PEG20000中试放大的工艺研究

在一定温度和催化剂作用下 ,分别利用本体聚合和溶剂聚合的方法 ,在 1L、10 0L不锈钢高压反应釜中合成了相对分子质量为 2 0 0 0 0的聚乙二醇 ,并讨论了聚合反应机理 ,研究了催化剂用量、反应温度、反应时间对聚合反应的影响。经过红外、核磁共振、凝胶色谱、化学分析等方法对产物进行了表征。     

A new efficient method for one‐pot conversions of aryl carboxylic acids into nitriles without solvent

A new efficient method for synthesising nitriles, important organic reagents, is reported in this paper. In an environmentally benign solvent‐free system, aryl carboxylic acids were converted into the corresponding nitriles via one‐pot reactions, by amidation with ethyl carbamate followed by dehydration with thionyl chloride, in excellent yields. The results showed that the method has the advantages of lower cost, higher yield, less pollution and greater ease of work‐up. Copyright © 2008 Society of Chemical Industry     

烯烃聚合单活性中心非茂催化剂的最新研究进展

综述了近几年来烯烃聚合用单活性中心非茂催化剂的研究进展。简要介绍了 2 3种由前、后过渡金属组成的配位化合物催化剂的结构与性能     

Phase behavior of ternary blends containing dimethylpolycarbonate,tetramethylpolycarbonate and poly[styrene‐co‐(methyl methacrylate)] copolymers (or polystyrene)

The miscibility and phase behavior of ternary blends containing dimethylpolycarbonate (DMPC), tetramethylpolycarbonate (TMPC) and poly[styrene‐co‐(methyl methacrylate)] copolymer (SMMA) have been explored. Ternary blends containing polystyrene (PS) instead of SMMA were also examined. Blends of DMPC with SMMA copolymers (or PS) did not form miscible blends regardless of methyl methacrylate (MMA) content in copolymers. However, DMPC blends with SMMA (or PS) blends become miscible by adding TMPC. The miscible region of ternary blends is compared with the previously determined miscibility region of binary blends having the same chemical components and compositions. The region where the ternary blends are miscible is much narrower than that of binary blends. Based on lattice fluid theory, the observed phase behavior of ternary blends was analyzed. Even though the term representing the Gibbs free energy change of mixing for certain ternary blends had a negative value, blends were immiscible. It was revealed that a negative value of the Gibbs free energy change of mixing was not a sufficient condition for miscible ternary blends because of the asymmetry in the binary interactions involved in ternary blends. Copyright © 2004 Society of Chemical Industry     

High char‐yielding poly[acrylonitrile‐co‐(itaconic acid)‐co‐(methyl acrylate)]: synthesis and properties

Polyacrylonitrile terpolymers of various compositions consisting of acrylonitrile (AN), itaconic acid (IA) and methyl acrylate (MA) were synthesized by solution polymerization in dimethylsulfoxide. Increase in concentration of either IA or MA retarded the overall polymerization rate and the polymer molecular weight. The system consisting of AN + MA and varying IA concentration was more prone to retardation in comparison with the system composed of AN + IA with variable MA concentration. The retardation factors were quantified. Minor quantities of MA boost the reactivity of IA in the terpolymer system. The terpolymer was richer in MA vis‐à‐vis the feed. The thermal characteristics of the terpolymer were examined as a function of its composition. In contrast to the copolymer of AN and IA requiring 1–1.5 mol% IA, the terpolymer required an IA content of approximately 2.5 mol% for optimum thermal stability. The polymer with 90 mol% AN, 2.5 mol% IA and 7.5 mol% MA exhibited reasonably good char‐forming characteristics and thermal stability. The overall crystallinity and crystallite size of the polymers were found to decrease on incorporation of the comonomers. The ‘aromatization index’ of the copolymer increased with the temperature of pyrolysis through re‐organization of the tetrahydropyridine ladder structure. Copyright © 2005 Society of Chemical Industry     

Preparation of flexible polyhedral particles via concentrated emulsion templating polymerization

This paper presents recent efforts on the preparation of flexible polyhedral particles via concentrated emulsion templating polymerization in which the hydrophilic monomer (acrylamide) and hydrophobic monomer (butyl acrylate) are polymerized simultaneously in the continuous and dispersed phase, respectively. Such templating polymerization has been enhanced in our systems owing to the introduction of acrylamide monomer and their higher polymerization rate in continuous phase as compared with butyl acrylate in dispersed phase. Diffusion between the different phases was also inhibited. Furthermore, the stability of the concentrated emulsion and the molecular weight of the produced poly(butyl acrylate) were found to be significantly affected by the amount of redox initiator. The morphology of the particles could be controlled by varying the volume fraction of the dispersed phase and the polyhedral particles were achieved at higher volume fraction. Copyright © 2005 Society of Chemical Industry     

Preparation of ultra‐low‐density microcellular materials

Microcellular polymeric materials can be obtained by the polymerization of a high‐internal‐phase emulsion. These materials are good candidates as targets toward inertial confinement fusion. This application requires severe specifications, including a very low density and a small cell size. In this study, we examined the influence of parameters such as emulsification conditions, surfactant nature, and the presence of a porogen on the obtainment of those requirements. It was possible to obtain microcellular polymeric foams with apparent densities as low as 0.0126 g/cm³. However, it was difficult to obtain very low material density and still maintain a small average pore size. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2053–2063, 2005     

Nanostructured polymer blends: Synthesis and structure

Nanostructured polymer blends prepared via anionic ring opening polymerizations of cyclic monomers in the presence of a pre-made polymer melt exhibit a number of special properties over traditional polymer blends and homopolymers. Here, we report on a simple and versatile method of in situ polymerization of macrocyclic carbonates in the presence of a maleic anhydride polypropylene (mPP) matrix and a surface-active compatibilizer (i.e. PC grafted onto a mPP backbone generated in situ) to yield a micro- and nanostructured polymer blends consisting of a polycarbonate (PC) minor phase, and a polypropylene (PP) major phase. By varying the processing conditions and concentration of the macrocyclic carbonate it was possible to reduce the size of the PC dispersions to an average minor diameter of 150 nm. NMR and TEM characterizations indicate that the PC dispersions do not influence crystal content in the PP phase. Overall, the results point to a simple strategy and versatile route to new polymeric materials with enhanced benefits.     

Identification of photoluminescence features of an epoxy resin based on components features and curing effects

Photoluminescence features in a commercial grade cured DGEBA-based epoxy resin have been investigated with as objective to determine which of the material compounds are responsible for cured resin emissions. The origin of the bands has been approached by considering photoluminescence of base resin and hardener taken separately, of their mixture, and in the course of curing. Most of the bands observed in the cured resin could be interpreted based on those found in the components taken separately. Fluorescence of the cured resin appears dominated by two broad bands that are characteristic of the hardener and exhibits a blue shift by up to 30 nm in the course of curing which could be used for cure monitoring purpose of the investigated system. Fluorescence of the base resin is clearly detected in the resin cured with tertiary amine as catalyser. However, it is very weak if the catalyser is not added. Two phosphorescence processes have been isolated in the cured resin, one of them being related to the base resin. Finally, a chemiluminescence spectrum has been recorded in the course of curing, which has been related to either curing-related reactions or to an oxidation process.