Formation of homogeneous nanocomposite films at ambient temperature via miniemulsion polymerization using graphene oxide as surfactant

A convenient and industrially scalable method for synthesis of homogeneous nanocomposite films comprising poly(styrene‐stat‐butyl acrylate) and nanodimensional graphene oxide (GO) or reduced GO (rGO) is presented. Importantly, the nanocomposite latex undergoes film formation at ambient temperature, thus alleviating any need for high temperature or high pressure methods such as compression molding. The method entails synthesis of an aqueous nanocomposite latex via miniemulsion copolymerization relying on nanodimensional GO sheets as sole surfactant, followed by ambient temperature film formation resulting in homogeneous film. For comparison, a similar latex obtained by physical mixing of a polymer latex with an aqueous GO dispersion results in severe phase separation, illustrating that the miniemulsion approach using GO as surfactant is key to obtaining homogeneous nanocomposite films. Finally, it is demonstrated that the GO sheets can be readily reduced to rGO in situ by heat treatment of the film. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2289–2297     

Rhodium-Catalyzed Enantioselective Radical Addition of CX4 Reagents to Olefins

We describe the synthetically useful enantioselective addition of Br−CX₃ (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)Rh^IIBrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.     

二硫化钼表面氧化行为的研究（Ⅱ）─—二硫化钼摩擦表面氧化与电子转移的研究

利用电子自旋共振谱和Ｘ射线光电子能谱研究了二硫化钼ＭｏＳ＿２摩擦表面的氧化和电子转移，发现ＭｏＳ＿２在摩擦过程中是以Ｍｏ￣（４＋）经由Ｍｏ￣（５＋）过渡态继而与氧作用生成稳定的Ｍｏ￣（６＋），并且是以ＭｏＯ＿３的形式存在，证明ＭｏＳ＿２的摩擦表面除有一般认为的Ｍｏ￣（４＋）和Ｍｏ￣（６＋）这两种化学状态以外，还有Ｍｏ￣（５＋）自由基离子这种从未发现的的中间态。Ｍｏ￣（５＋）是４ｄ￣１电子构型，其在室温下于空气或氧气中是稳定的，然而在摩擦环境或添加剂的作用下，Ｍｏ￣（５＋）所含不成对电子很容易发生转移而生成Ｍｏ￣（６＋），这种研究结果更加深入地揭示了ＭｏＳ＿２摩擦表面氧化过程的复杂性，因此，应当从摩擦化学角度重新认识ＭｏＳ＿２摩擦氧化产物及其形成机制，这于研究摩擦环境和添加剂对润滑剂的抗氧化协同效应具有重要意义。     

二硫化钼润滑失效的单电子转移机理研究

ＭｏＳ２是一种性能优良的固体润滑剂，为了考察它的润滑失效机理，在给定的试验条件下，对其在不同温度大气环境中的氧化状态与活性作了顺磁共振和Ｘ射线光电子能谱分析研究．在Ｍｏ混合氧化物的Ｍｏ３ｄ包络峰中解叠出２组峰，分别归属Ｍｏ６＋，Ｍｏ５＋和Ｍｏ４＋这３种化学状态，Ｍｏ５＋在４ｄ轨道上有１个未成对的电子，这是Ｍｏ氧化物中的一种过渡化合状态，具有４ｄ电子构型和顺磁性，可以在从室温到５００℃范围内稳定存在，而且活性较好，在光电离作用下形成Ｍｏ的终态化合物．因此，ＭｏＳ２在摩擦过程中由于周围环境和摩擦热等多种因素的作用，在摩擦表面生成Ｍｏ６＋而失效，这是一种单电子转多过程     

Thioxanthone–carbazole as a visible light photoinitiator for free radical polymerization

A thioxanthone (TX) derivative with the additional carbazole chromophore, namely thioxanthone‐carbazole (TX‐C) was synthesized and characterized. The photophysical properties and its efficiency to polymerize methyl methacrylate both in the presence and absence of N,N‐dimethylaniline (DMA) as coinitiator was investigated and compared with that of the commercially available TX. TX‐C was found to display better photophysical properties and in both cases initiate polymerization more efficiently. Detailed real‐time Fourier transform infrared studies revealed that high polymerization rates can be obtained when TX‐C in conjunction with DMA was used. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Preparation of a polyacrylonitrile/multi-walled carbon nanotubes composite by surface-initiated atom transfer radical polymerization on a stainless steel wire for solid-phase microextraction

We report on the fabrication and performances of a solid-phase microextraction (SPME) fiber based on a stainless steel wire coated with a covalently attached polyacrylonitrile (PAN)/multi-walled carbon nanotubes (MWCNTs) composite. This new coating is obtained by atom transfer radical polymerization (ATRP) of acrylonitrile mixed with MWCNTs. ATRP is initiated from 11-(2-bromo-2-methylpropionyloxy)-undecyl-phosphonic acid molecules grafted on the wire surface via the phosphonic acid group. The extraction performances of the fibers are assessed on different classes of compounds (polar, non-polar, aromatic, etc.) from water solutions by headspace extraction. The optimization of the parameters affecting the extraction efficiency of the target compounds was studied as well as the reproducibility and the repeatability of the fiber. The fibers sustain more than 200 extractions during which they remain chemically stable and maintain good performances (detection limits lower than 2 μg/l, repeatability, etc.). Considering their robustness together with their easy and inexpensive fabrication, these fibers could constitute promising alternatives to existing products.     

Overcoming the oxygen inhibition in the photopolymerization of acrylates: A study of the beneficial effect of triphenylphosphine

Triphenylphosphine (TPP) was used in free‐radical UV‐curable resins to reduce oxygen inhibition effect. The relative influence of concentration, monomer viscosity, light intensity and sample thickness on TPP efficiency was investigated by real time infrared spectroscopy. It is shown that TPP is an effective oxygen scavenger. The mechanism was investigated by means of Laser Flash Photolysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2462–2469, 2010