Water-in-Oil Emulsion Explosive Composition With Imidazoline Derivative Emulsifier

The present invention relates to water-in-oil (W/O) emulsion explosive compositions having excellent stability in storage, detonability at low temperature and explosion reactivity, which is obtained by the use of 1-hydroxyethyl-2-imidazoline derivative as an emulsifier.

Heretofore, the improvement of explosion reactivity (usually represented by the explosion velocity) in general explosives has been effected by (1) selecting the components of the explosive composition and (2) varying the mixed state between each component of the explosive composition. The above described former method (1) comprises selecting substances having a high reaction velocity, selecting substances which generate a large heat energy upon the reaction, that is, have a high explosion heat, and the like, as a means for enhancing the reactivity of explosive composition. The above described latter method (2) comprises contacting an oxidizer with a fuel in fine particle form, that is, increasing the contact area or dissolving these substances with each other through water to increase the contact area, as a means for enhancing the reactivity of mixed phase.

Accordingly, when a water soluble substance and a water insoluble substance are contained in a slurry explosive, it is very difficult to contact both the substances in a dissolution state through water, so that it is necessary to form a mixed phase wherein an aqueous solution of a water soluble substance and a water insoluble substance are contacted with each other in the state where both the substances are formed into particle state to increase the contact area.

Almost all of conventional slurry explosive compositions have been oil-in-water (referred to as O/W hereinafter emulsion explosive compositions, in which water of the major component envelops water insoluble substances or water soluble substances which can not be fully dissolved in water and remain in water. The major part of the water insoluble substances in the O/W emulsion explosive compositions are oxidizers, for example inorganic oxidizer salts, such as ammonium nitrate and the like and the major part of water insoluble substances are fuels or sensitizers which act as a fuel together, for example, aluminum, nitromethane and the like.

In general, in slurry explosive compositions, when the components are classified into water insoluble substances (referred to as "O") and water soluble substances (referred to as "W"), the compounding ratio by weight of O/W is generally not more than 25/75. When it is considered that the dispersed particle size in O/W emulsion and W/O emulsion is equal, the contact area O and W is larger in W/O emulsion wherein O which is smaller in the amount, envelops W which is larger in the amount, than in O/W emulsion. Accordingly, it is expected that the explosion reactivity is improved in W/O emulsion. As the results, the explosive wherein smoke is minimal and the after-detonation fume is good, can be obtained.

Thus, in view of increase of the contact area, a variety of W/O emulsion explosive compositions have been disclosed instead of the prior O/W emulsion explosive compositions in U.S. Pat. Nos. 3,161,551; 3,164,503; 3,212,945; 3,356,547; 3,442,727; 3,447,978; 3,617,406; 3,674,578; 3,765,964; 3,770,522 and 4,008,108. In these W/O emulsion explosive compositions, the quality of W/O emulsion explosive compositions is greatly influenced by the kind of emulsifier necessary for forming W/O emulsion. In the W/O emulsion explosive compositions described in the above described United States Patent specifications, emulsifiers shown in the following Table 1 are used.

It is commonly known that the above described various emulsifiers are used, but almost all W/O emulsion explosive compositions using an emulsifier other than sorbitan fatty acid ester are poor in the emulsion stability in storage, and are insufficient in the explosion reactivity and in the low temperature detonability (detonability at low temperature). Although W/O emulsion explosive compositions using sorbitan fatty acid ester are good in the emulsion stability in storage, the explosion reactivity and the like. Commercially available sorbitan fatty acid ester is not always composed of single component and often contains its isomers, polycondensate and the like. Therefore, it has been difficult to produce W/O emulsion explosive compositions having always stable performance by the use of commercially available sorbitan fatty acid ester.

The inventors have made various investigations for a long perid of time by taking the above described problems into consideration and found out that a substance, which has never hitherto been considered as an emulsifier for W/O emulsion explosive composition, can form a mixture of an aqueous solution of inorganic oxidizer salts, such as ammonium nitrate and the like, (an aqueous solution of oxidizer salt) and an oil and/or wax into W/O emulsion, and further found out that the W/O emulsion explosive composition obtained by the use of the emulsifier has excellent emulsion stability in storage, explosion reactivity, low temperature detonability and the like. As a result, the present invention has been accomplished.

That is, the present invention consists in a W/O emulsion explosive composition consisting of ammonium nitrate or a mixture of ammonium nitrate and the other inorganic oxidizer salts (referred to as "inorganic oxidizer salts, such as ammonium nitrate and the like" hereinafter), (b) water, (c) an oil and/or wax, (d) an emulsifier or 1-hydroxyethyl-2-imidazoline derivative represented by the following general formula ##STR1## wherein R represents an alkyl or alkenyl group having 10-26 carbon atoms, and (e) at least one of hollow microspheres and bubbles generated from a chemical foaming agent.

The W/O emulsion explosive composition according to the present invention is produced by a method, wherein (A) inorganic oxidizer salts, such as ammonium nitrate and the like, are wholly or partly dissolved in water at 55.degree.-75.degree. C. to prepare an aqueous solution of oxidizer salt, (B) an oil and/or wax is mixed with the above described 1-hydroxyethyl-2-imidazoline derivative (emulsifier) at 55.degree.-75.degree. C. to prepare a homogeneous liquid mixture of oil and/or wax and emulsifier, (c) the aqueous solution of oxidizer is mixed with the homogeneous liquid mixture of oil and emulsifier at 55.degree.-75.degree. C. under stirring to prepare an emulsion composition, (D) the emulsion composition is mixed with remaining inorganic oxidizer salts, such as ammonium nitrate and the like, in the case where the inorganic oxidizer salts have been partly added to water in the above described step (A), and (E) at least one of hollow microsphere and a chemical foaming agent is added to the emulsion composition, whereby the density of the emulsion composition is controlled by presence of at least one of the hollow microspheres and bubbles generated from the inorganic foaming agent. Components to be used in the present invention are as follows. Namely, as the other inorganic oxidizer salts used together with ammonium nitrate, use is made of nitrates, such as sodium nitrate, calcium nitrate and the like, chlorates, such as sodium chlorate and the like; perchlorates, such as sodium perchlorate and like. As the oil and/or wax, use is made of oils, such as light oil, heavy oil and the like, and waxes, such as paraffin wax, petrolatum wax, microcrystalline wax and the like. These oils and/or waxes may be used in various mixing ratios depending upon the consistency of the aimed explosive compositions. The 1-hydroxyethyl-2-imidazoline derivative to be used as an emulsifier is not particularly limited, but the number of carbons of R should be from 10 to 26, and is preferably from 12 to 22. As the hollow microsphere and/or chemical foaming agent (hereinafter referred to as density controlling agent), the following hollow microspheres and chemical foaming agents can be used. The hollow microspheres include glass hollow microsphere, synthetic resin hollow microsphere, silica hollow microsphere, shirasu hollow microsphere (shirasu is a kind of silica) and the like. It is not necessary that these hollow microspheres are fine and expensive hollow microspheres, but coarse hollow microspheres having an average particle size of about 500 .mu.m can be used. The chemical foaming agents include inorganic foaming agents, for example, a mixture of alkali metal borohydride or sodium nitrite with urea, and organic foaming agents, such as N,N'-dinitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile and the like.

The compounding recipe of these components for the W/O emulsion explosive composition of the present invention should be determined by taking oxygen balance, detonability, strength, consistency and productivity into consideration. In general, 50-90% (% means by weight) of inorganic oxidizer salts, such as ammonium nitrate and the like, 5-20% of water, 2-7% of an oil and/or wax, 1-5% of an emulsifier, 1-10% of a hollow microsphere and 0.1-2% of a chemical foaming agent are compounded.

The present invention will be explained in more detail referring to examples and comparative examples. In the examples, "parts" and "%" mean by weight.

In evaluation of W/O emulsion explosive compositions produced in the examples, the emulsion stability in storage was determined by the temperature cycle test and the low temperature detonability and explosion reactivity were determined by the initiation test and the detonation velocity at that time. The temperature cycle test was carried out in the following manners. A W/O explosive composition sample was kept at 0.degree. C. for 14 hours and then kept at 40.degree. C. for 7 hours, which was referred to one cycle. This was repeated and the cycle number when the W/O emulsion was broken, was determined. The initiation test and the measurement of detonation velocity were carried out in the following manner. A sample emulsion explosive composition was charged into a polyethylene tube having a diameter of 25 mm and a length of 200 mm and the tube end was sealed to obtain a cartridge. The cartridge was placed in a low-temperature thermostat so as to adjust the cartridge to a test temperature and then taken out from the thermostat. A probe was inserted into the cartridge and the explosive sample in the cartridge was initiated by a No. 6 electric blasting cap on sand under an unconfined state. The detonation velocity of the explosive sample was measured by means of a digital counter.

A W/O emulsion explosive composition having a compounding recipe shown in the following Table 2 was produced in the following manner. To 36 parts of water were added 160 parts of ammonium nitrate, 40 parts of sodium nitrate and 40 parts of calcium nitrate, and the resulting mixture was heated at about 65.degree. C. to dissolve the nitrates in water and to obtain an aqueous solution of the oxidizer salts. 8 parts of butyl stearate as an emulsifier was added to 14 parts of No. 2 light oil, and the resulting mixture was heated at about 65.degree. C. to obtain a homogeneous liquid mixture of the emulsifier and the oil. The aqueous solution of the oxidizers was gradually added to the homogeneous liquid mixture of the emulsifier and the oil, while agitating at a rate of about 300 rpm by means of a commonly used propeller blade-type agitator. After completion of the addition, the resulting mixture was further agitated at a rate of 1,500 rpm to prepare an emulsion composition kept at 65.degree. C. Successively, the emulsion composition was kneaded together with 24 parts of glass hollow microsphere as a density controlling agent to produce a W/O emulsion explosive composition.

The resulting W/O emulsion explosive composition was subjected to the temperature cycle test and the initiation test. The results obtained are shown in Table 2.

W/O emulsion explosive compositions having a compounding recipe shown in Table 2 were produced in the same manner as described in Comparative example 1. In this case, only in Comparative examples 3, 4 and 8, was emulsion formed. Accordingly, only the W/O emulsion explosive compositions of Comparative examples 3, 4 and 8 were subjected to the temperature cycle test and the initiation test. In comparative examples 2, 5, 6, 7 and 9, emulsion was not formed, and therefore glass hollow microsphere was not used (the amount of hollow microsphere described in Table 2 is an amount which would be used in the emulsifying stage).

A W/O emulsion explosive composition having a compounding recipe shown in Table 2 was prepared in the following manner. To 36 parts of water were added 160 parts of ammonium nitrate, 40 parts of sodium nitrate and 40 parts of calcium nitrate, and the resulting mixture was heated at about 65.degree. C. to dissolve the nitrates and to prepare an aqueous solution of the oxidizer salts. While, 8 parts of 1-hydroxyethyl-2-alkyl(rice bran oil)-2-imidazoline was added to 18 parts of No. 2 light oil, and the resulting mixture was heated at 65.degree. C. to obtain a homogeneous liquid mixture of the emulsifier and the oil. The aqueous solution of the oxidizer salts was gradually added to the homogeneous liquid mixture of the emulsifier and the oil, while agitating by means of a propeller blade-type agitator at a rate of about 300 rpm. After completion of the addition, the resulting mixture was further agitated at a rate of 1,500 rpm to produce an emulsion composition kept at about 65.degree. C. Successively, the emulsion composition was kneaded together with 24 parts of glass microspheres as a density controlling agent to produce a W/O emulsion explosive composition. The resulting W/O emulsion explosive composition was subjected to the temperature cycle test and the initiation test, and the detonation velocity was measured. The obtained results are shown in Table 2.

W/O emulsion explosive compositions having a compounding recipe shown in Table 2 were produced in the same manner as described in Example 1. The resulting W/O emulsion explosive compositions were subjected to the temperature cycle test and the initiation test, and the detonation velocity was measured. The obtained results are shown in Table 2. However, in Example 4, after a chemical foaming agent (dinitrosopentamethylenetetramine) as a density controlling agent was added to an emulsion composition, the resulting mixture was heated in a thermostat kept at about 50.degree. C. for 2 hours to decompose and foam the foaming agent. Comparative example Example 1 2 3 4 5 6 7 8 9 1 2 3 4 5 6 7 Compound- Aqueous ammonium ing solution nitrate 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 49.7 83.7 60.5 60.5 62.1 recipe of sodium (%) oxidizer nitrate 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 -- 15.1 15.1 15.5 calcium nitrate 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 12.4 -- -- -- -- water 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 11.2 10.3 11.2 11.2 11.5 Conven- (1) 2.5 -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- tional (2) -- 2.5 -- -- -- -- -- -- -- -- -- -- -- -- -- -- emulsifier (3) -- -- 2.5 -- -- -- -- -- -- -- -- -- -- -- -- -- (4) -- -- -- 2.5 -- -- -- -- -- -- -- -- -- -- -- -- (5) -- -- -- -- 2.5 -- -- -- -- -- -- -- -- -- -- -- (6) -- -- -- -- -- 2.5 -- -- -- -- -- -- -- -- -- -- (7) -- -- -- -- -- -- 2.5 -- -- -- -- -- -- -- -- -- (8) -- -- -- -- -- -- -- 2.5 -- -- -- -- -- -- -- -- (9) -- -- -- -- -- -- -- -- 2.5 -- -- -- -- -- -- -- Emulsifier (a) -- -- -- -- -- -- -- -- -- 2.5 2.5 2.5 1.8 -- -- 2.0 of this (b) -- -- -- -- -- -- -- -- -- -- -- -- -- 2.0 -- -- invention (c) -- -- -- -- -- -- -- -- -- -- -- -- -- -- 2.0 -- Oil or No. 2 light oil 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 -- 1.6 -- -- -- wax Unpurified micro- crystalline wax -- -- -- -- -- -- -- -- -- -- -- 4.3 1.6 3.8 3.8 3.8 Density Hollow glass 7.5 7.5 7 .5 7.5 7.5 7.5 7.5 7.5 7.5 7.5 -- -- -- 7.4 7.4 5.1 controlling micro- resin -- -- -- -- -- -- -- -- -- -- 7.5 -- -- -- -- -- agent sphere shirasu -- -- -- -- -- -- -- -- -- -- -- 7.5 -- -- -- -- Chemical foaming agent -- -- -- -- -- -- -- -- -- -- -- -- 1.0 -- -- -- Evalua- Emulsification emul not emul emul not not not emul not emul e mul emul emul emul emul emul tion Stability after break -- break break -- -- -- break -- good good good good good good good temperature cycle 1 1 2 1 30 30 30 30 30 30 30 Initiation test 20.degree. C. -- 20.degree. C. 20.degree. C. -- -- -- 20.degree. C. -- -20.degree. C. -20.degree. C. -20.degree. C. -20.degree. C. -20.degree. C. -20.degree. C. -20.degree. C. (after temperature cycle) not not not not do do do do do do do Detonation velocity (m/sec) (after temperature cycle) -- -- -- -- -- -- -- -- -- 4,080 4,210 3,330 3,810 4,170 4,210 4,150 Density (g/cc) -- -- -- -- -- -- -- -- -- 1.07 1.05 1.03 1.05 1.08 1.04 1.16 Note: (1) Chemical names of conventional emulsifiers (1)-(9) are as follows. (1) butyl stearate (2) potassium stearate (3) polyoxyethyleneoctadecylamine (4) alkyl (coconut oil) phosphoric acid ester (5) polyoxyethylene monooleate (6) polyoxyethylene cetyl ether (7) dodecylbenzenesulfonic acid (8) alkyl(coconut oil)alkylolamide (9) polyoxyethylene alcohol Note: (2) Chemical names of emulsifiers (a)-(c) of the present invention are as follows. (a) 1hydroxyethyl-2-alkyl(rice bran oil)2-imidazoline (b) 1hydroxyethyl-2-alkyl(coconut oil)2-imidazoline (c) 1hydroxyethyl-2-alkyl(tallow)-2-imidazoline Note: (3) The resin hollow microsphere is phenolic resin hollow microsphere Note: (4) As the chemical foaming agent, dinitrosopentamethylenetetramine was used. Note: (5) In the item of emulsification, the term "emul" means that emulsion was formed, and the term "not" means that emulsion was not formed. Note: (6) In the item of stability after temperature cycle, the numeral shows the repeated number of temperature cycles, and the term "good" means that goo emulsion state is still maintained after repeating temperature cycles shown by the numeral, and the term "break" means that the emulsion breaks in repeating temperature cycles shown by the numeral. Note: (7) In the item of initiation test, the upper line shows the test temperature and the term "do" in the lower line means that the explosive composition detonated, and the term "not" means that the explosive composition did no detonate. Note: (8) In the item of detonation velocity, the numeral shows the detonation velocity at the described initiation test.

The results of the above described comparative examples and examples will be explained in detail. In Comparative examples 2, 5, 6, 7 and 9, W/O emulsion explosive compositions were produced by the use of potassium stearate, polyoxyethylene monooleate, polyoxyethylene cetyl ether, dodecylbenzonesulfonic acid and polyoxyethylene alcohol as an emulsifier, respectively. However, emulsion was not be able to be formed. In Comparative examples 1, 3, 4 and 8, W/O emulsion explosive compositions were produced by the use of butyl stearate, polyoxyethyleneoctadecylamine, alkyl(coconut oil) phosphoric acid ester and alkyl(coconut oil)alkylolamide as an emulsifier respectively, and emulsion was able to be formed. However, when the above described temperature cycle test of the explosive compositions of Comparative examples 1, 3, 4 and 8, was carried out, emulsion was broken after one time, one time, two times and one time of temperature cycles respectively, and the broken emulsion explosive compositions were not able to be detonated at 20.degree. C. by a No. 6 blasting cap.

In Example 1, a W/O emulsion explosive composition was produced by the use of 1-hydroxyethyl-2-alkyl(rice bran oil)-2-imidazoline, and a good emulsion was formed. After as large as 30 times of temperature cycles, the emulsion explosive composition maintained its good emulsified state without any change, and was able to be detonated at -20.degree. C. by a No. 6 blasting cap, and had a high detonation velocity of 4,080 m/sec.

In Examples 2, 3 and 4, W/O emulsion explosive compositions were produced by the use of the same emulsifier as that used in Example 1 and by the use of resin hollow microsphere, shirasu hollow microsphere and dinitrosopentamethylenetetramine as a density controlling agent, respectively. When the emulsion explosive compositions were subjected to the temperature cycle test, the explosive compositions maintained their good emulsified state after as large as 30 times of temperature cycles, and were able to be detonated at -20.degree. C. by a No. 6 blasting cap and had detonation velocities of 4,210 m/sec, 3,330 m/sec and 3,810 m/sec, respectively. Low detonation velocity of the explosive composition using the shirasu hollow microsphere is due to the fact that particle size of the shirasu hollow microsphere is about 10 times larger than that of the glass hollow microsphere. In Examples 5 and 6, W/O emulsion explosive compositions were produced by the use of 1-hydroxyethyl-2-alkyl(coconut oil)-2-imidazoline and 1-hydroxyethyl-2-alkyl(tallow)-2-imidazoline as an emulsifier, respectively. The explosive compositions had the same excellent performance as that of explosive compositions of Examples 1-4. In Example 7, a smaller amount of a density controlling agent was used, and therefore the density of the resulting W/O emulsion explosive composition was higher. Accordingly, the detonability of the explosive composition was somewhat inferior to that of the explosive compositions in Examples 1-6.

It can be seen from the above described comparative examples and examples that the W/O emulsion explosive composition of the present invention is superior to conventional W/O emulsion explosive composition in the emulsion stability in storage, low temperature detonability and explosion reactivity.