic acid acylating agent (A) (I) is well known in the art and has been described in detail in the such as following U.S., Britain and Canadian Patent: U.S.Pat.Nos.3,024,237; 3,087,936; 3,163,603; 3,172,892; 3,215,707; 3,219,666; 3,231,587; 3,245,910; 3,254,025; 3,271,310; 3,272,743; 3,272,746; 3,278,550; 3,288,714; 3,306,907; 3,307,928; 3,312,619; 3,341,542; 3,346,354; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179; 3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169; 3,868,330; 3,912,764; 4,234,435 and 4,368,133; BP 944,136; 1,085,903; 1,162,436 and Isosorbide-5-Nitrae 40,219; With Canadian Patent 956,397.These patents are incorporated to herein by reference.

Disclosed in above-mentioned patent, there is the method that some prepare these acylating agents (A) (I).Generally speaking, these methods comprise make (1) ethylenically unsaturated carboxylic acids, sour halide, acid anhydrides or ester reactant and (2) ethylenically unsaturated hydrocarbons containing at least about 20 aliphatic carbon atoms or the chlorinated hydrocabon containing at least about 20 aliphatic carbon atoms temperature within the scope of about 100-300 DEG C under react.Described chlorinated hydrocabon or ethylenically unsaturated hydrocarbons reactant are preferably containing at least about 30 carbon atoms, more preferably at least about 40 carbon atoms, more preferably at least about 50 carbon atoms, and polar substituent, oily solubilising side base can be contained, and be undersaturated in the general restriction can illustrated above.

When preparing carboxylic acid acylating agent, described carboxylic acid reaction thing corresponds to formula Ro-(COOH) n usually, and wherein the feature of Ro is to there is the unsaturated carbon-to-carbon covalent bond of at least one olefinic, and n is the integer of 2-6 and is 2 in some embodiments.Described acid reactant also can be corresponding carboxylic acid halide, acid anhydrides, the acylating agent of ester or other equivalence and two or more mixture in these.Usually, in acid reactant, the sum of carbon atom can not exceed about 20, or about 10 or even about 6, the group based on carboxyl is not included.In some embodiments, acid reactant will at α, and position has at least one olefinic connecting key

For the preparation of the ethylenically unsaturated hydrocarbons reactant of these carboxylic acylating agents (A) (I) and chlorinated hydrocabon reactant in some embodiments, be the petroleum distillate and substantially saturated olefin polymer and corresponding chlorizate that middle-molecular-weihydroxyethyl (as defined above) is substantially saturated.Derived from being preferred containing 2 to the polymer of the monoolefine of about 30 carbon atoms and chlorinated polymeric.Useful especially polymer is the polymer of 1-monoolefine such as ethene, propylene, 1-butylene, isobutene, 1-hexene, 1-octene, 2-methyl isophthalic acid-heptene, 3-cyclohexyl-1-butylene and 2-methyl-5-propyl group-1-hexene.Internal olefin, namely wherein olefinic connecting key is not useful at the polymer of the alkene of terminal position equally.They are such as 2-butylene, 3-amylene and 4-octene.

The 1-monoolefine 1-monoolefine of such as illustrating above each other and can be polymerized olefinic substances such as atomatic olefins, cyclic olefin and polyolefinic interpretation mutually with other be also the useful source of ethylenic unsaturated reactant.This type of interpretation comprises such as, by making isobutene and styrene, and isobutene and butadiene, propylene and isoprene, propylene and isobutene, ethene and pentadiene, isobutene and chlorobutadiene, isobutene with to methyl-styrene, 1-hexene and 1,3-hexadiene, 1-octene and 1-hexene, 1-heptene and 1-amylene, 3-methyl-1-butene and 1-octene, 3,3-dimethyl-1-amylene and 1-hexene, isobutene is polymerized those that prepare with styrene and pentadiene etc.

For the consideration to hydrocarbon solubility, consider substantially to be preferably aliphatic series for the preparation of the interpretation of acylating agent of the present invention and substantially saturated, namely they should by weight containing at least about 80%, the preferably approximately unit derived from aliphatic monoolefine of 95%.Preferably, they contain and are no more than about 5% olefinic connecting key, based on the sum of the covalently bound key of carbon-to-carbon existed.

In one embodiment of the invention, polymer and chlorinated polymeric obtain as follows: make to have about 35 % by weight to the C of the isobutene content of about butene content of 75 % by weight and about 30 % by weight to about 60 % by weight ₄oil plant stream is polymerization under lewis acid catalyst such as aluminium chloride or boron trifluoride exist.The isobutylene repeat units of these polyisobutene preferably mainly containing (that is, being greater than about 80% of total repetitive) configuration like this :-[-CH ₂-C (CH ₃) ₂-]-.

Some embodiments that per molecule contains about 500 carbon atoms at the most for the preparation of the chlorinated hydrocabon of carboxylic acylating agent and ethylenically unsaturated hydrocarbons.The acylating agent be applicable to for component (A) (I) comprises containing having about 20 to about 500 carbon atoms, or about 30,40 or even 50 to those of the alkyl of about 500 carbon atoms.

Polybasic carboxylic acid acylating agent (A) (I) also can be prepared as follows: by hydrocarbon if above-mentioned olefin polymer halogenation is to prepare many-halogenated products, by described many-halogenated products changes into many nitriles, then by described many nitrile hydrolysis.They can by preparing with potassium permanganate, nitric acid or similar oxidizing polyalcohol.Another kind method is comprised hydrocarbon such as chloro polyisobutene and unsaturated polybasic carboxylic acid that alkene or polarity are replaced and is such as reacted by 2-amylene-1,3, the 5-tricarboxylic acid that the Dehydration of citric acid is standby.

Polybasic carboxylic acid acylating agent (A) (I) can also obtain as follows: the polyolefin that the hydrocarbon of the unsaturated replacement of chlorinated polyhydric carboxylic acid, acid anhydrides, acyl halide and analog and ethylenically unsaturated hydrocarbons or olefinic is such as above described and the polyolefin of replacement react by the mode described in U.S. Patent No. 3340281, and this patent is incorporated to herein by reference.

Polycarboxylic acid anhydrides (A) (I) can by obtaining corresponding acid dehydration.Dehydration easily realizes as follows: acid is heated to the temperature being greater than about 70 DEG C, preferably heating under dehydrating agent such as acetic anhydride exists.Cyclic acid anhydride is usually by having the butanedioic acid that such as replaced by the polybasic carboxylic acid being no more than the acidic group that three carbon atoms are isolated or glutaric acid obtains, and straight chain acid anhydrides is obtained by the polybasic carboxylic acid with the acidic group of being isolated by four or more carbon atom usually.

The sour halide of polybasic carboxylic acid can be prepared as follows: described acid or their acid anhydrides and halogenating agent such as phosphorus tribromide, phosphorus pentachloride or thionyl chloride are reacted.

The butanedioic acid that alkyl replaces and its acid anhydrides, sour halide and ester derivant are especially preferred acylating agent (A) (I).These acylating agents can be prepared as follows: make maleic anhydride and alkene or chlorinated hydrocabon such as chlorinated polyolefin hydrocarbon reaction.Described reaction is only included in about 100-300 DEG C, or heats described two kinds of reactants at the temperature of about 100-200 DEG C.The product deriving from this reaction is the succinyl oxide that alkyl replaces, and wherein said substituting group is derived from alkene or chlorinated hydrocabon.If necessary, can by standard hydrogenation program by described product hydrogenation to remove the unsaturated covalently bound key of all or part of any olefinic.Can by the succinyl oxide that described alkyl replaces being hydrolyzed into sour accordingly by water or steam treatment and by reacting to phosphorus halide, phenol or alcohol, described acid anhydrides or acid can being changed into corresponding sour halide or ester.In some embodiments, the alkyl of component (A) (I) contains 20,30,40 or even 50 carbon atom to 500 carbon atoms.In some embodiments, described hydrocarbyl derivative is from polyisobutene and have 800-1500,800-1200,900-1100 or even about 1000 number-average molecular weight.

As provided above such as described in the butanedioic acid that replaces of alkyl and acid anhydrides (A) (I) can be represented by formula (I) to (IV):

Each R wherein in each formula ¹the described hydrocarbyl substituent of (A) (I) and each R wherein in each formula independently ²hydrogen or methyl independently.In some embodiments, hydrocarbyl substituent is poly-(isobutene) base.In some embodiments, butanedioic acid and acid anhydrides are formula (I) and (II) form, and in other embodiments, butanedioic acid and acid anhydrides are formula (III) and (IV) form.In formula (I), (II), (III) and/or (IV), each R in each formula ¹the described hydrocarbyl substituent of (A) (I) and each R wherein in each formula independently ²hydrogen or methyl independently.In some embodiments, hydrocarbyl substituent is poly-(isobutene) base.Each R ¹can independently containing 20,30,40 or even 50 carbon atoms to 500,400 or even 350 carbon atoms.

Component (A) (I) can also comprise disuccans, such as by represent with following formula those:

Wherein R ¹and R ²as above the definition that faced by, formula (I)-(IV) provides.

In some embodiments, acylating agent (A) (I) is aliphatic polycarboxylic acid, or dicarboxylic acids.But (A) (I) also can be aromatic polycarboxylic acid or acidic compound.The benzene that described aromatic acid is preferably alkyl-replacement, dicarboxyl replaces, naphthalene, anthracene, luxuriant and rich with fragrance or similar aromatic hydrocarbon.Described alkyl can contain about 30 carbon atoms at the most.Described aromatic acid can also contain other substituting group such as halogen, hydroxyl, lower alkoxy etc.

component (A) (II)

The amine that can be used as component (A) (II) preparing salt composite of the present invention comprises ammonia, and primary amine, secondary amine and azanol.Component (A) (II) can comprise monoamine, polyamines and/or their mixture.The amine be applicable to comprises primary, secondary and/or tertiary; Aliphatic, alicyclic and/or aromatic amine.

Useful primary and secondary amine comprises aliphatic monoamine.Aliphatic monoamine comprises the amine that monoester race and two-aliphatic series replaces, and wherein aliphatic group can be saturated or unsaturated and straight chain or branched chain.Therefore, they are uncle or secondary aliphatic amine.This type of amine comprises, such as, the amine of list and two-alkyl-replacement, the amine that single and dialkylene replaces, and there is the amine of a N-alkenyl group and a N-alkyl substituent, and analog.The sum of the carbon atom in these aliphatic monoamines, preferably more than about 40, is no more than about 20 carbon atoms usually.The instantiation of this type of monoamine comprises ethamine, diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutyl amine, coco amine, stearylamine, lauryl amine, methyl lauryl amine, oleyl amine, N-methyl octylame, lauryl amine, octadecylamine etc.The example of the aliphatic amine of the aliphatic amine that the aliphatic amine of alicyclic replacement, aromatics replace and heterocyclic substituted comprises 2-(cyclohexyl)-ethamine, benzylamine, phenyl ethylamine and 3-(furyl propyl group) amine.

The amine be applicable to comprises alicyclic monoamine, and they are those monoamines that wherein there is a cycloaliphatic substituents be directly connected via the carbon atom in cyclic rings structure and ammonia nitrogen.The example of alicyclic monoamine comprises cyclohexylamine, cyclopentamine, cyclohexenyl group amine, cyclopentenyl amine, N-ethyl cyclohexylamine, dicyclohexylamine and analog.Aliphatic series replaces, aromatics replaces and the example of alicyclic monoamine of heterocyclic substituted comprises the cyclohexylamine of the cyclohexylamine of propyl group-replacements, cyclopentamine that phenyl replaces and pyranose replacement.

The amine be applicable to comprises aromatic monoamine, and they are those monoamines that the carbon atom of wherein aromatic ring structure is directly connected with ammonia nitrogen.Aromatic ring is monokaryon aromatic ring (that is, derived from the aromatic ring of benzene) normally, but can comprise fused aromatic ring, particularly derived from those of naphthylene.The example of aromatic monoamine comprises aniline, two (p-methylphenyl) amine, naphthylamines, N-(normal-butyl) aniline and analog.The naphthylamines that aliphatic series replaces, the example of the aromatic monoamine of alicyclic replacement and heterocyclic substituted comprises p-ethoxyaniline, replace lauryl amine, cyclohexyl and the aniline that thienyl replaces.

Heterocyclic polyamines can also be used.Term as used herein " heterocyclic polyamines " is intended to describe containing at least two primary amino radicals, at least two secondary amino groups, or at least each one, and at least one is as those heterocyclic amines of the heteroatomic nitrogen in heterocycle.As long as there are at least two primary amino radicals in heterocyclic polyamines, at least two secondary amino groups or at least each one, the assorted atom N in described ring can be tertiary ammonia nitrogen; That is, the assorted atom N of the hydrogen be not directly connected with ring nitrogen.Described assorted atom N can be one of secondary amino group; That is, it can be the ring nitrogen with the hydrogen be directly connected with it.Heterocyclic amine can be saturated or undersaturated and can contain various substituting group such as nitro, alkoxyl, alkyl thiol, alkyl, thiazolinyl, aryl, alkaryl or aralkyl substituents.Generally speaking, the sum of the carbon atom in described substituting group can not exceed about 20.Heterocyclic amine can containing the hetero atom, particularly oxygen beyond denitrogenating and sulphur.Obviously, they can contain more than one nitrogen heteroatom.5-and 6-unit heterocycle is preferred.

The heterocyclic polyamines be applicable to comprises aziridine, azetidine, aza-cyclopentane, four-and two-pyridinium hydroxide, pyrroles, indoles, piperadines, imidazoles, two-and four-hydrogen imidazoles, piperazine, iso-indoles, purine, morpholine, thiomorpholine, N-aminoalkylmorpholines, N-aminoalkyl thiomorpholine, N-aminoalkyl piperazine, N, N'-bis--aminoalkyl piperazine, azepines, azocine, a word used for translation ninth of the ten Heavenly Stems because of, azecine and above-mentioned in each four-, two-and perhydro derivative and these heterocyclic amines in two or more mixture.Useful heterocyclic polyamines is saturated 5-and 6-the unit heterocyclic polyamines, particularly piperidines of only nitrogenous, oxygen and/or sulphur in heterocycle, piperazine, thiomorpholine, morpholine, pyrrolidines and analog.Usually, aminoalkyl substituent group is substituted on the nitrogen-atoms of a formation heterocycle part.The instantiation of this type of heterocyclic amine comprises N-aminoethylpiperazine and N, N'-diamino ethyl piperazine.

The hydrazine of hydrazine and replacement can also be used.The substituting group that may reside on hydrazine comprises alkyl, thiazolinyl, aryl, aralkyl, alkaryl and analog.Usually, substituting group is alkyl, particularly low alkyl group, phenyl, and the phenyl replaced, the phenyl that such as lower alkoxy replaces or the phenyl that low alkyl group replaces.The instantiation of the hydrazine replaced is methyl hydrazine, N, N-dimethylhydrazine, N, N'-dimethylhydrazine, phenyl hydrazine, N-phenyl-N'-ethyl hydrazine, N-(p-methylphenyl)-N'-(normal-butyl)-hydrazine, N-(p-nitrophenyl) hydrazine, N-(p-nitrophenyl)-N-methyl hydrazine, N, N'-bis--(parachlorophenol) hydrazine, N-phenyl-N'-cyclohexyl hydrazine and analog.

Being suitable for another kind of amine of the present invention is branching polyalkylenepolyamines.Branching polyalkylenepolyamines is polyalkylenepolyamines, and wherein branched groups is relative to side chain (the i.e. NH of every 9 amino unit that main chain exists containing the amino alkylidenyl of at least one nitrogen keyed jointing average ₂-R-[-N (H)-R-] x-); Such as, on main chain, every 9 unit have the individual such side chain of 1-4, but preferably every 9 backbone units have 1 side chain unit.Therefore, these polyamines contain at least three primary amino radicals and at least one uncle amino.

Useful polyoxyalkylene comprises the polyoxyethylene of the mean molecule quantity with about 200 to about 2000 and polypropyleneoxide diamine and polyoxypropylene triamine.Polyoxyalkylene can be buied from JeffersonChemical Company, Inc. with trade name " Jeffamine ".By U.S. Patent No. 3,804,763 and 3,948,800 by application, they are incorporated to herein for the disclosure of this type of polyoxyalkylene.

As mentioned above, useful polyamines alkylene polyamine meets formula (VI):

Wherein n can be 1-10 or even 7; Each R and R' is hydrogen atom independently, containing at the most about 700,100,50 or the even alkyl of 30 carbon atoms or the alkyl of hydroxyl-replacements, condition is that in R, at least one and R', at least one is hydrogen; Described " alkylidene " is containing 1 to 18, or even 4 carbon atoms, and in some embodiments, alkylidene is ethylidene or propylidene.Useful alkylene polyamine is that wherein each R and each R' is those of hydrogen, wherein ethylene, and the mixture of ethylene is especially preferred.These alkylene polyamines comprise methylene polyamines, ethylene, butylidene polyamines, propylidene polyamines, pentylidene polyamines, hexylidene polyamines, sub-heptyl polyamines etc.Also comprise the higher homologue of this type of amine and the piperazine of relevant aminoalkyl replacement.

Useful alkylene polyamine comprises ethylenediamine, diethylenetriamines, trien, tetren, penten, trimethylene diamine, trimethylene diamine, hexamethylene diamine, eight methylene diamine, two (heptamethylene) triamine, tri propylidene tetramine, tetren, trimethylene diamine, penten, two (trimethylene) triamine, N-(2-aminoethyl) piperazine, Isosorbide-5-Nitrae-bis-(2-aminoethyl) piperazine and analog.Be can be used as the amine in the present invention by the higher homologue making two or more condensations in above-mentioned alkylene amines obtain, in any aforementioned polyamines, the mixture of two or more also can be used as the amine in the present invention.

Ethylene, such as above-mentioned those, be described in detail in The Encyclopedia ofChemical Technology, Third Edition, Kirk-Othmer, Volume7, pp.580-602, Wiley-Interscience Publication, John Wiley and Sons, 1979, under title " Diaminesand Higher Amines; Aliphatic ", these pages are incorporated to herein by reference.This compounds is optimally prepared as follows: make alkylidene chloride and ammonia react or make ethylenimine and Ring Opening Reagent such as ammonia react etc.These reactions cause the slightly complicated mixture producing alkylene polyamine, comprise cyclic condensation product such as piperazine.

Alkoxylate alkylene polyamine (such as, N, N-(diethanol) ethylenediamine) can be used.This type of polyamines can be prepared as follows: alkylene amines (such as, ethylenediamine) is reacted to the oxyalkylene (such as, ethylene oxide, be oxidized vaccenic acid) of about 20 carbon containing 2 with one or more.Also similar oxyalkylene-alkanolamine product can be used, such as, product by making aforementioned primary, secondary or tertiary alkanolamine and ethene, propylene or more senior epoxides obtain by 1:1 or 1:2 molar ratio reaction.Reactant ratio and the temperature of carrying out this kind of reaction are well known by persons skilled in the art.

Tetren, N-(3-hydroxyl butyl) tetra-methylenedimine etc. that the diethylenetriamines that the instantiation of alkoxylate alkylene polyamine comprises N-(2-ethoxy) ethylenediamine, two (2-the ethoxy)-ethylenediamine of N, N-, 1-(2-ethoxy) piperazine, list (hydroxypropyl) replace, two (hydroxypropyls) replace.By making above-mentioned hydroxy alkylidene polyamines via amino or be useful equally via the higher homologue that hydroxyl condensation obtains.Condensation via amino obtains higher amines, with ammonia removing, and obtains via the condensation of hydroxyl the product containing ether connecting key, removes with water.In any above-mentioned polyamines, the mixture of two or more is also useful.

The azanol be applicable to comprises uncle or secondary amine.They also can be tertiary amines, as long as described tertiary amine is also containing at least two hydroxyls.These azanols contain at least two >NH bases, at least two-NH ₂base, at least one-OH base and at least one >NH or-NH ₂base or at least two-OH bases.Term " azanol " and " amino alcohol " describe the compound of identical category and therefore can use interchangeably.

Azanol can be uncle or secondary alkanolamine or their mixture.This type of amine can each free style H ₂n-R'-OH and (H) (R) N-R'-OH represent, wherein R is containing 1 to the alkyl of about 8 carbon atoms or containing 2 alkyl replaced to the hydroxyl of about 8 carbon atoms, and R' contains about 2 to the bivalent hydrocarbon radical of about 18 carbon atoms.Group-R'-OH in these formulas represents the alkyl that hydroxyl replaces.R' can be acyclic, alicyclic or aromatic group.Usually, R' is the group such as acyclic straight chain or sub-branched alkyl such as ethylidene, 1,2-propylidene, 1,2-butylidene, 1,2-sub-octadecyl base.Usually, R is the low alkyl group containing 7 carbon atoms at the most.

Azanol also can be ether N-(alkyl of hydroxyl-replacement) amine.They are poly-(oxyl) analogs (these analogs also comprise the oxyalkylene analog that hydroxyl replaces) of the hydroxyl replacement of above-mentioned primary and secondary alkanolamine.This type of N-(hydroxyl replace alkyl) amine can conveniently by make epoxides and aforementioned amine react to prepare also can by formula H ₂n-(R'O) _x-H and (H) (R) N-(R'O) _x-H represents, wherein x is the number of about 2 to about 15, R and R' is as described above.

Also the polyamine analogs of these azanols can be used, especially alkoxylate alkylene polyamine (such as, N, N-(diethanol) ethylenediamine).This type of polyamines can be prepared as follows: alkylene amines (such as, ethylenediamine) is reacted to the oxyalkylene (such as, ethylene oxide, be oxidized vaccenic acid) of about 20 carbon containing 2 with one or more.Also similar oxyalkylene-alkanolamine product can be used, such as, product by making aforementioned uncle or secondary alkanolamine and ethene, propylene or more senior epoxides obtain by 1:1 or 1:2 molar ratio reaction.Reactant ratio and the temperature of carrying out this kind of reaction are well known by persons skilled in the art.

Hydroxyalkyl alkylene polyamine nitrogen-atoms with one or more hydroxyalkyl substituted groups is also useful.It is Lower hydroxy alkyl that the alkylene polyamine that useful hydroxyalkyl replaces comprises wherein hydroxyalkyl, namely containing those of hydroxyalkyl being less than 8 carbon atoms.The example of the polyamines of these hydroxyl-alkyl-replacements comprises N-(2-ethoxy) ethylenediamine, two (2-ethoxy) ethylenediamine of N, N-, 1-(2-ethoxy) piperazine, the diethylenetriamines of single hydroxypropyl replacement, the tetren, N-(3-hydroxyl butyl) tetra-methylenedimine etc. of dihydroxypropyl replacement.By making above-mentioned hydroxy alkylidene polyamines via amino or be useful equally via the higher homologue that hydroxyl condensation obtains.Condensation via amino obtains higher amines, and with ammonia removing, the condensation via hydroxyl obtains the product containing ether connecting key, removes with water.

The example of N-(hydroxyl replace alkyl) amine comprises list, two and triethanolamine, diethyl ethylene diamine, two-(3-hydroxypropyl) amine, N-(3-hydroxybutyl) amine, N-(4-hydroxybutyl) amine, N, N-bis--(2-hydroxypropyl) amine, N-(2-hydroxyethyl) morpholine and its thip-analogues, N-(2-hydroxyethyl) cyclohexylamine, N-3-hydroxycyclopent base amine, adjacent, and para-aminophenol, N-(hydroxyethyl) piperazine, N, N'-bis-(hydroxyethyl) piperazine and analog.

Other azanol is U.S. Patent No. 3,576, pass through general formula R in 743 _a-NH ₂the primary amine of the hydroxyl-replacement described, wherein Ra is the monovalent organic groups belonging to hydroxyl containing at least one alcohol.In Ra, the sum of carbon atom is no more than about 20.Aliphatic primary amine altogether containing the hydroxyl-replacement of about 10 carbon atoms is at the most useful.The alkanol primary amine that polyhydroxy as described below replaces is useful, namely wherein only has one and has one containing the amino (that is, primary amino radical) of the alkyl substituent of about 10 carbon atoms at the most and about 6 hydroxyls at the most.These alkanol primary amine correspond to Ra-NH ₂, wherein Ra is the alkyl of list or polyhydroxy-replacement.The instantiation of the primary amine of hydroxyl-replacement comprises 2-amino-n-butyl alcohol, 2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl) aniline, 2-amino-1-propyl alcohol, 3-amino-1-propyl alcohol, 2-amino-2-methyl-1, ammediol, 2-amino-2-ethyl-1, ammediol, N-(β-hydroxypropyl)-N'-(β-aminoethyl) piperazine, three-(methylol) aminomethanes (also known as trishydroxymethylaminomethane), 2-amino-n-butyl alcohol, monoethanolamine, β-(beta-hydroxy ethyoxyl) ethamine, aminoglucose, glusoamine, 4-amino-3-hydroxy-3-methyl-1-butylene (it can be prepared by making oxidizing isoprene and ammonia react according to program as known in the art), N-3-(aminopropyl)-4-(2-ethoxy)-piperidines, 2-amino-6-methyl-6-enanthol, 5-amino-1-amylalcohol, N-(beta-hydroxyethyl)-1, 3-diaminopropanes, 1, 3-diaminourea-2-hydroxy propane, N-(beta-hydroxy ethoxyethyl group) ethylenediamine and analog.U.S. Patent No. 3,576,743 are incorporated to herein by reference.

Except above-mentioned ammonia, primary amine, secondary amine and azanol, the amine that can be used as component (A) (II) also comprises tertiary list and polyamines.Tertiary amines is similar to above-mentioned primary amine, secondary amine and azanol, and difference is that they can be monoamine or polyamines and H-N< or-NH ₂hydrogen atom in group is substituted by alkyl.

Tertiary amine can aliphatic, alicyclic, aromatics or heterocycle, comprise aromatics, aliphatic alicyclic, the aliphatic heterocycle replaced replaced that aliphatic series replaces, the heterocycle of the aliphatic series of alicyclic replacement, the aromatics of alicyclic replacement, alicyclic replacement, the heterocycle that alicyclic, the aromatics that the aliphatic series that aromatics replaces, aromatics replace replaces, the aromatic amine of the aliphatic series of heterocyclic substituted, the alicyclic of heterocyclic substituted and heterocyclic substituted.These tertiary amines can be saturated or undersaturated.If unsaturated, then described amine is preferably not unsaturated containing acetylene series.Described tertiary amine can also contain substituents or group, as long as the reaction of these groups interfering component (B) and component (A) indistinctively.These substituents or group comprise lower alkoxy, low alkyl group, sulfydryl, nitro and insertion group such as-O-and-S-(such as, as at group-CH ₂cH ₂-X-CH ₂cH ₂-in, wherein X is-O-or-S-).

Described monoamine can by formula (R ¹) (R ²) (R ³) N represents, wherein R ¹, R ²and R ³it is identical or different alkyl.In some embodiments, R ¹, R ²and R ³to the alkyl of about 20 carbon atoms independently containing 1.

The example of useful tertiary amine comprises trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, monomethyl diethylamide, one ethyldimethyl amine, dimethyl propyl amine, dimethylbutyl amine, dimethyl amylamine, dimethylhexylamine, dimethyl heptyl amine, dimethyl octyl amine, dimethyl nonyl amine, dimethyl decyl amine, 3,5-dimethylphenyl amine, N, N-dioctyl-1-octylame, N, N-bis-(dodecyl)-1-dodecyl amine three cocoyl amine, three hydrogenated butter amines, N-methyl-dihydro beef tallow amine, N, N-dimethyl-1-dodecyl amine, N, N-dimethyl-1-tetradecylamine, N, N-dimethyl-1-cetylamine, N, N-dimethyl-1-octadecylamine, N, N-dimethylcocoamine, N, N-dimethyl soybean amine, N, N-dimethyl hydrogenated tallow amine etc.

Useful tertiary alkanol amine is by formula (R) (R) N-R ¹-OH represents, wherein each R is containing 1 to the alkyl of about 8 carbon atoms or containing 2 alkyl replaced to the hydroxyl of about 8 carbon atoms independently, R ¹to the bivalent hydrocarbon radical of about 18 carbon atoms containing about 2.Ji Tuan – R in this formula ¹-OH represents the alkyl that hydroxyl replaces.R' can be acyclic, alicyclic or aromatic group.Usually, R' is the group such as acyclic straight chain or sub-branched alkyl such as ethylidene, 1,2-propylidene, 1,2-butylidene, 1,2-sub-octadecyl.When two R group are present in same molecule, they or can connect via hetero atom (such as, oxygen, nitrogen or sulphur) and form 5-, 6-, 7-or 8-ring structure by direct carbon-carbon bond.The example of this type of heterocyclic amine comprises N-(hydroxyl low-grade alkyl) morpholine ,-thiomorpholine ,-piperidines ,-oxazolidines ,-thiazolidine and analog.But usually, each R is the low alkyl group containing 7 carbon atoms at the most.Described azanol also can be ether N-(alkyl of hydroxyl-replacement) amine.They are poly-(oxyl) analogs (these analogs also comprise the oxyalkylene analog that hydroxyl replaces) of the hydroxyl replacement of above-mentioned azanol.This type of N-(hydroxyl replace alkyl) amine can conveniently by make epoxides and aforementioned amine react to prepare also can by formula (R) (R) N-(-R ¹o-) _x-H represents, wherein x is the number of about 2 to about 15, R and R ¹as described above.

The alkali and alkaline earth metal ions that can be used as component (A) (II) can be any alkali metal or alkaline-earth metal.Described alkali metal is preferred.Sodium and potassium are especially preferred.Useful alkali and alkaline earth metal ions compound comprises, such as, and oxide, hydroxide and carbonate.NaOH and potassium hydroxide are especially preferred.

b component

Component of the present invention (B) is the compound containing at least two hydroxyls and at least one tertiary amino.This compound serves as the connecting bridge in said components (A) structure division between two.The compound being suitable as component (B) can be described as two-hydroxyl tertiary amine.

As mentioned above, in some embodiments, component (B) comprises the tertiary amine of at least one following formula:

Wherein each a, b and c are 0 or 1 independently, as long as a+b+c sum is at least 2, and wherein each R ³, R ⁴and R ⁵the alkyl containing 1-50 carbon atom or-(-R independently ⁶-O-) n-group, wherein R ⁶that n is the integer of 1-50 or 1-20 containing 1-6 carbon atom, the in some embodiments thiazolinyl of 2 carbon atoms.

In other words, as long as described compound contains two hydroxyls, then it may be applicable.In some embodiments, the R in formula (V) ³, R ⁴and/or R ⁵alkyl, or even thiazolinyl.In such embodiments, above, each-OH shown in formula (V) can connect in any position of described alkyl or thiazolinyl and not necessarily be present in described Group Terminal.In some embodiments, described-OH group is positioned at and serves as the alkyl of independent R group or the end of alkenylene chain.In some embodiments, two-OH groups are connected with same alkyl or thiazolinyl, and described alkyl or thiazolinyl can branching.Such as, Ji Tuan – R ¹-(OH) a, or other group any can comprise-CH ₂-CH (OH)-CH ₂-OH.In other embodiments, Ji Tuan – R ¹-(OH) a, or other corresponding group any can comprise such as-CH ₂-CH ₂-OH.

In some embodiments, component (B) comprises the tertiary amine of at least one following formula:

Wherein each R ⁸the alkyl containing 1-10 carbon atom and wherein R independently ⁹it is the alkyl containing 1-50 carbon atom.

The compound be applicable to comprises 3-(two (dodecyl) is amino) propane-1, 2-glycol, N methyldiethanol amine, N-ethyldiethanolamine, N-propyl group diethanol amine, N-n-butyldiethanolamine, N-tertiarybutyldiethanolamine, N-cyclohexyldi, N-2-ethylhexyl diethanol amine, N-amyl group diethanol amine, N-isobutyl group diethanol amine, N-sec-butyl diethanol amine, N-dodecyl diethanol amine, N-cetyl diethanol amine, N-hydrogenation vegetable seed alkyldiethanolamine, N-hydrogenated tallow alkyl diethanol amine, N-phenyldiethanol-amine, tolyl diethanol amine between N-.

The tertiary amine be applicable to also comprises two (2-ethoxy) octadecylamine (also known as N-octadecyldiethanol amine), two (2-ethoxy) cocoalkyl amines (also known as N-coco alkyl diethanol amine), two (2-ethoxy) oleyl amine (also known as N-oil base diethanol amine), two (2-ethoxy) soja alkylamin (also known as N-soya alkyl diethanol amine), two (2-ethoxy) tallow alkylamine (also known as N-tallow alkyldiethanol amine), and they all can from AkzoNobel with Ethomeen ^tMtrade name is buied.

Overlying material can be prepared by the ethoxylation of primary amine.Further ethoxylation is also possible.Also this type of material being suitable for being used as component (B) can represent by with following formula:

Wherein each n is the integer with 1-50 or the even value of 1-20 independently, R ¹⁰it is the alkyl containing 1-50 or even 1-20 carbon atom.In some embodiments, two n in formula (IX) have identical value.

The example of this type of material comprises polyoxyethylene (5) octadecylamine, polyoxyethylene (15) octadecylamine, polyoxyethylene (5) cocoalkyl amines, polyoxyethylene (15) cocoalkyl amines, polyoxyethylene (5) soja alkylamin, polyoxyethylene (15) soja alkylamin, polyoxyethylene (5) tallow alkylamine, polyoxyethylene (15) tallow alkylamine, polyoxyethylene (20) tallow alkylamine, and they all can from Akzo Nobel with Ethomeen ^tMtrade name is buied.

The material be applicable to can also react obtained by making dialkylamine and glycidol or glycerin chlorohydrin (3-chlorine-1,2-propylene glycol).The example of these materials comprises 3-(dimethylamino)-1,2-propane diols, 3-(diethylamino)-1,2-propane diols, 3-(dipropyl is amino)-1,2-propane diols, 3-(diisopropylaminoethyl)-1,2-propane diols, 3-(two (octadecyl) is amino)-1,2-propane diols, 3-(two cocyl alkyl aminos)-1,2-PD.

The combination of above-mentioned any material can also be used.In some embodiments, component (B) comprises 3-(two (dodecyl) is amino) propane-1,2-glycol, tallow-bis--(2-hydroxyethyl) amine, N methyldiethanol amine or their combination, they also can be combined with above-mentioned any material.

In some embodiments, component (B) can comprise one or more polyalcohols further, such as ethylene glycol.This type of material can also serve as connectivity compound.But in order to obtain effect of the present invention, the component (B) of remarkable ratio must be made up of one or more above-mentioned compounds containing at least two hydroxyls and at least one tertiary amino.

In some embodiments, component (B), and be even all used for the material of preparation table surface-active agent, be substantially free of to not containing non-containing amine polyol (they also can be described as without nitrogen polyalcohol).In other embodiments, component (B) can be at the most 40%, 25%, 10% or even 5 % by weight non-containing amine polyol, thus allow conventional polyol to be to a certain degree used as connectivity compound, but still obtain of the present invention by using the above-mentioned effect obtained containing at least two hydroxyls and the compound of at least one tertiary amino at least partially.

When there is optional polyalcohol, useful material comprises general formula R (OH) _mthose compounds, wherein R is the unit price or multivalent organic group (that is ,-COH, wherein carbon is not a part for carbonyl) that are connected with-OH group via carbon-oxygen bond, and m is 2 to about 10, or the integer of 2 to about 6.These alcohol can be the alcohol of aliphatic, alicyclic, aromatics and heterocycle, comprise alicyclic alcohol that aliphatic series replaces, heterocyclic alcohol that aromatic alcohol that aliphatic series replaces, aliphatic series replace, the aliphatic alcohol of alicyclic replacement, the heterocyclic alcohol of alicyclic replacement, the aliphatic alcohol of heterocyclic substituted, the alicyclic alcohol of heterocyclic substituted and heterocyclic substituted aromatic alcohol.Corresponding to the polyalcohol of formula R (OH) m preferably containing being no more than about 40 carbon atoms, more preferably no more than about 20 carbon atoms.Described alcohol can contain the group of substituents or the carboxylic acid not disturbing described alcohol and alkyl of the present invention to replace or anhydride reaction.These substituents or group comprise lower alkoxy, low alkyl group, sulfydryl, nitro and insertion group such as-O-and-S-(such as, as at group-CH ₂cH ₂-X-CH ₂cH ₂-in, wherein X is-O-or-S-).

Concrete alkyl comprise methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl, to octyl phenyl ethyl, cyclohexyl and analog.The carboxylic acid that can be used for preparing ester derivant is the butanedioic acid that list or polybasic carboxylic acid such as acetic acid, valeric acid, laurate, stearic acid, butanedioic acid and alkyl or alkenyl replace, and wherein said alkyl or alkenyl contains about 20 carbon atoms at the most.The member of this kind of alcohol can buy from various source; Such as, PLURONICS, the polyalcohol that can obtain from WyandotteChemicals Corporation; POLYGLYCOL112-2, the liquid triol derived from ethylene oxide and propylene oxide that can obtain from DowChemical Co.; PAG and their various derivatives, can obtain from Union Carbide Corporation.But the alcohol used must have average at least two free alcohol and belong to hydroxyl/polyoxygenated enol molecule.In order to describe these polyoxygenated enols, it is the hydroxyl be connected with the carbon atom not forming an aromatic kernel part that alcohol belongs to hydroxyl.

Alcohol used in the present invention also comprises aklylene glycol and polyoxygenated enol such as polyoxyethylene alcohol, polyoxypropylene alcohol, polyoxy butylidene alcohol and analog.These polyoxygenated enols (being sometimes called polyglycols) can contain about 150 oxyalkylenes at the most, and wherein said alkylidene contains about 2 to about 8 carbon atoms.This type of polyoxygenated enol is generally dihydroxylic alcohols.That is, the every one end of described molecule is by OH group end capping.In order to allow this type of polyoxygenated enol be useful, at least two OH groups must be there are.

Polyalcohol used in the present invention comprises polyhydroxy aromatic compounds.Multi-phenol and naphthols are useful hydroxy aromatic compounds.The aromatic compounds of these hydroxyl-replacements can also contain other substituting group such as halogen, alkyl, thiazolinyl, alkoxyl, alkyl thiol, nitro and analog except hydroxyl substituent.Usually, hydroxy aromatic compound contains 2 to about 4 hydroxyls.Aromatic hydroxy compound is by following instantiation example: resorcinol, catechol, p, p'-dihydroxybiphenyl, quinhydrones, 1,2,3,-thrihydroxy-benzene, phloroglucin, hexyl resorcin, orcin etc.

Polyalcohol preferably contains 2 to about 10 hydroxyls.They such as, by above-mentioned aklylene glycol and polyoxyalkylene diols such as ethylene glycol, diethylene glycol, triethylene glycol, TEG, DPG, tripropylene glycol, dibutylene glycol, three butanediols, and other wherein alkylidene containing 2 to the aklylene glycol of about 8 carbon atoms and polyoxyalkylene diols example.

Other useful polyalcohol comprises glycerine, the monoleate of glycerine, the monostearate of glycerine, the monomethyl ether of glycerine, pentaerythrite, the positive butyl ester of 9,10-dihydroxy stearic acid, 9, the methyl ester of 10-dihydroxystearic acid, 1,2-butanediol, 2,3-hexylene glycol, 2,4-hexylene glycol, pinacol, erythrite, arabite, D-sorbite, mannitol, 1,2-cyclohexanediol and Xylene glycol.Carbohydrate such as sugar, starch, cellulose etc. can be used equally.Described carbohydrate can by glucose, fructose, sucrose, rhamose, mannose, glyceraldehyde and galactolipin example.

The polyalcohol with at least 3 hydroxyls is useful, in them some, but not all by containing about 8 to mono carboxylic acid of aliphatic series such as sad, oleic acid, stearic acid, linoleic acid, the dodecylic acid or tall oil acid esterification of about 30 carbon atoms.Other instantiation of the polyalcohol of this type of partial esterification is the monoleate of D-sorbite, the distearate of D-sorbite, the monoleate of glycerine, the monostearate of glycerine, two-dodecylate of erythrite and analog.

Useful alcohol also comprises those polyalcohols containing about 12 carbon atoms at the most, particularly containing about 3 to those of about 10 or 6 carbon atoms.This kind of alcohol comprises glycerine, erythrite, pentaerythrite, dipentaerythritol, gluconic acid, mannitol, D-sorbite, glyceraldehyde, glucose, arabinose, 1, 7-heptandiol, 2, 4-heptandiol, 1, 2, 3-hexanetriol, 1, 2, 4-hexanetriol, 1, 2, 5-hexanetriol, 2, 3, 4-hexanetriol, 1, 2, 3-butantriol, 1, 2, 4-butantriol, chinic acid, 2, 2, 6, 6-tetra-(methylol) cyclohexanol, 1, 10-decanediol, digitalose, 2-hydroxy-methyl-2-methyl isophthalic acid, ammediol-(trimethylolethane), 2-methylol-2-ethyl-1, ammediol (trimethylolpropane) and analog.Aliphatic alcohol containing at least about 3 hydroxyls and about 10 carbon atoms is at the most useful.

In some embodiments, when the mixture of component (B) containing (i) one or more compounds containing at least two hydroxyls and at least one tertiary amino and (ii) one or more polyalcohols or polyalcohol, i the mol ratio of () and (ii) can be 1:0.5-10:1 or 1:1-5:1, or 2:1-3:1 or even 2.5:1-3:1 or even about 2.7:1.Be not wishing to be bound by theory, think that acquisition major benefit of the present invention is necessary, there is at least equal mixture, or even relatively without the compound containing at least two hydroxyls and at least one tertiary amino that the polyalcohol of nitrogen is at least necessarily excessive.

the formation of salt composite

Salt composite of the present invention can be prepared as follows: originally acidylate agent (A) (I) and component (B) and react and form intermediate; afterwards, make described intermediate and component (A) (II) react and form required salt.Optionally, but the method preparing these salt composites not too efficiently comprises makes component (A) (I) and (A) (II) react formation salt structure division each other, described salt structure division and component (B) is then made to react.

Ratio for the preparation of the reactant of salt composite of the present invention can change.Generally speaking, for every monovalent acylating agent (A) (I), use the component (B) of at least about two/monovalent.For every monovalent component (A) (I), corresponding use about 0.1 is to component (A) (II) of about 2 equivalents or more.The upper limit of component (B) is, based on every monovalent component (A) (I) (based on carboxyl), and about 1 equivalent (based on-OH base) component (B).

In some embodiments, reactant is to measure use as follows, 0.2 to 1.0 or even 0.4 to 0.6 equivalent component (B) is used for every monovalent component (A) (I), with 0.2 to about 2.0, or 0.2 to 1.0, or even 0.4 to 0.6 equivalent component (A) (II).

The equivalents of acylating agent (A) (I) depends on the sum of the carboxyl functional group be present in separately.When determining the equivalents of the often kind of acylating agent existed in (A) (I), not comprising can not as those carboxyl functional group of carboxylic acid acylating agent's reaction.But, generally speaking, for each carboxyl in these acylating agents, exist monovalent acylating agent (A) (I).Such as, in the acid anhydrides of the reaction derived from an olefin polymer and a mol maleic anhydride by existence two equivalent.Easily can obtain the routine techniques measuring carboxyl functional group number (such as, acid number, saponification number), therefore, those skilled in the art easily can measure the equivalents of often kind of acylating agent in (A) (I).

Agent (A) (I) can be acidylated react according to conventional ester and/or acid amides formation technology with component (B).This generally includes acylating agent (A) (I) and component (B), and be normally optionally liquid, the organic liquid solvent/diluent of inertia exists lower heating substantially.At least about 30 DEG C of temperature to the decomposition temperature of the reactive component and/or product with minimum decomposition temperature can be used.When acylating agent (A) (I) is acid anhydrides, temperature preferably at about 50 to about 130 DEG C, in the scope of more preferably about 80 to about 100 DEG C.On the other hand, when acylating agent (A) (I) is acid, temperature, preferably in the scope of about 100 to about 300 DEG C, is typically employed in the temperature within the scope of about 125 to 250 DEG C.

Reaction between component (A) (I) and (A) (II) uses routine techniques to carry out under salt-forming condition.Usually, component (A) (I) and (A) (II) are mixed and is heated to about 20 DEG C of decomposition temperatures to the reactive component and/or product with lowest decomposition temperature, temperature in the scope of namely about 20 to 130 DEG C, or about 40 to 110 DEG C; Be normally optionally liquid, the organic liquid solvent/diluent of inertia carries out, until formed required product under existing substantially.

Product between component (A) (I) and (A) (II) must containing at least some salt connecting key to allow described product effectively as emulsifying agent according to the present invention.In some embodiments; component (A) (II) that react with acylating agent (A) (I) at least about 10%, at least about 30%, at least about 50%; or even at least about 70%, and advantageously about 100% form salt connecting key respectively at the most.

explosive compositions

Explosive compositions of the present invention is water-in-oil emulsion, and this water-in-oil emulsion is detonator sensitiveness water-in-oil emulsion explosive in one embodiment, is detonator sensitiveness water-in-oil emulsion explosive in another embodiment.These emulsion explosives adopt salt composite of the present invention as emulsifying agent.Described explosive emulsion comprises at least one salt composite of the present invention of the discontinuous oxidant phase containing at least one oxygen-supplying component, the continuous organic phase containing at least one carbonaceous fuel and emulsifying amount.

Described continuous organic phase can by least about 2 % by weight, or about 2 % by weight to about 15 % by weight, or about 3.5 % by weight exist, based on the gross weight of explosive emulsion to about level of 8 % by weight.Described discontinuous oxidant mutually can by least about 85 % by weight, or about 85 % by weight to 98 % by weight, or about 92 % by weight exist, based on the gross weight of described explosive emulsion to about level of 96.5 % by weight.Salt composite of the present invention can by about 4 % by weight to about 40 % by weight, or about 12 % by weight exist, based on the gross weight of organic phase to about level of 20 % by weight.Oxygen-supplying component can by about 70% to about 95 % by weight, or about 85 % by weight to about 92 % by weight, or about 87 % by weight exist, based on the gross weight of oxidant phase to about level of 90 % by weight.Water can by about 5 % by weight to 30 % by weight, or about 8 % by weight to about 15 % by weight, or about 10 % by weight exist, based on the weight of oxidant phase to about level of 13 % by weight.

The carbonaceous fuel that can be used for explosive emulsion of the present invention can comprise most of hydrocarbon, and such as, alkane, olefinic, cycloalkanes, aromatics, saturated or unsaturated hydrocarbons, usually in oil or wax or its form of mixtures.Generally speaking, carbonaceous fuel is that water immiscibility can emulsifying hydrocarbon, and it is liquid or the highest about 95 DEG C, preferably approximately liquefiable at the temperature of 40 DEG C to about 75 DEG C.From the oil in various source, comprise natural and artificial oil and its mixture can be used as described carbonaceous fuel.

Natural oil comprises the mineral oil of the solvent-refined or acid treating of animal oil and vegetable oil (such as, castor oil, lard) and alkane, cycloalkanes or mixing alkane-naphthenic.The oil being derived from coal or shale is also useful.The alkene (such as, polybutene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes etc.) that the hydrocarbon ils that artificial oil comprises hydrocarbon ils and halogen substiuted is such as polymerized and is polymerized mutually; Alkylbenzene (such as detergent alkylate, Tetradecylbenzene, dinonyl benzene, two (2-ethylhexyl) benzene etc.); Many benzene (such as, biphenyl, terphenyl, alkylating many benzene etc.); And analog.

The artificial oil of another suitable class operable comprises the ester of dicarboxylic acids (such as phthalic acid, butanedioic acid, alkyl succinic acid, maleic acid, azelaic acid, suberic acid, decanedioic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic etc.) and various alcohol (such as butanols, hexanol, lauryl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, diethylene glycol monoether, propane diols, pentaerythrite etc.).The instantiation of these esters comprises dibutyl adipate, decanedioic acid (2-ethylhexyl) ester, the just own ester of fumaric acid two, di-n-octyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, dioctyl phthalate, didecyl phthalate, decanedioic acid eicosyl ester, the 2-ethylhexyl diester of linoleic acid dimer and one mole of decanedioic acid and two moles of TEGs and two moles of 2-ethyl-hexanoic and reacts the multiple ester formed, and analog.

The ester useful as artificial oil also comprises by C ₅-C ₁₂monocarboxylic acid and polyalcohol and polyol ethers etc. make those, described polyalcohol and polyol ethers are such as neopentyl glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol etc.

Silicon-based oil, such as poly-alkyl-, poly-aryl-, poly-alkoxyl-or poly-aryloxy group-silicone oil, silicic acid ester oil forms another kind of useful oil.They comprise, tetraethyl orthosilicate, silicic acid four isopropyl ester, silicic acid four-(2-ethylhexyl) ester, silicic acid four-(4-methylhexyl) ester, silicic acid four-(p-tert-butyl-phenyl) ester, hexyl-(4-methyl-2-amoxy) disiloxane, poly-(methyl) siloxanes, poly-(aminomethyl phenyl) siloxanes etc.Other useful artificial oil comprises the liquid ester (such as, the diethylester etc. of tricresyl phosphate, trioctyl phosphate, decane phosphonic acids) of phosphorous acid, polymerizing tetrahydrofuran and analog.

The oil (with mixture mutual separately) that is unpurified, refining and that re-refine of openly type above can be used.Unpurified oil directly to obtain from natural or synthesis source and without being further purified those of process.Such as, the shale oil directly obtained by retorting operation, the oil directly obtained by distillation or the ester oil of process further and use of not have to use directly obtained by esterification process are unpurified oil.The similar unrefined oil of refined oil, difference is that the former is processed further in one or more purification step, to improve one or more performances.Many such purification techniques are well known by persons skilled in the art, such as solvent extraction, distillation, acid or alkali extraction, filtration, diafiltration etc.Rerefined oils is by being similar to those techniques for obtaining refined oil to used refined oil application class and obtaining.Such rerefined oils also known as recovery or reprocessed oils, and is processed in addition frequently by the technology being intended to remove useless additive and oil decomposition product.

The example of useful oil comprises the slab oil that can obtain from Witco Chemical Company with trade name KAYDOL; The slab oil that can obtain from Shell with trade name ONDINA; With the mineral oil that can obtain from Pennzoil with trade name N-750-HT.

Carbonaceous fuel can be any wax of the fusing point with at least about 25 DEG C, such as petrolatum wax, microwax and paraffin, mineral wax such as ceresine and montan wax, and animal waxes is as spermacetic wax, and insect wax such as beeswax and Chinese wax.Useful wax comprises by trade name MOBILWAX57 (it can obtain from Mobil Oil Corporation); The wax that D02764 (it is the blended wax that can obtain from Astor Chemical Ltd.) and VYBAR (it can obtain from Petrolite Corporation) identifies.Preferred wax is the blend of microwax and alkane.

In one embodiment, carbonaceous fuel comprises the combination of wax and oil.In this embodiment, wax content is at least about 25% of organic phase, preferably approximately 25% to about 90 % by weight, and oil content is at least about 10% of organic phase, preferably approximately 10% to about 75 % by weight.These mixtures are especially suitable for detonator sensitive explosive emulsion.

Although existing of it is dispensable, described explosive emulsion can also contain about auxiliary fuel of 15 % by weight, such as aluminium, aluminium alloy, magnesium and analog at the most.Particulate aluminium is preferred auxiliary fuel.

Oxygen-supplying component is preferably at least one inorganic oxidant salt such as ammonium, alkali metal or alkaline earth metal nitrate, chlorate or perchlorate.Example comprises ammonium nitrate, sodium nitrate, calcium nitrate, ammonium chlorate, sodium perchlorate and ammonium perchlorate.Ammonium nitrate is particularly preferred.The mixture of ammonium nitrate and sodium nitrate or calcium nitrate is also preferred.In one embodiment, inorganic oxidant salt mainly comprises ammonium nitrate, but about at the most 25 % by weight of described oxidant phase can comprise another kind of inorganic nitrate (such as, alkali metal or alkaline earth metal nitrate) or inorganic perchlorate (such as, ammonium perchlorate or alkali metal or alkaline earth metal perchlorate) or their mixture.

In one embodiment of the invention, use closed pore, containing the material of cavity as sensitive component.Term " closed pore, material " containing cavity is used for referring to any granular materials comprising closed pore cavity in this article.Each particle of material can contain one or more closed pore, and gas, such as air can be contained in described hole, can be maybe find time or partial evacuation.In one embodiment of the invention, use enough materials containing closed pore cavity in the emulsion of gained, to produce about 0.8 to about 1.35g/cc, more preferably about 0.9 to about 1.3g/cc, more preferably the density of about 1.1 to about 1.3g/cc.Generally speaking, emulsion of the present invention can containing at the most about 15 % by weight, the preferably approximately material containing closed pore cavity of 0.25 % by weight to about 15 % by weight.The preferred material containing closed pore cavity has about 10 to the discrete glass marble of the granularity in about 175 micrometer ranges.Generally speaking, the bulk density of this type of particle can in about 0.1 scope to about 0.4g/cc.Operable useful glass microbubbles is by 3M Company and has about 10 to the nominal dimension in the size distribution in about 160 micrometer ranges and about 60-70 micrometer range, and about 0.1 to the microvesicle of the density within the scope of about 0.4g/cc; They comprise with the microvesicle of trade name B15/250 distribution.Other useful glass microbubbles is sold by Emerson & Cumming, Inc. with trade name ECCOSPHERES, and generally has the particle size range of about 44 to about 175 microns and the bulk density of about 0.15 to about 0.4g/cc.Other microvesicle be applicable to comprises the inorganic microspheres sold by Philadelphia QuartzCompany with trade name Q-CEL.Material containing closed pore cavity can be made up of inertia or reproducibility material.Such as, P-F microvesicle can use within the scope of the present invention.If use P-F microvesicle, then described microvesicle itself is the fuel element of explosive and should considers their fuel value when design water-in-oil emulsion explosive compositions.Operable within the scope of the present invention another kind is the saran microsphere sold by Dow Chemical Company containing the material of closed pore cavity.Described saran microsphere has the diameter of about 30 microns and the grain density of about 0.032g/cc.Due to the low bulk density of described saran microsphere, thus preferably only use in water-in-oil emulsion of the present invention about 0.25 to about 1 % by weight they.

By to add in composition and distributing gas produces the aqueous solution of material such as natrium nitrosum and bubble that original position produces and also can be used for sensitization explosive emulsion wherein.Other sensitive component be applicable to that can adopt separately or adopt together with above-mentioned comprises particulate matter solid from explosive; such as particle or thin slice TNT, DNT, RDX and analog and the water-soluble and/or organic sensitizer of hydrocarbon dissolubility; such as, amine nitrate, alkanolamine nitrate, hydroxyalkyl nitrate and analog.Explosive emulsion of the present invention can prepare the application for wide region.Any combination of sensitive component can be selected to provide the explosive compositions with almost any desired density, important intensity or cut off diameter.Solid can account for about at the most 40 % by weight of described total explosive compositions from explosive composition and amount that is water-soluble and/or the organic sensitizer of hydrocarbon dissolubility.The volume of the gas component closed can account for about at the most 50% of the volume of total explosive compositions.

Optional additional materials can be introduced in explosive emulsion of the present invention so that the susceptibility of the final explosive of further improvement, density, intensity, rheology and cost.Find that the typical material that can be used as optional additive comprises, such as, the nonmetal fuel of particulate such as sulphur, pitch and analog, particulate inert material such as sodium chloride, barium sulfate and analog, aqueous phase or hydrocarbon phase thickener such as guar gum, polyacrylamide, carboxymethyl or ethyl cellulose, biopolymer, starch, elastomeric material and analog, for the crosslinking agent such as potassium pyroantimonate and analog of thickener, buffer or pH value controlling agent such as Boratex, zinc nitrate and analog, crystal habit modifying agents is as Negel and analog, liquid phase extender such as formamide, ethylene glycol and analog and raising agent and the additive be usually used in explosive field.The amount of the optional additional materials used can account for about at the most 50 % by weight of total explosive emulsion.

A kind of method preparing explosive emulsion of the present invention comprises the following steps: (1) by water, inorganic oxidant salt (such as, ammonium nitrate) and, in some cases, some water soluble compounds supplemented mix in the first premix, (2) carbonaceous fuel, emulsification salt composite of the present invention and other optional oil-soluble compounds any are mixed in the second premix and (3) will be applicable to blender in described first premix will be added in the second premix, to form water-in-oil emulsion.If heat described first premix until all salt fully dissolves and needs can filter this solution to remove any insoluble residue.Also heat described second premix to liquefy to make composition.The equipment that can carry out any type of low or high shear mixing may be used for preparing these water-in-oil emulsions.By the material containing closed pore cavity, Gas Generating Material, solid is from explosive composition such as particulate TNT, solid fuel such as aluminium or sulphur, inert material such as barite or sodium chloride, undissolved solid oxidizer salt and other optional material (if employed) add in emulsion also blended simply until be evenly dispersed in whole composition.

Water-in-oil type explosive emulsion of the present invention can also be prepared as follows: the organic solution of the second premix liquefaction is added into mutually the first premix hydrothermal solution mutually in, stir to make phase reversal simultaneously fully.But than preferred anti-phase program, this method requires that significantly more energy is to obtain required dispersion usually.Or these water-in-oil type explosive emulsions are especially applicable to being prepared by method for continuously mixing, and wherein via the liquid phase that mixing apparatus pumping two is prepared separately, they merge and emulsification in this mixing apparatus.

Salt composite of the present invention can directly add in explosive emulsion of the present invention.Also can use inertia substantially, be normally that the organic diluent of liquid dilutes to form multifunctional additive for lubricating oils, diluent is such as mineral oil, naphtha, benzene, toluene or dimethylbenzene.Of the present invention salt composite of these concentrates usually containing about 10 % by weight to about 90 % by weight also can contain one or more other additives as known in the art or above-described in addition.

As everyone knows, more above-mentioned materials can interact in end formulation, so that the component of end formulation may be different from initial interpolation those.The product formed thus, comprises the product formed when the present composition uses in its intended application, may be not easy to describe.Even so, all these modifieds and product are included in the scope of the present invention; The composition prepared by mixing said ingredients is contained in the present invention.

Embodiment

Following examples illustrate the preparation of salt composite of the present invention.Except as otherwise noted, local with other in this description and claim in following examples, by weight, all temperature are degree Celsius (C) for all numbers and percentage.Although provide these embodiments to be used for the present invention is described, they are not used for limiting the present invention.

comparative example 1

Following preparation table surface-active agent: make 1033 grams of middle-molecular-weihydroxyethyl polyisobutylene succinic anhydride (PIBSA) derived from 1000 number-average molecular weights (Mn) polyisobutene (PIB) own and 31 grams of glycol reactions in 3 liters of reaction flasks under nitrogen blanket.React at the temperature of about 85 DEG C in flux oil.Described ethylene glycol to be added in described PIBSA along with the time and carry out reaction 3 hours to complete.Be obtained by reacting the diester of glycol coupling, there is the calculating productive rate of 99%.The coupling diester of 402 grams of (based on active material) gained is added 1 liter of reaction flask and makes it to react with 44 grams of diethyl ethylene diamines.React at the temperature of about 45-50 DEG C in flux oil.Add amine along with the time and carry out reaction 2 hours to complete.The surfactant of gained is the salt of glycol coupling, has the calculating productive rate of 99%, and total acid number (TAN) is 28.6, theory T AN is 31.7.This is comparative example.

embodiment 2

Following preparation table surface-active agent: make PIBSA and 344 gram tallow-bis-(2-ethoxy) amine reaction described in embodiment 1 above 2008 grams in 5 liters of reaction flasks under nitrogen blanket.React at the temperature of about 85 DEG C in flux oil.Described amine glycol to be added in described PIBSA along with the time and carry out reaction 3 hours to complete.Be obtained by reacting the diester of glycol amine coupling, there is the calculating productive rate of 100%.The coupling diester of 402 grams of (based on active material) gained is added 1 liter of reaction flask and makes it to react with 39 grams of diethyl ethylene diamines.React at the temperature of about 45-50 DEG C in flux oil.Add amine along with the time and carry out reaction 2 hours to complete.The surfactant of gained is the salt of glycol amine coupling, has the calculating productive rate of 100%, and TAN is 28.3, theory T AN is 28.2.

embodiment 3

Following preparation table surface-active agent: make PIBSA and the 26 gram of N methyldiethanol amine reaction described in embodiment 1 above 450 grams in 1 liter of reaction flask under nitrogen blanket.React at the temperature of about 92 DEG C in flux oil.Described amine glycol to be added in described PIBSA along with the time and carry out reaction 3 hours to complete.Be obtained by reacting the diester of the glycol amine coupling of salinization immediately.39 grams of dimethylethanolamines are added to and derives from the salt of first step.React at the temperature of about 45-50 DEG C in flux oil.Add amine along with the time and carry out reaction 2 hours to complete.The surfactant of gained is the salt of glycol amine coupling, has the calculating productive rate of 91%, and TAN is 33.3, theory T AN is 31.7.

embodiment 4

Following preparation table surface-active agent: PIBSA and 112 gram tallow-bis-(2-hydroxyethyl) amine described in embodiment 1 above making 900 grams reacts under nitrogen blanket in 2 liters of reaction flasks.React at the temperature of about 85-90 DEG C in flux oil.Described amine glycol to be added in described PIBSA along with the time and carry out reaction one hour, then along with the time adds 7.3 grams of ethylene glycol, at the temperature of about 85-90 DEG C, maintaining reaction.Be obtained by reacting the diester of glycol amine coupling, this diester also comprises some glycol couplings.The salinization immediately of this product.102 grams of diethyl ethylene diamines are added to and derives from the salt of first step.React at the temperature of about 45-50 DEG C in flux oil.Add amine along with the time and carry out reaction 2 hours to complete.The surfactant of gained is the salt of glycol amine coupling, has the calculating productive rate of 94%, and TAN is 29.5, theory T AN is 29.1.

embodiment 5

Following preparation table surface-active agent: make the coupling diester that 335 grams (based on active material, namely without oil and/or solvent-free) prepare according to the Part I of embodiment 2 above, react in 1 liter of reaction flask with 16 grams of diethyl ethylene diamines.React at the temperature of about 45-50 DEG C in flux oil.Add amine along with the time and carry out reaction 2 hours to complete.The surfactant of gained is the salt of glycol amine coupling, has the calculating productive rate of 99%, and TAN is 34.4, theory T AN is 29.5, and realizes with the amine charging reduced relative to embodiment 2.

embodiment 6

Following preparation table surface-active agent: make the gained coupling diester prepared in embodiment 2 first step above 335 grams (based on active materials), react in 1 liter of reaction flask with 24 grams of diethyl ethylene diamines.React at the temperature of about 45-50 DEG C in flux oil.Add amine along with the time and carry out reaction 2 hours to complete.The surfactant of gained is the salt of glycol amine coupling, has the calculating productive rate of 99%, and TAN is 34.0, theory T AN is 28.8, and realizes with medium amine charging relative to embodiment 2 and 5.

emulsion is evaluated

Embodiment 1-6 is used for preparing the emulsion with ammonium nitrate oxidizing agent aqueous phase and organic-fuel phase.Identical ammonium nitrate oxidizing agent aqueous phase is used in often kind of sample.Organic-fuel is 100N flux oil or diesel fuel mutually, as marked.Emulsion is characterized by inspection under the microscope.Then described emulsion is allowed to experience a series of Stress and stability test described in detail below.

Adopt two kinds of shearing tests.Use the test of low sheraing paint shaking machine, this shaking machine test simulation emulsion explosive from Workplace to its use time the transport of workplace.For this test, emulsion explosive compositions is placed in paint shaking machine device 4 hours.High shear syringe test simulation pumping emulsion explosive, such as, be pumped into it from reservoir vessel and will carry out the boring of igniting.In this test, via the osculum injection emulsion under stress of syringe.Test under 30 and 50psi injection pressure.

Adopt two kinds of stability tests.In ambient storage test, emulsion is stored 30 days at ambient temperature, then evaluates.In thermal cycling test, at-30 DEG C, keep emulsion 6 hours, then keep 6 hours at+50 DEG C.Then in this accelerated aging test five and ten these circulation post-evaluation emulsions.

Evaluate (proof) emulsion of fresh (untested) and stress/aging mistake under the microscope, to evaluate the performance of often kind of sample.Use microscopical evaluation to comprise the amount measuring ammonium nitrate crystal, less crystallization wishes.% coverage rate (crystal count) is lower, and emulsion is more stable.Generally speaking, crystal count be less than 5% be classified as qualified; Border emulsion has the crystal count of 5-10%, and defective have more than 10% crystallization.The result of this test is summarized in the following table:

Percentage crystallinity in Table A-diesel fuel emulsions, round 1 ⁵.

1 – contrast table surface-active agent 1 is the salt that the succinyl oxide that replaced by HMW alkyl and tertiary alkanol amine are formed, and does not have the structure of coupling.

2 – contrast table surface-active agents 2 are surfactants of ethylene glycol coupling prepared by the 1:1 mixture of the succinyl oxide of succinyl oxide and the low-molecular-weight alkyl replacement replaced by middle-molecular-weihydroxyethyl alkyl, and wherein said two kinds of acid anhydrides are connected by ethylene glycol and the compound tertiary alkanol amine salt of gained.

3 – contrast table surface-active agents 3 are the fine surface activating agent bags mixed by contrast table surface-active agent 1 and 2, and this makes its preparation more complicated and more expensive.

This sample showing in duration of test crystallization of 4 –, it is seriously underproof.

Each in emulsion in 5 – Table As has same recipe, just different in used surfactant.Often kind of emulsion uses identical aqueous phase and identical diesel fuel by identical amount, and often kind of sample is by 0.8 % by weight its concrete surfactant of active material level use.

Percentage crystallinity in table B-diesel fuel emulsions, round 2 ⁴.

Identical with above defined in Table A of 1 – contrast table surface-active agent 1.

Identical with above defined in Table A of 2 – contrast table surface-active agents 2.

3 – embodiments 1 are comparative examples, because it is not containing tertiary amine glycol connecting key.

Each showing in the emulsion in B of 4 – has same recipe, just different in used surfactant.Often kind of emulsion uses identical aqueous phase and identical diesel fuel by identical amount, and often kind of sample is by 0.8 % by weight its concrete surfactant of active material level use.

Percentage crystallinity in table C-100N fat liquor, round 3 ⁵.

Identical with above defined in Table A of 3 – contrast table surface-active agents 3.

4 – embodiments 1 are comparative examples, because it is not containing tertiary amine glycol connecting key.

Each showing in the emulsion in C of 5 – has same recipe, just different in used surfactant.Often kind of emulsion uses identical aqueous phase and identical 100N oil by identical amount, and often kind of sample is by 0.8 % by weight its concrete surfactant of active material level use.

Percentage crystallinity in table D-100N fat liquor, round 4 ³.

Identical with above defined in Table A of 1 – contrast table surface-active agent 3.

This sample showing in duration of test crystallization of 2 –, it is seriously underproof.

Each showing in the emulsion in D of 3 – has same recipe, just different in used surfactant.Often kind of emulsion uses identical aqueous phase and identical 100N oil by identical amount, and often kind of sample is by 0.8 % by weight its concrete surfactant of active material level use.

Result shows surfactant of the present invention, and the emulsion manufactured by it to solve in foregoing problems one or more.Such as, data show that the present composition can be provided to the performance of looking younger and working as with more uncomplicated and more inexpensive surfactant bag.Data also show, the present composition can provide the performance for stability of improvement, particularly in the stability of emulsion In transit, maintain enough performances in other field simultaneously.

The every section of document related to above is incorporated to herein by reference.Except in embodiment, or when separately clearly stating, in this description, all numerical value of prescribed material amount, reaction condition, molecular weight, carbon number etc. should be understood and modified by word " approximately ".Except as otherwise noted, all fraction values, ppm value and number value are by weight.Except as otherwise noted, the often kind of chemical substance related to herein or composition should be interpreted as being commercial grade material, they can comprise isomers, accessory substance, derivative and other it has been generally acknowledged that will exist with commerical grade in those materials.But do not including the amount providing often kind of chemical composition under any solvent or dilution oil condition, described solvent or flux oil can be present in commercial materials usually, except as otherwise noted.It should be understood that any upper and lower bound amount, scope and the ratio provided can combine independently herein.Similarly, the present invention's scope of often planting key element and amount can use with the scope of other key element any or together with measuring.Statement used herein " primarily of ... form " allowing to comprise can not the material of fundamental sum novel characteristics of composition in fact in influence research.

Claims

1. composition, it comprises: (A) is derived from the salt structure division of following material:

(A) (I) at least one polybasic carboxylic acid acylating agent, described acylating agent (A) (I) has at least one hydrocarbyl substituent containing average 20 to 500 carbon atoms, and

(A) (II) is selected from one or more in ammonia, at least one amine, at least one alkali metal or alkaline-earth metal and at least one alkali metal or alkaline earth metal compound;

Two in wherein said structure division (A) to be coupled at the compound of at least one tertiary amino containing at least two hydroxyls by (B) at least one together with,

Wherein component (B) comprises at least one with the tertiary amine of following formula:

Wherein each a, b and c are 0 or 1 independently, as long as a+b+c sum is at least 2, and wherein each R ³, R ⁴and R ⁵the alkyl containing 1-50 carbon atom or-(-R independently ⁶-O-) n-group, wherein R ⁶be the thiazolinyl containing 1-6 carbon atom, n is the integer of 1-50 or 1-20.

2. the composition of claim 1, wherein (A) (I) is derived from least one alpha-beta ethylenically unsaturated carboxylic acids or acidic compound, and described acid or acidic compound contain and be no less than 20 carbon atoms, and carboxyl is not included.

3. the composition of claim 1, wherein (A) (I) by with in following formula any one or more to represent:

Each R wherein in each formula ¹the described hydrocarbyl substituent of (A) (I) and each R wherein in each formula independently ²hydrogen or methyl independently.

4. the composition of claim 1, wherein the described hydrocarbyl substituent of (A) (I) is poly-(isobutene) base.

5. the composition of claim 1, wherein component (B) comprises at least one with the tertiary amine of following formula:

6. the composition of claim 1, wherein component (A) (II) comprises at least one with the alkylene polyamine of following formula:

Wherein n is the number of 1 to 10, each R ⁷hydrogen atom or containing the alkyl of 700 carbon atoms or the alkyl of hydroxyl-replacements at the most, described alkylidene contains 1 to 10 carbon atom independently.

7. the composition of claim 1, wherein component (B) comprising: 3-(two (dodecyl) is amino) propane-1,2-glycol, tallow-bis--(2-hydroxyethyl) amine, N methyldiethanol amine, N-ethyldiethanolamine, N-propyl group diethanol amine, N-n-butyldiethanolamine, N-tertiarybutyldiethanolamine, N-cyclohexyldi, N-2-ethylhexyl diethanol amine, N-amyl group diethanol amine, N-isobutyl group diethanol amine, N-sec-butyl diethanol amine, N-dodecyl diethanol amine, N-cetyl diethanol amine, N-hydrogenation vegetable seed alkyldiethanolamine, N-hydrogenated tallow alkyl diethanol amine, N-phenyldiethanol-amine, tolyl diethanol amine between N-, two (2-ethoxy) octadecylamine, two (2-ethoxy) cocoalkyl amines, two (2-ethoxy) oleyl amine, two (2-ethoxy) soja alkylamin, two (2-ethoxy) tallow alkylamine, polyoxyethylene (5) octadecylamine, polyoxyethylene (15) octadecylamine, polyoxyethylene (5) cocoalkyl amines, polyoxyethylene (15) cocoalkyl amines, polyoxyethylene (5) soja alkylamin, polyoxyethylene (15) soja alkylamin, polyoxyethylene (5) tallow alkylamine, polyoxyethylene (15) tallow alkylamine, polyoxyethylene (20) tallow alkylamine, 3-(dimethylamino)-1,2-PD, 3-(diethylamino)-1,2-PD, 3-(dipropylamino)-1,2-PD, 3-(diisopropylaminoethyl)-1,2-PD, 3-(two (octadecyl) is amino)-1,2-PD or their combination.

8. the composition of claim 1, wherein component (B) also comprises at least one polyalcohol.

9. the composition of claim 8, wherein in component (B), the mol ratio of tertiary amine and polyalcohol is 1:0.5-10:1.

10. the composition of claim 1, the composition also comprising diluent so that claim 1 is present in described composition by 10 % by weight to 90 % by weight, obtains concentrate composition.

The composition of 11. claims 1, also comprises: the oxidant phase containing at least one oxygen-supplying component and the organic phase containing at least one carbonaceous fuel, obtain explosive compositions.

The composition of 12. claims 1, wherein the described hydrocarbyl substituent of (A) (I) contain be less than 10 % by weight there is the alkyl being less than 20 carbon atoms.

13. emulsion explosive compositions, comprise: containing the discontinuous oxidant phase of at least one oxygen-supplying component, containing the continuous organic phase of at least one carbonaceous fuel, described carbonaceous fuel comprises at least one wax, and the composition of the claim 1 of emulsifying amount.

14. cartridges comprising cartridge sleeve pipe, described cartridge sleeve pipe contains detonator sensitiveness or detonator sensitive emulsion explosive, and described emulsion comprises containing the discontinuous oxidant phase of at least one oxygen-supplying component, the composition containing the continuous organic phase of at least one carbonaceous fuel and the claim 1 of emulsifying amount.