六(乙氧基吡咯烷酮)三聚磷腈的合成与表征

以N-羟乙基吡咯烷酮与氢化钠作用生成相应的钠盐,再将此钠盐与六氯三聚磷腈(HCCP)发生亲核取代反应,合成了六(乙氧基吡咯烷酮)三聚磷腈,用IR、31P NMR、1H NMR、13C NMR、DEPT、FABMS等现代谱学技术对其结构进行了表征。生物活性试验表明,此化合物1mg/mL时对腐生线虫Panagrellus redivivus的72h致死率为52·7%。     

六(甲氧基乙氧基乙氧基)三聚磷腈的合成与表征

以六氯三聚磷腈和甲氧基乙氧基乙醇为主要原料,合成了全取代的六(甲氧基乙氧基乙氧基)三聚磷腈,并用IR、31P NMR、1HNMR、13C NMR、FABMS等现代谱学技术对其结构进行了表征。经生物活性试验证明,此化合物对腐生线虫Panagrellus redivivus具有一定的毒杀活性。     

含咔唑生色团的三聚磷腈分子玻璃的合成

含咔唑生色团的三聚磷腈分子玻璃的合成;三聚磷腈;后重氮偶合;咔唑;光折变分子玻璃     

杂质对六氯环三聚磷腈热聚合的影响

利用红外光谱、磷核磁共振谱、广角X射线衍射、差示扫描量热、凝胶色谱等分析手段,研究了六氯环三聚磷腈(HCCP)在存放过程中产生的杂质,以及不同纯化方法对这些杂质的去除效果,探讨了这些杂质对HCCP单体真空热开环聚合反应的影响.HCCP在存放过程中接触空气中的水汽在环上氯基团处易被水解,产生Trimer-1、Gem-2、Dimmer-3等杂质,重结晶能去除Gem-2、Dimmer-3和少量的Trimer-1,升华能较好地去除Trimer-1.杂质Gem-2、Dimmer-3中的羟基引发聚二氯磷腈交联,生成不可溶的交联态聚二氯磷腈,而Trimer-1则会降低聚合速度,并在聚合物中引入磷氧基和亚胺基杂链,从而影响后续聚磷腈取代产物的性质,表现为聚合物中晶态发生变异,结晶度降低,玻璃化温度、晶态转化温度和熔融温度出现差别.用重结晶结合升华的方法对HCCP单体进行纯化后,应用FTIR或31P-NMR分析来验证纯化效果,以确保能控制聚合速度和时间,使聚合顺利进行.     

聚二乙氧基磷腈的制备及其膜对气体的透过性能

研究了聚二乙氧基磷腈(PEOP)的制备方法,对合成有机磷腈高聚物的Allcock法进行了改进;表征并研究了PEOP膜对O-2、N_2、H_2、CO_2、CH_4等气体的透过性能。结果表明:在严格的实验条件下,可得到线型结构的PEOP,产率高于Allcock法,达50％左右,所得PEOP为无色透明弹性体,具有良好的成膜性,其膜具有较高的气体透过系数和分离系数,是一类有潜在应用前景的新型膜分离材料。     

含双螺环三聚磷腈单元的苯并噁嗪树脂的结构和热稳定性

以双螺环取代三聚磷腈基双苯甲酰氯和4-氨基(N-苯基)苯并噁嗪单体为原料合成了一种含双螺环取代三聚磷腈结构单元的苯并噁嗪树脂单体(HCP-5);采用傅立叶变换红外光谱仪(FT-IR)和核磁共振谱仪(1 H NMR,13 C NMR,31P NMR)表征了苯并噁嗪树脂单体的结构,基于FT-IR和示差扫描量热法研究了其固化行为,并利用热重分析和示差热重分析研究了HCP-5树脂单体、均聚物及其与双酚A型苯并噁嗪树脂(Bz)共聚物的热稳定性.结果表明,HCP-5均聚物具有很好的热稳定性和成炭性,其在317℃下的热失重为5%,在800℃下的残炭率为50%,可用于普通苯并噁嗪树脂改性.此外,HCP-5/Bz(1∶1;质量分数)共聚物在332℃下的热失重为5%,在800℃下的残炭率为48%.     

环三聚磷腈多齿配体的合成及DNA的切割活性

为了得到具有核酸切割功能的人工核酸酶, 设计合成了5种环三聚磷腈多齿配体, 并初步检测了其对DNA的切割活性. 目标化合物的结构由IR, 1H NMR, 31P NMR, 13C NMR和ESI-MS确认. 在生理条件下对pUC19 DNA切割活性的初步实验结果表明, 在化合物5a～5e的Cu(Ⅱ)配合物存在下, 保温24 h后, pUC19 DNA由Form Ⅰ断裂为Form Ⅱ, 即合成目标化合物有明显的DNA切割活性. 同时, 考察了配合物5b+Cu在不同时间下对DNA的切割活性的影响.     

新型环磷腈类化合物的合成

六氯环三磷腈(1)分别与间苯二胺(2)和二苯氨基脲(3)经亲核取代反应合成了两个新型的环磷腈类化合物——六间苯二胺环三磷腈(4)和六二苯氨基脲环三磷腈(5),其结构经1H NMR,31P NMR和IR表征。合成4的最佳反应条件为:1 7.2 mmol,n(2)∶n(1)=6.17,于70℃反应12 h,产率72.68%。合成5的最佳反应条件为:1 2.8 mmol,n(3)∶n(1)=6.10,于70℃反应12 h,产率46.57%。     

氯化钪-氯化钠-氯化钾熔盐制备新工艺研究

研究了以Sc2O3为原料，盐酸回流溶解后与NaCl，KCl，NH4Cl溶液混合，经蒸发浓缩、结晶、真空预脱水，再在氩气保护下分段升温脱水、升华除去过量NI-hCl后制备ScCl3-NaCl-KCl熔盐的新工艺。研究表明，添加NH4Cl后加热脱水时，NH4Cl分解产生的HCl气体能抑制ScCl3水合物加热过程中的水解，溶解产生的水不溶性钪，从而有效地防止了Sc2O3等水不溶化合物的生成。制备的ScCl3-NaCl-KCl熔盐脱水完全、水不溶性钪含量很低，能满足熔盐金属热还原法制备金属钪及铝钪中间合金对熔盐原料的要求。     

磷氯化物(PCl_3,PCl_5,POCl_3)作为氯化试剂在有机合成中应用的研究进展

综述了近十几年来磷氯化物 (PCl3,PCl5,POCl3)作为氯化试剂在有机合成中应用的新进展 ,主要包括磷氯化物与羟基化合物、羧酸、羰基化合物、烯烃、含孤对电子基团化合物、磺酸及其盐、硅化合物、磷化合物的氯化反应 ,以及氢氯交换反应。     

Safer Pyrotechnic Obscurants Based on Phosphorus(V) Nitride

The potential of phosphorus(V) nitride, P₃N₅ , as a replacement for red phosphorus, P_R, in pyrotechnic obscurants has been theoretically and experimentally investigated. P₃N₅ can be safely mixed with KNO₃ and even KClO₃ and KClO₄ . The corresponding formulations are surprisingly insensitive to friction and only mildly impact‐sensitive. P₃N₅ /KNO₃ pyrolants with ξ=20–80 wt % P₃N₅ burn 200 times faster than the corresponding mixtures based on P_R and generate a dense smoke. Hence obscurants based on P₃N₅ /KNO₃ have a figure of merit that by far exceeds that of current state‐of‐the‐art P_R‐based obscurants. Furthermore, unlike P_R, which slowly degrades in moist air to phosphoric acids and phosphine (PH₃), P₃N₅ is stable under these conditions and does not produce any acids or PH₃ . P₃N₅ is hence a safe, stable, and powerful replacement for P_R for use in insensitive munitions.     

United in Nitride: The Highly Condensed Boron Phosphorus Nitride BP3N6

Owing to intriguing materials properties non‐metal nitrides are of special interest for both, solid‐state chemistry and materials science. Mixed ternary non‐metal nitrides, however, have only been sparsely investigated, as preparative chemistry lacks a systematic access, yet. Herein, we report on the highly condensed boron phosphorus nitride BP₃N₆, which was synthesized from (PNCl₂)₃, NH₄N₃ and h‐BN in a high‐pressure high‐temperature reaction. By increasing partial pressure of HCl during synthesis using NH₄Cl, single‐crystals of BP₃N₆ up to 80 μm in length were obtained. The unprecedented framework‐type structure determined by single‐crystal XRD blends structural motifs of both, α‐P₃N₅ and c‐BN, rendering BP₃N₆ a double nitride. The compound was further investigated by Rietveld refinement, EDX, temperature‐dependent PXRD, FTIR and solid‐state NMR spectroscopy. The formation of BP₃N₆ through use of reactive precursors exemplifies an innovative access to mixed non‐metal nitrides.     

PhPOCl2 as a potent catalyst for chlorination reaction of phenols with PCl5

Phenols are easily converted to the corresponding aryl chlorides by using phosphorus pentachloride (PCl₅) and a catalytic amount of phenylphosphonic dichloride (PhPOCl₂), which is a new efficient method for synthesis of aryl chloride in good yields.     

氯化钌氨作前驱体制备高活性的氨合成催化剂

以氯化钌和水合肼反应制备了新型的氧化钌氨前驱体Ru(NH3)5Cl3.透射电镜和CO化学吸附结果表明,由Ru(NH3)5Cl3前驱体制备的活性炭(AC)负载的RuN/AC催化剂中.钌纳米粒子分散度高,粒径分布均匀.与以氯化钌为前驱体制备的Ru/AC催化剂相比,RuN/AC催化剂具有更高的氨合成活性,在10 MPa和10 000 h-1条件下活性增幅超过10%.     

A High‐Pressure Polymorph of Phosphorus Nitride Imide

Phosphorus nitride imide, PN(NH), is of great scientific importance because it is isosteric with silica (SiO₂). Accordingly, a varied structural diversity could be expected. However, only one polymorph of PN(NH) has been reported thus far. Herein, we report on the synthesis and structural investigation of the first high‐pressure polymorph of phosphorus nitride imide, β‐PN(NH); the compound has been synthesized using the multianvil technique. By adding catalytic amounts of NH₄Cl as a mineralizer, it became possible to grow single crystals of β‐PN(NH), which allowed the first complete structural elucidation of a highly condensed phosphorus nitride from single‐crystal X‐ray diffraction data. The structure was confirmed by FTIR and ³¹P and ¹H solid‐state NMR spectroscopy. We are confident that high‐pressure/high‐temperature reactions could lead to new polymorphs of PN(NH) containing five‐fold‐ or even six‐fold‐coordinated phosphorus atoms and thus rivalling or even surpassing the structural variety of SiO₂.     

Nitridophosphates: A Success Story of Nitride Synthesis

Nitridophosphates and phosphorus nitrides are thoroughly investigated classes of nitrides. During thirty years of research, the methods for their synthesis evolved from the condensation of molecular precursors at moderate temperatures and ambient pressures to state‐of‐the‐art high‐pressure and high‐temperature processes. Landmark breakthroughs made in recent years led to a comprehension‐based proficiency in nitridophosphate synthesis that is illustrated by the large compositional and structural diversity of the nitridophosphates known today. Herein, we review the advances made in synthesis with regard to the prevalent problem of nitride synthesis: the susceptibility of nitride ions to oxidation.     

Reactions of Ammonium Alkylene Dithiophosphates with Phosphorus Trichloride and Thiophosphoryl Chloride *

Phosphorus trichloride and thiophosphoryl chloride derivatives of alkylene dithiophosphates of the type PCl_{3 ? n} () _n and P(S)Cl_{3? n} () _n (where G = -CH₂CH₂CHMe-, -CMe₂CMe₂-, -CH₂CH₂CH₂CH₂- and -CMe₂CH₂ CHMe-, n = 1, 2, 3] have been synthesized for the first time by reacting the ammonium salt of alkylene dithiophosphoric acid with phosphorus trichloride and thiophosphoryl chloride in different stoichiometric ratios under anhydrous reaction conditions. The newly synthesized derivatives are either colorless liquids or viscous semisolids, hygroscopic in nature and are soluble in common organic solvents. These are characterized by elemental analysis, molecular weight determinations and physicochemical studies IR, NMR (¹H and ³¹P). On the basis of above studies the formation of P-S-P and S = P–S–P(S) chemical linkages have been established. ²³¹P NMR studies provide convincing evidence regarding the chemical bonding mode in these derivatives.     

氯化锂插层氮化碳材料的可控制备及吸附性能

近年来, 有机废水对环境造成的污染已经引起了广泛的关注. 吸附法操作简单, 已经被广泛用于处理染料废水.通过在类石墨相氮化碳(g-C₃N₄)上用氯化锂(LiCl)插层制备了一系列Li/GCN-x复合材料, 并采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、N₂-吸脱附、场发射扫描电子显微镜(SEM)以及X射线光电子能谱(XPS)等对所得吸附剂的形貌和结构进行了表征. 测试结果表明, g-C₃N₄具有明显的层状结构, 使得LiCl在层间能够稳定地生长. LiCl的加入使得g-C₃N₄晶格膨胀, 层间距扩大, 表明LiCl成功插层. 此外, 插层后Li/GCN的比表面积远大于g-C₃N₄, 扩大的比表面积以及形成的 π 共轭体系使得Li/GCN在吸附方面具有较大的潜力. 通过控制实验条件, 研究了Li/GCN对有机染料亚甲基蓝(MB)的吸附性能. 结果表明, Li/GCN-5吸附剂在pH为6时, 5 min吸附量可达704 mg•g^–1. 通过动力学拟合, Li/GCN对MB的吸附过程是由准二级动力学模型占主导地位. 进一步通过Weber-Morris模型探究吸附控制过程, 结果表明MB的吸附由表面扩散和孔内扩散共同作用, 其中表面扩散占主导, 且新增官能团与MB分子间可形成氢键, 并通过π-π键相互作用增强吸附能力. 采用共混热聚合法所制备的Li/GCN吸附剂具有稳定、均一、比表面积大等优点, 且简单快速地实现对MB的吸附, 克服了常用吸附剂动力学缓慢的缺点, 为该材料的工业化应用提供一定的借鉴.