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31.
A kinetic investigation on the monoesterification reaction of the maleic anhydride residue (MA) in styrene-maleic anhydride copolymers with aliphatic alcohols was carried out in ethyl benzene solution. By comparison to classic catalysts such as tributylamine (TBA) and pyridine, 4-dimethylaminopyridine (4DMAP) is by far the most effective catalyst for this reaction. While both general base and nucleophilic mechanisms contribute to the reaction catalyzed by TBA or pyridine, a nucleophilic mechanism prevails with 4DMAP. This reaction is reversible, and its chemical equilibrium constant decreases significantly with increasing temperature. Both kinetic and thermodynamic results showed that in the presence of 4DMAP, the forward and reverse reactions are second and first order, respectively. The existence of side reactions, reactivity of two styrene-maleic anhydride copolymers of different MA contents as well as two aliphatic alcohols of different lengths are also addressed. © 1993 John Wiley & Sons, Inc. 相似文献
32.
Summary A rapid, robust and reproducible method providing excellent separation performance and simplicity using a 0.5% MC-4000 methyl
cellulosic sieving medium in DB-1 coated capillaries has been developed. The method is suitable for qualitative comparison
of DNA restriction profiles for fragments in the size range 100–1000 base pairs (bp). Efficiencies up to 8.5 million plates/m
(1057 bp fragment) were recorded. Peak resolution of 6 bp (291/297 bp, 335/341 bp) and 4 bp (238/242 bp, 341/345 bp) was achieved.
In addition, 1 bp partial resolution of 123/124 bp and 298/297 bp was obtained. Run-to-run (n=15), day-to-day (n=4), and capillary-to-capillary
(n=3) variations of 0.1–0.2% RSD, 0.3–0.5% RSD, and 0.1–0.3% RSD, respectively, were observed. The MC-4000 sieving matrix
was found to be better than hydroxypropyl methyl cellulose and hydroxypropyl cellulose, in terms of both performance and stability
in the DB-1 coated capillaries. The efficiency and resolution in DB-WAX capillaries were inferior to those obtained in DB-1
capillaries. The commercially available DB-1 capillaries were stable for months in the sieving medium at pH 8.3 and could
be regenerated to provide high efficiency after accidental current breaks. 相似文献
33.
The electrochemical oxidation of 1, 3-benzenedithiol was investigated in a 0. 100 mol/L tetrabutylammonium perchlorate/acetonitrile electrolyte. The electrochemical techniques used were potential sweep, bulk electrolysis, rotating disc and the potential step method. The combination of the techniques yielded the number of electrons transferred per molecule, the reaction order, the transfer coefficient, the diffusion coefficient and concentration of dithiol anions, the standard heterogeneous rate constant as well as the formal potential and equilibrium constant of the preceeding dissociation reaction. This paper also illustrates the methods for studying the electrode kinetics of reactions which (a) involve a chemical reaction preceeding the electron-transfer process, (b) have insoluble polymer products, and (c) are totally irreversible. 相似文献
34.
Daria E. Lonsdale Geoffrey Johnston‐Hall Amanda Fawcett Craig A. Bell Carl N. Urbani Michael R. Whittaker Michael J. Monteiro 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3620-3625
In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (Ctrs) determined using the Mayo method is equal to 3.8 × 10?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the Mn data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007 相似文献
35.
36.
Jie Xue Liang Chen Li Zhou Zhifeng Jia Yanping Wang Xinyuan Zhu Deyue Yan 《Journal of Polymer Science.Polymer Physics》2006,44(15):2050-2057
α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006 相似文献
37.
Sung‐Fu Hsu Tzong‐Ming Wu Chien‐Shiun Liao 《Journal of Polymer Science.Polymer Physics》2006,44(23):3337-3347
Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006 相似文献
38.
The kinetics of reactions occurring at the gas-exposed surfaces of charged mixed ionic electronic conductors (MIECs) are examined
from theoretical first principles. Analysis based on the classical electrochemical potential-transition state theory model
reveals that the nature of the reactions is electrochemical in general. However, the influence of the surface potential on
the reaction rate is opposite for adsorption and incorporation reactions. Two-dimensional finite volume models of an MIEC
as working electrode in a half-cell configuration are presented. The results for a simple, two-step reduction process show
that the effect of the surface potential on the rate of reactions is minimal for incorporation-limited reactions but more
influential for adsorption-limited reactions.
An erratum to this article is available at . 相似文献
39.
Andreas Lüttge 《Journal of Electron Spectroscopy and Related Phenomena》2006,150(2-3):248-259
The dependence of dissolution rates on the difference of Gibbs free energy is of critical importance for our understanding of crystal dissolution, reactive flow models and their applications to a variety of environmentally related problems. Here, we review experimental data generated with mineral powders and single crystals to develop a better understanding of apparent inconsistencies between otherwise internally consistent data sets. Additional information from direct surface observations and measurements with vertical scanning interferometry (VSI) and atomic force microscopy (AFM) of albite dissolution at 25, 150 and 185 °C may shed new light on this old but unsolved question. Our discussion is based on the importance of etch pit development, its ΔG dependence, and the pits’ role as a source for steps and step movement in the dissolution process. Results indicate that reaction history may be of critical importance in determining the overall reaction mechanism and its rate. Different rates are observed for systems having otherwise identical ΔGr acquired from increasing versus decreasing disequilibrium positions.
In this context, we finally discuss the validity of the common application of transition state theory (TST) to elementary and overall reactions governing the dissolution process. In this discussion of crystal dissolution, we contrast TST applications with a stochastic, many-body treatment that has led to the development of a stepwave model. This discussion also focuses on the controversy caused by the rivalry between surface adsorption models and a probabilistic model that seeks to incorporate the full three-dimensional crystal structure. 相似文献
40.
Leong‐Huat Gan Palaniswamy Ravi Bao Wei Mao Kam‐Chiu Tam 《Journal of polymer science. Part A, Polymer chemistry》2003,41(17):2688-2695
Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003 相似文献