Polymerisation von Vinylverbindungen in Gegenwart von Titan(III)-chlorid

Polymerization of Vinyl Compounds in the Presence of Titanium(III)Chloride The polymerization of styrene, acrylonitrile and some methacrylates initiated by a titanium(III) chloride dichloroacetic acid redox system was studied. The monomer selectivity of the polymerization in the presence of titanium(III) chloride was found to be affected by a reductive termination reaction. Titanium(III) chloride acts as a retarder in the polymerization of styrene initiated by azobisisobutyronitrile (AIBN). The polymerization of polar monomers like acrylonitrile, methyl, ethyl and propyl methacrylate by AIBN is inhibited by titanium(III) chloride.     

Synergistic Extraction of Am(III) and Eu(III) by Tris(2‐pyridylmethyl)Amine with Various Anions in 1,2‐Dichloroethane

The extraction equilibria of Am(III) and Eu(III) by using a tripodal ligand, tris(2‐pyridylmethyl)amine (tpa), with various lipophilic anions have been investigated. The extractability of both Am(III) and Eu(III) was increased by the combination of tpa and counteranions due to a synergistic effect. The separation factors between Am(III) and Eu(III) were also increased from 7.6 to 49 by the combination of counteranions and organic solvents. The extraction equilibria of Am(III) and Eu(III) with tpa in 1,2‐dichloroethane were determined by slope analysis. It was found that three anions and one molecule of the ligand coordinated to Am(III) and Eu(III) was extracted regardless of the anions.     

The Film Properties of Waterborne Polyurethane Modified by Epoxidized Soybean Oil and Styrene

The waterborne polyurethane (WPU) modified by epoxidized soybean oil (ESO) and styrene (St) (WPU-ESO-St) was synthesized by free-radical emulsion polymerization using styrene (St) as a monomer, and azodiisobutyronitrile (AIBN) as initiator. The research on the mechanical properties of the film showed that with the increasing of the [NCO]/[OH] ratio, the contents of ESO, DAAM and the St, the tensile strength increased, and elongation at break decreased. The surface morphology of the film was characterized by atomic force microscopy (AFM). The glass transition temperature (Tg) of the film was characterized by differential scanning calorimetry (DSC) analysis.     

Visible-light-induced photoelectrochemical behaviors of Fe-modified TiO2 nanotube arrays

Fe-modified TiO(2) nanotube arrays (TiO(2) NTs) were prepared by annealing amorphous TiO(2) NTs whose surface was covered with Fe(3+) by a dip-coating procedure, and characterized by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and UV-visible reflectance spectroscopy. The photoelectrochemical properties were evaluated by the photocurrent response and photoelectrocatalytic (PEC) degradation of methylene orange (MO) and 4-chlorophenol in water under visible-light irradiation (λ > 420 nm). The results showed that a Fe-modified TiO(2) NTs electrode exhibited a larger photocurrent response and higher PEC activity for the degradation of organic pollutants than a pure TiO(2) NTs electrode. At a bias potential of 0.4 V, the photocurrent response of a 0.5 M Fe-modified TiO(2) NTs electrode exceeded that of a pure TiO(2) NTs electrode by a factor of about 10, and the PEC degradation rates of MO and 4-chlorophenol on a 0.5 M Fe-modified TiO(2) NTs electrode exceeded those on a pure TiO(2) NTs electrode by a factor of about 2.5. The larger photocurrent response and higher PEC activity of Fe-modified TiO(2) NTs could be attributed to the enhancement of separation of charge-carriers at the external electric field and the extension of the light response range of TiO(2) to the visible-light region with the narrowing of the band gap.     

Synthesis and modification of trifunctional epoxy resin with amine terminated polydimethyl siloxanes for semiconductor encapsulation application

Epoxy resins based on the triglycidyl ether of tris(hydroxyphenyl)methane (TETM) possess a very high heat distortion temperature and superior thermal oxidative stability over other types of epoxy resins. The high performance trifunctional epoxy resin (TETM) was synthesized by the condensation of a hydroxybenzaldehyde with phenol followed by epoxidation with a halohydrin. The structure of the synthesized TETM was confirmed by infrared (IR), mass spectra (MS), and nuclear magnetic resonance (NMR) spectroscopy. Amine terminated polydimethylsiloxanes (ATPDMS) were used to reduce the stress of trifunctional epoxy resin cured with phenolic novolac resin for electronic encapsulation applications. The dispersed silicone rubbers effectively reduce the stress of cured epoxy resins by reducing the coefficient of thermal expansion (CTE) and flexural modulus, while the glass transition temperature (T_g) is depressed by only a small amount.     

LabVIEW-based sequential-injection analysis system for the determination of trace metals by square-wave anodic and adsorptive stripping voltammetry on mercury-film electrodes

The development of a dedicated automated sequential-injection analysis apparatus for anodic stripping voltammetry (ASV) and adsorptive stripping voltammetry (AdSV) is reported. The instrument comprised a peristaltic pump, a multiposition selector valve and a home-made potentiostat and used a mercury-film electrode as the working electrodes in a thin-layer electrochemical detector. Programming of the experimental sequence was performed in LabVIEW 5.1. The sequence of operations included formation of the mercury film, electrolytic or adsorptive accumulation of the analyte on the electrode surface, recording of the voltammetric current-potential response, and cleaning of the electrode. The stripping step was carried out by applying a square-wave (SW) potential-time excitation signal to the working electrode. The instrument allowed unattended operation since multiple-step sequences could be readily implemented through the purpose-built software. The utility of the analyser was tested for the determination of copper(II), cadmium(II), lead(II) and zinc(II) by SWASV and of nickel(II), cobalt(II) and uranium(VI) by SWAdSV.     

Statistics of stiff chain molecules: III. Chain length dependence of the mean square radius of gyration of cellulose- and amylose-tricarbanilates

The unperturbed mean square radii of gyration of the two isomeric chains of cellulose- and of amylose-tricarbanilates were measured over a wide range of degree of polymerisation. Both chains exhibit pronounced deviations from the Gaussian statistical conformation because of a remarkable chain stiffness. Four model calculations were performed to interpret the data: (a) the freely rotating chain model; (b) a chain with a symmetric potential of the hindered rotation around ? = ? = 0; (c) a chain with a hindrance potential symmetric around ? = ?* (d) an approximate model of (c). Because of the complicated ring conformation, the glucose units have to be approximated by a two-bond unit, or by a one-bond unit with variable valence angle. Model (d) differs from model (c) by the assumption that the valence angle of stiff chains is constant. Cellulose-tricarbanilate could be reasonably interpreted by model (b), while for amylose-tricarbanilate, helical conformations had to be taken into account. Eight helix conformations, discussed in the literature, were calculated on the basis of models (c) and (d). The experimental data could best be fitted by a helix of 4 residues per turn, a pitch height of 10.4 Å and a remarkable chain stiffness, The conception of chain stiffness is discussed, and it is shown that the chain extension or the chain expansion are not suitable stiffness parameters, while a generalised persistence length and a fluctuation parameter cos x, defined in the paper, are appropriate to describe the stiffness. The approximate model (d) appeared practically equivalent to the more elaborate model (c) for all helices considered.     

Rheological behavior and morphology of blends of copolymers of α-methylstyrene-co-acrylate with PVC

The copolymers of poly(α-methyl styrene–methyl acrylate) (PMSMA) and poly(α-methyl styrene–ethyl acrylate) (PMSEA) were synthesized by emulsion polymerization. The compatibility of these copolymers with poly(vinyl chloride) (PVC) was estimated by the solubility parameter method and scanning electron microscopy (SEM). The rheological behavior was investigated by a flow tester. The mechanical properties, rheological behavior, and morphology of these blends show that these copolymers can be used as a processing aid for PVC. © 1996 John Wiley & Sons, Inc.     

α,β-D-异蔗糖甲苷的合成

在盐酸催化作用下异蔗糖与甲醇反应合成α ,β D 异蔗糖甲苷 (2a)和 (2b) ,收率 95 %。该异头物 (2a)和 (2b)经乙酰化反应得混合物 2 ,3,4,6 四 O 乙酰基 α ,β D 异蔗糖甲苷 (3a)和(3b)。由核磁共振1H和13 C谱证明产物结构。     

Enhanced visible-light-driven photocatalysis of surface nitrided electrospun TiO2 nanofibers

Enhanced visible-light-driven photocatalysis of TiO(2) nanofibers have been prepared by the electrospinning method combined with a surface nitridation process. The visible-light-driven photo-catalytic activity of surface nitrided TiO(2) (N-TiO(2)) nanofibers has been evaluated using rhodamine B indicator, and it was found that the visible-light-driven photocatalytic activity of the electrospun TiO(2) nanofibers could be enhanced by nitridation in NH(3) atmosphere. The optimal visible-light photocatalytic activity of N-TiO(2) nanofibers exceeded that of pure TiO(2) nanofibers by a factor of more than 12. The nitridation temperature under NH(3) flow was found to play an important part in the performance of N-TiO(2) nanofibers, and the optimum temperature is 500 °C. Structure, morphology and photoluminescence of these nanofibers were studied by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscope (SEM) and photoluminescence (PL) spectroscopy. The mechanism of the enhancement of visible-light-driven photocatalytic activity by surface nitridation has been discussed.     

Fluorescent-magnetic nanocrystals: synthesis and property of YP(x)V(1-x)O4:Eu@GdPO4 core/shell structure

A fluorescent-magnetic YP(x)V(1-x)O(4):Eu@GdPO(4) core/shell nanostructure was prepared by a two-step method. The YP(x)V(1-x)O(4):Eu core was synthesized using a hydrothermal method, and it exhibits strong photoluminescence with the effective doping of phosphorus (P) and europium (Eu) into a YVO(4) matrix. The hydrothermal process provides a hydrophilic and fresh surface for coating GdPO(4) shell. As YP(x)V(1-x)O(4):Eu and GdPO(4) have the similar unit cell parameters, YP(x)V(1-x)O(4):Eu nanoparticles (NPs) were favorably coated by an epitaxial growth of GdPO(4) shell in aqueous phase. The core/shell nanostructure was identified by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The GdPO(4) shell not only possesses the paramagnetic character, but also enhances the photoluminescence efficiency by blocking the non-radiative de-excitation from the VO(4)(3-) groups to the surface quenching sites. These optical and magnetic properties promise outstanding fluorescent-magnetic bifunctional nanomaterials.     

Hydrogen peroxide sensors for cellular imaging based on horse radish peroxidase reconstituted on polymer-functionalized TiO₂ nanorods

We describe the reconstitution of apo-horse radish peroxidase (apo-HRP) onto TiO(2) nanorods functionalized with a multifunctional polymer. After functionalization, the horse radish peroxidase (HRP) functionalized TiO(2) nanorods were well dispersible in aqueous solution, catalytically active and biocompatible, and they could be used to quantify and image H(2)O(2) which is a harmful secondary product of cellular metabolism. The shape, size and structure of TiO(2) nanorods (anatase) were analyzed by transmission electron microscopy (TEM), high resolution TEM (HRTEM), electron diffraction (ED) and X-ray diffraction (XRD). The surface functionalization, HRP reconstitution and catalytic activity were confirmed by UV-Vis, FT-IR, CLSM and atomic force microscopy (AFM). Biocompatibility and cellular internalization of active HRP reconstituted TiO(2) nanorods were confirmed by a classical MTT cytotoxicity assay and confocal laser scanning microscopy (CLSM) imaging, respectively. The intracellular localization allowed H(2)O(2) detection, imaging and quantification in HeLa cells. The polymer functionalized hybrid system creates a complete sensor including a "cell positioning system" in each single particle. The flexible synthetic concept with functionalization by post-polymerization modification allows introduction of various dyes for sensitisation at different wavelengths and introduction of various anchor groups for anchoring on different particles.     

反应与精馏耦合水解醋酸甲酯(英文)

A process composed of a fixed-bed and a distillation column with a side withdraw, mainly methanol, is developed to hydrolyze methyl acetate (MA) as a typical byproduct in polyvinyl alcohol (PVA) and pure terephthalic acid (PTA) factory. The process is simulated by employing the equilibrium stage model RadFrac and plug flow model Rplug in Aspen Plus. Experiments are also carried out in a lab-scale to evaluate the process. The results show that at the molar ratio of water to methyl acetate about 4.0-5.0 in the feed stream and the volume ratio of distillate to feed MA above a critical value, the side product contains more than 80% (by mass) (MeOH) and less than 2% (by mass) MA, while the bottom contains more than 46% (by mass) acetic acid (HAc) and less than 0.5% (by mass) methanol with almost complete conversion of MA. Compared with the old catalytic distillation process we proposed before, this process can cut down 47.6% energy consumption and a distillation column.     

Polyethylenimine-modified sugarcane bagasse cellulose as an effective adsorbent for removing Cu(II) from aqueous solution

Polyethylenimine-modified sugarcane bagasse cellulose (SBCMP), as a new adsorbent, was synthesized by the reaction of polyethylenimine (PEI) with sugarcane bagasse cellulose and glutaraldehyde. The adsorption of Cu(II) by SBCMP was pH-dependent, and the higher removal efficiency of Cu(II) appeared in the range of pH 3.0–6.0. The adsorption isothermal data fitted well with the Langmuir model, and the maximum adsorption capacity of SBCMP was up to 107.5 mg/g. The adsorption kinetics was best described by the pseudo-second-order kinetic. The adsorption of Cu(II) by SBCMP was unfavorable at high temperatures, and thermodynamic analyses implied that the adsorption of Cu(II) by SBCMP was an exothermic reaction. Fourier transform infrared spectroscopy (FT-IR) combined with X-ray photoelectron spectroscopy (XPS) revealed that Cu(II) adsorption on SBCMP mainly controlled by the nitrogen atoms of  NH group in PEI. The results of regeneration cycles showed that SBCMP was suitable for reuse in the adsorption of Cu(II) from aqueous solution. These experimental results suggested that SBCMP is expected to be a new biomass adsorbent with high efficiency in removing Cu(II) from wastewater.     

Synthesis of a silicone containing allylic monomer and its uses in the waterborne polyurethane/vinyl acetate–acrylic hybrid emulsion copolymers

A new silicone containing allylic monomer, allyl 3-(triethoxysilyl) propyl carbamate (ATESPC), based on (3-isocyanatopropyl) triethoxysilane (ICPTES) and allyl alcohol (AAL) has been synthesized for formulation of waterborne polyurethane (WPU). Then a series of new siliconized WPU, vinyl acetate (VAc)/2-ethylhexylacrylate (2-EHA) and ATESPC hybrid latexes P(VAc-2-EHA)/PU/Si have been successfully synthesized by the emulsion copolymerization in the presence of a WPU dispersion by using potassium persulfate (KPS) as an initiator. The WPU dispersion has been synthesized by a polyaddition reaction of hexamethylene diisocyanate (HMDI), on polypropylene glycol (PPG-1000) and dimethylol propionic acid (DMPA) as chain extender. The NCO chain ends being reacted with water (which act as a further chain extender producing some urea bonds). Films were obtained for different hybrid latexes of various compositions. The resulted monomer characterized by Fourier transformer infrared spectroscopy (FTIR), proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes, respectively. The copolymers also were characterized by using Fourier transform infrared spectroscopy (FT-IR). Thermal properties of the copolymers were studied by using thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). The morphology of copolymers was investigated by scanning electron microscopy (SEM) and then the effects of silicone concentrations on the water absorption ratio, was examined.     

Dispersed phase morphology of impact PP copolymers. Effects of blend composition as determined by TREF

Polypropylene (PP) blends, commercially known as “impact polypropylene copolymers” (IPC), are produced by a sequential gas phase polymerization process. The final product is a complex mixture of polypropylene (PP) and a range of ethylenepropylene copolymers (EPC) with different ethylene contents. In the present work, the composition of three different IPC was estimated by performing a step elution mode Analytical Temperature Rising Elution Fractionation (TREF) separation. The recovered fractions were analyzed by Differential Scanning Calorimetry (DSC), Size Exclusion Chromatography (SEC) and Fourier Transform Infrared Spectroscopy (FTIR). The morphology was examined by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). Amorphous EPC were isolated in an independent way in order to perform a more careful characterization. The distinct particle size and shape of the dispersed phase for different IPC was interpreted in terms of the molecular characteristics of the blend components and their compositions.     

PH-induced structure change of poly(vinyl alcohol) hydrogel crosslinked with poly(acrylic acid)

The structure of the hydrogel of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) was investigated by small angle X-ray scattering (SAXS) of synchrotron radiation. A physically crosslinked blend gel, which was prepared by repetitive freezing and thawing of an aqueous solution of PVA and PAA, could be chemically crosslinked by esterfication of PVA with PAA even in the hydrogel state. The chemical crosslinking induced the destruction of physical crosslinks into a folded structure, indicating that the chemical crosslinking proceeds at the sites around the physical crosslinks that contain PVA and PAA in much higher concentration than other portion of the gel. The pH-induced structure changes of the PVA hydrogels, chemically crosslinked with poly(acrylic acid) (PAA) were investigated by SAXS on the samples of various chemical crosslinking time. The gels were shrunk at pH4, and swollen at pH8. The results of SAXS showed, that the Porod slope changed with chemical crosslinking time from -3.5 to ?2.9 at pH4, and from ?2.9 to ?2.4 at pH8. The results suggest that a folded structure as a structural domain, which is characterized by fractally rough interface, tends to change into the structure that corresponds to percolation cluster, particularly at pH8. The gels immersed in pH8 showed a remarkable structure change accompanying swelling. The results revealed that a conformational change of PAA chains, induced by the pH change, can be explained by the presence of a structural domain in the gel network, where both PVA chains and PAA chains get entangled and partially form a interpenetrating polymer network(IPN).     

Dithiooxamide-Immobilized Microalgal Residue for the Selective Recovery of Pd(II) and Pt(IV)

Microalgal residue was chemically modified by immobilizing a functional group of dithiooxamide to prepare a novel type of adsorbent. This adsorbent exhibited high adsorption affinity and selectivity for Pd(II) and Pt(IV) whereas the adsorption of coexisting base metal ions was negligible. From the adsorption isotherms, this adsorbent was found to exhibit remarkably high adsorption capacity. The thermodynamic parameters indicated that the adsorption is governed by an endothermic reaction. The effective separation of Pd(II) and Pt(IV) from Cu(II) was confirmed also by a dynamic adsorption test. The effectiveness of elution of adsorbed Pd(II) and Pt(IV) was 85% and 96%, respectively.     

Radiation synthesis of a thermo-pH responsive binary graft copolymer (PP-g-DMAEMA)-g-NIPAAm by a two step method

Summary  (PP-g-DMAEMA)-g-NIPAAm was synthesized using gamma radiation from a ⁶⁰Co source. Graft polymerization of N,N’-dimethylaminoethylmethacrylate (DMAEMA) onto polypropylene (PP) was accomplished in about 100 percent yield by the mutual irradiation technique at a dose of 10 kGy. Grafting of N-isopropylacrylamide (NIPAAm) onto PP-g-DMAEMA was carried out by the pre-irradiation method with doses from 20 to 100 kGy. The influence of temperature, reaction time, and monomer concentration on grafting yield was studied. Grafting processes were confirmed by infrared spectroscopy (FTIR-ATR). (PP-g-DMAEMA)-g-NIPAAm films were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The lower critical solution temperature (LCST) and critical pH point of the films were obtained by water contact angle and percent swelling measurements. The LCST was also determined by DSC. We report here hare a new binary graft copolymer which shows two LCST values, synthesized in two steps.     

高频脉冲电镀Ni-SiC纳米复合镀层影响因素的研究

采用脉冲电镀,在铜板上制备了N i-S iC纳米复合镀层。该复合镀液采用的分散剂由一种阴离子和一种阳离子表面活性剂混合而成,稳定性较好。采用络合滴定法对镀层中S iC的含量进行了测定。讨论了脉冲频率、阴极电流密度、镀液中S iC含量、镀液温度对镀层中微粒含量的影响。实验结果表明,镀层中S iC含量随着镀液中S iC含量的增加、电流密度的增大或温度升高都是先增加后减小;随着频率增大而逐渐降低。该复合镀层硬度可达960HV,表面细致,空隙较少。