CN106242932B - A kind of freeze proof aqueous gels and preparation method thereof - Google Patents
A kind of freeze proof aqueous gels and preparation method thereof Download PDFInfo
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- CN106242932B CN106242932B CN201610806806.9A CN201610806806A CN106242932B CN 106242932 B CN106242932 B CN 106242932B CN 201610806806 A CN201610806806 A CN 201610806806A CN 106242932 B CN106242932 B CN 106242932B
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- aqueous gels
- freeze proof
- proof aqueous
- nitrate
- antifreeze
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/32—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with a nitrated organic compound
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/009—Wetting agents, hydrophobing agents, dehydrating agents, antistatic additives, viscosity improvers, antiagglomerating agents, grinding agents and other additives for working up
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses a kind of freeze proof aqueous gels, it is using ammonium nitrate, methylamine nitrate, sodium nitrate, water, sesbania powder and crosslinking agent as raw material, addition density adjuster, antifreeze and crystalline form modifying agent obtain in as low as 20 DEG C spawns for still keeping good plasticity and mobility of temperature, wherein antifreeze is made of dimethyl sulfoxide (DMSO) and ethylene glycol, crystalline form modifying agent is made of lauryl sodium sulfate and cetyl trimethylammonium bromide, and density adjuster is sodium nitrite.Freeze proof aqueous gels of the present invention explosion property in as low as 20 DEG C of environment temperature is unaffected, can still be normally carried out bursting work, is adapted to the bursting work under northern China winter cold temperature condition to use.
Description
Technical field
The invention belongs to energetic material technical field, is related to a kind of aqueous gels with cryoprotective effects, and the explosive
Preparation method.The aqueous gels of the present invention can use in bursting work under -20 DEG C~0 DEG C of low temperature environment.
Background technology
Aqueous gels are using the aqueous solution of the inorganic salts such as methylamine nitrate, ammonium nitrate and sodium nitrate as main component, in water
The polysaccharide such as guar gum, sesbania gum are added in solution as gelling agent, make aqueous gels each component uniform and stable using crosslinking technological
Ground is distributed in a kind of commercial explosive in gel rubber system.This explosive has the dispersed system of molecular state, therefore it is anti-to explode
Should completely, demolition effect is excellent, dangerous sensitivity is relatively low, security is higher, stability is good, storage period length.
But since aqueous gels are aquogel systems, with the reduction of temperature, the Free water in system understands glaciation, nitre
The solubility of sour ammonium strongly reduces, and ammonium nitrate grain largely separates out, and not only influences the plasticity of aqueous gels, it is often more important that can shadow
The explosion property of aqueous gels is rung, prevents it from detonating and propagation of explosion.This allow under northern area and some low temperature environments into
Row bursting work is restricted when constructing using aqueous gels.For this reason, develop a kind of stable quality, cheap, green ring
The freeze proof aqueous gels protected, be able to can still used in as low as -20 DEG C of environment temperature, will promote aqueous gels to be passed through in its people
Ji plays the effect of bigger in building.
The content of the invention
The object of the present invention is to provide a kind of freeze proof aqueous gels of stable quality, make it in as low as -20 DEG C of environment temperature
When explosion property it is unaffected, can still be normally carried out bursting work.
The preparation method of the freeze proof aqueous gels is provided, is another goal of the invention of the present invention.
Freeze proof aqueous gels of the present invention are with ammonium nitrate, methylamine nitrate, sodium nitrate, water, sesbania powder and crosslinking agent
For raw material, and density adjuster, antifreeze and crystalline form modifying agent are added with wherein, it is a kind of in as low as -20 DEG C of temperature to obtain
The spawn of good plasticity and mobility is still kept, wherein, the antifreeze is with 1 by dimethyl sulfoxide (DMSO) and ethylene glycol
: the compound antifreeze of 1 mass ratio composition, crystalline form modifying agent by lauryl sodium sulfate and cetyl trimethylammonium bromide with
3: 1 mass ratio composition, density adjuster is sodium nitrite.
Compared with the antifreeze formamide or ethylene glycol that are usually added in aqueous gels, compound antifreeze of the present invention is not
The freezing point of water can be only substantially reduced, the water in aqueous gels is not freezed at -20 DEG C；And ammonium nitrate can be increased in low temperature
Solubility in system, makes the solid-state ammonium nitrate that is separated out at -20 DEG C and the amount under normal temperature state of substantially equal.Therefore, add
The aqueous gels of compound antifreeze of the invention still show at -20 DEG C the flowable gelatinous as in the case of room temperature
State.
Crystalline form modifying agent of the present invention is formed by anion surfactant and cationic surfactant compounding, can
To be effectively adsorbed in solid-state ammoniumnitrate prill surface, stable water-repellent layer is formed, prevents ammonium nitrate crystals from growing up, makes solid-state nitre
Sour ammonium particle is more tiny；Meanwhile the water-repellent layer charge that the surfactant of the compounding is declared is stronger, makes solid-state ammonium nitrate
It is mutually exclusive, it is impossible to which that coalescence is into closely knit, regular bulky grain.
Compared with other density adjusters such as expanded perlite, minimal amount of sodium nitrite is added, you can in aqueous gels
It is middle to introduce a large amount of micro-bubbles, ensure the cap-sensitivity of aqueous gels.Since the addition of density adjuster of the present invention is few, no
The transmission and diffusion of heat during influence aqueous gels explosive reaction, it is ensured that aqueous gels explode instead at low temperatures
It should remain to fully carry out.
Further, the antifreeze added in freeze proof aqueous gels of the present invention accounts for freeze proof aqueous gels gross mass
1~3%, crystalline form modifying agent accounts for the 0.1~0.3% of freeze proof aqueous gels gross mass, and density adjuster accounts for the total matter of freeze proof aqueous gels
The 0.07~0.1% of amount.
Further, freeze proof aqueous gels of the present invention are made of the raw material of following mass percentage：Nitre
Sour ammonium 40~50%, methylamine nitrate 30~35%, sodium nitrate 8~12%, water 7~12%, sesbania powder 0.8~1.2%, density adjuster
0.07~0.1%, crosslinking agent 0.07~0.1%, antifreeze 1~3%, crystalline form modifying agent 0.1~0.3%.
Be usually crosslinking agent using transition metal ions as sesbania powder in freeze proof aqueous gels, the present invention be also in this way,
Using one or more of arbitrary proportion mixtures in common sodium tetraborate, potassium bichromate, potassium pyroantimonate, potassium tartrate etc.
As crosslinking agent.
The present invention can also add pH buffer in the freeze proof aqueous gels, and the pH buffer is urea etc., its
Addition accounts for the 0.1~0.5% of freeze proof aqueous gels gross mass.
Further, present invention also offers a kind of preparation method of the freeze proof aqueous gels, the described method includes with
Lower step：
1）, the ammonium nitrate of the mass percentage, methylamine nitrate, water, sodium nitrate, sesbania powder, crystalline form modifying agent existed
Stirring and dissolving at 60~80 DEG C；
2）, adjust solution temperature to 45~55 DEG C, sequentially add pH buffer, antifreeze, density adjuster；
3）, adjust the temperature to 35~40 DEG C, add crosslinking agent, keep the temperature 10~30 minutes, up to freeze proof after full cross-linked
Aqueous gels.
Aqueous gels can freeze to be hardened at low temperature, lose explosion property.On the one hand its main cause is due to the heat of water
Appearance is very big, after the water in aqueous gels is frozen into ice, then makes its defrosting, vaporization need to absorb substantial amounts of heat, can make blasting cap initiation
Energy be largely lost, prevent " hot spot " from being emerged, aqueous gels is difficult to detonation and propagation of explosion；On the other hand, a large amount of bulky grains
The precipitation of ammonium nitrate grain, can reduce closeness of contact of the ammonium nitrate as other components in oxidant and aqueous gels, reduce
Its reactivity, makes the oxidation-reduction reaction in system be difficult to carry out.In order to solve the above technical problems, one aspect of the present invention exists
Antifreeze is added in aqueous gels to reduce the freezing point of water and prevent ice crystal from growing up, on the other hand, selects suitable surface-active
Material, the characteristic of surface tension is reduced using it, suppresses the relative velocity of each crystal face growth of ammonium nitrate, it is brilliant to reach control ammonium nitrate
The purpose of grain development, avoids the occurrence of square or column bulky grain, make the ammonium nitrate grain of precipitation for various change different forms it is loose,
Frangible crystal, makes it have the specific surface area of bigger, improves the reactivity and reaction speed of ammonium nitrate.The present invention is by upper
Addition antifreeze, crystalline form modifying agent, the technical measures of density adjuster component are stated, ensure that aqueous gels are still at -20 DEG C
Reveal flowable gel state, effectively improve the plasticity of aqueous gels at low temperature, improve its at low temperature quick-fried
Hong performance, is adapted to the bursting work under northern China winter cold temperature condition to use.
Using the freeze proof aqueous gels of the present invention under -20 DEG C~0 DEG C low temperature environment, risen with No. 8 commercial electric detonators
The explosion velocity and acting ability of quick-fried and propagation of explosion, explosion velocity and acting ability when explosion energy index under normal temperature environment with using are equal
Together, no explosion energy loss.
Strengthen its detonation since the freeze proof aqueous gels of the present invention need not add the high energy such as aluminium powder metallic addition
And explosion transfer performance, manufacture cost is lower, cheap.
Embodiment
Following embodiments are only the preferred technical solution of the present invention, those skilled in the art can be enable to be more fully understood
The present invention, but be not used to carry out any restrictions to the present invention.To those skilled in the art, the present invention can have various
Change and change.It is all without departing from the concept of the premise of the invention, any modification, equivalent replacement, improvement should all
Within protection scope of the present invention.
Embodiment 1
Freeze proof aqueous gels formula is as follows：Ammonium nitrate 45%, methylamine nitrate 30%, sodium nitrate 10.2%, water 10%, sesbania powder
1%th, sodium nitrite 0.07%, crosslinking agent 0.1%, urea 0.5%, antifreeze 3%, crystalline form modifying agent 0.13%.Wherein antifreeze is by two
Methyl sulfoxide is formed with ethylene glycol with 1: 1 mass ratio, and crystalline form modifying agent is by lauryl sodium sulfate and cetyl trimethyl
Ammonium bromide is formed with 3: 1 mass ratio.It is mass percent above.
Ammonium nitrate, methylamine nitrate, sodium nitrate, sesbania powder and crystalline form modifying agent are added to the water, 80 DEG C of stirring and dissolvings；Adjust
Temperature sequentially adds urea, antifreeze and density adjuster to 45 DEG C；Adjusting the temperature to 40 DEG C, add by sodium tetraborate and
The crosslinking agent that potassium bichromate is blended, keeps the temperature 20 minutes, freeze proof aqueous gels is obtained after full cross-linked.
Freeze proof aqueous gels density 1.15g/cm manufactured in the present embodiment3, it is seated in the PVC film powder charge of diameter 35mm
Test its explosion velocity in volume, explosion velocity 3268m/s under room temperature, do work ability 278mL, and explosion velocity 3175m/s under -20 DEG C of environment, does function
Power 275mL, performance do not change significantly.
Embodiment 2
Freeze proof aqueous gels formula is as follows：Ammonium nitrate 48%, methylamine nitrate 30%, sodium nitrate 10.2%, water 8%, sesbania powder 1%,
Mixture 0.1%, urea 0.5%, antifreeze 2%, the crystalline form modifying agent of sodium nitrite 0.09%, sodium tetraborate and potassium bichromate
0.11%.Wherein antifreeze is made of dimethyl sulfoxide (DMSO) and ethylene glycol with 1: 1 mass ratio, and crystalline form modifying agent is by dodecyl sulphur
Sour sodium is formed with cetyl trimethylammonium bromide with 3: 1 mass ratio.It is mass percent above.
Preparation method is the same as embodiment 1.Freeze proof aqueous gels density 1.17g/cm manufactured in the present embodiment3, it is seated in
Its explosion velocity is tested in the PVC film powder charge volume of diameter 35mm, and explosion velocity 3248m/s under room temperature, do work ability 280mL, under -20 DEG C of environment
Explosion velocity 3275m/s, do work ability 275mL, and performance does not change significantly.
Embodiment 3
Freeze proof aqueous gels formula is as follows：Ammonium nitrate 48%, methylamine nitrate 30%, sodium nitrate 10%, water 7%, sesbania powder 1.2%,
Mixture 0.1%, urea 0.5%, antifreeze 3%, the crystalline form modifying agent 0.1% of sodium nitrite 0.1%, sodium tetraborate and potassium bichromate.
Wherein antifreeze be made of dimethyl sulfoxide (DMSO) and ethylene glycol with 1: 1 mass ratio, crystalline form modifying agent by lauryl sodium sulfate and
Cetyl trimethylammonium bromide is formed with 3: 1 mass ratio.It is mass percent above.
Preparation method is the same as embodiment 1.Freeze proof aqueous gels density 1.08g/cm manufactured in the present embodiment3, it is seated in
Its explosion velocity is tested in the PVC film powder charge volume of diameter 35mm, and explosion velocity 3165m/s under room temperature, do work ability 267mL, under -20 DEG C of environment
Explosion velocity 3175m/s, do work ability 265mL, and performance does not change significantly.
Comparative example 1
Aqueous gels formula is as follows：Ammonium nitrate 48%, methylamine nitrate 30%, sodium nitrate 10%, water 7.3%, aluminium powder 3%, sesbania powder
1%th, the mixture 0.1% of sodium nitrite 0.1%, sodium tetraborate and potassium bichromate, urea 0.5%, crystalline form modifying agent 0.1%.Wherein with
Dextrin is crystalline form modifying agent.It is mass percent above.
Preparation method is the same as embodiment 1.Aqueous gels density 1.31g/cm manufactured in the present embodiment3, it is seated in diameter
Its explosion velocity is tested in the PVC film powder charge volume of 35mm, and explosion velocity 3864m/s under room temperature, do work ability 357mL, under -20 DEG C of environment completely
Freeze, it is impossible to detonated with No. 8 commercial electric detonators.
Comparative example 2
Freeze proof aqueous gels formula is as follows：Ammonium nitrate 45%, methylamine nitrate 30%, sodium nitrate 10%, water 10%, sesbania powder 1%,
Mixture 0.1%, urea 0.5%, antifreeze 3%, the crystalline form modifying agent of sodium nitrite 0.07%, sodium tetraborate and potassium bichromate
0.1%, wherein antifreeze is made of dimethyl sulfoxide (DMSO) and ethylene glycol with 1: 1 mass ratio, and crystalline form modifying agent is dextrin.Above
For mass percent.
Preparation method is the same as embodiment 1.Freeze proof aqueous gels density 1.15g/cm manufactured in the present embodiment3, it is seated in
Its explosion velocity is tested in the PVC film powder charge volume of diameter 35mm, and explosion velocity 3121m/s under room temperature, do work ability 272mL, under -20 DEG C of environment
Part is freezed, and can use No. 8 blasting cap initiations, but explosive reaction cannot hand on.
Claims (9)
1. a kind of freeze proof aqueous gels, be using ammonium nitrate, methylamine nitrate, sodium nitrate, water, sesbania powder and crosslinking agent as raw material, and
Be added with density adjuster, antifreeze and crystalline form modifying agent wherein, obtain in temperature as low as -20 DEG C still keep plasticity and stream
The spawn of dynamic property, wherein, the antifreeze is answered by dimethyl sulfoxide (DMSO) and ethylene glycol with what 1: 1 mass ratio formed
Antifreeze is closed, crystalline form modifying agent is made of lauryl sodium sulfate and cetyl trimethylammonium bromide with 3: 1 mass ratio, close
Degree conditioning agent is sodium nitrite.
2. freeze proof aqueous gels according to claim 1, it is characterized in that the antifreeze accounts for freeze proof aqueous gels gross mass
1~3%.
3. freeze proof aqueous gels according to claim 1, it is characterized in that to account for freeze proof aqueous gels total for the crystalline form modifying agent
The 0.1~0.3% of quality.
4. freeze proof aqueous gels according to claim 1, it is characterized in that to account for freeze proof aqueous gels total for the density adjuster
The 0.07~0.1% of quality.
5. according to any freeze proof aqueous gels in claim 1,2,3 or 4, it is characterized in that the crosslinking agent is tetraboric acid
One or more of arbitrary proportion mixtures in sodium, potassium bichromate, potassium pyroantimonate, potassium tartrate.
6. according to any freeze proof aqueous gels in claim 1,2,3 or 4, it is characterized in that the freeze proof aqueous gels by with
The raw material of lower mass percentage is made：Ammonium nitrate 40~50%, methylamine nitrate 30~35%, sodium nitrate 8~12%, water 7~12%,
Sesbania powder 0.8~1.2%, density adjuster 0.07~0.1%, crosslinking agent 0.07~0.1%, antifreeze 1~3%, crystalline form modifying agent
0.1~0.3%.
7. freeze proof aqueous gels according to claim 6, it is characterized in that anti-added with accounting in the freeze proof aqueous gels
Freeze the pH buffer of aqueous gels gross mass 0.1~0.5%.
8. freeze proof aqueous gels according to claim 7, it is characterized in that the pH buffer is urea.
9. the preparation method of freeze proof aqueous gels, comprises the following steps described in claim 7：
1）, by the ammonium nitrate of the mass percentage, methylamine nitrate, water, sodium nitrate, sesbania powder, crystalline form modifying agent 60~
Stirring and dissolving at 80 DEG C；
2）, adjust solution temperature to 45~55 DEG C, sequentially add pH buffer, antifreeze, density adjuster；
3）, adjust the temperature to 35~40 DEG C, add crosslinking agent, keep the temperature 10~30 minutes, up to freeze proof glue after full cross-linked
Explosive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107098785A (en) * | 2017-05-02 | 2017-08-29 | 安徽雷鸣科化股份有限公司 | A kind of special aqueous gels of psychro-environment and preparation method thereof |
| CN108586168A (en) * | 2018-05-07 | 2018-09-28 | 宜兴市阳生化工有限公司 | A kind of crushing resistance glue explosive and its preparation process for underwater demolition |
| CN109206281A (en) * | 2018-09-27 | 2019-01-15 | 佛山九陌科技信息咨询有限公司 | A kind of preparation method of freeze proof aqueous gels |
| CN112125766A (en) * | 2020-09-22 | 2020-12-25 | 山东圣世达化工有限责任公司 | Low-temperature-resistant water gel explosive and preparation method thereof |
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| CN1032000A (en) * | 1987-09-14 | 1989-03-29 | 阜新矿务局十二厂 | Water gel explosives for mine |
| CN101205157A (en) * | 2007-11-16 | 2008-06-25 | 南京理工大学 | Method for lowering crystallization point of ammonium nitrate supersaturated solution by using additives |
| CN101328099A (en) * | 2008-08-04 | 2008-12-24 | 耿一平 | Gel type emulsion explosive and preparation thereof |
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