New developments in speciality polymers: polymeric stabilizers

Many new speciality polymers have been developed in the last few years. In this paper polymeric stabilizers (antioxidants, flame retardants and ultraviolet stabilizers) will be discussed. Polymeric antioxidants of the hindered-phenol type, copolymers of 2,6-ditertiarybutyl-4-vinyl(or isopropenyl)phenol with styrene, methyl methacrylate, or more importantly butadiene or isoprene have been prepared; hydrogenation of the latter copolymers gave copolymers of the two polymerizable phenolic antioxidants with ethylene or ethylene/propylene. The polymeric antioxidants have been blended with diene polymers and selected polyolefins and have improved the long-term oxidative stability of these polymers. Polymeric flame retardants have been prepared by copolymerizing styrene and/or acrylonitrile with acrylates and methacrylates of aliphatic bromine-containing alcohols or bromine-containing phenols. Polymers with polymer-bound flame retardants have a higher limiting oxygen index compared with the original polymer. A new class of polymerizable ultraviolet stabilizers has also been developed; these stabilizers are styryl, α-methylstyryl, acryloyl and methacryloyl derivatives of 2(2-hydroxyphenyl)2H-benzotriazoles. These monomers have been copolymerized with styrene, acrylates and methacrylates. 2(2-Hydroxyphenyl)2H-benzotriazoles substituted in the 4 position of the benzotriazole ring with hydroxyl, acetoxy or carboxyl groups suitable for incorporation into polyesters, polycarbonates, polyamides and epoxy resins have also been synthesized. All 2(2-hydroxyphenyl)2H-benzotriazole ultraviolet absorbers and the polymers into which they are incorporated have high light absorbency with γ_max between 330 and 350 nm and extinction coefficients in some cases as high as 4.5 × 10⁴ 1 mol^?1 cm^?1.     

聚氧化乙烯—聚磷酸钠共混物的钠离子导电性

研究了聚氧化乙烯-聚磷酸钠共混物的钠离子导电性和低分子量多缩乙二醇对共混物导电性的改进作用。结果表明,降低多缩乙二醇的分子量以及增加其含量都有利于提高共混物的离子导电率。增塑剂改进共混物导电性的实质是提高共混物的非晶相含量,共混物内钠离子传导发生在非晶区,聚合物链段运动是离子传导的主要推动力。     

用直接实验设计方法优化PAN/PSF合金膜的制备条件

在大量单因素实验结果的基础上 ,以直接实验设计方法来设计制膜条件和用SAS软件包对所得实验数据进行优化并建立数学模型 ,得到优化的制膜条件。由该条件所制得的PAN/PSF合金膜的纯水通量提高 1 7倍 ,平均孔径扩大了 1 8倍。     

驻极体声传感器及其储电材料的现状

综述了驻极体声传感器及其储电材料近年来的迅猛发展。传统的FEP(tetrafluoroethylene—hexa—fluoropropylene copolymer)极体电容式声传感器及以铁电聚合物PVDF(poly vinylidene fluoride)家族为芯片的声传感器和超声抉能器仍焕发着青春活力。Si基微型驻极体声传感器的理论和实验研究已经日趋成熟，而用空间电荷型多孔聚合物驻极体压电薄膜为芯片可望研制出新一代声电和电声传感器、压力传感器和驱动器。     

Liquid–liquid extraction of a recombinant protein with reverse micelles

Recombinant cytochrome b₅ was extracted into the reversed micelle phase of an anionic surfactant (AOT) in octane and back-extracted to a final aqueous phase. The extraction of the protein was controlled by an electrostatic mechanism, since it was dependent on the global charge of the protein. This was directly demonstrated by experiments with native and mutant cytochromes obtained by site directed mutagenesis. The back-extraction of cytochrome b₅ to a fresh aqueous phase was decreased by factors that reduced the size of the water pool of the organic phase, such as high salt concentrations (1–2 mol dm^?3 NaCl) and low temperatures (4°C), probably because of an increase in a favourable interaction of this protein with the surfactant at closer distances.     

Effects of multiple weak interactions on the binding of phenolic compounds by polymeric adsorbents

To investigate the effects of multiple weak interactions on the binding of phenolic compounds by polymeric adsorbents, macroporous polystyrene (PS) resin and PS‐based adsorbents with different hydrogen‐bond acceptor atoms (PS CH₂( OCH₂CH₂)_n OCH₃, n = 0, 1, 2, and 3, denoted as PS‐EG₀, PS‐EG₁, PS‐EG₂, and PS‐EG₃) were prepared. The phenol adsorption strength order on these adsorbents was PS/PS‐EG₀ < PS‐EG₁ < PS‐EG₂ < PS‐EG₃, indicating that the adsorption on PS and PS‐EG₀ was driven by hydrophobic and π–π interactions, and the adsorption on PS‐EG₁, PS‐EG₂, and PS‐EG₃ was driven by a hydrogen bond in addition to hydrophobic and π–π interactions. PS‐EG₂ may adsorb a second phenol molecule on each binding site and PS‐EG₃ may adsorb second and third ones. The adsorption strength of resorcinol increased in the order of PS, PS‐EG₁, and PS‐EG₂, indicating that the adsorption was driven by 0, 1, and 2 hydrogen bonds in addition to hydrophobic and π–π interactions. Similarly, the adsorption of phloroglucinol on PS, PS‐EG₁, PS‐EG₂, and PS‐EG₃ was driven by 0, 1, 2, and 3 hydrogen bonds in addition to hydrophobic and π–π interactions because the adsorption strength increased in this order. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4652–4658, 2006     

Recovery of pyruvic acid with weakly basic polymeric sorbents

BACKGROUND: Carboxylic acids are among the most important substances that can be manufactured from biomass. However, the recovery of carboxylic acids from fermentation broths presents a challenging separation problem. To avoid the production of waste salts and net consumption of chemicals in the calcium carboxylate salt process, the use of reversible chemical complexation with polymeric sorbents and extractants is attractive for carboxylic acid recovery. Pyruvic acid is widely used in the manufacture of medicines, pesticides and foodstuffs and can be produced by fermentation. Since the acidity of pyruvic acid (pK_a = 2.49) is stronger than that of normal carboxylic acids, and as few reports on the recovery of pyruvic acid are available, the sorption of pyruvic acid from aqueous solution on two types of weakly basic polymeric sorbent, tertiary amine D301R and primary amine D392, was investigated over a wide pH range and at various salt (MgSO₄) concentrations. RESULTS: Overloading adsorption of pyruvic acid on both weakly basic polymeric sorbents occurred, with the overloading of D392 being greater than that of D301R. The adsorption of pyruvic acid on both sorbents was greatly affected by the solution pH and the salt concentration in the aqueous phase. An overloading model was able to predict the experimental uptake data very well. CONCLUSION: Solution pH is one of the most important operating conditions, and both polymeric sorbents D392 and D301R can be used to recover pyruvic acid from dilute aqueous solution with high efficiency at a solution pH around 2. The uptake by D392 is greater than that by D301R owing to steric hindrance of the tertiary amine. Copyright © 2008 Society of Chemical Industry     

New strategies for separations through reactions

Separations through reactions can provide reliable and economically viable alternatives to established methods of separation, particularly for close boiling substances. New strategies in ‘Dissociation Extraction’ and ‘Dissociation Extractive Crystallization’ for separation of close boiling acidic/basic mixtures have been highlighted. Separations with aqueous solutions of hydrotrope and aqueous micellar solutions have been brought out. Separations by membranes with facilitated transport is potentially attractive. This paper is dedicated to Dr L K Doraiswamy on his sixtieth birthday.     

Mixed Micelles of Surface Active Ionic Liquid (SAIL)–Octylphenol Ethoxylate: A Novel Reaction Medium for Selective Oxidation of Toluene to Benzaldehyde

Ionic liquids have been found to be suitable alternatives to volatile organic solvents in chemical transformation. Through a proper choice of cations and anions, the properties of an ionic liquid can be tuned so that it resembles an amphiphile. Such specially designed molecules are known as surface-active ionic liquids (SAIL). Like conventional surfactants, SAIL also form aggregates in an aqueous medium. Studies show that the mixing of SAIL with conventional surfactants leads to synergistic micellization. However, very few reports are available on the application of such systems as reaction media. Present study focuses on the application of mixed micelles of 1-tetradecyl-3-methylimidazol-1-ium bromide, ([C₁₄mim]Br) with nonionic surfactant, Octylphenol ethoxylate with 10 moles of ethylene oxide (OPE-10). Enhanced solubilization and selective catalytic oxidation of toluene using hydrogen peroxide as an oxidant and tungstic acid as a catalyst have been studied in detail using this system.     

The Interaction of Glymes with Surfactant Micelles

The critical micelle concentrations (CMC) values and counterion dissociation (α values) have been determined for a number of mixed micellar systems consisting of two typical ionic surfactants and glycol ethers (glymes) as cosurfactants, namely diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Conductance experiments were used to determine the CMC and α values of the mixed micelles as a function of glyme concentration in the aqueous mixed solvent. Favorable interactions between sodium dodecyl sulfate micelles and glyme cosurfactants were deduced from the decreases in the CMC values and the large increase in the α values of these systems as a function of increasing glyme concentration in the mixed solvents. In contrast to the anionic surfactant/glyme systems, in general, there appeared to be little favorable interactions between the surfactant and glymes when micelles of the cationic surfactant dodecyltrimethylammonium bromide were formed in water/glyme solvent systems containing an increasing amount of the glymes. The interaction of glymes with the surfactant micelles was examined closely via ¹³C nuclear magnetic resonance (NMR) chemical shifts for both surfactant and glyme carbons; these chemical shifts changes were interpreted in terms of the distribution and the localization of the glymes in the aggregates. Finally, partition constants, determined from two-dimensional diffusion-oriented spectroscopy (2D-DOSY) experiments, were used to calculate thermodynamic quantities of transfer of the glymes between the bulk phase and the self-assembled aggregates. All these results are interpreted in terms of the key contributions that both the glyme ethoxylated groups and alkyl endgroups make to the hydrophobic interactions.