Core–shell type multi‐arm azide polymers based on hyperbranched copolyether as potential energetic materials in solid propellants

A series of novel multi‐arm azide copolymers (POGs) with the same hyperbranched poly[3‐ethyl‐3‐(hydroxymethyl)oxetane] core (PEHO‐c) and different content of linear glycidyl azide polymer shell (GAP‐s) have been synthesized by sequential cationic ring‐opening polymerization and azidation. Detailed structural information of these copolyethers was deduced from Fourier transform infrared, ¹H NMR and inverse gated decoupled ¹³C NMR spectroscopies, matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry, gel permeation chromatography and elemental analysis. The molecular weight of POG having GAP‐s and PEHO‐c with a molar ratio 14.95:1 (R_s/c) was around 31 000 g mol^?1, far above that of linear GAP (around 4000 g mol^?1). The apparent viscosity and glass transition temperature (?51 to ?23 °C) decreased first and then slightly increased with increasing molecular weight. Thermal analysis revealed that all the obtained POGs exhibited excellent resistance to thermal decomposition up to 220 °C. Moreover, the energetic properties, investigated using oxygen bomb calorimetric measurements, indicated that the enthalpy of formation of the POGs was higher than that of general linear GAP, but similar to that of branched GAP under reasonable R_s/c. The compatibilities of the POGs with common materials used in solid propellants were studied using differential scanning calorimetry and the results indicated that the POGs had good compatibility with these materials. © 2017 Society of Chemical Industry     

Effects of metal oxide nanoparticles on combustion and gas-generating performance of NaN3/Al composite powders ignited using a microhotplate platform

We investigated the effects of different metal oxide (MO) nanoparticles (e.g., CuO, KIO₄, Fe₂O₃) on the combustion and gas-generating characteristics of sodium azide microparticle (NaN₃ MP; gas-generating agent) and aluminum nanoparticle (Al NP; heat source) composite powders. The NaN₃ MP/Al NP/MO NP composite powders were stably ignited using a microhotplate (MHP) heater. The addition of CuO and KIO₄ to the NaN₃ MP/Al NP composite powders resulted in relatively high burn rates and high pressurization rates upon MHP-assisted ignition. This suggests that the highly reactive CuO and KIO₄ NPs significantly increased the combustion of the Al NPs; as a result, sufficient heat energy was generated via the active aluminothermic reaction to thermally decompose the NaN₃ MPs. Finally, the gas generating properties of NaN₃ MP/Al NP composite powders mixed with various MO NPs were tested using homemade inflatable small airbags. The airbags were fully inflated within ~20 ms when CuO and KIO₄ NPs were added to the NaN₃ MP/Al NP composite powders. However, the addition of Fe₂O₃ NPs to the NaN₃ MP/Al NP composite powder resulted in a slow and only partial inflation of the airbag due to an incomplete aluminothermic reaction, which was due to a slow combustion reaction between the Al NPs and relatively weak oxidizer of the Fe₂O₃ NPs. This suggests that the rapid, stable, and complete thermal decomposition of NaN₃ MP/Al NP composites can be effectively achieved by employing highly reactive nanoscale oxidizers.     

1,4-二取代-1,2,3-三氮唑的合成研究

以苄基氯(1a)、4-氯苄基氯(1b)、特戊酸氯甲酯(1c)为原料,通过叠氮取代和1,3-偶极环加成反应合成了三种含羟基的三氮唑衍生物1-苄基-4-羟甲基-1H-1,2,3-三氮唑(3a)、1-(4-氯-苄基)-4-羟甲基-1 H-1,2,3-三氮唑(3 b)、1-(特戊酸甲酯基)-4-羟甲基-1 H-1,2,3-三氮唑(3 c),实验应用FT-IR、1HNMR、13CNMR对产物的结构进行了表征,结果证实了合成路线的可行性,目标产物的收率分别为85.32%、90.26%、72.62%。     

海洋工程应用水下涂装防污涂料的研究

将叠氮基团接枝到环氧树脂上以提高环氧树脂的湿态附着强度,然后将其与环氧树脂618按不同比例复配制备成水下涂装防污涂料,并对涂料的附着强度、铜离子渗出率及海洋防污性能进行研究。研究表明,随着叠氮化环氧树脂用量的增加,水下防污涂层的附着强度先升高后降低;铜离子渗透出率测定和实海浸泡表明该水下涂装防污涂料具有一定的防污性能。     

Orthogonal ligation to spherical polymeric microparticles: Modular approaches for surface tailoring

Modular ligation strategies for the functionalization of polymeric microspheres provide new perspectives for their applications in material science. In the current trend article we highlight variable synthetic procedures for generating functional microspheres via orthogonal modular conjugation chemistries. An overview of the different surface chemistries available is provided, followed by surface-sensitive characterization techniques relevant for the microparticles. Finally, we explore future trends in modular orthogonal modification approaches on microparticles and provide an outlook on the perspectives that the field of surface-modification of polymeric microparticles holds.     

Interpolymer radical coupling: A toolbox complementary to controlled radical polymerization

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system.     

聚叠氮缩水甘油醚/聚乙二醇双软段含能聚氨酯弹性体的性能

为改善聚叠氮缩水甘油醚(GAP)的性能,以三羟甲基丙烷(TMP)为交联剂,异佛尔酮二异氰酸酯(IPDI)为固化剂,选用聚乙二醇(PEG)制备出GAP/PEG/TMP/IPDI双软段含能聚氨酯弹性体,采用红外光谱(FT-IR)、差示扫描量热(DSC)等手段进行了表征。实验结果表明,弹性体中引入聚乙二醇(PEG),拉伸强度提高168%,延伸率提高77%,所选PEG软段分子量较小,弹性体中只出现了GAP软段的Tg。随交联剂含量的增大,GAP软段的Tg由-36.85℃上升到-34.81℃,继而又下降到-40.31℃,弹性体的热分解分两段进行,初始分解温度为183℃。     

端叠氮基聚乙二醇的合成与表征

以端羟基聚乙二醇(PEG)为反应底物,甲苯为溶剂,在80℃下用二氯亚砜对端羟基氯代;再在N,N-二甲基甲酰胺中,与叠氮化钠进行叠氮化反应得到端叠氮基聚乙二醇(N3PEG).用FT-IR、1H NMR、13C NMR、DSC等对产物进行了表征.结果表明,聚乙二醇端羟基峰消失,同时出现明显的叠氮基特征峰;聚乙二醇端羟基活泼...     

Metal‐Free Click Chemistry Reactions on Surfaces

In the last decade, interest in the functionalization of surfaces and materials has increased dramatically. In this regard, click chemistry deserves a central focus because of its mild reaction conditions, high efficiency, and easy post‐treatment. Among such novel click reactions, those that do not require any metal catalyst are of special interest, as metals may have undesirable effects in many fields. In this Review, the backgrounds and application of such metal‐free click reactions for the modification of surfaces are highlighted.