Living cationic polymerization of 2-chloroethyl vinyl ether: Kinetics,mechanism and application to polymer synthesis

The cationic polymerization of 2-chloroethyl vinyl ether initiated by HI/weak Lewis acid (I₂ or ZnI₂) systems has been studied from both a kinetic-mechanistic and a synthetic viewpoint. At low temperature and in toluene as solvent, the polymerization proceeds via a living process and the kinetic order with respect to monomer varies according to the nature of the Lewis acid activator. This behaviour can be explained by the coordination of the Lewis acid with both the monomer and the chain-end, the latter leading to a strong activation of the -I bond towards monomer insertion. The living polymerization obtained from divinylether precursors leads to -I ended telechelics, and their transformation into dihydroxytelechelic oligomers has been performed. The chemical modification of chloroalkyl side groups by phase transfer catalysis allows the attachment of specific groups without consumption of-OH ends.     

Incorporation of nonionic emulsifiers inside particles in emulsion polymerization: mechanism and methods of suppression

Emulsion polymerizations of styrene were carried out using two kinds of polyoxyethylene lauryl ether nonionic emulsifiers having different hydrophilic-lipophilic balances (HLB): Emulgen 109P (HLB 13.6); and Emulgen 150 (HLB 18.3). In both cases, incorporation of emulsifier inside polystyrene (PS) particles was clearly observed, as previously reported for the emulsion polymerization of styrene and methacrylic acid using polyoxyethylene nonyl phenyl ether (Emulgen 911, HLB 13.7) nonionic emulsifier. The generality of the incorporation phenomenon of nonionic emulsifier inside polymer particles in emulsion polymerization was clarified. In the case of Emulgen 109P, which is more hydrophobic than Emulgen 150, about 30% of the total amount was incorporated inside the PS particles, higher than for Emulgen 150 (15%). The difference seemed to be ascribed to the difference in the affinities between the nonionic emulsifiers and styrene, which cause the incorporation of emulsifier. On the basis of this idea, suppression of the incorporation was achieved by decreasing the polymerization temperature and the monomer-feed rate. This strongly supports the proposed incorporation mechanism.     

The preparation of a substituted titanocene-supported polymer and its application in catalytic reactions

A series of polymer-supported RCpCpTiCl₂ (Cp = η⁵  C₅H₅; RCp=η⁵  RC₅H₄) has been prepared and reduced by i-C₃H₇MgBr in situ, then used as catalysts in hydrogenation of styrene, isomerization of 1,5-cyclooctadiene and 1,5-hexadiene, and reduction of carbonyl compounds. In some cases, the introduction of a polymer ligand on the Cp ring restricts the aggregation of active sites and the formation of the inactive dimer of the titanocene species, and results in an increase of activity. Regeneration of polymer-supported titanocene catalysts was performed and the results are presented and briefly discussed.     

Aqueous mixtures of di-n-decyldimethylammonium chloride/polyoxyethylene alkyl ether: dramatic influence of tail/tail and head/head interactions on co-micellization and biocidal activity

Mixed aggregate formation and synergistic interactions of binary surfactant mixtures of di-n-decyldimethylammonium chloride, [DiC(10)][Cl], with polyoxyethylene alkyl ethers, C(i)E(j) (i=10, 12, j=4, 6, 8), have been investigated for various [DiC(10)][Cl]/C(i)E(j) ratios. The critical aggregation concentration of the binary mixtures has been determined by tensiometry, and the aggregate characteristics (i.e., size and composition, free ammonium concentration) have been estimated using the pulsed field gradient NMR spectroscopy and a [DiC(10)]-selective electrode. Diffusion coefficient measurements of micelles confirmed the synergistic interaction between the surfactants. It is thus shown that the formation of surface monolayers and mixed aggregates from [DiC(10)][Cl]/C(10)E(j) mixtures is driven by both tail/tail and head/head interactions, whereas [DiC(10)][Cl]/C(12)E(j) co-aggregation is mainly driven by tail/tail interactions. As a consequence, the co-aggregation phenomenon notably influences the biocidal activity of [DiC(10)][Cl] on the Candida albicans fungi. In the presence of C(12)E(j), the biocidal activity of the ammonium salt is inhibited due to the trapping of the cationic surfactants in the mixed aggregates, whereas in the presence of C(10)E(j), the biocidal activity of the surfactant mixture is maintained. The mode of action is also confirmed by a faster increase in the zeta potential of a C. albicans suspension in the presence of [DiC(10)][Cl]/C(10)E(8) than in the presence of [DiC(10)][Cl]/C(12)E(8). Therefore, a judicious adjustment of the alkyl (i) and polyoxyethylene (j) chain lengths of C(i)E(j) avoids its antagonistic effect on the biocidal activity of [DiC(10)][Cl].     

TEMPO addition into pre-irradiated fluoropolymers and living-radical graft polymerization of styrene for preparation of polymer electrolyte membranes

We prepared proton exchange membranes (PEMs) by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated living-radical graft polymerization (LRGP) of styrene into fluoropolymer films and subsequent sulfonation. Poly(vinylidene fluoride) (PVDF) and poly(ethylene-co-tetrafluoroethylene) (ETFE) films were first irradiated and then treated with TEMPO solutions in various solvents. TEMPO addition was confirmed by the test of styrene grafting into TEMPO-treated films at 60 °C, at which the LRGP never proceeds. This test enabled us to differentiate the LRGP from the conventional graft polymerization. In order to gain a deep insight about TEMPO-addition reaction, the TEMPO-penetration behavior into the base polymer films was examined by a permeation experiment and computer simulation. Xylene and dioxane were appropriate solvents for the complete introduction of TEMPO into PVDF and ETFE films, respectively. Then, the LRGP of styrene was performed based on the fully TEMPO-capped films at 125 °C with various solvents. By using an alcoholic solvent, the degree of grafting was enhanced and it reached a maximum of 38%. This grafted film was sulfonated to prepare a PEM showing an ion exchange capacity of 2.2 meq/g and proton conductivity of 1.6×10^?1 S/cm.     

One-step synthesis of silica@resorcinol-formaldehyde spheres and their application for the fabrication of polymer and carbon capsules

Core@shell spheres made up of a thin layer of resorcinol-formaldehyde enveloping a silica core were prepared by means of a one-step method under St?ber conditions. These spheres are used as a platform for the synthesis of carbon or polymeric capsules, and functionalized nanocomposites.     

Evaporation of sessile droplets of dilute aqueous solutions containing sodium n-alkylates from polymer surfaces: influences of alkyl length and concentration of solute

The evaporation of sessile droplets placed on polymer surfaces was studied by microscopic observation of the changes in shape of aqueous solution droplets in which the alkyl lengths and the initial concentrations of sodium n-alkylates were varied. Although the initial contact angles of the droplets were not significantly different, the evaporation process varied significantly with the alkyl length of the sodium n-alkylate employed. For the sodium dodecanoate (C 12), showing the highest surface activity, the concentration was found to have a significant effect on the evaporation process of the droplets. In the evaporation of water droplets, variations in the three distinct stages were caused by the different concentration of solutes distributed near or at the air/water interface. It is revealed that the concentration of droplet solute near the air/water interface requires not only solvent evaporation but also some affinity of the solute for the interface. The initial C 12 concentration-dependence of the evaporation of C 12 solution droplets is discussed with particular emphasis on the sudden spreading or sudden contraction of the contact area near the end of evaporation. It is suggested that the cluster formation by C 12 molecules at the air/liquid interface during the evaporation causes Marangoni instability in an evaporating droplet, and the clusters are expected to move dynamically, depending on the droplet concentration of C 12, from the droplet center to the contact line and vice versa, showing Marangoni flow along the air/water interface.     

Synthesis and characterization of Cr-MSU-1 and its catalytic application for oxidation of styrene

Chromium-containing mesoporous silica material Cr-MSU-1 was synthesized using lauryl alcohol-polyoxyethylene (23) ether as templating agent under the neutral pH condition by two-step method. The sample was characterized by XRD, TEM, FT-IR, UV-Vis, ESR, ICP-AES and N₂ adsorption. Its catalytic performance for oxidation of styrene was studied. Effects of the solvent used, the styrene/H₂O₂ mole ratio and the reaction temperature and time on the oxidation of styrene over the Cr-MSU-1 catalyst were examined. The results indicate that Cr ions have been successfully incorporated into the framework of MSU-1 and the Cr-MSU-1 material has a uniform worm-like holes mesoporous structure. After Cr-MSU-1 is calcined, most of Cr³⁺ is oxidized to Cr⁵⁺ and Cr⁶⁺ in tetrahedral coordination and no extra-framework Cr₂O₃ is formed. The Cr-MSU-1 catalyst is highly active for the selective oxidation of styrene and the main reaction products over Cr-MSU-1 are benzaldehyde and phenylacetaldehyde. Its catalytic performance remains stable within five repeated runs and no leaching is noticed for this chromium-based catalyst.     

Haloperidol imprinted polymer: preparation,evaluation, and application for drug assay in brain tissue

Several molecularly imprinted polymers (MIPs) were prepared in the present work, and their binding properties were evaluated in comparison with a nonimprinted polymer (NIP). An optimized MIP was selected and applied for selective extraction and analysis of haloperidol in rabbit brain tissue. A molecularly imprinted solid-phase extraction (MISPE) method was developed for cleanup and preconcentration of haloperidol in brain samples before HPLC-UV analysis. Selectivity of the MISPE procedure was investigated using haloperidol and some structurally different drugs with similar polarity that could exist simultaneously in brain tissue. The extraction and analytical process was calibrated in the range of 0.05–10 ppm. The recovery of haloperidol in this MISPE process was calculated between 79.9 and 90.4 %. The limit of detection (LOD) and the limit of quantification (LOQ) of the assay were 0.008 and 0.05 ppm, respectively. Intraday precision and interday precision values for haloperidol analysis were less than 5.86 and 7.63 %, respectively. The MISPE method could effectively extract and concentrate haloperidol from brain tissue in the presence of clozapine and imipramine. Finally, the imprinted polymer was successfully applied for the determination of haloperidol in a real rabbit brain sample after administration of a toxic dose. Therefore, the proposed MISPE method could be applied in the extraction and preconcentration before HPLC-UV analysis of haloperidol in rabbit brain tissue.     

Using electroless deposition for the preparation of micron sized polymer/metal core/shell particles and hollow metal spheres

Uniform and stable core-shell microspheres composed of a poly(methyl methacrylate) (PMMA) core and a thin metallic shell of nickel-phosphorus, cobalt-phosphorus, or mixed metal alloys (CoNiP, NiFeP, CoFeP) were prepared by dispersion polymerization of methyl methacrylate followed by electroless plating. The presence of the metallic shell around the particles was confirmed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and photoelectron spectroscopy. Transmission electron microscopy images of the cross-section of individual particles show that the thickness of the metal/alloy can be precisely tuned by adjusting the immersion time of the microspheres in the electroless bath. Depending on the deposited metallic material, various magnetic properties, from paramagnetic to ferromagnetic, are achieved. Finally, uniform hollow metallic spheres composed of nickel, cobalt, or nickel-cobalt alloy are obtained by dissolving the polymer core.     

Synthesis of a random copolymer and its compatibility for thermotropic liquid crystalline polymer/poly(ether ether ketone) blends

A random copolymer (RCP) containing poly(ether ether ketone) (PEEK) and thermotropic liquid crystalline polymer (TLCP) segments was synthesized. Its chemical structure and liquid crystalline properties were characterized by FT‐IR, differential scanning calorimetry (DSC) and polar light microscopy (PLM) respectively. A single glass transition temperature (T_g) at 134.0°C, a melting temperature (T_m) at 282.0°C and a temperature of ignition (T_i) at 331.3°C can be observed. Blends of PEEK and TLCP with and without RCP as compatibilizer were prepared by extrusion and the effect of RCP on the thermal properties, dynamic mechanical properties, morphology and static tensile mechanical properties of blends was investigated by means of DSC, dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), etc. Dynamic mechanical measurements indicated that there appeared to be only a single tan δ peak resulting from the glass transition of the PEEK‐rich phase and the T_g value shifted towards higher temperature due to the presence of compatibilizer, as suggested partial compatibility. Morphological investigations showed that the addition of RCP to binary blends reduced the dispersed phase size and improved the interfacial adhesion between the two phases. The ternary compatibilized blends showed enhanced tensile modulus compared to their binary blends without RCP. The strain at break decreased for the ternary blends due to embrittlement of the matrix by the incorporation of some RCP to the matrix phase. Copyright © 2007 John Wiley & Sons, Ltd.     

马拉硫磷分子印迹聚合物的制备及其在固相萃取中的应用

以马拉硫磷为模板分子,采用原位逐步聚合法制备了具有良好识别性能的分子印迹聚合物(MIPs),考察了马拉硫磷、甲基对硫磷、对硫磷及甲胺磷在马拉硫磷聚合物的选择性分离富集特性。用聚合物固相萃取了蜂蜜、蔬菜和天然水中的马拉硫磷。结果表明,聚合物对模板分子产生了印迹效应,对马拉硫磷有明显的选择性。流速为1.0 mL/min,进...     

Pyrolysis of 1-methacryloyl-3-phenylthiourea and its polymer: rate and mechanism

The rates of thermal decomposition of 1-methacryloyl-3-phenylthiourea (1a), 1-methacryloyl-3-(4-nitrophenyl)thiourea (1b), 1-methacryloyl-3-(4-chloro phenyl)thiourea (1c), 1-methacryloyl-3-(4-methylphenyl)thiourea (1d), 1-methacryloyl-3-(4-methoxyphenyl)thiourea (1e), poly-1-methacryloyl-3-phenylthiourea (2) and 1-acryloyl-3-phenylthiourea (3) have been measured between 390 and 465 K. The reactions were homogeneous and unimolecular with log A = 11.48, 11.48, 11.81, 11.43, 11.11, 11.21 and 11.87s⁻¹ and E_a = 119.7, 111.93, 120.07, 121.94, 120.84, 124.64 and 122.68 kJ mol⁻¹, respectively. Product analysis was used to outline feasible pathways for the elimination reaction of the compounds under study.     

Efficient preparation of dichloromethyl alkyl ethers and their application in the formylation of aromatic compounds: Scope and limitations

Practical preparations of dichloromethyl alkyl ethers are described, based on the reaction of alkyl formates with oxalyl chloride in the presence of N-methylformanilide. The method involves a simple procedure that does not require the use of harmful reagents. Dichloromethyl propyl and dichloromethyl butyl ethers represent secure synthetic equivalents to dichloromethyl methyl ether. Formylations of both electron-deficient and electron-rich aromatics with these dichloromethyl alkyl ethers in the presence of AlCl₃, FeCl₃, or TiCl₄ have been systematically investigated. A plausible mechanism of formylation is discussed.     

The preparation of bovine serum albumin surface-imprinted superparamagnetic polymer with the assistance of basic functional monomer and its application for protein separation

Currently, small proteins imprinting are more reported since large proteins molecular imprinting faces challenge due to their bulk size and complex structure. In this work, bovine serum albumin (BSA) surface-imprinted magnetic polymer was successfully synthesized based on atomic transfer radical polymerization (ATRP) method in the presence of common monomer (N-isopropylacrylamide) with the assistant of basic functional monomer (N-[3-(dimethylamino)propyl]-methacrylamide), which provides a achievable attempt for imprinting larger target proteins based on the ATPR with the mild reaction conditions. The BSA-imprinted polymer exhibited higher adsorption capacity and selectivity to BSA over the non-imprinted polymer. Competitive adsorption tests indicated the BSA-imprinted polymer had better selective adsorption and recognition properties to BSA in the mixture. The obtained BSA-imprinted polymer was applied to bovine serum, which also showed selectivity to BSA. In addition, a conventional aqueous two-phase solution of PEG/sulphate was used as elution for adsorbed BSA, which was compared with common NaCl elution.     

Optical properties of conjugated polymer: review of its change mechanism for ionizing radiation sensor

A review on the change mechanism of conjugated polymer upon radiation exposure is presented. The change mechanism is mainly focused on the polymer's optical properties instead of its electrical properties. This research explores the effect of ionizing radiation on the optical change of conjugated polymer. This study also reviewed the possibility of using conjugated polymer as a radiation sensor vis‐à‐vis radiation type and the optical response. From material point of view, topochemical reaction, conjugation length and the degree of anisotropy of the conjugated polymer itself were identified as factors affecting the polymer's optical properties. These factors are tunable to meet a required optical degree, thus making the observation using the optical properties of a conjugated polymer possible for a radiation sensing tool. Based on the review, alteration of the factors and its mechanism of change occurs at macromolecular level. Therefore, a material at its smallest size down to a single molecule could be possible for the indication of radiation. Thus, radiation sensor made of nano or micro colloidal conjugated polymer deserves attention for future development. Copyright © 2017 John Wiley & Sons, Ltd.     

Mesoporous hollow silicon spheres modified with manganese ion sieve: Preparation and its application for adsorption of lithium and rubidium ions

In this work, mesoporous hollow silicon spheres modified with 3‐aminopropyl‐ triethoxysilane (APTES) of loaded hydrogen manganese oxide lithium ion sieve (APTES/HMO‐ HS) was prepared. The structure and morphology of as‐prepared APTES/HMO‐HS were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, transmission electron microscopy and nitrogen adsorption‐desorption measurements. The Brunner‐Emmet‐Teller (BET) surface areas, pore diameters and pore volumes of APTES/HMO‐HS decreased gradually, while the Li:Mn:Si molar ratios range from 1:1:50 to 1:1:10. The obtained hierarchical porous APTES/50HMO‐HS has a high specific surface area (557.1694 m² g^‐1). The lithium and rubidium ions solutions were used to measure the adsorption performance of the APTES/HMO‐HS adsorbent. The pseudo‐first‐order and pseudo‐second‐order kinetics, Langmuir and Freundlich isotherms of APTES/HMO‐HS were investigated; suggesting that the adsorption kinetics can be described by the pseudo‐second‐order kinetic model and the adsorption isotherms well fits the Langmuir isotherm equation. The obtained results show that the prepared APTES/HMO‐HS exhibits excellent abilities to simultaneously and selectively recover Li⁺ and Rb⁺ (11.22 mg·g^‐1 and 8.31 mg·g^‐1) and have a promising application in the simultaneous adsorption of lithium and rubidium ions.     

An optical chemical sensor based on functional polymer films for controlling sulfur dioxide in the air of the working area: Acrylonitrile and alkyl methacrylate copolymers with brilliant green styrene sulfonate

The effects of the chemical and phase composition of acrylonitrile and alkyl methacrylate (Alkyl-MA) copolymers with styrene sulfonates (SS) of triphenylmethane dye cations on the gas permeability and sensing properties of their films were studied for developing an optical chemical sensor (OCS) for sulfur dioxide (SO₂) on the basis of functional polymers. Of the three triphenylmethane dyes tested, namely, fuchsine, Crystal Violet, and Brilliant Green (BG), only the last dye was selected for molecular design. It was shown that the copolymer of Decyl-MA with SS—BG with the degree of modification DM = 0.10 is the best material among the studied ones from the viewpoints of sensitivity, response time, and time stability of sensor characteristics. The conditions for fabricating polymer films and the parameters of their functioning in OCSs for SO₂ were optimized. The effect of annealing conditions on the sensitivity of spectra to SO₂ was studied. Working temperature, working wavelength, and the conditions for the regeneration of the initial spectral parameters were optimized. Calibration characteristics of OCSs for the dynamic admittance of SO₂—air mixtures were obtained. The calculated detection limit for SO₂ in an air flow for a sensor with a sensing film fabricated of the decyl-MA—SS—BG copolymer with DM = 0.10 was 0.16 vol %, or 4160 mg/m³. This points to the necessity of searching for more sensitive sensing materials among other classes of functional polymers.Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 3, 2005, pp. 307–315.Original Russian Text Copyright © 2005 by Soborover, Tverskoi, Tokarev.