On the Direct Addition of Amine N–H to Ch≡C Triple Bonds with Late Transition Metal Catalysts

The kinetics of the transition metal-catalysed direct addition of amine NH bonds to carbon--carbon multiple bonds (hydroamination) has been explored by in situ spectroscopic techniques. From an open mass balance it was concluded that an intermediate species was formed during the cyclisation of 6-aminohex-1-yne. This species was identified as the enamine 2-methylene-piperidine, which is the primary hydroamination product.     

POSS-based hybrid thermosets via photoinduced copper-catalyzed azide–alkyne cycloaddition click chemistry

An efficient approach for the preparation of inorganic/organic hybrid thermosets via photoinduced copper-catalyzed azide–alkyne cycloaddition click chemistry is established. Highly cross-linked thermoset polymers have been practically obtained by this technique using multifunctional compounds, tri-alkyne (1,1,1-tris[4-(2-propynyloxy) phenyl]-ethane) with octakis-azido-POSS or tri-azide (3,3′-((2-((3-azido-2-hydroxypropoxy)methyl)-2-ethylpropane-1,3-diyl)bis(oxy))bis(1-azidopropan-2-ol)) in the presence of Cu(II)Br₂/N,N,N′,N″,N?-pentamethyldiethylenetriamine/2-dimethoxy-2-phenyl acetophenone. The homogeneously distributed POSS nanoparticles are clearly detected in the TEM micrographs; whereas the TGA analysis shows that the obtained hybrid thermosets are thermally stable up to 360 °C and begin to lose weight at higher temperatures with a char yield of 23–50% at 800 °C.     

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.     

The base-mediated cyclization of selected benzyl alkynyl sulfones with aromatic aldehydes: novel synthetic access to aryl-substituted 5,6-dihydro-1,4-oxathiin S,S-dioxides

Based on an unexpected product isolated during the LDA-mediated intramolecular cyclization of a benzyl alkynyl sulfones, a conceptually new cyclization method for the formation of 5,6-dihydro-1,4-oxathiin S,S-dioxides is demonstrated. The reaction affords products with (het)aryl groups at the 5- and 6-positions in 7–54% yield.     

正烯烃和正炔烃熔点的经验计算公式

导出了从正烯烃和正快烃的碳原子数计算其熔点的经验公式。     

Chloro-Nickel and Chloro-Cobalt Complexes Containing Phosphine Ligands: Efficient Initiators for Polymerization of Alkynes

We have developed a new series of single-component air- and moisture-stable catalysts for alkyne polymerization based on chloro-nickel and chloro-cobalt complexes containing phosphine ligands. The polymerization of p-diethynylbenzene initiated by these complexes proceeds smoothly in the presence of amines at room temperature to afford soluble -conjugated polymers in yields as high as 81% with weight-average molecular weight up to 17 600.     

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.     

Synthesis of Hydrogen‐Substituted Graphyne Film for Lithium–Sulfur Battery Applications

Graphyne (GY) is a new type of carbon allotrope, which is viewed as a rapidly rising star in the carbon family referred to as 2D carbon allotropes due to its extraordinary properties. Considering the dynamic nature of the alkyne metathesis reaction, a hydrogen‐substituted graphyne (HsGY) film is successfully synthesized on a gas/liquid interface using 1,3,5‐tripynylbenzene (TPB) as the precursor. The synthesized HsGY film is used as a sulfur host matrix to be applied in lithium–sulfur batteries (LSBs). The HsGY@S electrode is prepared using S₈ as sulfur source and presents excellent electrochemical performance.     

新型C2催化剂稳定性实验及性能研究

通过改进C2加氢除炔催化剂LY-268A及LY-268B的不足,开发制备了新型ZB1^#J催化剂。对ZB1^#J进行了长周期稳定性实验及性能研究,并与进口先进同类型催化剂G-58C进行了加氢性能对比实验。结果表明,ZB1^#J可在空速4000～10000h^-1、入口温度40～70℃、n(H2)／n(C2H2)为0．7～1．2等较宽的工艺条件范围内使用;2ZB1^#J在入口温度为40～50℃,平均n(H2)／n(C2H2)为0．89的条件下,运行1007h后,乙炔转化率为57．02％,选择性为55．43％,乙炔转化量为0．69%,乙烯增量为0．39％,加氢性能显著;2ZB1^#J运行性能稳定,活性组分流失率低,绿油生成量和催化剂增重量比G-58C低,使用寿命长,综合性能达到并超过了G-58C。