KR102615219B1 - Method of Producing High Purity Hexanitrostilbene - Google Patents
Method of Producing High Purity Hexanitrostilbene Download PDFInfo
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- YSIBQULRFXITSW-OWOJBTEDSA-N 1,3,5-trinitro-2-[(e)-2-(2,4,6-trinitrophenyl)ethenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1\C=C\C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O YSIBQULRFXITSW-OWOJBTEDSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 claims abstract description 34
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000015 trinitrotoluene Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 114
- 239000000243 solution Substances 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- RYJATPLJVSILLB-UHFFFAOYSA-N 1-nitro-2-(2-phenylethenyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C=CC1=CC=CC=C1 RYJATPLJVSILLB-UHFFFAOYSA-N 0.000 claims 1
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000000376 reactant Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002360 explosive Substances 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000005474 detonation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003721 gunpowder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- PUJXVDWGOSEZMH-UHFFFAOYSA-N 2-(chloromethyl)-1,3,5-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(CCl)C([N+]([O-])=O)=C1 PUJXVDWGOSEZMH-UHFFFAOYSA-N 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 239000000006 Nitroglycerin Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012035 limiting reagent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/14—Preparation of nitro compounds by formation of nitro groups together with reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
Abstract
본 발명은 고순도 헥사나이트로스틸벤을 제조하는 방법에 관한 것으로서, 2,4,6-트라이나이트로톨루엔(TNT)과 차아염소산 나트륨의 반응 조건을 조절하여 반응물의 HNS의 합성 선택도를 높이고, 원심분리기를 이용하여 반응부산물과 분리함으로써 TNT로부터 99% 이상의 고순도 2,2´,4,4´,6,6´-헥사나이트로스틸벤을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing high purity hexanitrostilbene, which involves increasing the synthesis selectivity of HNS of the reactant by adjusting the reaction conditions of 2,4,6-trinitrotoluene (TNT) and sodium hypochlorite, This relates to a method of producing high purity 2,2´,4,4´,6,6´-hexanitrostilbene from TNT by separating it from reaction by-products using a centrifuge.
Description
본 발명은 고순도 헥사나이트로스틸벤의 제조방법에 관한 것으로서, 보다 상세하게는 2,4,6-트라이나이트로톨루엔(TNT)과 차아염소산 나트륨의 반응 조건을 조절하여 반응물의 HNS의 합성 선택도를 높이고, 원심분리기를 이용하여 반응부산물과 분리함으로써 TNT로부터 99% 이상의 고순도 2,2´,4,4´,6,6´-헥사나이트로스틸벤(2,2´,4,4´,6,6´-hexanitrostilbene, HNS)을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing high-purity hexanitrostilbene, and more specifically, to adjust the reaction conditions of 2,4,6-trinitrotoluene (TNT) and sodium hypochlorite to increase the selectivity for the synthesis of HNS as a reactant. By increasing and separating the reaction by-products using a centrifuge, high purity 2,2´,4,4´,6,6´-hexanitrostilbene (2,2´,4,4´, It relates to a method of producing 6,6´-hexanitrostilbene (HNS).
산업용 화약은 나이트로글리세린의 발견으로부터 시작되었으며, 19세기에 이르러서는 2,4,6-트라이나이트로톨루엔(2,4,6-trinitrotoluene, 이하 TNT)의 생산법이 개발되어 현재까지도 군용 화약의 많은 부분은 TNT가 차지하고 있다. 이후 에너지 물질의 개량연구를 통해 RDX나 HMX 등이 개발되어 사용되었지만, 이들 모두 안전성과 폭발성능 모두를 만족하기 힘든 한계를 가지고 있다. 일반적으로 폭발성능이 높으면 외부의 자극에 쉽게 반응하는 특성을 보이며, 반대로 외부의 자극에 둔감하면 화약의 성능이 떨어지기 때문이다. 이런 상반되는 특성을 극복하기 위한 화약들이 개발되어 왔으며 그 중 2,2´,4,4´,6,6´-헥사나이트로스틸벤은 높은 에너지와 둔감한 감도를 갖춘 내열성 고폭화약(Viswanath, D. S., 2018)으로, 물리적 및 화학적 안정성이 우수하고 기계적 감도가 낮아 정전기 불꽃에 민감하지 않고, 내방사선성이 높으면서도 폭발 성능이 뛰어나기 때문에 MDF(Mild Detonating Fuse), SDT(Shielded Detonation Train), ALSC(Aluminium Sheathed Linear Shaped Charge), SMDC(shielded mild detonating cord) 조성물에 응용되며 항공 우주 및 우주 기술에서도 중요한 역할을 하고 있다.Industrial gunpowder began with the discovery of nitroglycerin, and in the 19th century, a production method for 2,4,6-trinitrotoluene (TNT) was developed, which is still used in military gunpowder today. A large portion is occupied by TNT. Since then, RDX and HMX have been developed and used through improved research on energy materials, but they all have limitations that make it difficult to satisfy both safety and explosive performance. In general, if explosive performance is high, it shows the characteristic of easily reacting to external stimuli, and conversely, if it is insensitive to external stimuli, the performance of the gunpowder deteriorates. Explosives have been developed to overcome these conflicting characteristics, and among them, 2,2´,4,4´,6,6´-hexanitrostilbene is a heat-resistant high-explosive explosive with high energy and insensitive sensitivity (Viswanath, D. S., 2018), it has excellent physical and chemical stability and low mechanical sensitivity, so it is not sensitive to electrostatic sparks, and has high radiation resistance and excellent explosion performance, so it can be used in MDF (Mild Detonating Fuse), SDT (Shielded Detonation Train), It is applied to ALSC (Aluminum Sheathed Linear Shaped Charge) and SMDC (shielded mild detonating cord) compositions and plays an important role in aerospace and space technology.
알려진 HNS의 제조방법 중 대표적인 Shipp의 제조 방법(미국특허 제3,505,413호)에 따르면 TNT과 차아염소산 나트륨(sodium hypochlorite, 이하 NaClO)을 반응시켜 수득할 수 있다. 하지만 제조 반응 중 부반응이 일어나 부산물인 2,2´,4,4´,6,6´-헥사나이트로바이벤질(2,2´,4,4´,6,6´-hexanitrobibenzyl, 이하 HNBB)의 생성이 불가피하다는 단점이 있다. 부산물이 생성되면 순수한 HNS의 수득량이 줄어들 뿐만 아니라 분리하는 과정이 필요하게 되며 이는 생산단가의 상승으로 이어질 우려가 있다.According to Shipp's production method (U.S. Patent No. 3,505,413), which is representative of the known HNS production methods, it can be obtained by reacting TNT with sodium hypochlorite (NaClO). However, a side reaction occurs during the manufacturing reaction, resulting in the by-product 2,2´,4,4´,6,6´-hexanitrobibenzyl (HNBB). The disadvantage is that the creation of is inevitable. If by-products are generated, not only will the yield of pure HNS be reduced, but a separation process will be required, which may lead to an increase in production costs.
이러한 단점을 해결하기 위해서 생성된 HNBB을 산화시켜 HNS을 얻어내는 반응공정(미국특허 제4,270,012호)도 연구된 바 있으나, 이러한 반응은 추가적인 산화를 위한 촉매를 사용할 뿐만 아니라 유기용매를 추가로 사용하며, Shipp의 제조공정보다 높은 온도에서 이루어져 TNT로부터 얻는 공정보다 생산단가가 높을 수 밖에 없다.To solve these shortcomings, a reaction process (US Patent No. 4,270,012) to obtain HNS by oxidizing the produced HNBB has been studied. However, this reaction not only uses a catalyst for additional oxidation, but also uses an organic solvent. , it is performed at a higher temperature than Shipp's manufacturing process, so the production cost is inevitably higher than the process obtained from TNT.
이에, 본 발명자들은 상기 문제점을 해결하기 위하여 예의 노력한 결과, HNS과 공결정물질인 HNBB를 비롯해 반응의 중간물질인 2,4,6-트라이나이트로벤질 클로라이드(2,4,6-trinitrobenzyl chloride), 반응조건을 조절하고 원심분리를 통해 세척하는 과정을 통해 반응물인 TNT와 레드 오일(red oil)이라고 불리는 다양한 불순물들을 제거하여 순도 높은 HNS을 얻을 수 있음을 확인하고, 본 발명을 완성하게 되었다.Accordingly, the present inventors made diligent efforts to solve the above problems, and as a result, HNS and HNBB, a co-crystal material, as well as 2,4,6-trinitrobenzyl chloride, an intermediate material of the reaction, were obtained. , it was confirmed that high-purity HNS could be obtained by controlling the reaction conditions and removing various impurities called red oil and TNT as a reactant through a washing process through centrifugation, and the present invention was completed.
본 발명의 목적은 2,4,6-트라이나이트로톨루엔(2,4,6-trinitrotoluene)과 차아염소산 나트륨(sodium hypochlorite)을 반응시켜 높은 에너지와 둔감한 감도를 갖춘 내열성 고폭화약인 2,2´,4,4´,6,6´-헥사나이트로스틸벤(2,2´,4,4´,6,6´-hexanitrostilbene)을 높은 순도로 제조하는 방법을 제공하는데 있다.The purpose of the present invention is to react 2,4,6-trinitrotoluene with sodium hypochlorite to produce 2,2, a heat-resistant high-explosive explosive with high energy and insensitive sensitivity. The aim is to provide a method for producing ´,4,4´,6,6´-hexanitrostilbene (2,2´,4,4´,6,6´-hexanitrostilbene) with high purity.
삭제delete
상기 목적을 달성하기 위하여, 본 발명은 (a) TNT을 THF과 메틸알코올에 용해시킨 용액과 NaClO 수용액을 냉각시키는 단계; (b) 냉각된 TNT 용액과 NaClO 수용액을 혼합하여 일정시간 동안 온도와 pH를 유지하면서 반응시킨 다음, 반응을 종결시키는 단계; 및 (c) 메틸알코올, 물 및 아세톤으로 구성된 군에서 선택되는 2종의 혼합물을 첨가하여 반응이 종결된 혼합용액을 분산시키고 원심분리시켜 고체 생성물을 회수하는 단계를 포함하는 2,2',4,4',6,6'-헥사나이트로스틸벤의 제조방법을 제공한다.
In order to achieve the above object, the present invention includes the steps of (a) cooling a solution of TNT dissolved in THF and methyl alcohol and an aqueous NaClO solution; (b) mixing the cooled TNT solution and NaClO aqueous solution, reacting while maintaining the temperature and pH for a certain period of time, and then terminating the reaction; and (c) adding two mixtures selected from the group consisting of methyl alcohol, water, and acetone to disperse the reaction-complete mixed solution and centrifuging to recover the solid product. 2,2',4. A method for producing 4',6,6'-hexanitrostilbene is provided.
본 발명에 따른 HNS의 제조 공정은 매우 높은 순도를 가진 HNS을 생산하는 효율적인 제조 공정이다. 또한, 상기의 제조방법을 통해 제조된 HNS은 타입 I이지만 높은 순도를 가지고 있어 활용도가 높은 HNS 타입 IV로의 전환을 효율적으로 실시할 수 있다.The manufacturing process of HNS according to the present invention is an efficient manufacturing process that produces HNS with very high purity. In addition, although HNS produced through the above production method is Type I, it has high purity and can be efficiently converted to HNS Type IV, which is highly versatile.
도 1은 본 발명의 일 실시예 따른 공정을 수행할 수 있는 반응기의 구조도이다.
도 2는 본 발명의 일 실시예에 따른 냉각되어 준비된 용액을 혼합해 2,2´,4,4´,6,6'-헥사나이트로스틸벤 합성 반응을 시작하고 pH를 조절하여 2,2´,4,4´,6,6'-헥사나이트로스틸벤이 포함된 혼합용액을 수득하는 단계를 도식화하여 나타낸 것이다.
도 3은 본 발명의 일 실시예에 따른 실시예 3에서 수득한 고체의 2,2´,4,4´,6,6'-헥사나이트로스틸벤을 NMR 분석한 데이터를 도식화하여 나타낸 것이다.
도 4는 본 발명의 일 실시예에 따른 실시예 1의 반응 전 준비단계의 규모를 3배 증가시킨 조건으로 수행한 실시예 5의 실험결과를 NMR분석하여 결과를 도식화하여 나타낸 것이다.1 is a structural diagram of a reactor capable of performing a process according to an embodiment of the present invention.
Figure 2 shows the mixing of the cooled and prepared solution according to an embodiment of the present invention to start the 2,2',4,4',6,6'-hexanitrostilbene synthesis reaction and adjust the pH to produce 2,2 The steps for obtaining a mixed solution containing ´,4,4´,6,6'-hexanitrostilbene are shown schematically.
Figure 3 schematically shows NMR analysis data of solid 2,2',4,4',6,6'-hexanitrostilbene obtained in Example 3 according to an embodiment of the present invention.
Figure 4 schematically shows the results of NMR analysis of the experimental results of Example 5 performed under conditions in which the scale of the preparation step before the reaction of Example 1 according to an embodiment of the present invention was increased by three times.
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술 분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 갖는다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술 분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.
본 발명은 2,4,6-트라이나이트로톨루엔(2,4,6-trinitrotoluene, TNT)과 차아염소산 나트륨(sodium hypochlorite, NaClO)을 이용하여 2,2´,4,4´,6,6´-헥사나이트로스틸벤(2,2´,4,4´,6,6´-hexanitrostilbene, HNS)를 생산하는 공정에서 TNT과 NaClO의 비율, 반응 온도, 반응 시간, 원심분리를 통한 세척 공정이 순도 높은 HNS 생산에 중요한 요소임을 인식하고, 이를 조절하여 수행할 경우, HNS 생성 반응의 부반응을 억제하고 세척을 통해 불순물을 선택적으로 제거하여 효율적으로 순도 높은 HNS을 수득할 수 있음을 확인하였다.The present invention uses 2,4,6-trinitrotoluene (TNT) and sodium hypochlorite (NaClO) to produce 2,2´,4,4´,6,6 In the process of producing ´-hexanitrostilbene (2,2´,4,4´,6,6´-hexanitrostilbene, HNS), the ratio of TNT and NaClO, reaction temperature, reaction time, and washing process through centrifugation Recognizing that this is an important factor in producing high-purity HNS, it was confirmed that if this is controlled and performed, side reactions of the HNS production reaction can be suppressed and impurities can be selectively removed through washing to efficiently obtain high-purity HNS.
따라서, 본 발명은 일 관점에서 (a) TNT을 THF과 메틸알코올에 용해시킨 용액과 NaClO 수용액을 냉각시키는 단계; (b) 냉각된 TNT 용액과 NaClO 수용액을 혼합하여 일정시간 동안 온도와 pH를 유지하면서 반응시킨 다음, 반응을 종결시키는 단계; 및 (c) 메틸알코올, 물 및 아세톤으로 구성된 군에서 선택되는 2종의 혼합물을 첨가하여 반응이 종결된 혼합용액을 분산시키고 원심분리시켜 고체 생성물을 회수하는 단계를 포함하는 2,2´,4,4´,6,6'-헥사나이트로스틸벤의 제조방법에 관한 것이다.Therefore, in one aspect, the present invention includes the steps of (a) cooling a solution of TNT dissolved in THF and methyl alcohol and an aqueous NaClO solution; (b) mixing the cooled TNT solution and NaClO aqueous solution, reacting while maintaining the temperature and pH for a certain period of time, and then terminating the reaction; and (c) adding two mixtures selected from the group consisting of methyl alcohol, water, and acetone to disperse the reaction-complete mixed solution and centrifuging to recover the solid product. 2,2´,4. ,4´,6,6'-Hexanitrostilbene.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 바람직한 실시예에 따르면, (a) TNT을 테트라하이드로퓨란(tetrahydrofuran, 이하 THF)과 메틸알코올(methyl alcohol)에 녹인 용액과 차아염소산 나트륨(sodium hypochlorite, 이하 NaClO) 수용액의 농도를 조절하고 냉각시켜 준비하는 단계; (b) 냉각된 두 용액을 혼합해 반응을 시작한 후, 일정 시간 동안 수조에서 온도를 유지시킴과 동시에 황산(sulfuric acid)과 수산화 나트륨(sodium hydroxide) 수용액을 이용해 pH를 유지 및 반응을 종결시키는 단계; 및 (c) 메틸알코올, 물, 아세톤에 반응의 생성물들을 분산시키고 원심분리를 통해 고체 생성물을 회수하는 세척단계를 포함하는 제조방법에 대한 것이다.According to a preferred embodiment of the present invention, (a) adjusting the concentration of a solution of TNT dissolved in tetrahydrofuran (THF) and methyl alcohol and an aqueous solution of sodium hypochlorite (NaClO), Preparing by cooling; (b) After starting the reaction by mixing the two cooled solutions, maintaining the temperature in a water bath for a certain period of time and maintaining pH and terminating the reaction using aqueous solutions of sulfuric acid and sodium hydroxide. ; and (c) a washing step of dispersing the reaction products in methyl alcohol, water, and acetone and recovering the solid product through centrifugation.
본 발명에 따른 HNS의 제조방법은 다음 단계를 포함할 수 있다.The method for producing HNS according to the present invention may include the following steps.
(a) 반응물 용해와 냉각단계(a) Reactant dissolution and cooling step
본 발명에 따른 HNS의 제조방법은 TNT을 THF과 메틸알코올에 녹인 용액(A)과 NaClO 수용액(B)의 농도를 조절하고 냉각시켜 준비하는 단계를 포함한다. The method for producing HNS according to the present invention includes preparing a solution of TNT in THF and methyl alcohol (A) and an aqueous NaClO solution (B) by adjusting the concentration and cooling.
본 발명은 TNT과 NaClO의 비율을 조절하는 단계를 수행한다.The present invention performs the step of adjusting the ratio of TNT and NaClO.
상기 TNT 대비 NaClO의 몰비율이 1~10, 바람직하게는 2~3배에서 수행할 수 있다. 1배 미만의 비율에서 수행할 경우에는 TNT이 한계반응물이 되어 생성물에 포함되어 HNS의 순도가 낮아지는 문제점이 있으며, 10배를 초과할 경우에는 차아염소산의 강한 염기성과 반응성으로 인해 HNS이 추가적인 반응을 일으켜 선택도가 낮아지는 문제점이 있다.It can be performed at a molar ratio of NaClO to TNT of 1 to 10, preferably 2 to 3 times. If the ratio is less than 1 times, there is a problem that TNT becomes a limiting reactant and is included in the product, lowering the purity of HNS. If the ratio is more than 10 times, HNS undergoes additional reaction due to the strong basicity and reactivity of hypochlorous acid. There is a problem that selectivity is lowered.
본 발명은 물의 양을 조절해 NaClO 수용액(B)의 농도를 조절할 수 있다.The present invention can control the concentration of the NaClO aqueous solution (B) by adjusting the amount of water.
상기 NaClO 수용액의 농도는 1~10중량%, 바람직하게는 5~7중량%일 수 있다.The concentration of the NaClO aqueous solution may be 1 to 10% by weight, preferably 5 to 7% by weight.
본 발명은 THF과 메틸알코올의 양과 비율을 조절해 TNT 용액(A)의 농도를 조절할 수 있다.In the present invention, the concentration of the TNT solution (A) can be adjusted by adjusting the amount and ratio of THF and methyl alcohol.
상기 상기 (a) 단계의 TNT 용액의 용매인 THF와 메틸알코올의 양(부피)은 NaClO 수용액의 0.5~5배의 부피를 가질 수 있고, 바람직하게는 1~2배의 부피에서 수행할 수 있다.The amount (volume) of THF and methyl alcohol, which are solvents of the TNT solution in step (a), may be 0.5 to 5 times the volume of the NaClO aqueous solution, and preferably 1 to 2 times the volume. .
상기 THF와 메틸알코올의 용매의 비율은 THF 대비 메틸알코올의 부피비율이 0 초과 2 이하의 배수, 바람직하게는 0.25~0.75배에서 수행할 수 있다.The ratio of the solvent between THF and methyl alcohol can be performed when the volume ratio of methyl alcohol to THF is a multiple of 0 and 2 or less, preferably 0.25 to 0.75 times.
본 발명은 TNT을 THF과 메틸알코올에 녹인 용액(A)과 NaClO 수용액(B)을 냉각하는 단계를 수행한다.The present invention carries out the step of cooling a solution of TNT dissolved in THF and methyl alcohol (A) and an aqueous NaClO solution (B).
상기 냉각온도는 -10~10℃, 바람직하게는 -5~5℃에서 수행할 수 있다. 영하 -10℃ 미만의 온도까지 냉각할 경우에는, NaClO 수용액의 어는점보다 낮아져 반응물끼리 혼합하는데 문제가 생기며, 10℃를 초과하는 경우에는 정반응이 발열반응이기 때문에 부산물의 비율이 높아져 수득률이 낮아지고 순도 또한 낮아지는 문제점이 있다. The cooling temperature may be -10 to 10°C, preferably -5 to 5°C. When cooled to a temperature below -10℃, the freezing point of the NaClO aqueous solution becomes lower and problems arise in mixing the reactants. When the temperature exceeds 10℃, the proportion of by-products increases because the forward reaction is exothermic, lowering the yield and purity. There is also a problem of it being lowered.
(b) 일정온도와 pH 조절을 통한 반응진행 단계(b) Reaction progress step through constant temperature and pH control
본 발명에 따른 HNS의 제조방법은 냉각된 두 용액을 혼합해 반응을 시작한 후, 일정 시간 동안 수조에서 온도를 유지시킴과 동시에 황산과 수산화나트륨 수용액을 이용해 pH를 유지 및 반응을 종결시키는 단계를 포함한다. The method for producing HNS according to the present invention includes the steps of mixing two cooled solutions to start the reaction, maintaining the temperature in a water bath for a certain period of time, maintaining pH using aqueous solutions of sulfuric acid and sodium hydroxide, and terminating the reaction. do.
본 발명은 반응중인 혼합용액의 pH를 일정 시간 동안 유지하는 단계를 수행한다.The present invention performs the step of maintaining the pH of the reacting mixed solution for a certain period of time.
상기 유지시키는 pH의 값은 9~12, 바람직하게는 10~11에서 수행할 수 있다.The pH value maintained may be 9 to 12, preferably 10 to 11.
상기 pH 유지에 사용되는 황산 수용액의 농도는 10~50중량%, 바람직하게는 20~30중량%에서 수행할 수 있다. 또한, 수산화나트륨 수용액의 농도는 1~10중량%, 바람직하게는 4~6중량%에서 수행할 수 있다. 농도가 낮으면 pH 조절을 위해 사용되는 수용액에 의해 첨가되는 물의 양이 많아져 반응의 평형이 깨져서 불순물이 많아질 수 있으며, 농도가 높을 경우에는 pH의 조절이 힘들어 반응 중 pH 값이 요동치게 되어 불순물이 생길 수 있다.The concentration of the aqueous sulfuric acid solution used to maintain the pH may be 10 to 50% by weight, preferably 20 to 30% by weight. In addition, the concentration of the sodium hydroxide aqueous solution can be 1 to 10% by weight, preferably 4 to 6% by weight. If the concentration is low, the amount of water added by the aqueous solution used to adjust the pH may increase, which may break the equilibrium of the reaction and increase the number of impurities. If the concentration is high, it may be difficult to control the pH, causing the pH value to fluctuate during the reaction. Impurities may occur.
상기 (b) 단계의 pH 유지는 냉각된 TNT 용액과 NaClO 용액을 첨가한 후 50초 내지 1분 30초, 바람직하게는 60초가 경과한 다음 pH 10.5가 될 때까지 산성 수용액을 적가하고, pH 10.0가 아래로 떨어지면 염기성 수용액을 적가하여 pH 10.5를 유지하는 단계에 의해 수행될 수 있다. 여기서, 상기 산성 수용액은 10~50중량%의 황산 수용액이고, 상기 염기성 수용액은 1~10중량%의 수산화나트륨 수용액일 수 있다.The pH in step (b) is maintained by dropping the acidic aqueous solution until pH 10.5 after 50 seconds to 1 minute and 30 seconds, preferably 60 seconds, after adding the cooled TNT solution and NaClO solution, and then pH 10.0. When it falls below, it can be performed by adding a basic aqueous solution dropwise to maintain pH 10.5. Here, the acidic aqueous solution may be a 10 to 50% by weight aqueous sulfuric acid solution, and the basic aqueous solution may be a 1 to 10% by weight aqueous sodium hydroxide solution.
상기 반응 시간은 0.5~12시간, 바람직하게는 0.5~10시간, 더욱 바람직하게는 1~2시간에서 수행할 수 있다.The reaction time may be 0.5 to 12 hours, preferably 0.5 to 10 hours, and more preferably 1 to 2 hours.
본 발병은 반응중인 혼합용액의 pH를 낮춰서 반응을 종결시키는 단계를 수행한다.In this outbreak, a step is performed to terminate the reaction by lowering the pH of the reacting mixed solution.
상기 반응을 종결시키는 pH 값은 3~7, 바람직하게는 4~7, 더욱 바람직하게는 6~7, 가장 바람직하게는 6.5에서 수행할 수 있다. The pH value for terminating the reaction may be 3 to 7, preferably 4 to 7, more preferably 6 to 7, and most preferably 6.5.
(c) 분리정제 단계(c) Separation and purification step
본 발명에 따른 HNS의 제조방법은 메틸알코올, 물 및 아세톤으로 구성된 군에서 선택되는 2종의 혼합물에 반응의 생성물들을 분산시키고 원심분리를 통해 고체 생성물을 회수하는 세척단계를 포함한다.The method for producing HNS according to the present invention includes a washing step of dispersing the reaction products in a mixture of two types selected from the group consisting of methyl alcohol, water and acetone and recovering the solid product through centrifugation.
본 발명은 반응이 종결된 용액에 메틸알코올, 물 및 아세톤으로 구성된 군에서 선택되는 2종의 혼합물을 이용해 희석하는 단계를 수행한다.The present invention performs the step of diluting the solution in which the reaction has been completed using a mixture of two types selected from the group consisting of methyl alcohol, water, and acetone.
상기 물과 메틸알코올의 비율은 물의 부피 대비 메틸알코올의 부피비가 1~10배, 바람직하게는 4~7배에서 수행할 수 있다.The ratio of water and methyl alcohol can be performed at a volume ratio of 1 to 10 times the volume of methyl alcohol to the volume of water, preferably 4 to 7 times.
상기 물과 메틸알코올의 혼합용액의 양은 반응이 종결된 혼합용액의 부피대비 2~20배, 바람직하게는 5~10배에서 수행할 수 있다.The amount of the mixed solution of water and methyl alcohol may be 2 to 20 times, preferably 5 to 10 times, the volume of the mixed solution in which the reaction is completed.
본 발명은 원심분리를 이용해 HNS을 분리해내는 단계를 수행한다.The present invention performs the step of separating HNS using centrifugation.
상기 원심분리의 회전속도는 5000~12000rpm, 바람직하게는 8000~1000rpm에서 수행할 수 있다.The centrifugation can be performed at a rotation speed of 5000 to 12000 rpm, preferably 8000 to 1000 rpm.
상기 원심분리의 동작시간은 5~30분, 바람직하게는 10~20분에서 수행할 수 있다.The centrifugation operation time can be 5 to 30 minutes, preferably 10 to 20 minutes.
본 발명은 원심분리 후 상층액을 버린 침천물을 물과 메틸알코올의 혼합용액, 메틸알코올과 아세톤의 혼합용액 또는 아세톤과 물의 혼합용액에 분산시키는 단계를 포함한다.The present invention includes the step of dispersing the sediment from which the supernatant was discarded after centrifugation in a mixed solution of water and methyl alcohol, a mixed solution of methyl alcohol and acetone, or a mixed solution of acetone and water.
상기 물과 메틸알코올의 비율은 물의 부피 대비 메틸알코올의 부피비가 1~10배, 바람직하게는 4~7배일 수 있다.The ratio of water and methyl alcohol may be 1 to 10 times the volume ratio of methyl alcohol to the volume of water, preferably 4 to 7 times.
상기 물과 메틸알코올의 혼합용액의 양은 10~100mL, 바람직하게는 30~50mL일 수 있다.The amount of the mixed solution of water and methyl alcohol may be 10 to 100 mL, preferably 30 to 50 mL.
상기 물과 메틸알코올의 혼합용액에 분산시키고 원심분리를 통해 상층액을 버리는 횟수는 1~10회, 바람직하게는 2~4회일 수 있다.The number of times the mixture is dispersed in the mixed solution of water and methyl alcohol and the supernatant is discarded through centrifugation may be 1 to 10 times, preferably 2 to 4 times.
상기 메틸알코올과 아세톤의 비율은 메틸알코올의 부피 대비 아세톤의 부피비가 1~10배, 바람직하게는 4~7배일 수 있다.The ratio of methyl alcohol to acetone may be 1 to 10 times the volume ratio of acetone to the volume of methyl alcohol, preferably 4 to 7 times.
상기 메틸알코올과 아세톤의 혼합용액의 양은 10~100mL, 바람직하게는 30~50mL일 수 있다.The amount of the mixed solution of methyl alcohol and acetone may be 10 to 100 mL, preferably 30 to 50 mL.
상기 메틸알코올과 아세톤의 혼합용액에 분산시키고 원심분리를 통해 상층액을 버리는 횟수는 1~10회, 바람직하게는 2~4회일 수 있다.The number of times of dispersing in the mixed solution of methyl alcohol and acetone and discarding the supernatant through centrifugation may be 1 to 10 times, preferably 2 to 4 times.
상기 물과 아세톤의 비율은 아세톤의 부피 대비 물의 부피비가 1~10배, 바람직하게는 4~7배일 수 있다.The ratio of water and acetone may be 1 to 10 times the volume ratio of water to the volume of acetone, preferably 4 to 7 times.
상기 물과 아세톤의 혼합용액의 양은 10~100mL, 바람직하게는 30~50mL일 수 있다.The amount of the mixed solution of water and acetone may be 10 to 100 mL, preferably 30 to 50 mL.
상기 물과 아세톤의 혼합용액에 분산시키고 원심분리를 통해 상층액을 버리는 횟수는 1~10회, 바람직하게는 2~4회일 수 있다.The number of times the supernatant is dispersed in the mixed solution of water and acetone and the supernatant is discarded through centrifugation may be 1 to 10 times, preferably 2 to 4 times.
본 발명은 원심분리를 이용한 세척이 끝난 후 침전물을 용매를 이용해 회수하고 용매를 증발시켜 고체의 HNS을 회수하는 단계를 포함한다.The present invention includes the step of recovering the precipitate using a solvent after washing using centrifugation and evaporating the solvent to recover solid HNS.
상기 용매는 물, 메틸알코올, 아세톤을 이용하여 수행할 수 있다.The solvent may be water, methyl alcohol, or acetone.
상기 용매를 증발시키기 위한 온도는 30~100℃, 바람직하게는 50~70℃에서 수행할 수 있다.The temperature for evaporating the solvent may be 30 to 100°C, preferably 50 to 70°C.
HNS은 비표면적, 불순물 함유량 같은 조건에 따라 타입 I(HNS I), 타입 II(HNS II), 타입 IV(HNS IV)로 분류되는데, 본 발명의 제조방법을 통해 제조된 HNS은 타입 I이지만 높은 순도를 가지고 있어 활용도가 높은 HNS 타입 IV로의 전환을 효율적으로 실시할 수 있다.HNS is classified into Type I (HNS I), Type II (HNS II), and Type IV (HNS IV) depending on conditions such as specific surface area and impurity content. HNS produced through the production method of the present invention is Type I, but has a high Because of its purity, conversion to HNS type IV, which is highly usable, can be carried out efficiently.
또한 본 발명은 다른 관점에서, 상기 방법에 따라 HNS을 제조할 수 있는 반응기에 관한 것이다. 도 1을 참고하면, pH 미터 및 온도계(1), 튜브(2), 수조(3), 자기 교반 막대(4), 자기교반기(5)로 구성된다.Additionally, from another aspect, the present invention relates to a reactor capable of producing HNS according to the above method. Referring to Figure 1, it consists of a pH meter and thermometer (1), a tube (2), a water tank (3), a magnetic stirring bar (4), and a magnetic stirrer (5).
상기 튜브(2)는 반응용액의 양에 따라 단면적을 조절하여 일정한 높이를 맞춰준다.The tube 2 adjusts its cross-sectional area according to the amount of reaction solution to maintain a constant height.
상기 높이는 바람직하게는 pH 미터가 자기교반막대와 닿지 않으면서 pH 미터의 검출부가 충분히 잠길 정도의 높이부터 온도유지를 위한 수조의 높이까지의 조건에서 수행할 수 있다.The height can preferably be adjusted under conditions ranging from a height at which the detection part of the pH meter is sufficiently submerged without the pH meter contacting the magnetic stirring bar to the height of a water tank for temperature maintenance.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as limited by these examples.
[실시예][Example]
실시예 1: 반응물 용해와 냉각단계Example 1: Reactant dissolution and cooling step
2,4,6-트라이나이트로톨루엔(2,4,6-trinitrotoluene, TNT)을 테트라하이드로퓨란(tetrahydrofuran, THF)과 메틸알코올에 녹인 용액과 차아염소산 나트륨(sodium hypochlorite, NaClO)을 물에 녹인 수용액을 준비해 냉각하였다. A solution of 2,4,6-trinitrotoluene (TNT) dissolved in tetrahydrofuran (THF) and methyl alcohol and sodium hypochlorite (NaClO) dissolved in water. An aqueous solution was prepared and cooled.
TNT 0.165 g에 THF 2 mL를 넣고 메틸알코올 1 mL를 추가로 넣어 충분히 용해시켰다. NaClO 용액이 5.9%가 되도록 물로 희석한 용액 2 mL를 TNT 용액과 함께 얼음이 든 수조에 넣어 5℃로 냉각시켰다.2 mL of THF was added to 0.165 g of TNT and an additional 1 mL of methyl alcohol was added to sufficiently dissolve it. 2 mL of the NaClO solution diluted with water to 5.9% was placed in an ice water bath together with the TNT solution and cooled to 5°C.
실시예 2: 반응후 pH 유지와 pH 조절을 통한 반응의 중단Example 2: Maintenance of pH after reaction and cessation of reaction through pH adjustment
실시예 1에서 냉각되어 준비된 용액을 혼합해 2,2´,4,4´,6,6´-헥사나이트로스틸벤(2,2´,4,4´,6,6´-hexanitrostilbene, HNS) 합성 반응을 시작하고 pH를 조절하여 HNS이 포함된 혼합용액을 수득하였다.The cooled solution prepared in Example 1 was mixed to produce 2,2´,4,4´,6,6´-hexanitrostilbene (2,2´,4,4´,6,6´-hexanitrostilbene, HNS). ) The synthesis reaction was started and the pH was adjusted to obtain a mixed solution containing HNS.
이하 도 2를 참조로 HNS 합성 반응을 다음과 같이 수행하였다.With reference to FIG. 2 below, the HNS synthesis reaction was performed as follows.
실시예 1에서 준비된 용액들을 자기교반 막대가 교반 중인 반응기에 넣고 혼합한 직후 급격한 발열반응을 하는 60초 가량 그대로 기다린 후, 25% 황산수용액을 이용하여 pH를 10.5로 떨어뜨려 주었다. 수조는 15℃를 유지하도록 하였다. 이후 2시간 동안 pH가 10.0 아래로 떨어질 때마다 6%의 수산화나트륨 수용액을 넣어 pH가 10.5가 넘지 않는 선에서 pH를 올려주었다. 반응을 시작한지 2시간이 지난 시점에서 25% 황산수용액을 이용하여 pH를 6.5로 낮춰주고 pH 미터와 자기교반 막대를 반응기에서 제거하여 HNS이 포함된 혼합용액을 수득하였다.The solutions prepared in Example 1 were placed in a reactor being stirred by a magnetic stirring bar and mixed. After waiting for about 60 seconds for a rapid exothermic reaction, the pH was lowered to 10.5 using a 25% aqueous sulfuric acid solution. The water tank was maintained at 15°C. Over the next 2 hours, whenever the pH fell below 10.0, 6% sodium hydroxide solution was added to raise the pH so that it did not exceed 10.5. Two hours after starting the reaction, the pH was lowered to 6.5 using a 25% aqueous sulfuric acid solution, and the pH meter and magnetic stirring bar were removed from the reactor to obtain a mixed solution containing HNS.
실시예 3: 분리정제단계Example 3: Separation and purification step
실시예 2에서 수득한 HNS이 포함된 혼합용액에서 HNS을 원심분리를 이용해 분리하고 회수하였다.HNS was separated and recovered from the mixed solution containing HNS obtained in Example 2 using centrifugation.
실시예 2에서 수득한 혼합용액을 50mL 코니칼 튜브에 옮겨 담은 후, 물 5mL, 메틸알코올 30mL를 넣어 고상의 생성물들을 분산시켜 준비하였다. 준비된 용액을 원심분리기를 이용하여 10000rpm에서 10분간 분리시켜주고, 상층액을 제거하여 첫 번째 침전물을 수득하였다. 이후 물 10mL와 메틸알코올 30mL를 넣고 흔들어서 다시 분산시키고 같은 조건으로 원심분리하여 분리하는 단계를 4번 수행하였다. 다음으로는 물 10mL 와 아세톤 30mL를 넣고 흔들어 분산시키고 같은 조건으로 원심분리하여 분리하는 단계를 2번 수행하였다. 마지막으로 수득한 침전물을 메틸알코올을 이용하여 비커로 옮긴 후, 60℃에서 용매를 증발시켜 HNS을 수득하였다.The mixed solution obtained in Example 2 was transferred to a 50 mL conical tube, and then 5 mL of water and 30 mL of methyl alcohol were added to disperse the solid products. The prepared solution was separated at 10000 rpm for 10 minutes using a centrifuge, and the supernatant was removed to obtain the first precipitate. Afterwards, 10 mL of water and 30 mL of methyl alcohol were added, shaken to disperse again, and separation by centrifugation under the same conditions was performed four times. Next, 10 mL of water and 30 mL of acetone were added, shaken to disperse, and separation by centrifugation under the same conditions was performed twice. Finally, the obtained precipitate was transferred to a beaker using methyl alcohol, and the solvent was evaporated at 60°C to obtain HNS.
실시예 4: 생성물의 정량분석 Example 4: Quantitative analysis of product
본 실시예에서는 실시예 3에서 수득한 고체의 HNS을 1H-NMR 분석을 이용하여 정량, 정성분석을 진행하였다.In this example, the solid HNS obtained in Example 3 was subjected to quantitative and qualitative analysis using 1 H-NMR analysis.
수득한 HNS을 소량 덜어내어 디메틸설폭사이드-d6에 녹이고 상온에서 1H-NMR분석을 수행하였다.A small amount of the obtained HNS was dissolved in dimethyl sulfoxide-d6 and 1 H-NMR analysis was performed at room temperature.
도 3은 실시예 3에서 수득한 HNS을 1H-NMR 분석한 자료를 나타낸 것으로, [수학식 1]을 이용하여 계산한 결과 수득한 생성물은 99.67%의 질량비를 가진 HNS임을 확인하였다.Figure 3 shows 1 H-NMR analysis data of HNS obtained in Example 3. As a result of calculation using [Equation 1], it was confirmed that the obtained product was HNS with a mass ratio of 99.67%.
[수학식 1][Equation 1]
실시예 5: 실험규모의 확대 결과Example 5: Results of expansion of experimental scale
실시예 1 내지 4의 과정 중 실시예 1의 반응 전 준비단계의 규모를 3배 증가시킨 조건으로 실험을 수행한 것을 제외하고는 실시예 1 내지 4의 과정을 동일하게 실시하였으며, 그 1H-NMR 결과를 분석하였다.The processes of Examples 1 to 4 were carried out in the same manner as in Examples 1 to 4, except that the experiment was conducted under conditions in which the scale of the pre-reaction preparation step of Example 1 was increased by 3 times. NMR results were analyzed.
TNT 0.495 g에 THF 6 mL를 넣고 메틸알코올 3 mL를 추가로 넣어 충분히 용해시켰다. NaClO 용액이 5.9% 가 되도록 물로 희석한 용액을 6 mL를 TNT 용액과 함께 냉동실에 넣어 0℃로 냉각시킨다. 이후의 실험은 실시예 2~4의 과정과 동일하게 수행하였다.6 mL of THF was added to 0.495 g of TNT and an additional 3 mL of methyl alcohol was added to sufficiently dissolve it. Dilute the NaClO solution with water to 5.9%, place 6 mL of the solution in the freezer together with the TNT solution, and cool to 0°C. The subsequent experiments were performed in the same manner as in Examples 2 to 4.
도 4는 상기의 실험으로 수득한 HNS을 1H-NMR 분석한 자료를 나타낸 것으로, [수학식 1]을 이용하여 계산한 결과 수득한 생성물은 99.99%의 순도를 가진 HNS임을 확인하였다.Figure 4 shows 1 H-NMR analysis data of HNS obtained through the above experiment. As a result of calculation using [Equation 1], it was confirmed that the obtained product was HNS with a purity of 99.99%.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. will be. Accordingly, the actual scope of the present invention will be defined by the claims and their equivalents.
Claims (12)
(a) 2,4,6-트라이나이트로톨루엔(2,4,6-trinitrotoluene, TNT)을 테트라하이드로퓨란(tetrahydrofuran, THF)과 메틸알코올에 용해시킨 용액과 NaClO 수용액을 -10 ~ -5℃의 온도로 냉각시키는 단계;
(b) 냉각된 TNT 용액과 NaClO 수용액을 혼합하여 일정시간 동안 온도와 pH를 유지하면서 반응시킨 다음, 반응을 종결시키는 단계로서, 상기 pH를 9 내지 12를 유지하되, 냉각된 TNT 용액과 NaClO 용액을 첨가한 후 50초 내지 1분 30초가 경과한 다음 pH 10.5가 될 때까지 산성 수용액을 적가하고, pH 10.0가 아래로 떨어지면 염기성 수용액을 적가하여 pH 10.5를 유지하는 단계; 및
(c) 메틸알코올, 물 및 아세톤으로 구성된 군에서 선택되는 2종의 혼합물을 첨가하여 반응이 종결된 혼합용액을 분산시키고 원심분리시켜 고체 생성물을 회수하는 단계.
Method for preparing 2,2',4,4',6,6'-hexanitrostilbene comprising the following steps:
(a) A solution of 2,4,6-trinitrotoluene (TNT) dissolved in tetrahydrofuran (THF) and methyl alcohol and an aqueous NaClO solution at -10 to -5℃. Cooling to a temperature of;
(b) A step of mixing the cooled TNT solution and the NaClO aqueous solution to react while maintaining the temperature and pH for a certain period of time, and then terminating the reaction, maintaining the pH at 9 to 12, and mixing the cooled TNT solution and the NaClO solution After 50 seconds to 1 minute and 30 seconds have passed, adding an acidic aqueous solution dropwise until the pH reaches 10.5, and maintaining pH 10.5 by adding a basic aqueous solution dropwise when the pH falls below 10.0; and
(c) adding two mixtures selected from the group consisting of methyl alcohol, water, and acetone to disperse the reaction-complete mixed solution and centrifuging to recover the solid product.
The preparation of 2,2´,4,4´,6,6´-hexanitrostilbene according to claim 1, wherein the molar ratio of NaClO in step (a) is 1 to 10 times that of the TNT. method.
The method for producing 2,2´,4,4´,6,6´-hexanitrostilbene according to claim 1, wherein the concentration of the NaClO aqueous solution in step (a) is 1 to 10% by weight. .
The method of claim 1, wherein the amount (volume) of THF and methyl alcohol, which are solvents of the TNT solution in step (a), is 0.5 to 5 times the volume of the NaClO aqueous solution. Method for producing 6,6´-hexanitrostilbene.
2,2',4,4',6,6'-hexanitrostilbene according to claim 1, wherein the volume ratio of THF:methyl alcohol in step (a) is greater than 1:0 and less than or equal to 2. Manufacturing method.
The method of claim 1, wherein step (b) is performed for 0.5 to 12 hours.
The method of claim 1, wherein the reaction in step (b) is completed at pH 3 to 7. .
The method of claim 1, wherein the centrifugation in step (c) is performed at 5000 to 12000 rpm.
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| US4270012A (en) | 1980-01-16 | 1981-05-26 | The United States Of America As Represented By The Secretary Of The Army | Preparation of HNS from HNBB using oxygen |
| SE468434B (en) * | 1987-01-21 | 1993-01-18 | Nobel Kemi Ab | PROCEDURE FOR PURIFICATION OF HNS (2,2 ', 4,4', 6,6'-HEXANITROSTILBEN) AND PREPARATION OF HNSII |
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