KR20160125746A - Preparation method for submicron and micron size- spherical rdx particles, and spherical rdx particles prepared by the same - Google Patents

Preparation method for submicron and micron size- spherical rdx particles, and spherical rdx particles prepared by the same Download PDF

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KR20160125746A
KR20160125746A KR1020150056602A KR20150056602A KR20160125746A KR 20160125746 A KR20160125746 A KR 20160125746A KR 1020150056602 A KR1020150056602 A KR 1020150056602A KR 20150056602 A KR20150056602 A KR 20150056602A KR 20160125746 A KR20160125746 A KR 20160125746A
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rdx
particles
solution
spherical
solvent
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KR101714736B1 (en
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이근득
채주승
한상근
구기갑
김재경
심홍민
이세은
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국방과학연구소
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0066—Shaping the mixture by granulation, e.g. flaking

Abstract

The present invention relates to a method for manufacturing a submicron and micron-sized spherical RDX (cyclotrimethylene trinitramine) particle and a spherical RDX particle manufactured thereby. More specifically, the method for manufacturing the submicron and micron-sized spherical RDX particle comprises: a step for manufacturing an RDX solution by dissolving RDX in an organic solvent; a step for precipitating an RDX particle by mixing the RDX solution with an antisolvent; and a step for obtaining the precipitated RDX particle. Before the RDX solution and the antisolvent are mixed, a surfactant is added to the RDX solution or the antisolvent to be mixed. According to the present invention, a submicron and micron-sized spherical RDX particle is manufactured with productivity higher than that of a conventional method. In the case of a spherical shaped RDX particle, ignition pressure can be maximized due to increase in filling density and a relatively insensitive RDX particle can be manufactured due to a smooth surface. In addition, due to a size of a fine particle, an energy release rate is high, whereby it can be widely used as a civil and military composition such as high explosive gunpowder, a solid composite propellant, and the like.

Description

서브마이크론과 마이크론 크기의 구형 RDX 입자 제조방법 및 이에 의해 제조된 구형 RDX 입자{PREPARATION METHOD FOR SUBMICRON AND MICRON SIZE- SPHERICAL RDX PARTICLES, AND SPHERICAL RDX PARTICLES PREPARED BY THE SAME}TECHNICAL FIELD The present invention relates to a method for producing spherical RDX particles having a submicron size and a micron size, and to a method for producing spherical RDX particles using the spherical RDX particles,

본 발명은 서브마이크론과 마이크론 크기 구형 RDX(Cyclotrimethylene trinitramine) 입자를 제조하는 방법에 관한 것으로서, RDX가 녹아있는 용매에 반용매(anti-solvent)를 첨가하여 재결정(recrystallization)하는 기술로 구형 RDX(Cyclotrimethylene trinitramine) 입자 제조방법 및 이에 의해 제조된 구형 RDX 입자에 관한 것이다.
The present invention relates to a method for preparing submicron and micron sized cyclotrimethylene trinitramine (RDX) particles, which comprises recrystallization by adding an anti-solvent to a solvent in which RDX is dissolved, trinitramine) particles and spherical RDX particles produced thereby.

Henning에 의해 hexamethylenetetramine(HMT)의 니트로화에 의해 처음 합성된 RDX는 탄약, 고체 복합 추진제로 널리 이용되고 있는 니트라민계열 고폭 화약이다. 흰색 결정 상태의 RDX는 가소제, 둔감화제, 점조제, 다른 폭약과 혼합된 조성물로서 이용되고 있으며 실온에서 매우 안정하고 강력하므로 Comp. A, Comp. B., Comp. C, Comp. D, HBX, C-4, H-6, C-4 등 군용 및 발파용 폭약으로 이용된다.RDX, first synthesized by the nitration of hexamethylenetetramine (HMT) by Henning, is a nitramine series high explosive which is widely used as ammunition and solid propellant. White crystalline RDX is used as a composition mixed with plasticizer, desensitizer, viscous agent and other explosives, and is very stable and strong at room temperature. A, Comp. B., Comp. C, Comp. D, HBX, C-4, H-6 and C-4.

미국은 1960년대 베트남 전쟁 당시 USS Oriskany, USS Forrestal을 필두로 MK24, 레이저 유도 미사일 등 많은 탄두/탄약을 적재한 항공모함과 병기창에서 폭발사고에 의한 인명과 막대한 자산 손실을 경험한 이후 이를 최소화하기 위한 전략으로 비의도 외부 자극원인 열, 충격(shock), 총격, 동조 기폭(sympathetic detonation) 등에 의한 폭풍파, 탄자 또는 파편 피격, 화재에 대해 전혀 반응하지 않거나 급격한 기폭 현상을 회피하여 연소 수준을 보이는 둔감화약 및 조성물에 대한 개발 연구되고 있다.In the 1960s, during the Vietnam War, USS Oriskany, USS Forrestal, MK24, laser-guided missiles, and many other warheads / ammunition carriers, As a result of the strategy, non-intentional external stimulus causes no combustion or rapid ignition of the storm wave, bullet or debris caused by heat, shock, shooting, sympathetic detonation, Development of damping agents and compositions has been studied.

둔감화약을 주로 구성하는 조성물(formulation)의 둔감도(insensitivity)는 고폭 화약의 자체 물리화학적 특성(양론비, oxygen balance, 평균 입경, 입도 분포, 형상, 결함)과 조성물 특성(고분자 결합제, 가소제, 다른 첨가제)에 주로 좌우되며, 고폭 화약의 둔감도는 개별 입자의 외부 특성(입도 분포와 평균 입경)과 내부 특성(내포물, 불순물, heterophase 존재, 결함 농도, 공극 등)이 제어되고 있다.The insensitivity of the formulation consisting mainly of a desensitizing agent is determined by the physical properties of the high explosives such as the stoichiometric ratio, the oxygen balance, the average particle size, the particle size distribution, the shape and the defect and the composition characteristics (polymer binder, (Particle size distribution and average particle size) and internal properties (inclusions, impurities, heterophase presence, defect concentration, voids, etc.) of the individual particles are controlled.

예를 들어, 고폭 화약의 평균 입경이 작아질 경우 결정 내부에 포함되어 있는 결정 결함 농도와 공극 감소로 인해 비교적 과열점(hot spot) 생성이 촉진될 수 있는 반응점(reaction site)이 감소되며, 또한 고폭 화약의 형상이 다각형 또는 구형에 가까워질 경우에는 기계적 강도 향상과 아울러 외부 충격이 입자 표면에서 균일하게 분산되거나 입자간 공극률이 감소되어 기폭 압력이 상승되는 유리한 점이 있다. 이 때, 고폭 화약에 대한 비의도적인 자극을 열, 충격, 표면 접촉으로 분류한다면 이들은 완속 또는 급속 가열, 충격 민감도(impact sensitivity), 마찰 민감도(friction sensitivity), 쇼크 민감도(shock sensitivity)에 의해 정량화될 수 있다.For example, when the average particle diameter of the high-explosive powder is small, the reaction site where the generation of hot spots can be relatively accelerated due to the crystal defect concentration and void reduction included in the crystal is reduced, and When the shape of the high-explosive powder is close to the polygonal or spherical shape, there is an advantage that the mechanical strength is improved and the external impact is uniformly dispersed on the particle surface or the inter-particle porosity is decreased, thereby increasing the crushing pressure. At this time, if unintentional stimulation of high explosives is classified as heat, shock, or surface contact, they can be quantified by slow or rapid heating, impact sensitivity, friction sensitivity, and shock sensitivity .

쇼크 민감도(shock sensitivity)는 고폭 화약(high explosive)의 충격파(shock wave)에 대한 응답특성이며, 이는 고폭 화약의 화학적 에너지 방출에 의한 충격파 증폭(shock wave amplification) 현상으로 이로 인해 기폭이 발생한다.Shock sensitivity is the response characteristic of a high explosive shock wave. This is a shock wave amplification phenomenon caused by the chemical energy release of a high explosive, which causes ignition.

여러 물리화학적 특성에서 쇼크 민감도(shock sensitivity)와 관련 깊은 것은 고폭 화약의 입자 크기(particle size)와 표면 거칠기(surface roughness)이며, 유액(Emulsion), 액체폭발물(liquid explosive), 다공성 고체 폭발물(porous solid explosive), 플라스틱 접착폭약(plastic bonded explosive, PBX)와 같은 복합 화약의 쇼크 민감도(shock sensitivity)에서 개별 구성된 고폭 화약의 입자 크기에 따라 달라지는 현상이 관측되고 있다.What is deeply related to shock sensitivity in various physico-chemical properties is the particle size and surface roughness of a high explosive, and it is known to be an emulsion, a liquid explosive, a porous solid explosive a solid explosive, and a plastic bonded explosive (PBX) have been observed to vary depending on the particle size of the individually formed high explosive in shock sensitivity.

고폭 화약의 입자 크기에서 복합화약의 쇼크 민감도(shock sensitivity)가 상반되는 현상에 대해 Khasainov는 충격압(shock pressure)이 고폭 화약의 임계 점화 압력(critical ignition pressure)보다 매우 크게 되면 고폭 화약의 평균 입경이 작아질수록 쇼크 민감도는 민감해지지만, 임계 과열점(hot spot) 크기가 복합 화약을 구성하는 고폭 화약의 평균 입경과 거의 비슷하게 되면 고폭화약의 입자 크기가 작아질수록 복합화약의 쇼크 민감도는 둔감해진다.As for the phenomenon that the shock sensitivity of the composite powder is opposite in the particle size of the high explosive powder, Khasainov suggests that if the shock pressure is much higher than the critical ignition pressure of the high explosive, The smaller the size of the high-explosive particle, the less susceptibility of the composite powder to shock sensitivity becomes, as the size of the critical hot spot becomes close to the average particle size of the high-explosive composition of the composite explosive, .

또한, 과열점(hot spot) 생성 속도가 쇼크 민감도(shock sensitivity)를 좌우하게 되고 고폭 화약 입자의 연소 면적은 임계 과열점 크기(size)로 인해 제한되게 된다. 대부분 공극이 없는 플라스틱 접착폭약(PBX)은 충격압(shock pressure)이 임계 점화 압력(critical ignition pressure)보다 매우 작으므로 입자 크기가 작아질수록 쇼크 민감도(shock sensitivity)는 둔감해진다.In addition, the rate of hot spot generation affects the shock sensitivity, and the combustion area of the high explosive particles is limited due to the critical superheating point size. Plastic explosive explosives (PBXs), which are mostly void-free, have a shock pressure that is much smaller than the critical ignition pressure, so the smaller the particle size, the less susceptible the shock sensitivity.

Armstrong은 고폭 화약의 충격 민감도(impact sensitivity)와 입자 크기의 상관관계로 pile-up dislocation mechanism을 제시하였으며, 이는 RDX 입자가 커질수록 과열점(hot spot) 크기는 커지고 방출되는 열량은 많아지며 민감한 것이다.Armstrong proposed a pile-up dislocation mechanism as a function of the impact sensitivity and particle size of the high-explosive powder. The larger the RDX particle size, the larger the hot spot size and the greater the amount of heat released .

RDX가 복합화약 형태의 플라스틱 접착폭약(PBX) 조성물로 주로 이용되므로 충격 민감도와 쇼크 민감도를 낮추기 위해서는 입자 크기 감소가 요구된다. 평균 입경이 0.01 내지 10 ㎛ 정도인 RDX에 대한 연구로부터 RDX의 추산된 과열점(hot spot) 크기는 약 1 ㎛로 알려져 있으며, 과열점(hot spot)의 붕괴에 의해 485 K까지 온도 상승이 일어난다. 대부분 고폭 화약의 임계 온도가 400 내지 600 범위에 있고 임계 응력(critical stress)이 1×104 내지 2.5×104 atm 사이에 있으므로 임계 과열점(hot spot) 크기는 0.1 내지 10 ㎛ 정도로 추산된다. 그러므로 민감도를 낮추기 위한 적정한 RDX 입자의 평균 입경은 알려져 있지 않지만 대략적으로 과열점(hot spot) 크기를 고려하게 될 경우 RDX 입자 크기는 약 1 ㎛정도 또는 그 부근이 적합하다.Since RDX is mainly used as a composite gunpowder type plastic adhesive explosive (PBX) composition, a reduction in particle size is required to lower impact sensitivity and shock sensitivity. From studies on RDX with an average particle size of about 0.01 to 10 μm, the estimated hot spot size of RDX is about 1 μm and the temperature rise to 485 K due to the collapse of the hot spot . In most cases, the critical temperature of the high explosive is in the range of 400 to 600 and the critical stress is in the range of 1 × 10 4 to 2.5 × 10 4 atm. Therefore, the critical hot spot size is estimated to be about 0.1 to 10 μm. Therefore, the average particle size of RDX particles suitable for lowering the sensitivity is not known. However, when roughly considering the hot spot size, about 1 μm or about RDX particle size is suitable.

Bellitto 등은 RDX 표면에 대한 AFM(Atom Force Microscopy) 분석과 조성분석으로부터 RDX의 쇼크 민감도는 HMX 함량과 무관하며 RDX 표면 거칠기(surface roughness)와 통계적으로 유의한 상관관계가 있음을 밝혔으며, Czerki 등에 의하면 평균 입경 10 내지 30 ㎛인 RDX와 평균 입경 100 내지 300 ㎛인 RDX를 대상으로 RDX 입자의 쇼크 민감도는 내부의 공극(internal void)과 상관관계가 없으며 입자 표면의 딤플(dimple)과 같은 다른 입자간의 마찰이 쉽게 일어날 수 있는 모서리가 많은 형태와 판상 형태와 같은 충진 밀도 감소가 밀접한 관계가 있음을 밝혔다.Bellitto et al. Found that the sensitivity of RDX was independent of the HMX content and that there was a statistically significant correlation with the surface roughness of RDX from Atom Force Microscopy (AFM) analysis and compositional analysis of RDX surface. Czerki et al. , The RDX particle with an average particle diameter of 10 to 30 μm and the RDX with an average particle diameter of 100 to 300 μm have no correlation with the internal void and the other particles such as a dimple on the surface of the particle And the reduction of the packing density such as the plate shape is closely related to each other.

입자-입자 또는 결정-결정 사이의 표면 마찰에 의한 에너지는 소산되지 않고 모서리 또는 각이 진 표면에 집중되지만 표면이 매끈하고 둥근 입자는 입자간 마찰에 의해 축적된 마찰 에너지가 빠르게 소산되어 쇼크 민감도가 감소된다. 그리고 입자 형상이 각진 형태가 아닐 경우 입자간 공극이 줄어들어 고폭 화약의 충진 밀도가 높아지는 장점이 있다. 그러므로 쇼크 민감도를 낮추기 위해 고폭 화약의 특성은 충진 밀도 및 기계적 강도를 높이기 위해 구형에 가까운 입자 형상, 매끈한 입자 표면상태, 작은 입자 크기 등이 요구되고 있다.The energy due to the surface friction between the particle-particle or crystal-crystal is not dissipated but is concentrated on the corners or angled surface, but the smooth surface particles have a shock sensitivity that is rapidly dissipated by the friction energy accumulated by the inter- . When the shape of the particles is not angular, the intergranular voids are reduced and the filling density of the high explosive powder is increased. Therefore, in order to lower the shock sensitivity, the properties of the high-explosive powder are required to have a spherical shape, a smooth particle surface state, and a small particle size in order to increase the filling density and the mechanical strength.

한편, 고폭 입자의 형상을 표현하는 종횡비(aspect ratio)가 커질 경우 즉, 입자의 이방성이 심하게 되며 조성물 제조 과정에서 외부 응력과 입자간 충돌에 의해 고폭 화약이 파쇄되어 파편 발생과 개재물이 생성된다. 이럴 경우 고폭 화약은 높은 충진 밀도를 얻기 어려우며 입자간 마찰에 의해 마찰 민감도가 높아질 수 있다.On the other hand, when the aspect ratio expressing the shape of the high-density particles is large, the anisotropy of the particles becomes severe, and the high-density powder is broken by the external stress and the collision between the particles in the process of manufacturing the composition. In this case, the high explosive powder is difficult to obtain a high filling density, and the frictional sensitivity can be increased by the intergranular friction.

낮은 종횡비에 따른 구형이 고폭 화약의 이상적인 형상으로 인식되는 이유는 기폭 압력(detonation pressure)과 밀접한 관련이 있다. 분자화약의 위력은 기폭 압력(detonation pressure, P)으로 표현되는 데, 이는 기폭 속도(D, detonation velocity)와 분자 화약의 충진 밀도(

Figure pat00001
)로 계산되며, 이를 식으로 표현하면,
Figure pat00002
이다.The reason why the spherical shape according to the low aspect ratio is recognized as the ideal shape of the high explosive gun is closely related to the detonation pressure. The power of the molecular gunpowder is expressed as the detonation pressure (P), which is the rate of detonation (D) and the packing density of the molecular gunpowder
Figure pat00001
), Which is expressed by the equation,
Figure pat00002
to be.

기폭 이론에 의해 고폭 화약의 기폭 압력은 충진 밀도와 고유 물성인 기폭 속도에 의해 결정되며, 고폭 화약이 에너지 조성물 제조 과정에서 사압 현상(dead pressure)이 발생되지 않도록 공극이 충분히 적은 높은 충진 밀도를 유지하게 될 때 분자 화약의 최고 기폭 압력이 나타나며 위력이 극대화될 수 있다.The ignition pressure of the high explosive is determined by the filling density and the specific physical property, and the high explosive is maintained at a high filling density with sufficient pore size so that dead pressure does not occur during the energy composition manufacturing process The maximum explosive pressure of the molecular gunpowder appears and the power can be maximized.

그리고 고폭 화약의 형상이 점점 구형에서 벗어나게 되면 충진 부피의 역수로 계산된 충진 밀도는 낮아지게 되며, 고폭 에너지 조성물의 충진 과정에서 다른 평균 입경의 분자 화약이 혼합될 경우에는 큰 입자사이의 공간에 작은 입자들이 채워지게 되어 충진 밀도가 높아지게 되고, 이때 고폭 화약의 형상이 구형이면 매우 유리하므로 고폭 화약은 이상적인 구형, 매끈한 표면, 작은 입자 크기가 요구되고 있다.When the shape of the high-explosive powder gradually deviates from the spherical shape, the filling density calculated by the reciprocal of the filling volume becomes low. When the high molecular weight powder of the average particle diameter is mixed during the filling process of the high-energy composition, As the particles fill up and the filling density becomes higher, and the shape of the high explosive powder is spherical at this time, it is very advantageous that the high explosive requires an ideal spherical shape, a smooth surface and a small particle size.

따라서, 추진제 조성물을 비롯한 여러 에너지 조성물 제조에 적합한 기계적 강도, 유동성(free flowing), 충진 밀도, 기폭 성능을 갖는 고폭 화약 입자의 제조를 위해 많은 기술들이 개발되고 있다.
Accordingly, many techniques have been developed for the production of high-explosive particles having mechanical strength, free flowing, filling density, and aerating performance suitable for manufacturing various energy compositions including propellant compositions.

일본 특허공개공보 제01-313382호Japanese Patent Application Laid-Open No. 01-313382

Khasainov, B. A., Ermolaev, B. S., Presles, Vidal, P., On the Effect of Grain Size on Shock Sensitivity of Heterogeneous High Explosives, Shock Waves, 7, 89-105, 1997Khasainov, B. A., Ermolaev, B. S., Presles, Vidal, P., On the Effect of Grain Size on Shock Sensitivity of Heterogeneous High Explosives, Shock Waves, 7, 89-105, 1997 Armstrong, R. W., Coffey, C. S., DeVost, V. F., Elban, W. L., Crystal Size Dependence for Impact Initiation of Cyclotrimethylenetrinitramine Explosive, J. Appl. Phys., 68(3), 979-984, 1990Armstrong, R. W., Coffey, C. S., DeVost, V. F., Elban, W. L., Crystal Size Dependence for Impact Initiation of Cyclotrimethylenetrinitramine Explosive, J. Appl. Phys., 68 (3), 979-984, 1990 Bellitto, V., Melnik, M. I., Atomic Force Microscopy - Imaging, Measuring and Manipulating Surfaces at the Atomic Scale, Intech, 2012Bellitto, V., Melnik, M. I., Atomic Force Microscopy - Imaging, Measuring and Manipulating Surfaces at the Atomic Scale, Intech, 2012 Czerki, H., Proud, W. G., Relationship between the Morphology of Granular Cycltrimethylene-trinitramine and Its Shock Sensitivity, Journal of Applied Physics, 102, 113515, 2007Czerki, H., Proud, W. G., Relationship between the Morphology of Granular Cycltrimethylene-Trinitramine and Its Shock Sensitivity, Journal of Applied Physics, 102, 113515, 2007

RDX 입자 제조는 습식분쇄(wet milling), 진공석출(vacuum deposition), 초임계유체를 이용한 RESS(rapid expansion of supercritical solutions)이나 SAS(supercritical anti-solvent), 분무건조(spray drying), 저온 플라즈마 방법 등이 알려져 있는데 이런 방법의 경우 일부 구형 RDX 입자 제조가 가능하지만 고온, 고압, 고에너지 조건이 동반되어 공정상으로 대량의 RDX 입자 제조 조건이 불리하며, RDX 입자는 구형과 타원형을 제외하고 침상, 판상, 주상정일 경우 단립체로 얻어지지만, 구형 또는 타원형 RDX 입자의 경우 대부분 응집된 상태로 제조되어 RDX 입자를 효율적으로 제조하기 힘들고, 불가피하게 초음파와 같은 2차적인 분산 장치가 소요되는 점이 있다. 또한, 서브마이크론 크기 RDX 입자의 제조를 위해서 RDX 농도가 매우 낮아지는 점이 있다. 따라서 기존 방법에 비해서 초음파와 같은 혼합 조건 회피와 단립 상태의 RDX 입자와 과열점(hot spot) 크기인 1 ㎛보다 평균입경이 작은 RDX 입자가 요구되고 있다.The RDX particle preparation can be performed by wet milling, vacuum deposition, rapid expansion of supercritical solutions (RESS) using supercritical fluids, supercritical anti-solvent (SAS), spray drying, In this method, it is possible to manufacture some spherical RDX particles. However, RDX particles are disadvantageous in terms of mass production of RDX particles due to high temperature, high pressure and high energy conditions. In addition, In the case of tabular and columnar crystals, it can be obtained as a monolith. However, in case of spherical or elliptic RDX particles, it is difficult to efficiently produce RDX particles because it is produced in a flocculated state. Inevitably, a secondary dispersion device such as ultrasonic waves is required. In addition, the RDX concentration is very low for the production of submicron size RDX particles. Therefore, it is required to avoid mixing conditions such as ultrasonic waves and RDX particles having a smaller average particle size than 1 ㎛, which is the size of the RDX particles and the hot spots in the solid state, as compared with the conventional methods.

이에 따라 상기와 같은 점을 감안한 본 발명은 적절한 유기 용매(solvent)에 RDX를 용해시키고, 이 용액과 RDX에 대해 용해도가 극히 낮은 반용매(anti-solvent)를 혼합하여 RDX를 석출시키고 수득하는 과정으로 서브마이크론 및 마이크론 크기의 구형 RDX 입자 제조방법 및 이에 의해 제조된 구형 RDX 입자의 제공에 목적이 있다.
Accordingly, the present invention, taking the above points into consideration, is a process for dissolving RDX in an appropriate organic solvent and mixing the solution with an anti-solvent having an extremely low solubility in RDX to precipitate RDX To provide a method for producing spherical RDX particles of submicron and micron size, and to provide spherical RDX particles produced thereby.

상기와 같은 목적을 달성하기 위해 본 발명의 구형 RDX 입자 제조방법은 유기 용매에 RDX를 용해시켜 RDX 용액을 제조하는 단계; 상기 RDX 용액과 반용매를 혼합하여 RDX 입자를 석출하는 단계; 및 석출된 RDX 입자를 수득하는 단계;를 포함하며, 상기 RDX 용액과 반용매를 혼합하기 전에 상기 RDX 용액 또는 상기 반용액에 계면활성제를 첨가하는 것을 특징으로 한다.In order to achieve the above object, the present invention provides a method for preparing spherical RDX particles, comprising: preparing an RDX solution by dissolving RDX in an organic solvent; Mixing the RDX solution and an anti-solvent to precipitate RDX particles; And obtaining a precipitated RDX particle, wherein a surfactant is added to the RDX solution or the semi-solution before mixing the RDX solution and the half-solvent.

상기 유기 용매는 DMSO(dimethyl slufoxide), DMF(N,N-dimethylformamide), DMA(N,N-dimethylacetamide), NMP(n-methyl-2-pyrrolidone), acetone, γ-butyrolactone, cyclohexanone 중에서 선택되는 어느 1종 이상일 수 있다.The organic solvent may be selected from the group consisting of dimethyl sulphoxide (DMF), N-dimethylformamide (DMF), N-dimethylacetamide (DMA), n-methyl-2-pyrrolidone It may be more than one kind.

상기 계면활성제는 PVP-co-PVA(polyvinyl pyrrolidone-co-polyvinylacetate), PVP-co-DMA(n(polyvinylpyrrolidone-co-dimethyl maleic anhydride)), PVP-co-DMAEM(poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate)), PVP-co-VA(poly(1-vinylpyrrolidone-co-vinylacetate)), PVP-co-Styrene(poly(1-vinylpyrrolidone-co-styrene)), Poly[(2-ethyldimethylammonioethyl meth acrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] 중에서 선택되는 어느 1종 일 수 있다.The surfactant may be selected from the group consisting of polyvinyl pyrrolidone-co-polyvinylacetate (PVP-co-PVA), polyvinylpyrrolidone-co-dimethyl maleic anhydride (PVP- 2-dimethylaminoethyl methacrylate), poly (1-vinylpyrrolidone-co-vinylacetate), PVP-co-styrene, poly [(2-ethyldimethylammonioethyl meth acrylate ethyl sulfate) -co- (1-vinylpyrrolidone)].

상기 반용매는 RDX에 대해 용해도가 극히 낮은 용매로 유기 용매와 섞이는 어떠한 용매도 상관없으며, 바람직하게는 물을 사용할 수 있다.The semi-solvent is an extremely low-solubility solvent for RDX. It does not matter which solvent is mixed with the organic solvent, and preferably water can be used.

상기 RDX 용액을 제조하는 단계는 15 내지 100 ℃정도의 온도에서 상기 RDX와 상기 유기 용매를 2:100 내지 5:100의 질량비율로 혼합하여 용해시킬 수 있다.In the step of preparing the RDX solution, the RDX and the organic solvent may be mixed and dissolved at a mass ratio of 2: 100 to 5: 100 at a temperature of about 15 to 100 ° C.

상기 RDX 입자를 석출하는 단계는 상기 RDX 용액과 상기 반용매를 1:15 내지 1:120의 질량비율로 혼합하여 용해시키며, 여기서 상기 반용매의 온도는 0 내지 25 ℃ 범위이다.In the step of precipitating the RDX particles, the RDX solution and the semi-solvent are mixed and dissolved in a mass ratio of 1:15 to 1: 120, wherein the temperature of the semi-solvent is in a range of 0 to 25 ° C.

또한, 상기 계면활성제는 상기 RDX 용액과 상기 반용매가 혼합된 혼합물에 1 내지 10 질량% 로 첨가될 수 있다.The surfactant may be added to the mixture of the RDX solution and the semi-solvent in an amount of 1 to 10 mass%.

또한, 본 발명의 구형 RDX 입자 제조방법은 수득된 RDX 입자를 세척 및 건조하는 단계를 더 포함할 수 있다.In addition, the method for preparing spherical RDX particles of the present invention may further comprise washing and drying the obtained RDX particles.

앞서 설명한 제조방법에 따라 제조된 구형 RDX 입자는 평균 입경이 0.2 내지 3 범위인 구형 입자이며, 또한, RDX 입자의 가로 길이(La)와 세로 길이(Lb)의 비(La/Lb)가 1.0 내지 1.4의 범위인 것을 특징으로 한다.
The spherical RDX particles produced according to the above-described manufacturing method are spherical particles having an average particle diameter in the range of 0.2 to 3. The ratio (La / Lb) of the transverse length (La) to the transverse length (Lb) 1.4. ≪ / RTI >

이러한 본 발명의 구형 RDX 입자 제조방법은 단순히 RDX를 용매에 용해시킨 용액과 반용액을 혼합하여 서브마이크론 및 마이크론 크기 구형 RDX 입자를 제조함으로써, 별도의 고온, 고압, 고전압, 고 에너지 등을 요구하지 않으므로 공정 운용상의 비용이 대폭 감소되는 효과가 있다.The method of producing the spherical RDX particles of the present invention requires separate high-temperature, high-pressure, high-voltage, high-energy, and the like by preparing submicron and micron spherical RDX particles by simply mixing a solution in which RDX is dissolved in a solvent and a half- Therefore, the cost of the process operation is greatly reduced.

또한, 기존 방법과는 달리 응집 상태를 회피하여 단순하게 RDX를 용해시킨 용매와 RDX 침전을 일으키는 반용매를 일시에 혼합하여 구형 RDX 입자를 제조할 수 있으며, 생산량 향상이 가능하다.In addition, unlike conventional methods, it is possible to manufacture spherical RDX particles by mixing RDX-dissolving solvent and semi-solvent which cause RDX precipitation at a time, avoiding aggregation and improving production.

또한, RDX 입자를 1 ㎛ 이하 정도의 서브마이크론 크기로 제조하면, 민감도를 결정하는 과열점(hot spot)의 크기가 작아져, 민감도가 낮아질 수 있는 점이 있고 또 크기의 축소로 인해 넓은 비표면적으로 기폭 에너지 발생 속도를 비약적으로 높일 수 있다.In addition, when the RDX particles are produced at a submicron size of about 1 占 퐉 or less, the size of the hot spot for determining the sensitivity is reduced, and the sensitivity may be lowered. Also, It is possible to dramatically increase the rate of generation of aerial energy.

또한, 구형으로 인해 표면 거칠기가 감소되어 쇼크 민감도(shock sensitivity)가 낮아지며 에너지 조성물 제조 과정에서 점도가 낮아질 수 있으며, 평균 입경의 감소에 따라 충진 밀도 상승에 따른 기폭 압력 극대화, 응집 상태 회피로 인하여 비교적 둔감한 RDX 입자의 제조가 가능하며 미세 입자 크기로 인해 빠른 에너지 방출 속도를 보이므로 고폭 화약 및 고체 복합 추진제(solid composite propellant) 등 민수용 및 군용 조성물로서 널리 이용될 수 있다.
In addition, since the spherical shape reduces the surface roughness, the shock sensitivity is lowered and the viscosity can be lowered in the process of manufacturing the energy composition. As the average particle diameter is decreased, the filling pressure is maximized due to the increase of the filling density, It is possible to produce insensitive RDX particles and it can be widely used as a civil and military composition such as a solid composite propellant since it exhibits fast energy release rate due to its fine particle size.

도 1은 본 발명의 일 실시예에 따른 구형 RDX 입자 제조방법의 공정 흐름도이다.
도 2는 본 발명의 실시예1에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 3은 본 발명의 실시예2에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 4는 본 발명의 실시예3에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 5는 본 발명의 실시예4에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 6은 본 발명의 실시예5에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 7은 본 발명의 실시예6에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 8은 본 발명의 실시예7에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 9는 본 발명의 실시예8에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 10은 본 발명의 실시예9에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 11은 본 발명의 실시예10에서 제조된 구형 RDX 입자의 SEM 사진이다.
도 12는 본 발명의 비교예1에서 제조된 구형 RDX 입자의 SEM 사진이다.1 is a process flow diagram of a method for manufacturing spherical RDX particles according to an embodiment of the present invention.
2 is an SEM photograph of spherical RDX particles prepared in Example 1 of the present invention.
3 is an SEM photograph of spherical RDX particles prepared in Example 2 of the present invention.
4 is a SEM photograph of spherical RDX particles prepared in Example 3 of the present invention.
5 is a SEM photograph of spherical RDX particles prepared in Example 4 of the present invention.
6 is a SEM photograph of spherical RDX particles prepared in Example 5 of the present invention.
7 is a SEM photograph of spherical RDX particles prepared in Example 6 of the present invention.
8 is a SEM photograph of spherical RDX particles prepared in Example 7 of the present invention.
9 is a SEM photograph of spherical RDX particles prepared in Example 8 of the present invention.
10 is an SEM photograph of spherical RDX particles prepared in Example 9 of the present invention.
11 is a SEM photograph of spherical RDX particles prepared in Example 10 of the present invention.
12 is an SEM photograph of spherical RDX particles prepared in Comparative Example 1 of the present invention.

이하에서 앞서 설명한 본 발명을 더욱 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.

도 1에 나타난 바와 같이, 본 발명에 따른 구형 RDX 입자 제조방법은 유기 용매에 RDX를 용해시켜 RDX 용액을 제조하는 단계(S110), 상기 RDX 용액 또는 반용액에 계면활성제를 첨가하는 단계(S120), 상기 RDX 용액과 상기 반용매를 혼합하여 RDX 입자를 석출시키는 단계(S130), 석출된 RDX 입자를 수득하는 단계(S140) 및 수득된 RDX 입자를 세척 및 건조하는 단계(S150)를 포함한다.As shown in FIG. 1, the method for preparing spherical RDX particles according to the present invention comprises the steps of preparing an RDX solution by dissolving RDX in an organic solvent (S110), adding a surfactant to the RDX solution or semi-solution (S120) Mixing the RDX solution and the semi-solvent to precipitate RDX particles (S130), obtaining precipitated RDX particles (S140), and washing and drying the obtained RDX particles (S150).

상기 RDX 용액을 제조하는 단계(S110)에서 상기 유기 용매는 DMSO(dimethyl slufoxide), DMF(N,N-dimethylformamide), DMA(N,N-dimethylacetamide), NMP(n-methyl-2-pyrrolidone), acetone, γ-butyrolactone, cyclohexanone 중에서 선택되는 어느 1종 이상의 혼합물도 가능하다. 특히 DMA(N,N-dimethylacetamide)는 실온에서 점도가 낮으며 RDX에 대한 용해도가 높으므로 바람직하게 사용할 수 있다.The organic solvent may be selected from the group consisting of dimethyl sulphoxide (DMF), N-dimethylformamide (DMF), N-dimethylacetamide (DMA), n-methyl pyrrolidone (NMP) acetone,? -butyrolactone, cyclohexanone, and mixtures thereof. In particular, DMA (N, N-dimethylacetamide) has a low viscosity at room temperature and has high solubility in RDX.

또한, 유기 용매에 RDX가 용해되는 온도 범위는 용해도로부터 15 내지 100 ℃가 적합하고, 특히 25 내지 90 ℃의 온도 범위가 바람직하며, 일정한 온도로 유지되는 어떤 형태의 용기에서도 충분히 진행될 수 있다.The temperature range in which the RDX dissolves in the organic solvent is suitably from 15 to 100 DEG C from the solubility, more preferably from 25 to 90 DEG C, and can be sufficiently advanced in any type of container maintained at a constant temperature.

그리고 유기 용매에서 RDX 농도는 온도 범위 15 내지 100 ℃에서의 RDX 용해도로부터 결정되며, 일반적으로 RDX 용해도는 유기 용매 100g에 대해서 온도 범위 15 내지 90 ℃에서 2.5 내지 100g 정도이다. 여기서, 상기 온도 범위인 15 내지 100 ℃를 벗어날 경우 나중에 혼합되는 반용매 온도를 상승시켜 응집된 형태의 RDX 입자가 석출되거나 처리되는 RDX 농도가 매우 낮아질 수 있다.And the RDX concentration in the organic solvent is determined from the RDX solubility at a temperature range of 15 to 100 DEG C, and generally the RDX solubility is about 2.5 to 100 g at a temperature range of 15 to 90 DEG C for 100 g of the organic solvent. Here, when the temperature is in the range of 15 to 100 캜, the later-added semi-solvent temperature may be raised to precipitate or treat the agglomerated RDX particles, which may result in a very low RDX concentration.

또한, RDX와 유기 용매를 2:100 내지 5:100의 질량 비율로 혼합하여 용해시키는 것이 적합하다. 그러나 여기서 상기 질량 비율 범위를 벗어날 경우, 제조되는 RDX 입자의 평균 입경이 1 ㎛ 이상으로 매우 커지거나 제조되는 RDX 입자의 양이 적을 수 있으므로 상기 질량비율의 범위를 만족하는 것이 바람직하다.It is also preferable that RDX and the organic solvent are mixed and dissolved in a mass ratio of 2: 100 to 5: 100. However, when the above-mentioned mass ratio range is exceeded, it is preferable that the range of the mass ratio is satisfied, since the average particle diameter of the RDX particles to be produced is extremely large to 1 占 퐉 or more or the amount of the RDX particles to be produced may be small.

RDX가 유기용매에 완전히 용해된 RDX 용액 또는 반용액에 계면활성제가 첨가되며(S120), 상기 계면활성제는 RDX 용액의 점도와 계면 장력에 영향을 미치며, 입자간 응집 상태를 크게 변화시킬 수 있다.The surfactant is added to the RDX solution or semi-solution in which the RDX is completely dissolved in the organic solvent (S120), and the surfactant affects the viscosity and the interfacial tension of the RDX solution and can significantly change the intergranular aggregation state.

본 발명에서 계면활성제는 PVP(polyvinylpyrrolidone) 계열 공중합체에서 선택되는 1종을 사용할 수 있다.In the present invention, a surfactant selected from PVP (polyvinylpyrrolidone) -based copolymers may be used.

예를 들어 PVP 계열 공중합체(PVP copolymer)로는 Sigma-Aldrich사의 시약으로 PVP-co-PVA(polyvinyl pyrrolidone-co-polyvinylacetate), PVP-co-DMA(n(polyvinylpyrrolidone-co-dimethyl maleic anhydride)), PVP-co-DMAEM(poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate)), PVP-co-VA(poly(1-vinylpyrrolidone-co-vinylacetate)), PVP-co-Styrene(poly(1-vinylpyrrolidone-co-styrene)), Poly[(2-ethyldimethylammonioethyl meth acrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] 중에서 선택되는 어느 1종을 사용할 수 있으며, 특히 PVP-co-PVA(polyvinyl pyrrolidone-co-polyvinylacetate)가 적합하다.For example, PVP copolymers include polyvinyl pyrrolidone-co-polyvinylacetate (PVP-co-PVA), polyvinylpyrrolidone-co-dimethyl maleic anhydride (PVP) (1-vinylpyrrolidone-co-vinylacetate), PVP-co-styrene (poly (1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate) (PVP-co-PVA) (polyvinyl pyrrolidone-co-PVA-co-PVA) may be used as the polyvinyl pyrrolidone- polyvinylacetate) are suitable.

여기서 PVP(polyvinylpyrrolidone) 계열 공중합체는 RDX 표면에서 vinylpyrrolidone 기의 질소원자(N)가 RDX와 복합체(complex)를 형성할 경우 RDX 표면의 음전하를 상쇄시켜 전기적으로 중성상태를 만들게 되고 이로 인해 정전기에 의한 기폭 가능성이 낮아지기 때문에 계면활성제로 바람직하게 사용할 수 있다.In this case, PVP (polyvinylpyrrolidone) -based copolymers can neutralize the negative charge on the RDX surface when the nitrogen atom (N) of the vinylpyrrolidone group forms a complex with RDX on the surface of RDX, thereby making it electrically neutral, It is preferable to use it as a surfactant because the possibility of attack is low.

이렇게 RDX 용액 또는 반용매에 첨가되는 계면활성제의 양은 RDX 용액과 반용매가 혼합된 혼합물의 1 내지 10 질량%로 첨가되는 것이 적합하다. 이때 상기 계면활성제의 질량백분율 범위를 벗어날 경우, 나중에 수득된 RDX 입자를 세척한 후에도 RDX 입자 표면에 잔류된 계면활성제가 RDX의 기폭 특성, 저장 성능, 제품 순도에 영향을 미칠 수 있다.The amount of the surfactant added to the RDX solution or the semi-solvent is suitably 1 to 10% by mass of the mixture of the RDX solution and the half-solvent. At this time, if the weight percentage of the surfactant is out of the range, the surfactant remaining on the surface of the RDX particles may affect the aerobic characteristics, storage performance, and product purity of the RDX even after washing the RDX particles obtained later.

RDX 입자를 석출시키는 단계(S130)는 계면활성제의 첨가 이후, RDX 용액이 반용매(anti-solvent)와 혼합되어 RDX를 석출하게 된다.In step S130 of precipitating the RDX particles, after the addition of the surfactant, the RDX solution is mixed with an anti-solvent to precipitate the RDX.

상기 반용매는 RDX 입자를 RDX 용액의 유기 용매와 섞이는 어떠한 용매도 상관없으나 바람직하게 물이 사용될 수 있으며, 이는 나노 크기 및 마이크로 크기의 RDX 입자 생성을 위해 요구되는 최대 과포화도(supersaturation ratio, S)가 약 100 %를 이상으로 할 수 있고, 비교적 저렴한 가격으로 극대화할 수 있으며 휘발에 따른 화재와 공정상의 위험이 덜하기 때문이다.The semi-solvent does not matter what solvent the RDX particles are mixed with the organic solvent of the RDX solution, but preferably water can be used because the maximum supersaturation ratio (S) required to produce nanoscale and micro-sized RDX particles is This is because it can be more than about 100%, it can be maximized at a relatively low price, and there is less fire and process risk due to volatilization.

RDX 용액과 반용매는 1:15 내지 1:120의 질량비율로 혼합되는 것이 적합하며, 보다 바람직하게는 1:15 내지 1:60의 질량비율이 적합하다. 이때, 상기 질량비율 범위를 벗어날 경우 석출된 RDX 입자의 재용해 또는 입자 크기가 매우 작아서 회수가 불가능할 수 있으며 수득되는 RDX 입자의 양이 적을 수 있다.The RDX solution and the semi-solvent are preferably mixed in a mass ratio of 1:15 to 1: 120, more preferably a mass ratio of 1:15 to 1:60. At this time, when the mass ratio is out of the range, redissolution or particle size of the precipitated RDX particles may be too small to be recovered, and the amount of the obtained RDX particles may be small.

상기 반용매의 온도는 RDX 용액과 반용매의 혼합에 의해 발생되는 과포화도를 고려해서 40 ℃이하이면 충분하며, 특히 0 내지 25 ℃ 범위가 적합하다.Considering the degree of supersaturation generated by the mixing of the RDX solution and the half-solvent, the temperature of the semi-solvent is preferably 40 占 폚 or lower, more preferably 0 to 25 占 폚.

RDX 용액과 반용매의 혼합에 의해 RDX 입자가 석출되면, 석출된 RDX 입자를 수득하는 단계(S140)는 현탁된 용액을 hydrophilic PTFE(polytetrafluoroethylene) 재질로 공극 크기(pore size)가 0.1 ㎛이고, 직경이 47 mm인 멤브레인 필터(membrane filter)에서 여과하여 RDX 입자를 수득한다.When the RDX particles are precipitated by mixing the RDX solution and the half-solvent, the step (S140) of obtaining the precipitated RDX particles is performed by using a hydrophilic PTFE (polytetrafluoroethylene) material with a pore size of 0.1 탆, Is filtered through a 47 mm membrane filter to obtain RDX particles.

또한, 본 발명의 구형 RDX 제조방법은 세척 및 건조 단계(S150)를 더 포함하며, 수득된 RDX 입자를 세척하여, 진공 오븐에서 65 ℃ 온도로 12 시간 동안 건조한다.In addition, the method for manufacturing a spherical RDX of the present invention further comprises a washing and drying step (S150), wherein the obtained RDX particles are washed and dried in a vacuum oven at 65 DEG C for 12 hours.

본 발명에 따른 구형 RDX 제조방법에 의해 제조된 RDX 입자는 구형(bead) 입자로 입경이 0.2 내지 3 범위이며, 이와 같은 RDX 입자의 형상에서 RDX 입자의 가로 길이(La)와 세로 길이(Lb)의 비율을 종횡비(aspect ratio)=La/Lb로 정의하면, 이에 따라 상기 제조된 RDX 입자의 종횡비는 1.0 내지 1.4 범위이다.The RDX particles produced by the method for manufacturing a spherical RDX according to the present invention are bead particles having a particle size in the range of 0.2 to 3. The transverse length La and longitudinal length Lb of the RDX particles in the shape of the RDX particles, Is defined as aspect ratio = La / Lb, the aspect ratio of the RDX particles thus prepared ranges from 1.0 to 1.4.

이렇게 제조된 RDX 입자는 소량 채취된 후, 사이클로헥산(cyclohexane)에 초음파로 분산하고 금 코팅되어 주사전자현미경(scanning electron microscope, SEM)에 의해 RDX 입자의 형상, 입도 분포, 평균 입경을 관측한다.The RDX particles thus obtained are collected in a small amount, dispersed by ultrasonication in cyclohexane, coated with gold, and the shape, particle size distribution and average particle diameter of the RDX particles are observed by a scanning electron microscope (SEM).

이상에서 설명한 본 발명을 다음의 실시예에 의거하여 더욱 상세히 설명하겠으나, 본 발명의 권리범위가 다음의 실시예에 의해 한정되는 것은 아니다.The present invention described above is explained in more detail based on the following examples, but the scope of the present invention is not limited by the following examples.

실시예 1은 90 ℃에서 0.5g RDX를 10g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 0.5g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.Example 1 is an RDX solution prepared by completely dissolving 0.5 g RDX in 10 g DMA (N, N-dimethylacetamide) at 90 占 폚. Add 0.5 g of polyvinylpyrrolidone-co-vinylacetate (PVP-co-PVA) as a surfactant to the solution completely dissolved in RDX. 300 g of water as an anti-solvent maintained at 0 ° C and RDX solution The aqueous solution from which the particles are precipitated is filtered to obtain RDX particles.

도 2에 도시된 바와 같이, 실시예 1에 따라 제조된 구형 RDX 입자의 평균 입경은 1.66 ㎛ 이다.As shown in Fig. 2, the spherical RDX particles prepared according to Example 1 had an average particle diameter of 1.66 mu m.

또 다른 실시예 2는 90 ℃에서 0.5g RDX를 20g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA (poly(vinylpyrrolidone-co-vinylacetate) 0.25g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In another embodiment 2, an RDX solution is prepared by completely dissolving 0.5 g RDX in 20 g DMA (N, N-dimethylacetamide) at 90 占 폚. To the RDX solution in which RDX is completely dissolved, 0.25 g of polyvinylpyrrolidone-co-vinylacetate (PVP-co-PVA) as a surfactant is added. 300 g of water as an anti-solvent maintained at 0 ° C and the RDX solution The aqueous solution from which the RDX particles precipitate is filtered to obtain RDX particles.

도 3에 도시된 바와 같이, 실시예 2를 통해 제조된 구형 RDX 입자의 평균 입경은 1.93 ㎛ 이다.As shown in Fig. 3, the spherical RDX particles prepared in Example 2 had an average particle diameter of 1.93 mu m.

또 다른 실시예 3은 90 ℃에서 0.5g RDX를 10g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 1g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In another embodiment 3, RDX solution is prepared by completely dissolving 0.5 g RDX in 10 g DMA (N, N-dimethylacetamide) at 90 캜. Add 1 g of polyvinylpyrrolidone-co-vinylacetate (PVP-co-PVA) as a surfactant to RDX solution in which RDX is completely dissolved, 300 g of water as an anti- The aqueous solution from which the particles are precipitated is filtered to obtain RDX particles.

도 4에서처럼, 실시예 3에 따라 제조된 구형 RDX 입자의 평균 입경은 1.27 ㎛ 이다.As shown in Fig. 4, the spherical RDX particles prepared according to Example 3 had an average particle diameter of 1.27 mu m.

또 다른 실시예 4는 90 ℃에서 0.5g RDX를 10g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 2g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In another embodiment 4, an RDX solution is prepared by completely dissolving 0.5 g RDX in 10 g DMA (N, N-dimethylacetamide) at 90 占 폚. Add 2 g of polyvinylpyrrolidone-co-vinylacetate (PVP-co-PVA) as a surfactant to RDX solution completely dissolved in RDX. 300 g of water, which is an anti-solvent maintained at 0 ° C, The aqueous solution from which the particles are precipitated is filtered to obtain RDX particles.

도 5에서처럼, 실시예 4를 통해 제조된 구형 RDX 입자의 평균 입경은 2.52 ㎛ 이다.As shown in Fig. 5, the spherical RDX particles prepared in Example 4 had an average particle diameter of 2.52 mu m.

또 다른 실시예 5는 90 ℃에서 0.2g RDX를 10g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 1g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In another Example 5, an RDX solution is prepared by completely dissolving 0.2 g RDX in 10 g DMA (N, N-dimethylacetamide) at 90 占 폚. Add 1 g of polyvinylpyrrolidone-co-vinylacetate (PVP-co-PVA) as a surfactant to RDX solution in which RDX is completely dissolved, 300 g of water as an anti- The aqueous solution from which the particles are precipitated is filtered to obtain RDX particles.

도 6에서와 같이, 실시예 5에 따라 제조된 구형 RDX 입자의 평균 입경은 1.87 ㎛ 이다.As shown in Fig. 6, the spherical RDX particles prepared according to Example 5 had an average particle diameter of 1.87 mu m.

또 다른 실시예 6은 90 ℃에서 0.2g RDX를 10g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 0.2g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In another Example 6, an RDX solution is prepared by completely dissolving 0.2 g RDX in 10 g DMA (N, N-dimethylacetamide) at 90 占 폚. To the RDX solution in which RDX is completely dissolved, 0.2 g of poly (vinylpyrrolidone-co-vinylacetate) (PVP-co-PVA) as a surfactant is added. 300 g of water as an anti- The aqueous solution from which the RDX particles precipitate is filtered to obtain RDX particles.

도 7에서와 같이, 실시예 6을 통해 제조된 구형 RDX 입자의 평균 입경은 1.05 ㎛ 이다.As shown in Fig. 7, the spherical RDX particles prepared in Example 6 had an average particle diameter of 1.05 mu m.

또 다른 실시예 7은 90 ℃에서 0.2g RDX를 10g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 0.2g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In another Example 7, an RDX solution is prepared by completely dissolving 0.2 g RDX in 10 g DMA (N, N-dimethylacetamide) at 90 占 폚. To the RDX solution in which RDX is completely dissolved, 0.2 g of poly (vinylpyrrolidone-co-vinylacetate) (PVP-co-PVA) as a surfactant is added. 300 g of water as an anti- The aqueous solution from which the RDX particles precipitate is filtered to obtain RDX particles.

도 8에 나타난 바와 같이, 실시예 7에 따라 제조된 구형 RDX 입자의 평균 입경은 1.52 ㎛ 이다.As shown in Fig. 8, the spherical RDX particles prepared according to Example 7 had an average particle diameter of 1.52 mu m.

또 다른 실시예 8은 80 ℃에서 0.2g RDX를 5g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 0.2g를 첨가한다. 0℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In another Example 8, an RDX solution is prepared by completely dissolving 0.2 g RDX in 5 g DMA (N, N-dimethylacetamide) at 80 캜. To the RDX solution in which RDX is completely dissolved, 0.2 g of poly (vinylpyrrolidone-co-vinylacetate) (PVP-co-PVA) as a surfactant is added. 300 g of water as an anti- The aqueous solution from which the RDX particles precipitate is filtered to obtain RDX particles.

도 9에 나타난 바와 같이, 실시예 8에 따라 제조된 구형 RDX 입자의 평균 입경은 0.85 ㎛ 이다.As shown in Fig. 9, the spherical RDX particles prepared according to Example 8 had an average particle diameter of 0.85 mu m.

또 다른 실시예 9는 80 ℃에서 0.2g RDX를 5g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 0.2g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In another Example 9, an RDX solution is prepared by completely dissolving 0.2 g RDX in 5 g DMA (N, N-dimethylacetamide) at 80 캜. To the RDX solution in which RDX is completely dissolved, 0.2 g of poly (vinylpyrrolidone-co-vinylacetate) (PVP-co-PVA) as a surfactant is added. 300 g of water as an anti- The aqueous solution from which the RDX particles precipitate is filtered to obtain RDX particles.

도 10에 도시된 바와 같이, 실시예 9를 통해 제조된 구형 RDX 입자의 평균 입경은 0.98 ㎛ 이다.As shown in Fig. 10, the spherical RDX particles prepared in Example 9 had an average particle diameter of 0.98 mu m.

또 다른 실시예 10은 80 ℃에서 0.1g RDX를 2.5g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. RDX가 완전히 용해된 RDX 용액에 계면활성제인 PVP-co-PVA(poly(vinylpyrrolidone-co-vinylacetate) 0.2g를 첨가한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 현탁된 수용액을 얻었으며 여과에 의해 RDX 입자를 수득한다.In another example 10, RDX solution is prepared by completely dissolving 0.1 g RDX in 2.5 g DMA (N, N-dimethylacetamide) at 80 占 폚. To the RDX solution in which RDX is completely dissolved, 0.2 g of poly (vinylpyrrolidone-co-vinylacetate) (PVP-co-PVA) as a surfactant is added. 300 g of water as an anti- An aqueous solution in which RDX particles were suspended was obtained and RDX particles were obtained by filtration.

도 11에 나타난 것처럼, 실시예 10에서 제조된 구형 RDX 입자의 평균 입경은 0.27 ㎛ 이다.As shown in Fig. 11, the spherical RDX particles prepared in Example 10 had an average particle diameter of 0.27 mu m.

그리고, 비교예 1은 80 ℃에서 0.2g RDX를 5g DMA(N,N-dimethylacetamide)에 완전히 용해시켜 RDX 용액을 제조한다. 0 ℃로 유지한 반용매인 물 300g과 상기 RDX 용액을 일시에 혼합시켜 RDX 입자가 석출되어 나온 수용액을 여과하여 RDX 입자를 수득한다.In Comparative Example 1, RDX solution was prepared by completely dissolving 0.2 g of RDX at 80 ° C in 5 g of DMA (N, N-dimethylacetamide). 300 g of water, which is an anti-solvent maintained at 0 占 폚, and RDX solution are mixed at the same time to obtain RDX particles by filtering the aqueous solution from which the RDX particles precipitate.

도 12에 도시된 바와 같이, 비교예 1을 통해 제조된 RDX 입자는 응집된 상태이며, 응집체를 구성하는 1차 입자의 평균 입경은 1.65 ㎛ 이다.As shown in FIG. 12, the RDX particles prepared in Comparative Example 1 were aggregated, and the average particle diameter of the primary particles constituting the agglomerates was 1.65 μm.

앞서 살펴본 실시예는 본 발명이 속하는 기술 분야에서 통상의 지식을 가진자(이하 '당업자'라고 한다)가 본 발명을 용이하게 실시할 수 있도록 하는 바람직한 실시예일 뿐, 전술한 실시예 및 첨부한 도면에 한정되는 것이 아니므로 이로 인해 본 발명의 권리범위가 한정되는 것은 아니다. 따라서, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능하다는 것이 당업자에게 있어 명백할 것이며, 당업자에 의해 용이하게 변경 가능한 부분도 본 발명의 권리범위에 포함됨은 자명하다.
The foregoing embodiments are merely preferred embodiments of the present invention so that those skilled in the art can easily carry out the present invention. And thus the scope of the present invention is not limited thereto. It will be apparent to those skilled in the art that various substitutions, modifications and variations are possible within the scope of the present invention, and it is obvious that those parts easily changeable by those skilled in the art are included in the scope of the present invention .

Claims (12)

유기 용매에 RDX를 용해시켜 RDX 용액을 제조하는 단계;
상기 RDX 용액과 반용매를 혼합하여 RDX 입자가 석출되는 단계; 및
석출된 RDX 입자를 수득하는 단계;를 포함하며,
상기 RDX 용액과 반용매를 혼합하기 전에 상기 RDX 용액 또는 상기 반용액에 계면활성제를 첨가하는 것을 특징으로 하는 구형 RDX 입자 제조방법.
Dissolving RDX in an organic solvent to prepare an RDX solution;
Mixing the RDX solution and an anti-solvent to precipitate RDX particles; And
Thereby obtaining precipitated RDX particles,
Wherein a surfactant is added to the RDX solution or the semi-solution before mixing the RDX solution and the semi-solvent.
제 1 항에 있어서, 유기 용매는 DMSO(dimethyl slufoxide), DMF(N,N-dimethylformamide), DMA(N,N-dimethylacetamide), NMP (n-methyl-2-pyrrolidone), acetone, γ-butyrolactone, cyclohexanone 중에서 선택되는 어느 1종 이상인 것을 특징으로 하는 구형 RDX 입자 제조방법.
The method of claim 1, wherein the organic solvent is selected from the group consisting of dimethyl sulphoxide (DMF), N-dimethylformamide (DMF), N-dimethylacetamide (DMA), n-methyl- cyclohexanone, and cyclohexanone.
제 1 항에 있어서, 상기 계면활성제는 PVP-co-PVA(polyvinyl pyrrolidone-co-polyvinylacetate), PVP-co-DMA(n(polyvinylpyrrolidone-co-dimethyl maleic anhydride)), PVP-co-DMAEM(poly(1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate), PVP-co-VA(poly(1-vinylpyrrolidone-co-vinylacetate)), PVP-co-Styrene(poly(1-vinylpyrrolidone-co-styrene), Poly[(2-ethyldimethylammonioethyl meth acrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] 중에서 선택되는 어느 1종인 것을 특징으로 하는 구형 RDX 입자 제조방법.
The method of claim 1, wherein the surfactant is selected from the group consisting of polyvinyl pyrrolidone-co-polyvinylacetate (PVP-co-PVA), polyvinylpyrrolidone-co-dimethyl maleic anhydride (PVP) 1-vinylpyrrolidone-co-2-dimethylaminoethyl methacrylate), poly (1-vinylpyrrolidone-co-vinylacetate), PVP-co-styrene 2-ethyldimethylammonioethyl methacrylate ethyl sulfate) -co- (1-vinylpyrrolidone)].
제 1 항에 있어서, 상기 반용매는 물인 것을 특징으로 하는 구형 RDX 입자 제조방법.
The method of claim 1, wherein the semi-solvent is water.
제 1 항에 있어서, 상기 RDX 용액을 제조하는 단계는 상기 RDX와 상기 유기 용매를 2:100 내지 5:100의 질량 비율로 혼합하여 용해시키는 것을 특징으로 하는 구형 RDX 입자 제조방법.
The method of claim 1, wherein the step of preparing the RDX solution comprises mixing and dissolving the RDX and the organic solvent at a mass ratio of 2: 100 to 5: 100.
제 1 항에 있어서, 상기 RDX 용액을 제조하는 단계는 15 내지 100 ℃의 온도에서 유기 용매에 RDX를 용해시키는 것을 특징으로 하는 구형 RDX 입자 제조방법.
The method of claim 1, wherein the step of preparing the RDX solution comprises dissolving RDX in an organic solvent at a temperature of 15 to 100 ° C.
제 1 항에 있어서, 상기 RDX 입자를 석출하는 단계는 상기 RDX 용액과 상기 반용매를 1:15 내지 1:120의 질량 비율로 혼합하는 것을 특징으로 하는 구형 RDX 입자 제조방법.
The method of claim 1, wherein the step of precipitating RDX particles comprises mixing the RDX solution and the semi-solvent at a mass ratio of 1:15 to 1: 120.
제 1 항에 있어서, 상기 반용매의 온도가 0 내지 25 ℃ 범위인 것을 특징으로 하는 구형 RDX 입자 제조방법.
The method of claim 1, wherein the temperature of the semi-solvent is in the range of 0 to 25 占 폚.
제 1 항에 있어서, 상기 계면활성제는 상기 RDX 용액과 상기 반용매가 혼합된 혼합물에 1 내지 10 중량%로 첨가되는 것을 특징으로 하는 구형 RDX 입자 제조방법.
The method of claim 1, wherein the surfactant is added to the mixture of the RDX solution and the semi-solvent in an amount of 1 to 10 wt%.
제 1 항에 있어서, 수득된 RDX 입자를 세척 및 건조하는 단계를 더 포함하는 것을 특징으로 하는 구형 RDX 입자 제조방법.
2. The method of claim 1, further comprising washing and drying the obtained RDX particles.
제 1 항 내지 제 10 항 중 어느 한 항의 제조방법에 의해 제조된 RDX 입자는 구형 입자이며, 입경이 0.2 내지 3 ㎛ 범위인 것을 특징으로 하는 구형 RDX 입자.
A spherical RDX particle characterized in that the RDX particles produced by the process of any one of claims 1 to 10 are spherical particles and have a particle size in the range of 0.2 to 3 mu m.
제 11 항에 있어서, 상기 RDX 입자는 가로 길이(La)와 세로 길이(Lb)의 비(La/Lb)가 1.0 내지 1.4의 범위인 것을 특징으로 하는 구형 RDX 입자.
12. The spherical RDX particle according to claim 11, wherein the RDX particle has a ratio La / Lb of the transverse length La to the transverse length Lb of 1.0 to 1.4.
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