Emulsifier‐free cationic latexes based on vinylbenzyl chloride and 2‐(dimethylamino)ethyl methacrylate with adjusted hydrophilic–hydrophobic properties

Functional emulsifier‐free cationic latexes based on styrenic monomer vinylbenzyl chloride (VBC) and acrylic monomer 2‐(dimethylamino)ethyl methacrylate (DMA) were successfully prepared with dual quaternary ammonium ions (36–63 mol %) on both monomer moieties in two‐stages. First, [2‐(methacryloyloxy)ethyl]dimethylhexadecylammonium bromide monomer (DMA(C₁₆)), prepared via quaternization of DMA with 1‐bromohexadecane, was utilized as a comonomer (5–20%) as well as a surfactant in the emulsion polymerization of VBC. Next, the quaternization of chloromethyl groups in the VBC moiety in latex particles with trimethylamine and N,N‐dimethylhexadecylamine created a second type of quaternized sites on the latex particles. The percentages of the quaternary ammonium ions of the first‐stage latexes (P[VBC‐DMA(C₁₆‐x)]) and the second‐stage latexes (P[VBC(R)‐DMA(C₁₆‐x)]) were determined using bromide and chloride ion‐selective electrodes. The particles were characterized with a scanning electron microscope, Zetasizer, measuring water contact angles of their pellets. The polymer structure and the alkyl group length in their quaternary ammonium ions played an important role on the sizes, zeta potentials and hydrophilic–hydrophobic balances of the latexes. The water contact angles of the pellets of the latex particles varied from 50.3 to 109.6° depending on both the polymer structure and the alkyl group length. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42775.     

Smart carboxymethylchitosan hydrogels that have thermo‐ and pH‐responsive properties

Thermo‐responsive poly(N‐isopropylacrylamide) (poly(NIPAAm)) and pH‐responsive poly(N,N′‐diethylaminoethyl methacrylate) (poly(DEAEMA)) polymers were grafted to carboxymethylchitosan (CMC) via radical polymerization to form highly water swellable hydrogels with dual responsive properties. Ratios of CMC, NIPAAm to DEAEMA used in the reactions were finely adjusted such that the thermo and pH responsiveness of the hydrogels was retained. Scanning electron microscopy (SEM) indicated the formation of an internal porous structure for the swollen CMC hydrogels upon incorporation of poly(NIPAAm) and poly(DEAEMA). Effect of temperature and pH changes on water swelling properties of the hydrogels was investigated. It was found that the water swelling of the hydrogels was enhanced when the solution pH was under basic conditions (pH 11) or the temperature was below its lower critical solution temperature (LCST). These responsive properties can be used to regulate releasing rate of an entrapped drug from the hydrogels, a model drug, indomethacin was used to demonstrate the release. These smart and nontoxic CMC‐based hydrogels show great potential for use in controlled drug release applications with controllable on‐off switch properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41505.     

Influence of polymer morphology on the adsorption behaviors of molecularly imprinted polymer‐methacrylic acid functionalized β‐cyclodextrin

The influence of molecularly imprinted polymer‐methacrylic acid functionalized β‐cyclodextrin (MIP(MAA‐β‐CD)) morphology on the adsorption behavior studies towards benzylparaben (BzP) was explored. The effects of time, concentration, and temperature towards BzP uptake were extensively evaluated. The adsorption performance of MIP(MAA‐β‐CD) was compared with that on the molecularly imprinted polymer‐methacrylic acid (MIP(MAA)) synthesized without β‐CD. The MIP(MAA‐β‐CD) was synthesized to obtain a spherical and spongy‐porous texture with a broad pore size distribution. The MIP(MAA‐β‐CD) showed fast kinetic and the intra‐particle diffusion model demonstrated a three step (surface and pore) adsorption process. The Koble‐Corrigan isotherm was the most suitable model for data fitting, which indicated that MIP(MAA‐β‐CD) had homogeneous and heterogeneous surfaces. This finding clearly demonstrated that the large uptake and strong affinity of MIP(MAA‐β‐CD) did not only probably result from the monomer‐template interactions, but also due to the morphological MIP(MAA‐β‐CD) structure. In contrary to MIP(MAA‐β‐CD), MIP(MAA) synthesized with uniform morphology and narrow pore size distribution had lower adsorption capacities and its kinetic data fitted the pseudo‐second order diffusion model, indicating a two‐step (surface only) adsorption process. The MIP(MAA) adsorption process followed the Langmuir isotherm model referred to solely homogeneous uptake. The calculated thermodynamic parameters showed that the BzP uptake was exothermic, spontaneous, and physisorption process onto MIPs, which supported the results of kinetics and isotherm adsorption data. This study clearly revealed that the presence of β‐CD improved the morphology of synthesized MIP, and automatically enhanced the adsorption behavior of MIP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42720.     

Molecularly imprinted polymers for the selective recognition of l‐phenylalanine based on 1‐buty‐3‐methylimidazolium ionic liquid

To enhance the affinity of 4‐vinyl pyridine to l ‐phenylalanine (l ‐Phe) and convert the imprinting process from the aqueous phase to the organic phase, an oil‐soluble amino acid ionic liquid was introduced as a template. In this study, 1‐butyl‐3‐methylimidazolium α‐aminohydrocinnamic acid salt was first applied to prepared surface molecularly imprinted polymers (MIPs) in acetonitrile for the selective recognition of l ‐Phe. Fluorescence quenching analysis of the functional monomer on the template was investigated under different conditions to study the imprinting mechanism. Several binding studies, such as the sorption kinetics, sorption thermodynamics, and solid‐phase extraction application, and the chiral resolution of racemic phenylalanine were investigated. The binding isotherms were fitted by nonlinear regression to the Freundlich model to investigate the recognition mechanism. The affinity distribution analysis revealed that polymers imprinted by ionic liquid showed higher homogeneous binding sites than those imprinted by l ‐Phe. The competition tests were conducted by a molecularly imprinting solid‐phase extraction procedure to estimate the selective separation properties of the MIPs for l ‐Phe. The target MIP was shown to be successfully for the separation of l ‐Phe from an amino acid mixture. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42485.     

酪素胶束结构及其纳米功能化的研究进展

总结了国内外关于酪素胶束微观结构及其胶束结构表征手段的研究,重点阐述了纳米粒子改性酪素胶束结构以获得功能材料的研究进展,希望对从事酪素研究的工作者有所帮助。     

The effect of tunable modification parameters on the structure and properties of polypropylene with cyclotrimerization surface of isocyanates

The cyclotrimerization of methylene diphenyl 4,4‐diisocyanate (MDI) and 3‐isopropenyl‐α,α′‐dimethylbenzene isocyanate (TMI) was applied on the bead/membrane surfaces of a polypropylene (PP)‐bearing isocyanate group to synthesize a protective networked polymer. Chemical structures of these molecules were characterized through attenuated total reflectance–Fourier transform infrared spectroscopy. Results showed that the absorption peak of isocyanate group at 2255 cm^?1 became negligible after the reaction was completed. The absorption peaks of the isocyanurate groups appeared simultaneously at 1600 cm^?1 and at 1510–1560 cm^?1; this result indicated that the grafted isocyanates were almost consumed, thereby forming isocyanurates. Energy X‐ray dispersive spectroscopy revealed that oxygen content increased; indeed, isocyanurate was formed on the PP surface. Pure PP beads, PP‐g‐TMI, and cyclotrimerization products were also subjected to thermal property tests to investigate their corresponding thermal stabilities. Cyclotrimerization could result in the increase in PP‐grafted decomposition temperature, even slightly higher than pure PP. Rheological behavior in oscillatory flow was also evaluated; the storage modulus, loss modulus, and complex viscosity of cyclotrimerization products were higher than those of the PP‐grafted membranes. Surface morphology was further observed through field‐emission scanning electron microscopy and atomic force microscopy. The cyclotrimerization products contained blocks and exhibited a rough surface. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43327.     

Quaternized poly(phenylene oxide) anion exchange membrane for alkaline direct methanol fuel cells in KOH‐free media

A series of anion exchange membrane (AEM) electrolytes with quaternary ammonium moiety are fabricated from poly (phenylene oxide) for its application in alkaline direct methanol fuel cells (ADMFCs). In the first step, poly(phenylene oxide) (PPO) is successfully chloromethylated by substituting chloromethyl groups in the aryl position of polymer. In the second step, the chloromethylated PPO (CPPO) is further homogeneously quaternized and ion‐exchanged to form an AEM. From the second step, series of AEMs are prepared by changing the mole ratio of amine in relation to CPPO. The presence of quaternary ammonium group in the membrane was confirmed by elemental analysis. The fabricated membranes are subjected to cell polarization studies in ADMFCs, wherein quaternized poly(2,6‐dimethyl‐1,4‐phenylene oxide) (CPPO:amine of 1:8) membrane exhibits higher peak power density of 3.5 mW cm^?2 when compared with the other ratios of CPPO:amine in the absence of KOH solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43693.     

POSS‐based fluorinated azobenzene‐containing polymers: Photo‐responsive behavior and evaluation of water repellency

The photoresponsive polyhedral oligomeric silsesquioxanes (POSS) based fluorinated azobenzene‐containing polymers were prepared and characterized by NMR, FT‐IR, GPC, XRD, TG and UV–Vis spectra. The thermal property of the polymers was improved by the introduction of POSS cage. The trans‐cis photoisomerization of the polymers in solution was similar to that of the fluorinated azobenzene monomer and in accordance with the first‐order reaction kinetics equation within the first 250 seconds UV irradiation. The cotton fabrics coated with the polymers showed excellent water repellency and possessed switchable wettability under UV irradiation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43540.