Highly refractive polymer resin derived from sulfur‐containing aromatic acrylate

New sulfur‐containing polymers with high‐refractive indices and low birefringences have been developed as UV‐curable high‐refractive polymer resins. The polymers derived from 2,7‐bis[(2‐acryloylethyl)sulfanyl]thianthrene (2,7‐BAST) and 4,4′‐bis[(acryloyloxyethylthio)diphenylsulfide (4,4′‐BADS) were prepared by photopolymerization under UV irradiation. Transparent UV‐cured films were obtained in both cases. Both polymers showed good thermal stability, such as a 5% weight‐loss temperature at 355 °C under nitrogen and glass transition temperatures (T_g) in the range of 94–143 °C. They also showed high‐refractive indices of 1.6531 and 1.6645 at 632.8 nm and low birefringences of 0.0039 and 0.0069 in addition to high transparency in the visible region. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2604–2609, 2010     

Correlation between nanohole volume and mechanical properties of amine‐cured epoxy resin blended with poly(ethylene oxide)

A set of diglycidylether of bisphenol‐A (DGEBA)/4,4′‐diaminodiphenylmethane (DDM) epoxy matrix modified with poly(ethylene oxide) (PEO), pre‐cured at two different temperatures, was examined by positron annihilation lifetime spectroscopy (PALS). The aim was to investigate the correlation between local free volume and mechanical properties. A negative deviation from the linear additivity rule of the local free volume is observed at both cure schedules. Using together the local free volume and mechanical results allows to conclude that the cure temperature makes small contribution to the flexural strength and modulus of blends but is responsible for the composition‐dependent rise of the fracture toughness. It is proposed that this behavior is a consequence of the nearest‐neighbor intrachain contacts or self‐association of the epoxy‐OH groups during cure leading to a non‐uniform space distribution of the DGEBA–PEO contacts, which causes the deflection of the crack path. Copyright © 2008 John Wiley & Sons, Ltd.     

A 13C NMR study of the methylol derivatives of 2,4′‐ and 4,4′‐dihydroxydiphenylmethanes found in resol phenol–formaldehyde resins

A total of 13 of the 16 possible methylol derivatives of 2,4′‐ and 4,4′‐dihydroxydiphenylmethane have been synthesized, isolated, and identified. These compounds are found as intermediates in the cure process of resol phenol–formaldehyde (PF) resins. Analysis of the ¹³C NMR spectra (in acetone‐d₆) of these compounds provided a way to evaluate the seven methylolphenol ring types (methylol derivatives of 2‐hydroxyphenyl and 4‐hydroxyphenyl rings) found in typical resol PF resins using the ipso carbon region from 150 to 160 ppm. A simple diagnostic test was developed using the chemical shift values of the methylol methylene carbon atoms to identify the presence of intermediates containing either a 2‐hydroxyphenyl or a 4‐hydroxyphenyl ring. Using these data it is now possible to analyze the major components in extracted prepreg PF resins. Copyright © 2002 John Wiley & Sons, Ltd.     

Acetylene-grafted resins derived from phenolics via azo coupling reaction

Novel phenolic resins with high ethynyl contents were realized via azo coupling reaction between phenol units and diazonium of 3-ethynylaniline. If Novolac and high-ortho Novolac resins were used as the starting materials directly, the ratio of ethynyl groups to phenolic rings was ca 70%; while the ratio was 100% for the resin from Friedel-Craft polycondensation of 4-(3-ethynylphenyl)salicyl alcohol. All the resins were readily soluble in acetone and ethanol, and meltable at temperatures below 100 °C. The resins underwent thermal addition-type cure with a broad exotherm of around 140-280 °C, and the starting curing temperature showed a downward drift with increase in the ethynyl content. The thermal properties of the cured resins, determined from thermogravimetric analysis (TGA), were considerably superior to those of Novolac- and Resole-type phenolic resins. The initial decomposition temperatures were at ca 400 °C, and the anaerobic carbon yields were ca 80% for all the resins.     

Sorption kinetics for the removal of aldehydes from aqueous streams with extractant impregnated resins

The sorption kinetics for the removal aldehydes from aqueous solutions with Amberlite XAD-16 and MPP particles impregnated with Primene JM-T was investigated. A model, accounting for the simultaneous mass transfer and chemical reaction, is developed to describe the process. It is based on the analogy to the diffusion and reaction in a stagnant liquid sphere, but corrected for the porosity and particle properties influencing the diffusion. The developed model describes the kinetic behavior of the process in the low concentration region rather well. However, in the high concentration region, larger discrepancies are observed. Initially, the influence of the flow rate was investigated to eliminate the effect of the external mass transfer. The influence of the particle morphology was investigated for both physical and reactive sorption. Physical sorption experiments were used to determine the factor τ that takes the particle properties influencing the diffusion into account. It was shown that the diffusion is faster in XAD-16 than in MPP impregnated systems. Reaction rate constant k _x was determined by fitting the model to the experimental data. Sorption of benzaldehyde appears to be significantly slower (k _x ∼10⁻⁴ l/mol s) than the sorption of pentanal (k _x ∼10⁻³ l/mol s) due to the slower chemical reaction. The influence of the particle size was investigated for the sorption of pentanal with XAD-16. It was observed that the particle size does influence the diffusion term, but does not have an effect on the reaction rate. On the other hand, the extractant loading influences the reaction rate slightly in the low concentration region, whereas the initial concentration of the solute has more pronounced effect.     

玻璃纤维带隙间环氧胶渗流特性的试验研究

 对环氧胶在含有玻璃纤维带的间隙中的渗流进行了试验研究. 通 过试验确定纤维的松紧度、输胶压力、抽口真空度和输胶温度等不同参 数对渗流流速的影响，为环氧胶的VPI(真空压力浸渍或浇铸)工艺提供 工艺参数.     

PEG化的聚合物载体树脂研究进展

组合化学已成为发现和优化新药、亲和配体和催化过程中的重要组成部分.高分子载体树脂在组合化学中起着关键的作用,各种类型的聚合物树脂在有机合成中已被广泛开发为载体、反应物和催化剂.与传统的Merrifield树脂相比较,聚乙二醇(PEG)化的聚合物树脂具有与极性溶剂更好的相容性、更高的溶剂吸收和溶胀性能.本文主要综述与PEG相关联的聚合物树脂在有机合成载体领域中的最新成果.     

Initial step of anthracene‐sensitized photoacid generation from diphenyliodonium hexafluorophosphate in an epoxy matrix studied by steady‐state and laser‐flash photolyses

The anthracene‐sensitized photodecomposition of diphenyliodonium hexafluorophosphate was studied in an epoxy matrix. From steady‐state photolysis, the generation of protons, which are considered to be the actual initiators of the polymerization of epoxides, was confirmed. In addition, 9‐phenylanthracene was detected as a main product from anthracene. From time‐resolved laser‐flash photolysis, a broad absorption band with a peak at about 500 nm was observed that was thought to be due to the precursor of 9‐phenylanthracene. On the basis of these results, we propose electron transfer from anthracene in the excited singlet state to the diphenyliodonium cation as the initial step of photoacid generation. This process is followed by fast chemical reactions, which generate 9‐phenylanthracene and protons, and back electron transfer from the diphenyliodine radical to the anthracene cation radical. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2937–2946, 2001     

Photoinitiated alternating copolymerization of dialkyl maleates and fumarates with vinyl ethers

A systematic study of the free radical photoinitiated alternating crosslinking copolymerizations of dialkyl maleates and furmarates with multifunctional vinyl ethers was carried out. The photocopolymerizations were fast and highly efficient when carried out using a variety of α‐cleavage photoinitiators. The effects of the structures of the both the unsaturated esters and the vinyl ether monomers were examined. Dialkyl maleates were observed to be more reactive than the corresponding fumarate esters. The photopolymerization rates of several of these comonomer pairs were compared with standard diacrylate and dimethacrylate monomers. A range of different physical properties can be obtained by varying the length of the alkyl chain on alcohol portion of the unsaturated ester monomer. Prospects for the use of these comonomer systems in UV curable coatings, adhesives, printing inks, and composites are discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs–Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition.