KR100697335B1 - Emulsifier for producing Emulsion Explosive - Google Patents

Abstract

The present invention relates to an oil-in-water type emulsion explosive emulsifier, wherein the polyalkenyl epoxide including at least one epoxide ring and the polyamine having at least one basic nitrogen atom react with an amine and a amine to form a salt. It provides an explosive emulsifier derived from one acid compound. The emulsifiers of the present invention not only improve the long-term storage stability and impact stability of emulsion explosives, but also significantly improve low temperature stability.

 Water-in-oil emulsion explosives, polyalkenyl epoxides, polyamines, acids, emulsifiers, stability

Description

Emulsifier for emulsion explosives {Emulsifier for producing Emulsion Explosive}

The present invention relates to emulsifiers used in the preparation of water-in-oil emulsion explosives, and more particularly to polyalkenyl epoxides comprising at least one epoxide ring and at least one polyamine. An emulsifier for emulsion explosives derived from at least one acid compound capable of reacting with an amine to form a salt.

Common components of emulsion explosives are divided into continuous fuels, discontinuous oxidizers and emulsifiers for emulsifying them. Fuels are composed of carbonaceous organic materials, and oxidants are inorganic compounds such as ammonium nitrate and sodium nitrate, which are oxygen supplies, and It is composed of water, and an emulsifier is a compound having a structure in which a lipophilic group and a hydrophilic group component are combined. Water-in-oil emulsion explosives are prepared by dispersing a solution of oxidant in a small particle state in a continuous organic fuel agent, wherein the amount of water contained in the oxidant is 5% by weight or less, and in some cases may not contain water. . Here, water is added to suppress the explosion of an oxidant such as ammonium nitrate to improve stability.

Industrially, the most important factors of emulsion explosives are storage stability and maintaining stability when handling explosives. In other words, the oxidant particles dispersed in the fuel are crystallized by the association between the particles during mechanical stirring or explosive handling, and the crystallization between the oxidant particles gradually progresses even during long-term storage, thereby reducing the explosive performance. Various emulsifiers have been developed in the past.

One example of explosive emulsifiers conventionally used is carboxylic acid acylated derivatives which are added to fuels and lubricants to act as dispersants. The acylated compounds include olefins containing at least 10 to 50 carbon atoms (e.g., polyalkylenes such as polyisobutylene) and unsaturated carboxylic acids or derivatives thereof such as acrylic acid, maleic acid, fumaric acid, anhydride It is prepared by reacting maleic acid or methyl acrylate. Such techniques for preparing emulsifiers using carboxylic acids are disclosed in detail in US Pat. Nos. 3,087,936, 3,379,515, 3,697,428, 3,836,470, 4,234,435, 4,471,091 and the like. In addition, U.S. Patent No. 3,216,936 discloses the reaction of carboxylic acid acylated compounds with alkylene amines containing at least one NH group, and aliphatic carboxylic acids such as acetic acid, oleic acid, formic acid, lead acid, and dodeca. A technique for producing a dispersant by reacting with nonacid and stearic acid is disclosed.

EP 0,156,572 discloses compounds in which hydrophilic and lipophilic components are covalently bonded as surfactants useful in water-in-oil emulsions. The patent discloses that a saturated or unsaturated hydrocarbon having 30 to 500 carbon atoms is used as the lipophilic component, and anionic groups such as phosphate, sulfate, and methyl carboxylate are used as the hydrophilic component, for example, polyisobutenyl anhydride. A compound prepared by reacting maleic acid with ethanol amine and phosphoric acid is disclosed.

US Patent No. 4,710,248 also discloses a method for preparing an emulsion explosive by dispersing an oxidizing agent in a fuel comprising an emulsifier composed of a lipophilic group and a hydrophilic group.A hydrophilic group component of the emulsifier is a carboxylic acid or a carboxylic acid. Functional groups to decompose were used, and saturated or unsaturated hydrocarbons were used as lipophilic components.

However, when introducing a carboxyl group as a hydrophilic binding medium to an alkylene group, corrosive chlorine gas must be used in the reaction process to increase the yield. The reaction temperature is also high, and the manufacturing process is not easy and the manufacturing cost is high. do. In addition, there is a side reaction in which the carboxyl compound is tarized, and the separation process of chlorine gas and unreacted carboxyl compound has a disadvantage. In particular, maleic anhydride, which is mainly used as the carboxyl compounds of the prior arts, exists as a solid at room temperature, and thus, not only a problem in the manufacturing process but also a problem in that stability is reduced at low temperatures due to emulsifier performance.

Accordingly, an object of the present invention is to provide a new emulsifier which can prevent crystallization of an oxidizing agent and improve the long-term storage stability and handling stability of an emulsion explosive. Another object of the present invention is to provide a new emulsifier that can significantly improve the low temperature stability of emulsion explosives.                         

It is another object of the present invention to provide an emulsifier which does not require the use of chlorine gas in the manufacturing process, is free from side reactions, is prepared at low temperatures, and is easy to separate unreacted materials.

In order to achieve the above object, the present invention is capable of producing a salt by reacting a polyalkenyl epoxide including at least one epoxide ring (A) and a polyamine (B) having at least one basic nitrogen atom and an amine. It provides an explosive emulsifier made of at least one acid compound (C).

Hereinafter, the present invention will be described in detail.

The present invention uses a liquid organic acid in place of chlorine gas, and introduces an epoxidation reaction that proceeds at low temperatures, thereby producing an emulsifier, which is a problem in the process of preparing emulsion emulsifiers for conventional emulsion explosives, such as side reactions and separation of unreacted materials. I solved the problem. In addition, the emulsifier of the present invention is excellent in long-term storage stability and handling stability by using a polyalkenyl epoxide having high low temperature fluidity as a hydrophilic binding medium, compared to carboxylic acids such as maleic anhydride used as a conventional binding medium. The polyalkenyl epoxide (A), polyamine (B) and acid compound (C) used in the preparation of the emulsifier of the present invention will be described in detail.

Polyalkenyl Epoxide (A):

The polyalkenyl epoxide forms an oxirane ring by the epoxidation reaction of the polyolefin to become a polyalkenyl epoxide. Polyalkenyl epoxides are prepared from polyolefins having an average molecular weight of 200 to 5,000, preferably 200 to 2,500. Preparation examples thereof are known from US Patent No. 5,034,471, US Patent No. 5,089,028, International Patent Application WO 92-14806, Korean Patent Publication No. 99-60043, and the like.

Polyolefins are generally mixtures of molecules with different molecular weights and may have one or more side chains per six carbon atoms, preferably one or more side chains per four carbon atoms, and polyolefins having one or more side chains per two carbon atoms Particularly preferred. Such polyolefins may be prepared from olefins of 2 to 6 carbon atoms, preferably olefins of 3 to 4 carbon atoms, and polybutenes prepared by reacting isobutylene or C4 fractions containing isobutylene are most preferred.

These polyolefins have double bonds in their molecules, and these double bonds form oxirane rings by various oxidizing agents to become polyolefin epoxides. The oxidant which can be used for the preparation of the polyolefin epoxide can be any known oxidant. Suitable oxidizing agents include hydrogen peroxide, peracetic acid, perbenzoic acid, performic acid, monoperphthalic acid, percamporic acid, persuccinic acid and pertrifluoroacetic acid, and the like, preferably hydrogen peroxide.

When hydrogen peroxide is used as an oxidizing agent, an additional organic acid such as formic acid or acetic acid, which is a catalyst, is added. In particular, when using an organic acid having two or more carbon atoms, including acetic acid, adding an inorganic acid such as sulfuric acid or phosphoric acid as a promoter to improve the yield desirable. Hydrogen peroxide is added so that the mole ratio of olefin to hydrogen peroxide is 1: 0.2 to 1: 3.0, preferably 1: 0.4 to 1: 1.5, and the organic acid is 1: 0.1 to 1: 1.5, preferably molar ratio of olefin to organic acid. Is added so that 1: 0.2 to 1: 1. On the other hand, when using an organic acid having two or more carbon atoms including acetic acid, the inorganic acid is added so that the molar ratio of olefin to inorganic acid is 1: 0.1 to 1: 0.6, preferably 1: 0.2 to 1: 0.4.

As for reaction temperature, 20-90 degreeC is preferable. The reaction product may be washed with water to remove peroxides and organic acids and solvents are removed by distillation under reduced pressure, or polyalkenyl epoxide may be obtained by directly distilling under reduced pressure without washing.

Representative structures of polyalkenyl epoxides (including hydroxy polyalkenyl epoxides) prepared by the above method are represented by the following Chemical Formula 1.

In Formula 1, m is an integer of 1 to 10, preferably an integer of 1 to 2, R ¹ is alkyl derived from a polyolefin having a molecular weight of 200 to 5,000, preferably of a molecular weight of 200 to 2,500, R ² , R ³ , R ⁴ , R ⁵ may be the same or different from each other, and are each hydrogen or alkyl having 1 to 10 carbon atoms, preferably hydrogen or alkyl having 1 to 2 carbon atoms.

Polyamine (B):

The reactant polyamine (B) is a compound having at least one basic nitrogen atom and at least one basic nitrogen atom having at least one hydrogen atom, for example, ammonia, ethylenediamine, hexamethylenediamine, diethylenetriamine, Triethylenetetraamine, di (trimethylene) triamine, dipropylenetriamine, tetraethylenepentaamine, 1,2-propylenediamine, 1,3-propylenediamine, dimethylaminopropylenediamine, dipropylenetriamine, 2-amino Ethanol, 2- (2-aminoethylamino) ethanol, 1-amino-2-propanol, 3-amino-1-propanol, 4-aminophenol, N-methylamine, N-ethylamine, Nn-propylamine, N Isopropylamine, Nn-butylamine, N-isobutylamine, N-sec-butylamine, N-tert-butylamine, Nn-pentylamine, N-cyclopentylamine, Nn-hexylamine, N-cyclohexyl Amines, N, N-dimethylamine, N, N-diethylamine, N-di-n-propylamine, N, N-diisopropylamine, N, N-di-n-butylamine, N, N-diisobutylamine, N, N-di (2-hydroxyethyl) amine, N, N-di (3-hydroxy Selected from oxypropyl) amine, N, N-di (ethoxyethyl) amine, N, N-di (propoxyethyl) amine, and among them, ethylenediamine, diethylenetriamine, triethylenetetraamine, 2 Particular preference is given to using -aminoethanol. Representative structure of the polyamine is represented by the formula (2).

In Chemical Formula 2, R ⁶ and R ⁷ may be the same as or different from each other, hydrocarbons each containing an aromatic ring having 6 to 10 carbon atoms or alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ may be the same as or different from each other, and each is hydrogen, a hydrocarbon containing an aromatic ring having 6 to 10 carbon atoms, an alkyl having 1 to 10 carbon atoms, or a hydroxyalkyl having the formula (3). . r and s may be the same as or different from each other, and are each an integer of 0 to 10, preferably an integer of 0 to 3, respectively.

-R ¹² -OH

In the said Formula (3), R <^12> is hydrocarbon containing a C6-C10 aromatic ring or C1-C10 alkylene, Preferably it is C1-C5 alkylene.

The reaction of the polyalkenyl epoxide or hydroxypolyalkenyl epoxide with the amine component is generally carried out purely at 100 to 280 ° C., preferably at 180 to 250 ° C. or with a solvent. The reaction pressure is generally determined by the reaction temperature, the presence of a solvent and the boiling point of the amine component.

The molar ratio of polyalkenyl epoxide or hydroxypolyalkenyl epoxide to amine is from 1: 1 to 1:10, preferably from 1: 1 to 1: 5. The combination of a large number of polyalkenyl epoxides or hydroxypolyalkenyl epoxides in one amine is undesirable because of poor yield, such as lower yield, compared to polyalkenyl epoxides or hydroxypolyalkenyl epoxides. This is preferably used.

The reaction of polyalkenyl epoxides or hydroxypolyalkenyl epoxides with amines is generally carried out in the presence or absence of a catalyst in the absence of oxygen. When a catalyst is used, suitable catalysts include solid acids containing Lewis acids such as aluminum trichloride, boron trifluoride, titanium tetrachloride and ferric chloride and Brenstead and Lewis acid sites such as alumina, silica and silica-alumina. Organic acids and water can also be used. The catalyst may be added with a polyalkenyl epoxide or hydroxypolyalkenyl epoxide to catalyst weight ratio of from 1: 0.01 to 1: 0.5, preferably from 1: 0.02 to 1: 0.3.

The reaction can also be carried out with or without a reaction solvent. The reaction solvent is generally used when it is necessary to reduce the viscosity of the reaction product. These solvents should be stable and inert to the reactants and reaction products, and aliphatic or aromatic hydrocarbons or aliphatic alcohols may be used, preferably hexane, cyclohexane, heptane, octane, benzene, toluene, xylene, butanol, pentanol , Hexanol, octanol and the like are used, more preferably toluene or xylene is used. The solvent may be added at a reactant to solvent weight ratio of from 1: 0.1 to 1: 1.

The reaction time may vary depending on the reaction temperature, the type of polyalkenyl epoxide or hydroxypolyalkenyl epoxide, the type of amine, and the use of a catalyst. The reaction time is 1 hour to 30 hours, preferably 2 hours. To 20 hours.

After completion of the reaction, the reaction mixture can be extracted with hydrocarbon-water or hydrocarbon-alcohol-water medium to remove unreacted amine or amine salt, and then the solvent is removed by vacuum distillation to separate the product. The mixture can be directly distilled under reduced pressure to remove unreacted amine and solvent.

Acid Compound (C):

The acid compound (C) used in the present invention may be either inorganic or organic acid, and specific examples of the inorganic acid include nitric acid, nitrous acid, sulfuric acid, sulfurous acid, hydrochloric acid, silicic acid, boric acid, perchloric acid, chloric acid, chloric acid, hypochloric acid, Permanganic acid, chromic acid, dichromic acid, hydrofluoric acid, hydrobromic acid, hydrofluoric acid, hydrosulfic acid, phosphoric acid, thiophosphoric acid, phosphorous acid, oxiaphosphoric acid, thiophosphoric acid, and the like.

Organic acids include monocarboxylic acid derivatives such as formic acid, acetic acid, chloroacetic acid, propionic acid, butyric acid, acrylic acid, benzoic acid, cyclohexanoic acid, dodecanoic acid, palmitic acid, decanoic acid, oleic acid, lauric acid, stearic acid, Chlorostearic acid, myristic acid, linoleic acid, naphtanic acid, etc. may be used, and dicarboxylic acid derivatives such as maleic acid, maleic anhydride, chloromaleic anhydride, malonic acid, succinic acid, succinic anhydride, glutaric acid, Anhydrous glutaric acid, adipic acid, pimalic acid, azelanic acid, sebacic acid, glutamic acid, citraconic acid, itaconic acid, arylsuccinic acid, cetylmalonic acid and the like can be used, and formic acid or acetic acid is preferably used.

The final product, an emulsifier, is prepared by reacting reactant (C) with a reaction product of reactant (A) and reactant (B) at 30-100 占 폚, preferably 60-90 占 폚, with or without an organic solvent. The organic solvent is an aliphatic or aromatic hydrocarbon having 4 to 20 carbon atoms, preferably an aliphatic or aromatic hydrocarbon having 6 to 12 carbon atoms, and more preferably toluene, xylene, hexane, heptane, octane, benzene and the like. The organic solvent is added at 5% to 90% by weight, preferably 10% to 50% by weight relative to the total weight of the reactants.

The reaction time is 10 minutes to 5 hours, preferably 1 hour to 3 hours. The base-acid equivalent ratio of reactant (B) and reactant (C) is 10: 1 to 1: 1, preferably 3: 1 to 1.2: 1, and when out of the above range, the amount of salt produced by the acid-base reaction Small hydrophilicity is reduced, or the pH of the emulsion solution is acidic due to the excess acid, which is undesirable because it reduces the emulsion stability.

The emulsifiers according to the invention are used to prepare water-in-oil emulsion explosive compositions, and are particularly useful for detonating explosives. The emulsion explosive consists of a discontinuous oxidant comprising at least one oxygen supply material, a continuous fuel comprising at least one carbonaceous fuel, and an emulsifier provided in the present invention. Hereinafter, the explosive composition using the emulsifier of the present invention will be described in more detail.

The fuel and emulsifier in the explosive composition are 2 to 15% by weight, preferably 4 to 8% by weight, based on the total weight of the explosive composition, and the emulsifier is 4 to 40% by weight relative to the total weight of the fuel and emulsifier, preferably Consists of 12% to 20% by weight.

The oxidant is 85 to 98% by weight, preferably 92 to 96% by weight relative to the total weight of the explosive composition, and the oxygen supply material is 70 to 95% by weight, preferably 87 to 90% by weight relative to the total weight of the oxidant. It is composed. Water is also preferably included in an amount of 5% to 30% by weight, more preferably 10% to 13% by weight of the total weight of the oxidant.

As the carbonaceous fuel included in the fuel, most hydrocarbons, such as paraffin, olefins, aromatic hydrocarbons, and the like, may be used in the liquid phase at room temperature up to about 95 ° C, preferably 40 ° C to 75 ° C. In addition, natural or synthetic oils may be used. Preferred natural oils are animal oils, vegetable oils or paraffins, mineral oils in the form of lead, and synthetic oils are preferably polymers and crosslinking neutralizers such as polybutene, polypropylene, and propylene. Isobutylene copolymers, chlorinated polybutenes and alkylbenzenes such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, di-2-ethylhexyl benzene and polyphenyls such as biphenyl, terphenyl, Alkyl polyphenyls and the like. Still other synthetic oils may include esters derived from carboxylic acids and aliphatic alcohols, such as dibutyl adipic acid, didosil phthalate, di-normalhexyl fumaric acid, and the like. Ethyl, tetraisopropyl silicate, tetra- (2-ethyl-hexyl) silicate, tetra- (4-methylhexyl) silicate, polymethylsiloxane, poly- (methylphenyl) -siloxane and the like can be used.

In addition, mineral oil produced through the refining process of petroleum can also be used as a fuel. For example, "KAYDOL" from Witco Chemical, "ONDINA" from Shell, "MENTOL 28" from Exxon, "40N oil" from Sun, "LT- from unchanged petroleum" 350 "and so on.

As another carbonaceous fuel, a wax having a melting point of at least 25 ° C. or higher can be used. For example, waselin wax, microcrystalline wax, paraffin wax, mineral wax, animal wax and the like. More specifically, "MOBIL WAX 57" of Mobil Oil, "D02764" of Astor Chemical, "VYBAR" of Petrolite, etc. may be used.

Meanwhile, as the carbonaceous fuel, a mixture of natural oil or synthetic oil and wax described above can be used. The wax content is at least 25% by weight, preferably 25% to 90% by weight of the total weight of the fuel, and the natural or synthetic oil content is at least 10% by weight, preferably 10% to 75% by weight of the total fuel. % to be.

Oxygen constituents that make up the oxidant include inorganic oxidants in at least one salt form, such as nitrates, hydrochlorides and perchlorates of ammonium or alkaline earth metals. For example, ammonium nitrate, sodium nitrate, calcium nitrate, ammonium hydrochloride, ammonium perchlorate, sodium perchlorate and the like. Among the above components, ammonium nitrate is more preferable, and a mixture of ammonium nitrate and sodium nitrate or calcium nitrate is also preferable.

The explosives in which the emulsifier of the present invention is used may further include a "micro hollow sphere" as a Sensitizer. "Micro hollow sphere" refers to a material that contains a gas, such as air, in one particle, or that has a confined space, one or more pores, in a partially vacuum state. “Micro hollow spheres” are mixed to improve the density of the emulsion in the range of about 0.8 to 1.35 g / cc, preferably about 0.9 to 1.3 g / cc, more preferably about 1.1 to 1.3 g / cc. In general, the "microspheres" can be included up to about 15% by weight, preferably 0.25-15% by weight of the emulsion. The particle size of the "microspheres" is suitably about 10 to 175 microns. Generally, the bulk density of the particles ranges from 0.1 to 0.4 g / cc.

An example of a useful glassy microsphere is 3M's “microbubble B15 / 250” with a particle size distribution of about 10 to 160 microns, a normal size of 60 to 70 microns and a density of about 0.1 to 0.4 g / cc. . Another example is the "ECCOSPHERE" product from Emerson & Cumming, with a particle size distribution of 44 to 175 microns and a bulk density of about 0.15 to 0.4 g / cc.

In order to improve the emulsion explosive sensitivity, a gas-generating substance, for example, sodium nitrite and an aqueous solution of urea may be dispersed in the explosive composition instead of the fine hollow spheres. As other preservatives, non-insoluble self-explosive particles such as Trinitrotoluene (TNT), Dinitrotoluene (DNT), Research department explosive (CD) (cycloclomethylenetrinitramine), and the like, are water-soluble or hydrocarbon-soluble organic preservatives such as amine nitrates. , Alkanolamine nitrate, hydroxyalkyl nitrate and the like can be used. The amount of gaseous material in the pretreatment agent may be collected up to about 50% by volume of the total explosive composition, and the amount of self-explosive particles and the water-soluble or hydrocarbon-soluble organic foreing agent may include up to 40% by weight of the total explosive component.

Meanwhile, auxiliary materials may be further added to improve the sensitivity, density, strength, flowability, and the like of the explosive. The material is an optional additive, for example, high chlorinated paraffin hydrocarbons, ammonium nitrate, calcium nitrate, perchlorate and the like atomized metals, such as aluminum, silicon and other non-particulated particles, such as sulfur, gilsonite, etc. Inert substances such as sodium chloride, barium sulfate and the like or water phase or hydrocarbon phase enhancers such as polyacrylamide, carboxymethyl or ethyl cellulose, raw polymers, starch, elastomers and the like, and as crosslinkers of the enhancers, for example, fatigue antimony Potassium acid and the like, sodium borate, zinc nitrate, and the like as a buffer or pH adjuster, and alkylnaphthalene sodium sulfate and the like may be used as the crystallizer. The auxiliary material may comprise up to about 50% by weight of the explosive composition, the actual amount depending on the explosive nature and action.

The method for producing an emulsion explosive according to the present invention is divided into three steps as follows.

(1) First, water and an oxygen supply material, such as ammonium nitrate and sodium nitrate, are mixed in advance while heating to a temperature at which the liquid is liquefied (25 to 120 ° C).

(2) The carbonaceous fuel and the emulsifier and other oil soluble materials prepared by the present invention are mixed while heating to a temperature (25 to 120 ° C) to be liquefied.

(3) Adding the mixture prepared in the first step to the mixture prepared in the second step and mixing with a suitable stirring device to prepare a water-in-oil emulsion explosive.

In some cases, fine tool bodies, gas generating materials, self-exploding elements such as TNT particles, solid fuels such as aluminum and sulfur, inerts such as sodium chloride and other auxiliary materials can be added to the emulsion and mixed until uniformly dispersed. have.

Hereinafter, the present invention will be described in detail through examples.

Preparation Example 1 Preparation of Polybutene Epoxide

200 g of polybutene (Daelim polybutene PB-900, molecular weight 920), 100 g of xylene and 10.2 g of formic acid were placed in a 500 ml flask with a condenser and stirred. 15 g of 60% hydrogen peroxide was added for 1 hour using an injection pump while maintaining the temperature in the flask at 50 ° C, and the reaction was continued for 4 hours. When the epoxidation reaction was completed, the aqueous solution layer in the reaction mixture was separated using a 1,000 ml separatory funnel, and then the solvent in the organic layer was removed by distillation under reduced pressure to obtain 195 g of polybutene epoxide having a slightly yellow color. The production of epoxide was confirmed using NMR, the polybutene epoxide yield was 96% by weight when analyzed by column chromatography using silica. When the product is developed by chromatography in normal-hexane, unreacted polybutene is released in hexane, and the yield of polybutene epoxide can be obtained by evaporating hexane and measuring the weight of the remaining portion.

Preparation Example 2 Preparation of Polybutene Epoxide

Polybutene epoxide when prepared in the same manner as in Preparation Example 1 using 200 g of polybutene (Daelim polybutene PB-680, molecular weight 680), 100 g of xylene, 13.5 g of formic acid, and 20.0 g of 60% hydrogen peroxide. Yield 97% by weight.

Preparation Example 3 Preparation of Hydroxypolybutenyl Amine

80 g of polybutene epoxide prepared in Preparation Example 1, 30 g of diethylenetriamine, and 3 g of water were placed in a high pressure reactor and reacted at 230 ° C. for 20 hours while maintaining the inside of the reactor in a nitrogen state. After completion of the reaction, unreacted amine was removed by distillation under reduced pressure for 1 hour at 200 ° C. and 100 Torr while generating nitrogen bubbles to obtain hydroxypolybutenyl amine. The content of polybutene-derived amine compound in the reaction product was measured by column chromatography using silica. When the reaction product is developed in a silica column with a solution containing normal hexane and diethyl ether in a 1: 1 volume ratio, unreacted polybutene and polybutene derivatives without amine bonding are developed, and normal hexane and diethyl in this solution are developed. The content of the polybutene-derived amine compound can be determined by distilling off the ether and weighing the remaining components.

As a result, the content of the polybutene-derived amine compound in the reaction product was 42% by weight and the basic nitrogen was 1.51% by weight.

Preparation Example 4 Preparation of Hydroxypolybutenyl Amine

Hydroxyalkyl amine was prepared by adding 80 g of polybutene epoxide prepared in Preparation Example 2, 30 g of diethylenetriamine, and 3 g of water to a high-pressure reactor in the same manner as in Preparation Example 3 for 20 hours at 230 ° C. . As a result of analyzing the reaction product using a silica column as in Preparation Example 3, the content of the hydroxyalkyl amine compound was 60% by weight, and the basic nitrogen was 1.71% by weight.

Example 1 Hydroxypolybutenyl Amine and Maleic Anhydride Reaction

80 g of hydroxypolybutenyl amine prepared in Preparation Example 3 and 8.5 g of maleic anhydride were added to a reactor, heated to 80 to 90 ° C., and stirred for 3 hours. After the reaction was completed, cooled to room temperature to obtain a final product.

Example 2: Hydroxypolybutenyl amine and maleic anhydride reaction

 80 g of hydroxypolybutenyl amine prepared in Preparation Example 4 and 8.5 g of maleic anhydride were added to a reactor, heated to 80 to 90 ° C., and stirred for 3 hours. After the reaction was completed, cooled to room temperature to obtain a final product.

Example 3: Hydroxypolybutenyl Amine and Stearic Acid Reaction

100 g of hydroxypolybutenyl amine prepared in Preparation Example 4 and 10 g of stearic acid were added to a reactor, heated to 80 to 90 ° C., and stirred for 3 hours. After the reaction was terminated and cooled to room temperature to obtain the final product.

Example 4: Hydroxypolybutenyl Amine and Phosphoric Acid Reaction

120 g of hydroxypolybutenyl amine prepared in Preparation Example 3 was added to a reactor and heated to 80 to 90 ° C., and then 14 g of phosphoric acid was injected for 1 hour and further reacted for 2 hours. After the reaction was completed, cooled to room temperature to obtain a final product.

Example 5: Hydroxypolybutenyl Amine and Acetic Acid Reaction

100 g of hydroxypolybutenyl amine prepared in Preparation Example 4 was added to a reactor, heated to 80 to 90 ° C, and then 8.8 g of acetic acid was injected for 1 hour and further reacted for 2 hours. After the reaction was completed, cooled to room temperature to obtain a final product.

Example 6: Hydroxypolybutenyl Amine and Formic Acid Reaction

100 g of hydroxypolybutenyl amine prepared in Preparation Example 4 was added to a reactor and heated to 80 to 90 ° C., 8.9 g of formic acid was injected for 1 hour and further reacted for 2 hours. After the reaction was completed, cooled to room temperature to obtain a final product.

Experimental Example 1 Preparation of Emulsion and Observation of Crystallization Phenomenon

Emulsions were prepared with the compositions shown in Table 1 below using emulsifiers from Examples 1, 3, 5 and 6. In the manufacturing method, first, an oxidizing agent, that is, ammonium nitrate and water are mixed and heated to 80 ° C. Thereafter, the mineral oil as a fuel ingredient and the emulsifier obtained in the preparation example are mixed, heated to 90 ° C. to make a liquid state, and the oxidant solution prepared above is added while stirring at 1500 rpm using a laboratory mixer. Thereafter, the mixture was stirred for about 2 minutes to prepare an emulsion. EXAMPLES Emulsions were easily produced in all of the products and remained stable without crystallization when left at room temperature.

ingredient Emulsion Composition (wt%) One 2 3 4 Ammonium Nitrate 84.7 84.7 84.7 84.7 Mineral oil 3.0 3.0 3.0 3.0 water 10.3 10.3 10.3 10.3 Emulsifier of Example 1 2.0 Emulsifier of Example 3 2.0 Emulsifier of Example 5 2.0 Emulsifier of Example 6 2.0

Experimental Example 2: Storage Stability Test

In order to confirm the storage stability, the emulsion explosive was prepared in the composition shown in Table 2, and then left for 60 hours at 60 ° C. for 24 hours at -20 ° C. for 4 weeks to check the degree of crystallization visually. Manufacturing method is the same as Experimental Example 1. In the table below it was confirmed that even after 4 weeks the degree of crystallization is very small, high stability is maintained.

ingredient Emulsion Composition (wt%) One 2 3 4 Ammonium Nitrate 84.7 84.7 84.8 84.8 water 10.3 10.3 10.3 10.3 Mineral oil 3 4 0.66 1.16 Wax 2.5 2 Emulsifier of Example 6 2 One 1.84 1.84 Degree of crystallization (1-10) 1 week 0 0 0 0 2 weeks 0 0 0 0 3 weeks 0 One One 0 4 Weeks One 2 2 One

The degree of crystallization was given 0 when there was no change and 10 when the entire surface was crystallized.

Comparative Example 1 Storage Stability Comparison

After using the conventional commercial product carboxyl derivative PIBSA (polyisobutylene succinic anhydride) based emulsifier and the emulsifier prepared according to the present invention to prepare an emulsion as shown in Table 3, the storage stability was compared. The test method is the same as Experimental Example 2. As a result of measuring the degree of crystallization after storage for 4 weeks, it was confirmed that the stability of the emulsifier prepared by the present invention as shown in Table 3 below.

ingredient Emulsion Composition (wt%) One 2 Ammonium Nitrate 84.7 84.7 Mineral oil 3.0 3.0 water 10.3 10.3 Product of Example 6 2.0 PIBSA-based emulsifier 2.0 Crystallization degree after 4 weeks (0 to 10) One 2

 As described above, the composition for emulsion explosives using the emulsifier of the present invention can prevent the crystallization of the oxidizing agent, thereby improving the long-term storage stability and handling stability of the emulsion explosives, in particular, significantly improves the low temperature stability of the emulsion explosives. In addition, the emulsifier of the present invention can be prepared at low temperatures without using chlorine gas, without side reactions, and is easy to separate unreacted materials.

Claims (6)

(A) a polyalkenyl epoxide containing at least one epoxide ring represented by the following formula (1), (B) a polyamine having at least one basic nitrogen atom, and (C) an amine to form a salt An explosive emulsifier prepared by reacting at least one acid compound present. [Formula 1]

(In Formula 1, m is an integer of 1 to 10, R ¹ is alkyl derived from a polyolefin having a molecular weight of 200 to 5,000, R ² , R ³ , R ⁴ , R ⁵ may be the same or different from each other, Hydrogen or alkyl having 1 to 2 carbon atoms, respectively.) delete The explosive emulsifier of claim 1, wherein the polyolefin is prepared by reacting C4 fraction containing isobutylene or isobutylene. The explosive emulsifier of claim 1, wherein the polyolefin has a molecular weight of 200 to 2,500. The emulsifier for explosives according to claim 1, wherein the polyamine is a compound represented by the following Chemical Formula 2. [Formula 2]

In Formula 2, R ⁶ and R ⁷ may be the same as or different from each other, and are each an aromatic ring having 6 carbon atoms or alkylene having 2 to 6 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are the same as each other. And hydrogen, an aromatic ring having 6 carbon atoms, alkyl having 1 to 6 carbon atoms, or hydroxyalkyl having the formula 3. Each of r and s may be the same as or different from each other, and is an integer of 0 to 10, respectively. [Formula 3] -R ¹² -OH In Formula 3, R ¹² is an aromatic ring having 6 carbon atoms or alkylene having 1 to 5 carbon atoms.) The method of claim 1, wherein the acid compound is an inorganic acid or an organic acid compound, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, hydrochloric acid, silicic acid, boric acid, perchloric acid, chloric acid, chloric acid, hypochlorous acid, permanganic acid, chromic acid, dichromic acid, hydrofluoric acid, embrittlement Hydrochloric acid, hydrofluoric acid, hydrosulfic acid, phosphoric acid, thiophosphoric acid, phosphorous acid, oxia phosphoric acid, thiophosphoric acid, formic acid, acetic acid, chloroacetic acid, propionic acid, butyric acid, acrylic acid, benzoic acid, cyclohexanoic acid, dodecanoic acid, palmitic acid, decane Acids, oleic acid, lauric acid, stearic acid, chlorostearic acid, myristic acid, linoleic acid, naphthaic acid, maleic acid, maleic anhydride, chloromaleic acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid Group consisting of finic acid, pimaline acid, azelanic acid, sebacic acid, glutamic acid, citraconic acid, itaconic acid, arylsuccinic acid, cetylmalonic acid and mixtures thereof In that the compound explosive is selected emulsifier according to claim.