Reactions of chitosan (degree of deacetylation 67%, weight-average molecular weight 850,000) with formaldehyde were performed in a dilute aqueous acetic acid solution at a molar ratio of amino groups of the polymer to HCHO of 0.06:O.1 mol/L and at different temperatures (45, 60, and 75°C). In each case the pH of the reaction mixtures was 3.4 during the experiments. The process was investigated by measuring the kinetic changes of the free formaldehyde concentration and the sum of free formaldehyde and methylol groups produced. No gelation of the reaction product was observed. The experimental results led to the conclusion that the methylol groups formed by the addition of HCHO to chitosan functions take part in some intramolecular reactions with amino and/or hydroxyl groups of chitosan. Initially, the concentration of the resultant methylene bridges grows rapidly and then drops again until an equilibrium is established. This rather unusual decomposition of the methylene links once formed without changing the reaction conditions is accompanied by a substantial growth of the amount of methylol derivative whose concentration at the beginning of the process increased rather slowly. 相似文献
Degree of branching (DB) is a crucial structure parameter of hyperbranched polymers, which can be determined by 1H NMR, quantitative 13C NMR, degradative method, etc. However, for complicated hy-perbranched polymers, intricate structure and severe overlap of spectral signals hinder the determina-tion of DB using traditional methods. In this work, the architecture of complicated hyperbranched polymers has been elucidated with the help of 2D NMR techniques. Using such a method, overlapped NMR signals can be well separated into a two-dimensional space, and additional structural information is also available. Correspondingly, quantitative analysis for complicated systems can be realized. De-termination of DBs for three types of complicated hyperbranched polymers synthesized from step-polymerization, self-condensation vinyl polymerization and self-condensation ring-opening po-lymerization is shown as examples. 相似文献
The analytical expressions of the various structural units and the average degree of branching for the hyperbranched polymers resulted from AB2 polycondensation with substitution effect were derived by the kinetic mechanism.The reactivity difference between the B group in linear unit and that in terminal group has great effect on the molecular parameters of the products obtained.The concentration of terminal units has a maximum with the increase of the conversion of A groups(x).The higher the reactivity ratio(r) of linear B group to branched one is,the later the maximum appears and the larger it is.The degree of branching of the hyperbranched polymers obtained is controllable by adjusting the parameters of r and x,which increases with increasing both x and r. 相似文献
The asymmetric aldol reaction with formaldehyde is a fundamental carbon‐carbon bond‐forming reaction in organic synthesis, as well as in the quest of the origin of life, as it is thought to have been the first “molecular brick” involved in the synthetic path to complex sugars. Products of aldol reactions, i.e., the β‐hydroxy carbonyl compounds, are versatile building blocks used to access a great variety of functionalised molecules. The employment of formaldehyde, as a C1 symmetric electrophile, in aldol reactions can be likely considered the most challenging, yet simplest, process to introduce a hydroxymethyl group in an asymmetric fashion. In this account, an overview of the progress achieved in the asymmetric metal‐ and organocatalysed aldol reaction, using readily available formalin or paraformaldehyde sources, is illustrated. Our recent contribution to this area, with the application of asymmetric hydroxymethylation in cascade processes for the synthesis of γ‐butyrolactones, is also shown.
Hyperbranched polymers, HBPs, formed via a stepwise polymerization of A2, Bg type monomers with the addition of end-capping molecules, AR, were investigated by means of recursive and kinetic models. First, gelation curves were established based on the initial compositions of reactants at various functionalities, g, of monomers Bg. According to this guide, the hyperbranched polymers without gel fraction can be obtained. The molecular structures of HBPs, such as molecular weight and the degree of branching were calculated as related to conversion. It is shown that they can be controlled by the composition of reactants. With the addition of molecules AR, the gelation can be avoided at high conversion, and the distribution of molecular weights of polymers becomes narrower. 相似文献
This study focuses on the experimental and molecular-level investigation of epoxy acrylate formation. Epoxy acrylate vinyl ester resin was prepared by a reaction of diglycidyl ether of bisphenol-A-based epoxy resin and acrylic acid, using benzimidazole as a catalyst. It was confirmed that benzimidazole can effectively catalyze this reaction. FTIR analysis of the product revealed a simple addition esterification reaction between the epoxide group and carboxylic group of acrylic acid excluding the side reactions (e.g., etherification). DFT computational studies were performed to theoretically explore the insights of reaction mechanisms. The calculations revealed that the benzimidazole-catalyzed reaction dominates the uncatalyzed reaction. A comparison of calculated activation energies showed that concerted mechanisms are less significant in such reactions owing to their high activation barriers. 相似文献
Apparent viscosity measurements have been made to characterize the effects of shear rate and temperature on the partially hydrolyzed polyacrylamide solutions. The power-law model for the viscosity behavior has been modified to develop empirical correlations that combine effects of shear rate and temperature. Nonlinear regression was performed on the experimental data to develop the proposed correlation. The viscosities of the polymer solutions were measured in the temperature range of 25°C to 80°C, while the shear rate was varied from 1 to 1000 1/s. The proposed correlation should prove supportive for the preliminary selection of the polymers for enhanced oil recovery applications. 相似文献
The reaction kinetics of bisphenol-S epoxy resin with methyl-acrylic acid in the presence of quaternary ammonium salt catalyst was studied. The reaction rate constants at different temperatures were determined. The reaction is first order with respect to epoxy group, zero order with respect to methylacrylic acid and 0.71 order with respect to quaternary ammonium salt catalyst, respectively. The mechanism of this reaction was discussed. 相似文献
A series of hyperbranched polyurethane-benzyltetrazoles(H-PBTZs) with different linkage structures were synthesized via the polycondensation of hexamethylenediisocyanate as an A2 type monomer with(4-(1H-tetrazol-5- yl)benzyl)-diethanolamine(TBDEA) as a BB’2 type monomer in the absence of catalyst at different temperatures.The FTIR, and 13C and 1H-NMR spectroscopy were used to characterize the molecular structures of TBDEA and H-PBTZs as well as the counterpart linear polyurethane-benzyltetrazole(L-PBTZ).The molecular composition was determined by the reaction selectivity that the isocyanate group reacted with the hydroxyl group in diethanolamine segment or the active hydrogen atom on tetrazole ring.Raising reaction temperature was propitious to the reaction of isocyanate group with the active hydrogen atom on tetrazole ring.The degrees of branching(DB) for H-PBTZs obtained from the 1H-NMR spectra increased with raising reaction temperature.The wider molecular weight distribution of 1.7-2.9 for H-PBTZs was obtained via GPC analysis.TGA results showed that H-PBTZs had high thermal stability compared with L-PBTZ. 相似文献
Russian Journal of Organic Chemistry - Some peculiar features of two most commonly used catalytic systems (Cul and CuSOVsodium ascorbate) controlling the regioselectivity of 1,3-dipolar... 相似文献
Some advantages, disadvantages, and anomalies of various donors in glycosidations are discussed. By studying several two‐component donor/acceptor‐diol reactions, it is shown that regiopreferences are not very sensitive to the type of donor used. However, in competitive glycosidations within a given type of donor and between different types of donor, it is shown that regio‐ and chemoselectivities must be indexed to donor reactivity. 相似文献