New intramolecular effect observed for polyesters: An anomeric effect

A series of polyesters was prepared to evaluate hydrolytic stability as a function of cyclohexyl dibasic acid content. The three cyclohexyl dibasic acids: 1,2; 1,3; and 1,4 were formulated into polyesters with two glycols. The proportion of cis and trans isomers was evaluated via ¹H NMR. The hydrolytic stability of short chain polyesters was evaluated in an acetone/water mixture which solubilized the polyesters to mimic oligoester behavior within a thermosetting polyester coating environment. The rate of hydrolysis was monitored by acid titration and corroborated by GPC. Surprisingly, 1,2-cylohexyl diacid-based polyesters were robust, and 1,3-cyclohexyl diacid-based polyesters were the most susceptible to hydrolysis. Evidently, a 1,2-anchimeric effect for cyclohexyl dibasic acid polyesters was not an important consideration, while the 1,3-cyclohexyl ester interaction was. Consequently, an anomeric effect was proposed. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 12–14, 2003, in Philadelphia, PA.     

Gas transport in poly(n-alkyl acrylate)/poly(m-alkyl acrylate) blends

Poly(n-alkyl acrylate)s can have side chains that crystallize independently of the main chain; side-chain length can thus be used as a tunable parameter to control the gas permeability of membranes. The gas permeation response of poly(n-alkyl acrylate) and poly(m-alkyl acrylate) blends as a function of temperature is reported for varying side-chain lengths, n and m, and blend composition in the semi-crystalline and molten states. Macroscopic homogeneity is observed for a small range of n and m where |n − m| ≤ 2-4 methylene units. Thermal analysis indicates that the blend components crystallize independently of one another; however, crystallization is hindered by the presence of the other component. Permeation responses of the blends investigated in some cases exhibited two distinct permeation jumps or increases at the melting temperature of each component. Blends with continuous permeation responses but higher effective activation energies of permeation (i.e., more thermally responsive) were observed for some blends over the temperature of interest for membranes to be used for modified atmosphere packaging.     

Effects and properties of poly(arylene ether benzonitrile)s of various molecular weights blended with sulfonated poly(ether ether ketone)

Poly(arylene ether benzonitrile) (PAEBN) was synthesized with 2,6‐dichlorobenzonitrile and biphenol. PAEBNs with various molecular weights (MWs), 1,640,000 and 185,000 g/mol, were synthesized by control of the stoichiometry of the monomers and were blended with sulfonated poly(ether ether ketone) (SPEEK). The effects of MW on the water uptake, swelling, methanol permeability, and proton conductivity of the SPEEK/PAEBN blend membranes were investigated. The molecular mobility of the SPEEK/PAEBN blends was also examined in this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of the surface conditions on permeation in the deuterium–MANET system

The condition of the surfaces is of crucial importance for the deuterium permeation through materials. In this work a study of the surface constants for the adsorption (σk₁) and release (σk₂) of deuterium under different surface conditions on the martensitic steel DIN 1.4914 (MANET) has been carried out. The growth of an oxide surface layer (Cr₂O₃) of about 25–30 nm in a MANET sample, heat treated in an oxidizing environment, compared to the bare MANET that have a ‘natural' oxide of about 5 nm has provoked a reduction of both the permeation rate and the recombination coefficient (about 3 orders of magnitude). In addition, the permeation governing process has changed from diffusion-limited to surface-limited. The measurements of the permeation rate of deuterium were performed by a gas-phase permeation technique over the temperature range 574–746 K and for deuterium driving pressures in the range from 3 to 10⁵ Pa.     

Ultrasonic study of molecular association of poly(vinyl chloride) solution in tetrahydrofuran

Ultrasonic absorption, velocity, adiabatic compressibility, relaxation time and relaxation amplitude measurements are reported on poly(vinyl chloride) (PVC) solution in tetrahydrofuran (THF) using pulsed ultrasonic apparatus operating at 2 MHz and 313 K. Results show a linear increase of velocity. density, viscosity, absorption coefficient, relaxation time and relaxation amplitude values with the increase of PVC concentration in THF. In contrast the compressibility decreases with increasing PVC concentration. This suggests interaction between PVC and THF molecules.     

Modification of phenol–formaldehyde resol resins by lignin,starch, and urea

Lignin‐based chemicals, starch, and urea were used as modifiers for phenol–formaldehyde resol resins. The effects of the addition stage of the modifiers used in the synthesis of the resins and the type of modification reagent on the structures of the resins and their molar masses and reactivities were investigated. The modifications with corn starch and lignin promoted condensation; this was verified by increased molar masses and high ratios of methylene bridges to the sum of free ortho and para aromatic groups with respect to the corresponding reference resin without a modification reagent. The later the modifier was added to the resin condensation mixture, the more methylene bridges were formed with respect to the amounts of free ortho and para aromatic groups. In addition, when urea or wheat starch was added in the later condensation stage, the final condensation also reached high stages. The modifications with lignosulfonate and starch, as well as the early addition of urea, enhanced p–p′ bridge structures. The lowest condensation stage and, therefore, the highest reactivity were found when wheat starch was added with the starting reagents. The curing heat of the wheat‐starch‐modified resins decreased according to the deferred addition point of starch. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 582–588, 2003     

电化学方法研究碳钢高温水体系中的氢扩散和渗透

本文应用Devanathan渗透装置的原理,设计了一套能用于测量碳钢-高温水体系中氢在碳钢中的扩散和渗透的实验装置,找出了该装置用于测量的最佳工作参数,并用该装置测量了373—473K下氢在碳钢中的扩散系数和扩散速率,讨论了氢在碳钢上还原的机理。     

Selective gas transport in miscible PPO-PS blends

The permeation rates of He, CO₂ and CH₄ though miscible blends of polystyrene and poly(phenylene oxide) at 35°C are reported as a function of pressure. Sorption isotherms for CO₂ and CH₄ are also presented. By using ratios of the permeabilities of the pure gases the separation factors for the gas pairs He---CH₄ and CO₂---CH₄ can be estimated. For both pairs the estimated separation factor goes through a prominent maximum, thus indicating that these blends are more permselective than expected from the behaviour of polystyrene and poly(phenylene oxide). This stems from mobility considerations rather than solubility effects and a qualitative free volume argument is proposed as an explanation. The sorption and transport data have been interpreted and correlated using the dual sorption-mobility models developed previously for glassy polymers. Since the commercial polystyrene used contained a small amount of mineral oil to improve flow behaviour, the effect of this additive on polystyrene properties was explored in some detail.     

分离有机水溶液的聚离子复合膜（Ⅱ）

本文研究用聚离子昨合膜进行渗透汽化分离乙醇水溶液的特性，探讨了进料温度、浓度、膜后压力，进料液循环量等操作条件对膜分离性能的影响。