Promising CL‐20‐Based Energetic Material by Cocrystallization

A novel cocrystal (NEX‐1) of CL‐20 and MDNT is presented herein. The CL‐20: MDNT cocrystal, obtained in high yield by resonant acoustic mixing, shows new properties versus the discrete components. This is the first example of cocrystallization of CL‐20 where the new material is less sensitive to friction than CL‐20 itself, while demonstrating similar impact and ESD sensitivity. The CL‐20: MDNT cocrystal shows promise in the production of new energetic materials of interest by the cocrystallization of well‐characterized components.     

Preparation and Performance of a BTF/DNB Cocrystal Explosive

An energetic cocrystal containing benzotrifuroxan (BTF) and 1,3‐dinitrobenzene (DNB) in 1 : 1 molar ratio was prepared by slow evaporation of solvent. The structure of the cocrystal was determined by single crystal X‐ray diffraction (XRD). It belongs to the monoclinic crystal system with space group P2₁/c. The performance of the cocrystal was evaluated on the basis of thermolysis, impact sensitivity, and detonation properties. Differential scanning calorimetry (DSC) revealed that the cocrystal has a melting point of 130 °C, which is an increase of 38 °C compared to pure DNB; the decomposition temperature is similar to that of pure BTF. The cocrystal exhibits an impact height with 50 % ignition probability of 88 cm, suggesting a substantial reduction in impact sensitivity compared to pure BTF. Furthermore, the cocrystal is predicted to have a detonation velocity of about 7373 m s⁻¹ and a detonation pressure of about 24 GPa, respectively, indicating excellent detonation performance.     

布洛芬-烟酰胺共晶制备及其溶解度测定

采用乙醇-水混合溶剂,对布洛芬-烟酰胺共晶的溶液结晶法制备过程进行了研究,制备样品的PXRD和DSC表征结果证明了通过溶液结晶法大规模制备布洛芬 烟酰胺共晶的可行性。制备过程研究结果表明,当混合溶剂中乙醇与水的体积配比为1.82～7.11时,可以制备出布洛芬-烟酰胺共晶;而且随着乙醇与水体积配比的增大,共晶收率呈现先增大再减小的趋势,当体积配比为2.76时,共晶收率达到最大值(76.31%)。还在不同温度下测定了布洛芬-烟酰胺共晶在不同体积配比乙醇-水混合溶剂中的溶解度,结果表明随着温度和乙醇体积比例的升高,布洛芬-烟酰胺共晶的溶解度增大,最后用 Apelblat方程对溶解度数据进行拟合。     

茶碱、烟酰胺与异丙醇三元系统在298.15和308.15 K的相图研究

以茶碱、烟酰胺通过分子间氢键形成的共晶为例研究了共晶的热力学性质,测量了以异丙醇为溶剂茶碱 烟酰胺共晶在298.15和308.15 K 下的溶解度,同时测定了茶碱 烟酰胺共晶的溶度积（KSP）。通过对溶解度数据的分析表明茶碱 烟酰胺共晶在溶液中会形成1∶1的溶液络合,测定了溶液中共晶的溶度积及络合常数以及共晶组元对共晶溶解度的影响,同时考察了温度对溶度积和络合常数的影响。为了深入了解共晶在不同温度下的形成规律,绘制了在298.15和308.15 K茶碱 烟酰胺在异丙醇中的三元相图,分析了共晶的三元相图随温度的变化趋势,为药物共晶生产中目标产物的控制提供理论支持。     

Preparation and Performance of a HNIW/TNT Cocrystal Explosive

A novel cocrystal explosive composed of 2,4,6,8,10,12‐hexanitrohexaazaiso‐wurtzitane (HNIW) and 2,4,6‐trinitrotoluene (TNT) in a 1 : 1 molar ratio was effectively prepared by solvent/nonsolvent cocrystallization adopting dextrin as modified additive. The structure, thermal behavior, sensitivity, and detonation properties of HNIW/TNT cocrystal were studied. The morphology and structure of the cocrystal were characterized by scanning electron microscopy (SEM) and single crystal X‐ray diffraction (SXRD). SEM images showed that the cocrystal has a prism type morphology with an average size of 270 μm. SXRD revealed that the cocrystal crystallizes in the orthorhombic system, space group Pbca, and is formed by hydrogen bonding interactions. The properties of the cocrystal including sensitivity, thermal decomposition, and detonation performances were discussed in detail. Sensitivity studies showed that the cocrystal exhibits low impact and friction sensitivity, and largely reduces the mechanical sensitivity of HNIW. DSC and TG tests indicated that the heterogeneous exothermic decomposition of the cocrystal occurs in the temperature range from 170 °C to 265 °C with peak maxima at 220 °C and 250 °C and significantly increases the melting point of TNT by 54 °C. The cocrystal has excellent detonation properties with a detonation velocity of 8426 m s⁻¹ and a calculated detonation pressure of 32.3 MPa at a charge density of 1.76 g cm⁻³, respectively. Moreover, the results suggested that the HNIW/TNT cocrystal not only has unique performance itself, but also effectively alters the properties of TNT and HNIW. Therefore, the cocrystal formed by HNIW and TNT could provide a new and effective method to modify the properties of certain compounds to yield enhanced explosives for further application.     

Energetic Materials: Crystallization,Characterization and Insensitive Plastic Bonded Explosives

The product quality of energetic materials is predominantly determined by the crystallization process applied to produce these materials. It has been demonstrated in the past that the higher the product quality of the solid energetic ingredients, the less sensitive a plastic bonded explosive containing these energetic materials becomes. The application of submicron or nanometric energetic materials is generally considered to further decrease the sensitiveness of explosives. In order to assess the product quality of energetic materials, a range of analytical techniques is available. Recent attempts within the Reduced‐sensitivity RDX Round Robin (R4) have provided the EM community a better insight into these analytical techniques and in some cases a correlation between product quality and shock initiation of plastic bonded explosives containing (RS‐)RDX was identified, which would provide a possibility to discriminate between conventional and reduced sensitivity grades.     

An Energetic N‐Oxide and N‐Amino Heterocycle and its Transformation to 1,2,3,4‐Tetrazine‐1‐oxide

This study reports the preparation of 1‐amino‐1,2,3‐triazole‐3‐oxide (DPX2) and its transformation to 1,2,3,4‐tetrazine‐1‐oxide. DPX‐2 provides insight into a novel N‐oxide/N‐amino high‐nitrogen system, being the first energetic material in this class. The ability of this material to undergo a nitrene insertion forming 1,2,3,4‐tetrazine‐1‐oxide was also studied, and evidence for this material, the first non‐benzoannulated 1,2,3,4‐tetrazine‐1‐oxide, is presented. The existence of both of these materials opens new strategies in energetic materials design. DPX2 was characterized chemically (Infrared, Raman, NMR, X‐ray) and as a high explosive in terms of energetic performances (detonation velocity, pressure, etc.) and sensitivities (impact, friction, electrostatic). DPX‐2 was found to possess good thermal stability and moderate sensitivities, indicating the viability of N‐amino N‐oxides as a strategy for the preparation of new energetic materials.     

A Novel Cocrystal Explosive of HNIW with Good Comprehensive Properties

In order to improve the safety of the high explosive 2,4,6,8,10,12‐hexanitrohexaazaisowurtzitane (HNIW), we cocrystallized HNIW with the insensitive explosive DNB (1,3‐dinitrobenzene) in a molar ratio 1 : 1 to form a novel cocrystal explosive. Structure determination showed that it belongs to the orthorhombic system with space group Pbca. Therein, layers of DNB alternate with bilayers of HNIW. Analysis of interactions in the cocrystal indicated that the cocrystal is mainly formed by hydrogen bonds and nitro‐aromatic interactions. Moreover, the thermal behavior, sensitivity, and detonation properties of the cocrystal were evaluated. The results implied that the melting point of the cocrystal is 136.6 °C, which means an increase of 45 °C relative that of pure DNB. The predicted detonation velocity and detonation pressure of the cocrystal are 8434 m s⁻¹ and 34 GPa, respectively, which are similar to that of the reported HNIW/TNT cocrystal, but its reduced sensitivity (H₅₀=55 cm) makes it an attractive ingredient in HNIW propellant formulations.     

Low Risk Synthesis of Energetic Poly(3‐Azidomethyl‐3‐Methyl Oxetane) from Tosylated Precursors

Azidated oxetanic polymers such as poly(3‐azidomethyl‐3‐methyl oxetane), are under investigation as “energetic” binder to be used as an alternative to polybutadiene in solid rocket propellants. The classic synthetic route for the production of the polymer is through an azidated monomer where the N₃⁻ functionality has been previously introduced by nucleophilic displacement of a suitable, usually a halogen, leaving group. However, this could involve critical steps with manipulation of a highly unstable liquid monomer. Here it is shown that the azidation can be performed as the final step of the preparation by substitution of the tosyl group in a preformed polymer. The procedure assures good yield and purity of the product and satisfactory rate of reaction, being the energetic functionality always kept in a safe form, which shows low shock and friction sensitivity. Poly(3‐azidomethyl‐3‐methyl oxetane) was prepared by azidation of poly(3‐tosyloxymethyl‐3‐methyl oxetane) in dimethylsulfoxide, testing several operating conditions. Moreover, hypothesizing a second order kinetics, the rate constant and the activation energy for the azidation step have been estimated.     

一种新型卡马西平共晶的合成及表征

以卡马西平（CBZ）作为药物活性成分（API）,以没食子酸甲酯（MTG）作为共晶形成物（CCF）,在室温条件下制得一种新的药物共晶CBZ-MTG。通过X-射线单晶衍射测得了其晶体结构,并进行了红外光谱、X-射线粉末衍射、热重分析和差示扫描量热的表征。此外,利用HPLC测得其溶解性质并测试了稳定性,其共晶在溶解性,稳定性和生物利用度上都有了明显的改观。各种结构性质的表征,为其在药物领域的应用提供了基础数据和理论基础,为卡马西平-没食子酸甲酯共晶化合物作为药物应用及在制剂领域提供了新的选择。     

Structure and Properties of Cocrystals of Phenazine and Fumaric‐, 2,3‐Dihydroxyfumaric‐, and Oxalic Acid

Phenazine and the dicarboxylic acids fumaric‐, 2,3‐ dihydroxyfumaric‐, and oxalic acid form 1 : 1 cocrystals. X‐ray analysis shows that the molecules are arranged as linear tapes, mainly held together by strong O‐H…︁N and weak C(sp ²)‐H…︁O hydrogen bonds. Individual molecules form staples which are surrounded by staples of the other molecules. The angle between neighbouring tapes varies from ca. 90° in the cocrystal of phenazine and fumaric acid to ca. 70° in the co‐crystal of phenazine and 2,3‐dihydroxyfumaric acid, and ca. 25° in the cocrystal of phenazine and oxalic acid. The molecules assume an offset face‐to‐face arrangement in individual phenazine staples. Negligible π‐stacking is observed in the cocrystals of phenazine with fumaric‐ and 2,3‐dihydroxyfumaric acid. The absence of the CC double bond as spacer in oxalic acid leads to appreciable π‐overlap of phenazine molecules in the cocrystal. As a consequence, the latter cocrystal displays special properties. An irreversible lightinduced electron transfer generates initially singlet and triplet biradicals with the unpaired electrons positioned on neighbouring phenazine molecules. Partially, the electrons are transformed to magnetically independent electrons which show strong exchange narrowing in the e.p.r. spectrum at temperatures > 0 °C. The proposed model is supported by UV/Vis‐e. s.r.‐, and SQUID measurements.     

共结晶分离技术研究进展

使用共结晶技术分离有机小分子,特别是一些不能成盐的、高纯度要求的原料药(API)的分离是晶体工程应用的前沿。其原理是通过分子间的识别作用形成共晶,改变目标分子的晶格能或溶解特性,从而实现分离。针对共结晶在分离中的应用,本文从共结晶分离的热力学原理出发,系统综述了共结晶在分离纯化非手性分子以及手性API及中间体中的实例。从分子结构、分子间的相互作用力、溶度积常数、溶剂体系等不同角度对分离实例进行分析。针对该技术现存的问题如共晶形成物的选择缺乏规律性,实际API纯化体系的复杂性,共晶形成物回收利用的可行性,指出建立系统的共晶形成物选择方法、深入地研究热力学行为是未来的主要研究方向。     

Effects of rosin‐type nucleating agent on polypropylene crystallization

In this investigation the effects of a rosin‐type nucleating agent, which was prepared from cocrystallizing of dehydroabietic acid and Na‐dehydroabietate, on polypropylene (PP) crystallization were studied. The results of differential scanning calorimetry and X‐ray diffraction proved that a cocrystal of dehydroabietic acid and Na‐dehydroabietate was formed. The lower melting point of the cocrystal caused it to be uniformly dispersed in PP. When cocrystals were added as nucleating agent, the mechanical properties, heat distortion temperature, and crystallization temperatures of PP were obviously improved, and the size of spherulites was also decreased. This proved that the cocrystals of dehydroabietic acid and Na‐dehydroabietate could act as an effective nucleating agent for PP. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1069–1073, 2002     

柠檬酸处理对FCC干气与苯烷基化催化剂的影响

采用ZSM-5/ZSM-11共结晶分子筛催化剂,在固定床反应装置上对催化裂化干气与苯制乙苯进行考察。 NH₃-TPD结果表明,随着水热处理条件的苛刻, 催化剂的酸量和酸强度均下降, 虽然这些催化剂上干气中乙烯转化率变化不明显, 但产物中二甲苯含量大幅度下降。 柠檬酸对分子筛催化剂进行改性处理后, 可明显降低催化裂化干气与苯制乙苯中二甲苯杂质含量, 原因可能为催化剂大的比表面积和孔容改善了原料的传质能力, 从而抑制了二甲苯的生成。     

应用于固体推进剂的石墨烯及其复合材料制备技术研究进展

系统介绍了多种石墨烯的制备、改性和复合方法,制备方法主要有机械剥离和湿法剥离,改性方法主要有非共价改性和共价改性,复合方法主要有非原位合成和原位合成。从石墨烯在固体推进剂中应用的角度分析比较了不同制备方法的优缺点,指出今后用作燃烧催化剂的石墨烯及其复合材料的制备技术重点应集中在如下几方面:(1)将微乳液法等纳米材料制备方法应用于石墨烯复合材料制备中;(2)应加强负载有机金属盐和含能催化剂的石墨烯负载型燃烧催化剂的研究;(3)开展石墨烯负载物的晶体生长研究。附参考文献57篇。     

不同组分比的HMX/DMI共晶炸药结构与性质的理论研究

利用分子动力学,研究了分子摩尔比对HMX/DMI共晶炸药几个重要晶面成键能的影响,对于不同分子的摩尔比的力学性质也进行了估算,借助M06-2x/6-311+G(2df,2p)方法对HMX/DMI复合物的溶剂效应也进行了研究。计算结果表明,(020)和(100)取代基模型具有最高的成键能和稳定性,1∶1和2∶1的化合物最稳定且具有最高的力学性能。分子间相互作用能和N–NO_2键离解能的变化对HMX/DMI共晶炸药的稳定性有较大影响。制备稳定的HMX/DMI共晶炸药应选用较低介电常数作溶剂。     

Effects of rosin‐type cocrystal nucleating agents on the crystallization process and the properties of polypropylene

A new kind of rosin‐type nucleating agent for polypropylene (PP), the cocrystal of dehydroabietic acid, potassium dehydroabietate, and sodium dehydroabietate, was prepared, and the effects of the nucleating agents on the mechanical and crystallization properties of PP were also studied. The results of differential scanning calorimetry and X‐ray diffraction proved that the cocrystal of dehydroabietic acid and compound alkali dehydroabietate was formed rather than a simple blend of dehydroabietic acid and single alkali dehydroabietate. When it was added to PP, the size of the PP spherulite decreased; the mechanical properties, crystallization temperature, and transparency of PP were substantially improved. Thus, the cocrystal of dehydroabietic acid, potassium dehydroabietate, and sodium dehydroabietate acted as a more effective nucleating agent for PP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2137–2141, 2003     

Fabrication of CL-20/HMX Cocrystal@Melamine–Formaldehyde Resin Core–Shell Composites Featuring Enhanced Thermal and Safety Performance via In Situ Polymerization

Safety concerns remain a bottleneck for the application of 2,4,6,8,10,12-hexanitro- 2,4,6,8,10,12-hexaazaisowurtzitane (CL-20)/1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) cocrystal. Melamine–formaldehyde (MF) resin was chosen to fabricate CL-20/HMX cocrystal-based core–shell composites (CH@MF composites) via a facile in situ polymerization method. The resulted CH@MF composites were comprehensively characterized, and a compact core–shell structure was confirmed. The effects of the shell content on the properties of the composites were explored as well. As a result, we found that, except for CH@MF–2 with a 1% shell content, the increase in shell content led to a rougher surface morphology and more close-packed structure. The thermal decomposition peak temperature improved by 5.3 °C for the cocrystal enabled in 1.0 wt% MF resin. Regarding the sensitivity, the CH@MF composites exhibited a significantly reduced impact and friction sensitivity with negligible energy loss compared with the raw cocrystal and physical mixtures due to the cushioning and insulation effects of the MF coating. The formation mechanism of the core–shell micro-composites was further clarified. Overall, this work provides a green, facile and industrially potential strategy for the desensitization of energetic cocrystals. The CH@MF composites with high thermal stability and low sensitivity are promising to be applied in propellants and polymer-bonded explosive (PBX) formulations.     

Amphiphilic block copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene: synthesis and self‐assembly

The triblock energetic copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene (PLA‐b‐GAP‐b‐PS) was synthesized successfully through atom‐transfer radical polymerization (ATRP) of styrene and ring‐opening polymerization of d,l ‐lactide. The energetic macroinitiator GAP‐Br, which was made from reacting equimolar GAP with α‐bromoisobutyryl bromide, firstly triggered the ATRP of styrene with its bromide group, and then the hydroxyl group on the GAP end of the resulting diblock copolymer participated in the polymerization of lactide in the presence of stannous octoate. The triblock copolymer PLA‐b‐GAP‐b‐PS had a narrow distribution of molecular weight. In the copolymer, the PS block was solvophilic in toluene and improved the stability of the structure, the PLA block was solvophobic in toluene and served as the sacrificial component for the preparation of porous materials, and GAP was the basic and energetic material. The three blocks of the copolymer were fundamentally thermodynamically immiscible, which led to the self‐assembly of the block copolymer in solution. Further studies showed that the concentration and solubility of the copolymer and the polarity of the solvent affected the morphology and size of the micelles generated from the self‐assembly of PLA‐b‐GAP‐b‐PS. The micelles generated in organic solvents at 10 mg mL^?1 copolymer concentration were spherical but became irregular when water was used as a co‐solvent. The spherical micelles self‐assembled in toluene had three distinct layers, with the diameter of the micelles increasing from 60 to 250 nm as the concentration of the copolymer increased from 5 to 15 mg L^?1. © 2017 Society of Chemical Industry     

Synthesis,molecular dynamic simulation,and density functional theory insight into the cocrystal explosive of 2,4,6-trinitrotoluene/1,3,5-trinitrobenzene

This paper reports the experimental and theoretical studies of the synthesis and behavior of a cocrystal energetic material 2,4,6-trinitrotoluene/1,3,5-trinitrobenzene (TNT/TNB). The performance tests show that this material is more powerful and less sensitive than TNT and TNB. A molecular dynamic simulation is conducted for the cocrystal TNT/TNB by using a COMPASS force field with an NPT ensemble. The density function theory is applied to investigate the band structure and the density of states for various pressures and temperatures. The results show that the TNT/TNB crystal is sensitive to pressures in the interval of 35–50 GPa, and the melting temperature of the crystal is around ≈320 K, which agrees well with experimental results. The Hirshfeld analysis is carried out to ascertain weak interactions and associated two-dimensional fingerprint plots. The crystal packing is demonstrated to be ensured by H· · · O, C· · · O, and O· · ·O contacts.