Reactive surfactants in heterophase polymerization. XVII. Influence of the surfactant on the mechanical properties and hydration of the films

In the context of a European union‐supported network on “Reactive Surfactants for Heterophase Polymerization,” different polymerizable surfactants (surfmers) have been synthesized and engaged in the emulsion polymerization of styrene, butyl acrylate, and acrylic acid. The thermomechanical properties of films cast from these different latices are reported in this article. The evolution of the mechanical properties with temperature and the effect of water molecules on these properties are studied. We observed that the studied surfactants do not influence the properties of the dry films. However, some differences due to grafting of reactive surfactants appeared when the films were wet. The amount of water uptake is drastically decreased when only reactive surfactants are present in the film. Concerning the mechanical behavior of the wet films, a decrease of the plastic flow stress is observed for all the samples whatever the nature of the surfactant (reactive or conventional). Hence, calorimetric measurements and dynamic mechanical analysis are used to identify the possible mechanisms that induce the change in the mechanical behavior of the latex films. In the case of reactive surfactant grafted to the polymer, the very low value of water uptake is accompanied by a plasticization of the polymer. In contrast, no plasticizing effect is observed in the case of nonreactive surfactant, even if the amount of water is very large. Finally, the tensile behavior of the styrene–butyl acrylate copolymer versus temperature is analyzed in the frame of the quasi point defects (qpd) model. Both rubber elasticity and chain orientation effects are taken into account to describe the behavior laws at large extensions (i.e., ? ≈ 1.2). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1686–1700, 2002; DOI 10.1002/app.10548     

Effect of temperature and span series surfactant on the structure of polysulfone membranes

A macrovoid structure was found in polysulfone membranes formed by the wet‐inversion method using N‐methylpyrrolidinone (NMP) and water as the solvent/nonsolvent pair. The addition of Span series surfactants in the casting solution was found to inhibit the macrovoid formation. Sorbitan monooleate (Span‐80) was more effective in inhibiting macrovoids than was sorbitan monolaurate (Span‐20). The phenomenon of macrovoid suppression became more prominent at higher temperature. The cloud‐point shift might account for the temperature effect. But there was no simple explanation for the effect caused by Span‐80. The cloud‐point position, the demixing rate, and the viscosity of the casting solution were measured. None of them could explain the effect of macrovoid inhibition by the addition of Span‐80. However, the penetration test indicated that the penetration of a nonsolvent into a surfactant‐free casting solution was caused by a convective flow, but that into Span‐80 was through diffusion. It was found that the retardation of nonsolvent penetration was the major cause of macrovoid inhibition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 166–173, 2002     

Preparation and properties of water‐soluble polyester surfactants. II. Preparation and surface activity of silicone‐modified polyester surfactants

We prepared a novel series of water‐soluble silicone‐modified polyesters [poly(ethylene glycol) (PEG)–silicone polyesters] by reacting organopolysiloxane with a hydroxy‐terminated polyester. The polyesters were obtained by the polymerization of maleic anhydride and PEGs (molecular weights = 2000, 4000, 6000, 8000, and 10000). These water‐soluble PEG–silicone polyesters can be used as auxiliaries in dyeing process because they exhibit good surface activities such as surface tension, low foaming, and wetting power. The presence of these surfactants also retarded the rate of nylon dyeing with acid dyes. The retarding effect and low‐foaming property of these novel PEG–silicone polyesters make it possible for these surfactants to be used as leveling agents for modern nylon dyeing with acid dyes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3005–3012, 2002     

Effectiveness test of alginate‐derived polymeric surfactants

A series of alginate‐derived polymeric surfactants (APSs) with a linear alkyl group (C8, C12, C16) was synthesized by oxidation followed by reductive amination of 2,3‐dialdehydic alginate. The products were characterized by measuring IR spectra, NMR spectra, surface tension and critical micelle concentration (cmc). They were also tested for the solubilization of azobenzene and adsorption of heavy metal. In the case of 40% CHO‐C8 APSs, the lowest interfacial tension value (31.5 m Nm^?1) was obtained at the cmc value of 1.35 g dm^?3. The dissolving capacity of 40% CHO‐C8 APS towards azobenzene was 27 times greater than that of alginate. The overall cobalt (Co²⁺) removal efficiency by adsorption using APSs was high compared with that of sodium alginate at pH 3, 5 and 7. Equilibrium aspects of cobalt adsorption onto 10% CHO‐APSs were studied, and the results show that APSs had high equilibrium capacities for cobalt uptake, 115.5 mgg^?1. © 2002 Society of Chemical Industry     

Mixed monolayer and mixed micelle formation in binary mixture of surfactants—Systems for trioxyethylenated dodecyl sulfonate and some polyoxyethylenated fatty alcohol ether nonionic surfactants

The interaction and synergism of some polyoxyethylenated fatty alcohol ether (POE) nonionic surfactants (C₁₂E₂, C₁₂E₃, C₁₀E₅, C₁₀E₇, where C_x indicates number of carbon atoms in the chain and E_y indicates number of oxyethylene glycol ethers) with trioxyethylenated dodecyl sulfonate (C₁₂E₃S) in mixed monolayer formation at the surface and in mixed micelle formation in aqueous solutions were studied at 25 and 40°C by calculating interaction parameters (β_α, β_M) from surface tension-concentration data by use of Rosen's equations based on the nonideal solution theory. All the systems investigated adapt reasonably well to the nonideal model, with negative values of β_σ and β_M (where M means micelle and σ refers to the air-liquid interface) indicating a favorable interaction between the mixed surfactants. Either at a monolayer or in a mixed micelle, the attractive interaction becomes stronger when the alkyl chain in the POE surfactant is longer, i.e., when the POE becomes more hydrophobic. The interaction increases in the order C₁₀E₇<C₁₀E₅<C₁₂E₃, C₁₂E₂. For the two C₁₀E _n (n= 5,7)/C₁₂E₃S systems, as temperature increases from 25 to 40°C, the interaction increases in a mixed micelle, but it decreases in a mixed monolayer. Synergism in mixed micelle formation exists for C₁₂E₃S/C₁₀E _n mixtures when X₁ ^M , the mole fraction of POE in a mixed micelle, is ≈0.4–0.8, whereas synergism does not occur in the systems of C₁₂E₃S/C₁₂E _m due to the large difference between CMC₁ and CMC₂, i.e., large |In(C ₁ ^M /C ₂ ^M )| value (where CMC=critical micelle concentration). The degree of synergism in mixed micelle formation is temperature independent and is 0.23, 0.18, and close to zero for C₁₀E₅/C₁₂E₃S, C₁₀E₇/C₁₂E₃S, and C₁₂E _m (m=2,3)/C₁₂E₃S systems, respectively. Synergism in surface tension reduction effectiveness occurs in C₁₂E₃S/C₁₂E₂ and C₁₂E₃S/C₁₂E₃ systems. The mole fractions of POE in the solution phase are 0.302 and 0.333 for the two mixtures at the point of maximum synergism.     

Synthesis and characterization of dehydroabietic acid derivatives suitable for surfactant synthesis

The syntheses of derivatives of dehydroabietic acid suitable for further manipulation into surfactants are presented. The compounds are produced at very high yields and purity. They contain several different functional groups, e.g., carboxylic acid, amine, ester, alcohol, and an aromatic group. The functional groups are useful as the linking unit to the hydrophilic part in synthesizing surfactants.     

纳米CaCO_3的表面改性及其在软PVC中的应用

本文合成了系列表面改性剂ADDP ,并将其用于改性纳米CaCO3。研究了表面改性后纳米CaCO3 的性质及其随ADDP分子结构和用量的变化规律。最后 ,将改性纳米CaCO3 充填改性软质PVC。     

A Systematic Study of Mixed Surfactant Solutions of a Cationic Ester-Bonded Dimeric Surfactant with Cationic, Anionic and Nonionic Monomeric Surfactants in Aqueous Media

A novel cationic biodegradable dimeric (gemini) surfactant, ethane-1,2-diyl bis(N,N-dimethyl-N-hexadecylammoniumacetoxy) dichloride (16-E2-16), containing an ester-linked spacer was synthesized. Its pure and mixed micellization properties with monomeric surfactants cetyl trimethyl ammonium chloride, cetyl pyridinium chloride, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyl alcohol ethoxylate (20EO) and tert-octylphenol ethoxylate (9.5EO) were investigated by surface tension measurements at 30 °C. The critical micelle concentration (CMC) of 16-E2-16 is well below that of cetyl trimethyl ammonium chloride containing the same number of carbon atoms in the hydrophobic tail per polar head. At different mole fractions of the gemini surfactant, the CMCs of the gemini-conventional binary mixtures were determined and were found to be less than the ideal CMC values in all the cases indicating synergistic interactions. Aggregation number and Stern–Volmer constant, obtained by the fluorescence quenching technique, also support the synergistic behavior of the surfactant systems.     

Surface and Biological Activity of Some Prepared Iminium Surfactants Based on Schiff Bases

A series of novel iminium surfactants were prepared through quaternization of different prepared fatty Schiff bases with benzyl chloride. The chemical structures were confirmed using FTIR, ¹H-NMR and mass spectroscopy. The surface properties and biological activity of these surfactants were investigated. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γ_max) and minimum surface area (A _min), Efficiency (PC₂₀) and Effectiveness (π_CMC) as well as the free energy of micellization ( $ \Updelta G_{\text{mic}}^{\text{o}} $ ) and adsorption ( $ \Updelta G_{\text{ads}}^{\text{o}} $ ) were calculated. It was found that the prepared compounds have good surface and biological activity.     

高分散[Pd-Pt]/C催化喹啉加氢制备1,2,3,4-四氢喹啉

利用双表面活性剂( Tween-20和Brij-35 )保护的方法,合成并表征了一系列[Pd-Pt]/C催化剂。将其应用于喹啉催化加氢制备1,2,3,4-四氢喹啉反应中,结果表明,5wt%[Pd-Pt(1:3)]/C的催化活性最高。优化反应参数,以乙醇为溶剂,初始底物浓度为2.4mol/L,在130℃, 2.5MPa下反应50min,喹啉转化率100%,1,2,3,4-四氢喹啉选择性100%。