In‐Reactor Compounding Metallocenic Isotactic Poly(propylene)/Nucleation Agent Compositions by Employing the Nucleation Agent as a Catalyst Support

A nucleation agent, 1,3,2,4‐dimethylbenzylidene sorbitol (DMBS), was used as a support for C₂‐symmetric metallocene rac‐Me₂Si[2‐Me‐4‐Naph‐Ind]₂ZrCl₂. Propylene polymerization with the supported catalyst resulted in i‐PP polymers with granular morphology. The role of a catalyst support ensures a good dispersion of the nucleation agent in the formed i‐PP matrix. The employment of a nucleation agent as catalyst support provides a unique solution to in‐reactor compounding metallocenic i‐PP/nucleation agent compositions.

     

Optimizing Melt‐Processing Conditions for the Preparation of iPP/Fumed Silica Nanocomposites: Morphology,Mechanical and Gas Permeability Properties

A series of iPP/SiO₂ nanocomposites, containing 1, 2.5, 5, 7.5, and 10 wt.‐% fumed silica nanoparticles, were prepared by melt mixing in a twin screw co‐rotating extruder. The effect of different extrusion parameters was evaluated. The size of aggregates increased with increase in SiO₂ content and repetition of the mixing process improved the filler's dispersion. A similar effect was also exhibited by either increasing the rotor speed or the mixing temperature, with the latter being more pronounced at the ranges studied. The mechanical properties of the prepared nanocomposites were evaluated and various models used to explain the observed enhancements. However, only the three‐phase model could provide some correlation with the experimental results. All nanocomposites displayed lower permeability to gases.

     

Effect of synthesis method and buffer composition on the LCST of a smart copolymer of N‐isopropylacrylamide and acrylic acid

Responsive polymers have been the focus of many studies during the past decade because of their ability to change according to environmental stimuli. In this paper, we report on the development of a method to synthesize a pH/temperature‐sensitive linear copolymer, poly(N‐isopropylacrylamide‐ co‐acrylic acid)(poly(NIPAAm‐co‐AAc)), with a molecular weight of about 10⁶–10⁵ Da in water using azobisisobutyronitrile (AIBN) as the initiator. The effects of the following on the lower critical solution temperature (LCST) of the copolymer and homopolymer of NIPAAm were investigated: the type of buffer salts and pH changes of test solutions, molecular weight and concentration of homopolymer/copolymer solutions, and AAc monomer molar feed ratio (mol%). The effects of different synthesis methods on the molecular weight and on the AAc content were also evaluated. The mechanism of action in environments with different pH values is discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Novel amphiphilic fluorescent graft copolymers: synthesis,characterization, and potential as gene carriers

Amphiphilic fluorescent graft copolymer (PVP‐PyATAm) was successfully synthesized by the free radical copolymerizations of hydrophobic monomer N‐acryloyl‐thioureylene‐4‐(1‐pyrene)‐butyryl amide (PyATAm) with hydrophilic precursor polymers of vinyl‐functionalized poly (N‐vinylpyrrolidone) (Acryloyl‐PVP) in DMF. FT‐IR, ¹H NMR, TEM, gel permeation chromatography‐multi‐angle laser light scattering, UV‐vis spectroscopy, viscometric measurement, and fluorescence spectroscopy were used to characterize this copolymer. The TEM observation showed that the copolymer PVP‐ PyATAm formed spherical micelles in an aqueous solution and the size of micelles was between 50 and 70 nm in diameter. The interaction of PVP‐PyATAm copolymer and plasmid DNA was examined by agarose gel electrophoresis and TEM. Results indicated that the copolymer–DNA complexes were self‐assembled and the size of complexes was between 90 and 120 nm in diameter. Cytotoxity studies using MTT colorimetric assays suggested good biocompatibility of PVP‐PyATAm in vitro. These results suggested the potential of this graft copolymer as gene delivery carrier. Copyright © 2007 John Wiley & Sons, Ltd.     

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

Our recent extensive research on Lewis acid catalysts with a weak base for the cationic polymerization of vinyl ethers led to unprecedented living reaction systems: fast living polymerization within 1–3 s; a wide choice of metal halides containing Al, Sn, Fe, Ti, Zr, Hf, Zn, Ga, In, Si, Ge, and Bi; and heterogeneously catalyzed living polymerization with Fe₂O₃. The use of added bases for the stabilization of the propagating carbocation and the appropriate selection of Lewis acid catalysts were crucial to the success of such new types of living polymerizations. In addition, the base‐stabilized living polymerization allowed the quantitative synthesis of star‐shaped polymers with a narrow molecular weight distribution via polymer‐linking reactions and the precision synthesis and self‐assembly of stimuli‐responsive block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1801–1813, 2007.     

Isothermal vapor–liquid equilibrium at 303.15 K and excess molar volumes at 298.15 K for the ternary system of propyl vinyl ether + 1-propanol + 2,2,4-trimethyl-pentane and its binary sub-systems

Isothermal vapor–liquid equilibrium data determined by the static method at 303.15 K are reported for the binary systems propyl vinyl ether + 1-propanol, 1-propanol + 2,2,4-trimethylpentane and propyl vinyl ether + 2,2,4-trimethylpentane and also for the ternary system propyl vinyl ether + 1-propanol + 2,2,4-trimethyl-pentane. Additionally, new excess volume data are reported for the same systems at 298.15 K. The experimental binary and ternary vapor–liquid equilibrium data were correlated with different G^E models and excess molar volume data were correlated with the Redlich–Kister equation for the binary systems and the Cibulka equation for the ternary system, respectively.     

快速消解分光光度法测定高氯废水中低浓度化学需氧量

建立快速消解分光光度法检测高氯废水中低浓度化学需氧量(COD)的方法。通过提高催化液中硫酸银的浓度(46 g/L)充分络合氯离子,同时降低消解液中重铬酸钾的浓度至0.061 2 mol/L来抑制重铬酸钾与氯离子的反应,达到有效消除Cl~–干扰的目的。水样在165℃消解30 min,于600 nm波长检测吸光度,标准曲线法计算COD。实验结果表明,水样中COD质量浓度为20 mg/L时,2 000 mg/L的Cl~–不干扰COD的测定(相对误差小于10%),并且随着COD质量浓度的增加,Cl~–产生的干扰误差逐渐降低。对国家环境保护部标准样品进行了测定,COD测定值与标准值一致。样品加标回收率为97.0%~103.7%,测定结果的相对标准偏差为2.01%~6.33%(n=6)。该法快速,有毒试剂用量小,成本低,具有较高的准确度和良好的精密度,可以用于多数工业废水中COD的测定。     

原位掺杂法制备氮掺杂中孔炭及乙炔氢氯化反应性能

聚氯乙烯(PVC)是世界五大工程塑料之一,在工业、农业、建筑、电力及通信等领域有着非常广泛的应用.氯乙烯(VCM)作为合成 PVC的单体,其生产工艺以源于煤化工路线的乙炔氢氯化法工艺为主,但是该工艺目前采用的是氯化汞催化剂,存在较为严重的环境污染问题.开发新型无汞催化剂成为电石法生产 VCM亟待解决的问题.氮掺杂炭基非金属催化剂成本低廉,制备简单,在诸多反应中展现了较好的性能,成为近几年多相催化领域的一个研究热点,在乙炔氢氯化反应中也具有较好的活性,但是对活性中心的鉴别及制备方法的研究还有待深入.本文报道了一种一步原位尿素掺杂氮的中孔炭的制备方法,采用氮气吸附-脱附、高分辨透射电子显微镜、元素分析和X射线光电子能谱(XPS)等表征手段研究了氮掺杂中孔炭的结构、氮含量及存在形式,并与两步尿素改性方法做了对比,探究了氮掺杂形式与中孔炭乙炔氢氯化反应性能之间的关系,同时考察了尿素用量对氮掺杂中孔炭的氮含量和存在形式的影响.元素分析结果表明,原位合成法能有效地将氮掺杂进骨架中,随着制备过程中尿素用量增加,得到的氮掺杂中孔炭中的氮含量增加,可达3.6 wt%.后处理法的掺氮效果较差,材料氮含量仅为0.2 wt%. XPS测试进一步表明,一步法原位法可以得到石墨型氮占据主导地位的氮掺杂中孔炭,石墨型氮约占70%左右,后处理制备的氮掺杂中孔炭中石墨氮、吡啶氮和吡咯氮三种形式含量相差不大.对不同方法合成的氮掺杂介孔炭的乙炔氢氯化反应催化性能进行了评价,结果显示,无论是原位合成还是后处理制备的氮掺杂中孔炭,其活性均比中孔炭得到一定提升.氮的引入能有效提高材料的乙炔氢氯化反应性能.原位合成法制备的氮掺杂中孔炭在乙炔氢氯化反应中的催化性能远高于后处理法.对于原位合成的氮掺杂中孔炭,在一定范围内,随着氮含量的增加,催化活性提高,但当尿素用量过高时,虽然氮含量增加,催化活性却有所下降,这归因于孔结构坍塌和比表面积下降.     

均苯三甲酰胺-胺的合成及表征

以均苯三甲酰氯(TMC)和1,3-二氨基-2-丙醇(DAP)为原料,通过酯化、酰胺化和酯胺解反应,合成了树枝状大分子化合物均苯三甲酰胺-胺(TMAAM),并优化了合成工艺.考察了甲醇用量、缚酸剂种类及用量和原料DAP用量等对反应收率的影响,分析了酯胺解反应机理.用红外光谱(IR)、核磁(NMR)和高分辨质谱(HRMS)分析了TMAAM的化学结构.该合成方法反应条件温和,操作简单,后处理方便,并具有较高的反应经济性,产品收率最高可达57%.