The polymerizations of isobutylene initiated with the system tert-butyl chloride (t-BuCl)/SnCl4 and carried out in CH2Cl2 at −20°C and −78°C were investigated. The results obtained demonstrate that the presence of t-BuCl in the polymerizing system gives rise to a PIB product with a distinctly bimodal MWD. The higher-molecular weight (HMW) PIB, M̄n = 20000, I=M̄w/M̄n ∼ 2.5, is the result of existence of the protogenic initiation with residual water in the reaction system. The lower-molecular weight (LMW) PIB, M̄n < 600, M̄w/M̄n ≤ 1.4, is the product of polymerization initiated presumably with a complex t-BuCl-SnCl4-H2O. To elucidate the reaction mechanism of the polymerization initiated with the complex, a series of similar isobutylene polymerizations using the initiation system 2,5-dichloro-2,5-dimethylhexane (DDH)/SnCl4 was run and the oily LMW PIB samples were investigated by 1H-NMR. A new polymerization mechanism describing the role of DDH and t-BuCl is suggested. 相似文献
Pressure, volume, temperature (PVT) measurements reveal that during the intramolecular cyclization reaction of poly(acrylonitrile) (PAN) and poly(styrene-co-acrylonitrile) (SAN) the volume decreases. This volume contraction becomes smaller with increasing styrene content in the random copolymers and should be related to the simultaneous decrease of longer acrylonitrile homo-sequences. The onset temperature of the cyclization reaction is raised with higher styrene contents in the random copolymers. Thus, it can be excluded that the cyclization reaction has a major influence on the discoloration process of SAN samples having relatively small acrylonitrile contents (less than 50 mol-%) during thermal annealing below 300°C. 相似文献
A short overview on the general mechanistic principles of the allyl metal complex catalyzed stereo-specific butadiene polymerization is given. The present state of knowledge on the mechanism of stereoregulation and in the understanding of the catalytic structure reactivity relationships is discussed comparatively for allyl nickel and allyl lanthanide catalysts. 相似文献
Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe2 layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (Eg) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells. 相似文献
A new way to fabricate monodisperse polymer particles in a microfluidic device without UV‐light and without the need for high temperatures is described in this article. By applying an activator regeneration by electron transfer ‐ atom transfer radical polymerization (ARGET‐ATRP) initiator system in a co‐capillary microfluidic setup and by separating the monomer mixture in an initiator and a catalyst phase, a fast polymerization of the droplets at low temperature without premature curing and thus clogging of the capillaries can be achieved. The influence of the flow rates on the particle sizes and their polydispersity as well as the controlled character of the polymerization are investigated. The particle size is well adjustable, but the reaction is not controlled due to the high radical concentration needed for rapid polymerization. In addition, particles with incorporated UV‐dyes are produced as a proof of concept at low temperature.
An investigation into the rapid detection of mycotoxin-producing fungi on corn by two mid-infrared spectroscopic techniques was undertaken. Corn samples from a single genotype (RWA2, blanks, and contaminated with Fusarium graminearum) were ground, sieved and, after appropriate sample preparation, subjected to mid-infrared spectroscopy using two different accessories (diffuse reflection and attenuated total reflection). The measured spectra were evaluated with principal component analysis (PCA) and the blank and contaminated samples were classified by cluster analysis. Reference data for fungal metabolites were obtained with conventional methods. After extraction and clean-up, each sample was analyzed for the toxin deoxynivalenol (DON) by gas chromatography with electron capture detection (GC-ECD) and ergosterol (a parameter for the total fungal biomass) by high-performance liquid chromatography with diode array detection (HPLC-DAD). The concentration ranges for contaminated samples were 880–3600 g/kg for ergosterol and 300–2600 g/kg for DON. Classification efficiency was 100% for ATR spectra. DR spectra did not show as obvious a clustering of contaminated and blank samples. Results and trends were also observed in single spectra plots. Quantification using a PLS1 regression algorithm showed good correlation with DON reference data, but a rather high standard error of prediction (SEP) with 600 g/kg (DR) and 490 g/kg (ATR), respectively, for ergosterol. Comparing measurement procedures and results showed advantages for the ATR technique, mainly owing to its ease of use and the easier interpretation of results that were better with respect to classification and quantification. 相似文献
The effect of chloride ion concentration and pH of solution on the corrosion behavior of aluminum alloy AA7075 coated with
phenyltrimethoxysilane (PTMS) immersed in aqueous solutions of NaCl is reported. Potentiodynamic polarization, linear polarization,
open circuit potential, and weight loss measurements were performed. The surface of samples was examined using SEM and optical
microscopy. Elemental characterization of the coating by secondary ion mass spectrometry indicates an intermediate layer between
coating and aluminum alloy surface. The corrosion behavior of the aluminum alloy AA7075 depends on chloride concentration
and pH of solution. In acidic or neutral solutions, general and pitting corrosion occur simultaneously. On the contrary, exposure
to alkaline solutions results in general corrosion only. Results further reveal that aluminum alloy AA7075 is susceptible
to pitting corrosion in all chloride solutions with concentrations between 0.05 M and 2 M NaCl; an increase in the chloride
concentration slightly shifted both the pitting and corrosion potentials to more active values. Linear polarization resistance
measurements show a substantially improved corrosion resistance value in case of samples coated with PTMS as compared to uncoated
samples in both neutral (pH = 7), acidic (pH = 0.85 and 3), and alkaline chloride solutions (pH = 10 and 12.85). The higher
corrosion resistance of the aluminum alloy coated with PTMS can be attributed to the hydrophobic coating which acts as a barrier
and prevents chloride ion penetration and subsequent reaction with the aluminum alloy. 相似文献