Synthesis of cationic hemicellulosic derivatives with a low degree of substitution in dimethyl sulfoxide media

A series of water‐soluble cationic 2‐hydroxylpropyltrimethylammonium hemicellulosic derivatives with low average degrees of substitution (DS's) were prepared by the incorporation of the cationic moiety 2,3‐epoxypropyltrimethylammonium chloride (ETA) onto the backbone of hemicelluloses in the presence of NaOH as a nucleophilic catalyst in homogeneous dimethyl sulfoxide (DMSO) media. The dependence of the homogeneous reaction on the different affecting factors was investigated. The average DS was calculated from the N/C ratio in the products and from the weight gain. The degree of substitution determined by the nitrogen content (DS_N) values up to 0.25 in a one‐step synthesis of the etherified hemicelluloses could be controlled by the adjustment of the amount of solvent used and the molar ratio of NaOH or ETA to the anhydromonomer units in the hemicelluloses. The structure of the cationic hemicellulosic derivatives formed was determined by Fourier transform infrared spectroscopy and further confirmed with solution‐state ¹³C‐NMR spectroscopy. In comparison, no significant degradation of the hemicellulosic derivatives occurred during the etherification of the polymers in the homogeneous DMSO system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of thermosensitive glycopolymers containing D‐glucose residue: Copolymers with N‐isopropylacrylamide

A new glycomonomer, 3‐acrylamido‐3‐deoxy‐1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose, was synthesized from D ‐glucose. This monomer was homopolymerized and copolymerized with N‐isopropylacrylamide in different compositions by free‐radical polymerization. The composition of the copolymer was determined with ¹H‐NMR spectroscopy. On acid hydrolysis, water‐soluble deprotected copolymers were obtained. The protected and deprotected copolymers showed a sharp cloud‐point temperature. A linear correlation was obtained between the lower critical solution temperatures and the concentration of glycomonomer in the copolymers © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Development of a superporous hydroxyethyl cellulose‐based hydrogel by anionic surfactant micelle templating with fast swelling and superabsorbent properties

The self‐assembling anionic surfactant, sodium n‐dodecyl sulfonate (SDS) micelles were used as pore‐forming templating for fabricating novel superporous hydroxyethyl cellulose‐grafting‐poly(sodium acrylate)/attapulgite (HEC‐g‐PNaA/APT) hydrogels. The network characteristics, morphologies of the hydrogels and removing of SDS micelles from the final product by washing with ethanol/water (v/v, 7 : 3) procedure were determined by Fourier transform infrared spectroscopy and scanning electron microscopy, as well as by determination of swelling ratio, swelling rate, and stimuli response to salts and pHs. The results showed that the added‐SDS concentration significantly affected the morphologies and pore structure of the hydrogel, and 2 mM SDS facilitates to form a homogeneous and well‐defined pore structure in the gel network to extremely improve the swelling ratio and swelling rate. The 2 mM SDS‐added superporous HEC‐based hydrogel not only had highest equilibrium swelling ratio (Q_eq, 1118, 102 g g^?1 in distilled water and 0.9 wt % NaCl solution), rapid swelling rate (k_is, 5.2840 g g s^?1), also showed multistimulus responses to salts and pHs, which may allow its applications in several areas such as adsorption, separation and biomedical materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42027.     

Smart anionic polyelectrolytes based on natural polymer for complexation of cationic surfactant

The thermosensitive polyelectrolytes were obtained by grafting 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) onto hydroxypropylcellulose (HPC), a biodegradable polysaccharide. The interactions of the polymers with dodecyltrimethylammonium chloride (DTAC), a model cationic surfactant, were studied. It was found by the measurements of the surface tension and the analysis of fluorescence emission of pyrene used as a fluorescent probe, that the HPC–AMPS graft polymers strongly interact with DTAC with the formation of polymer–surfactant complexes. The critical aggregation concentrations of these polymer–surfactant systems were found to be of the order of 10^?5 mol/dm³. The polymers were found to be potentially useful in the purification of water from cationic surfactants. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2401–2407, 2006     

Selection of a precursor of a monofunctional polyhedral oligomeric silsesquioxane reacted with aromatic diamines

With the aim of selecting a precursor of a polyhedral oligomeric silsesquioxane (POSS) reacted with aromatic diamines for its incorporation into an epoxy network, to generate an organic–inorganic hybrid material containing POSS, a polyhedral oligomeric silsesquioxane (glycidylisobutyl–POSS) was reacted with the diamines 4,4′‐methylenebis(2,6‐diethylaniline) (MDEA), 4,4′‐diaminediphenylmethane (DDM), and 4,4′‐(1,3‐phenylenediisopropylidene)bisaniline (BSA), at 160°C and different times, in a proportion rich in amines. The distribution of species in the reaction was followed by gel permeation chromatography (GPC). From the experimental data obtained the selected precursor was POSS/BSA reacted at 160°C for 20 or 30 min, to ensure that all the POSS was reacted, that there was a maximum of the monosubstituted amines, and that there was no degradation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1576–1583, 2004     

Cationic polymerization of ethylene oxide with Maghnite‐H as a clay catalyst in the presence of ethylene glycol

The activated‐monomer cationic ring‐opening polymerization of ethylene oxide, initiated with ethylene glycol and using an acid‐exchanged montmorillonite clay called Maghnite‐H⁺ as an effective catalyst, was carried out to obtain the corresponding homopolymers with narrow polydispersity ratios. The molecular weights of the obtained polymers were controlled with the feed ratio of the monomer to the initiator. The effects of the amount of the catalyst and time on the polymerization yield and viscosity of the polymers were studied. The structure was confirmed with proton nuclear magnetic resonance and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Interactions between cationic conjugated polyelectrolyte and DNA and a label‐free method for DNA detection based on conjugated polyelectrolyte complexes

The electrostatic complexes of single‐stranded deoxyribonucleic acid (ssDNA) and a cationic conjugated polyelectrolyte (CPE), poly{9,9‐di[3‐(1‐ethyl‐1,1‐dimethyl ammonio)propyl]‐2,7‐fluorenyl‐alt‐1,4‐phenylene dibromide} (PFN), were investigated. Fluorescence emission of PFN solution (10 μmol/L) can be drastically quenched to about one fourth of its original intensity in the presence of a trace amount (2.6 μmol/L) of ssDNA. The effect of oligonucleotide length on the fluorescence quenching behavior was also investigated. In contrast to single‐stranded DNA with 20 bases (ssDNA‐20), ssDNA with 40 bases (ssDNA‐40) induces a relatively higher quenching efficiency and larger red‐shift of PFN emission maximum. The binding constant of ssDNA‐20 and PFN is estimated to be 1.12 × 10²¹. At extremely low concentration (10 nmol/L), PFN can respond to 0.2 nmol/L (or 2 × 10^?10 mol/L) of ssDNA‐20 by significant enhancement of its emission intensity. The result is contrary to the observation in the relative higher concentration, and its mechanism is postulated. Based on the high binding ability of ssDNA with cationic CPE, a label‐free method for ssDNA detection is designed. It uses an electrostatic complex of cationic PFN and an anionic CPE, which exhibits fluorescence resonance energy transfer (FRET) between the two components. Addition of ssDNA improves the FRET extent, indicated by obvious change of fluorescence spectra of the conjugated polyelectrolyte complex. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Gel permeation chromatography calibration based on fractal geometry

The previously developed model [Polym Bull 2000, 44, 525] used to characterize the porous gel inside a gel permeation chromatography (GPC) column, has been extended to also include the interstitial space between the macroscopic gel particles. The hydrodynamic dimensions for 12 polystyrene (PS) standards, measured by GPC with differential refractive index (DRI), differential viscometry (VISCO), and multiangle laser light scattering (MALLS) detectors, have been used to determine the fractal parameters of the polystyrene–divinylbenzene gel corresponding to four commercial columns. The new developed model enables to predict the calibration curve for the sets of coupled columns based on the parameters of each column. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 771–777, 2004     

Development of a fast drying hybrid lacquer in a low‐relative‐humidity environment based on kurome lacquer sap

Hybrid lacquers that dry quickly in a low‐relative‐humidity environment were synthesized with the repeated kurome lacquer process and an organic silicone compound. An investigation by gel permeation chromatography showed that fractions with different molecular weights showed a lower monomer concentration than the pure kurome lacquer. Fourier transform infrared spectra of the hybrid lacquers revealed that absorption due to the ether of the quinone olefin and/or dibenzofuran appeared around 1470 and 1080 cm^?1 and increased with the number of drying days. The gel fractions in the lacquer films increased according to the number of drying days, and this showed that the hybrid lacquers had higher gel fractions than the pure kurome lacquer in the initial stage of dryness. In addition, the drying mechanism of the hybrid lacquers was analyzed with an automatic drying time recorder and rigid‐body pendulum physical property testing measurements. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1055–1061, 2005     

Aggregation behavior of 3,6‐O‐carboxymethylated chitin in aqueous solutions

The aggregation behavior of 3,6‐O‐carboxymethylated chitin (3,6‐O‐CM‐chitin) in aqueous solutions was investigated by viscometry, gel permeation chromatography (GPC), and GPC combined with laser light scattering (GPC‐LLS) techniques. 3,6‐O‐CM‐chitin has a strong tendency to form aggregates in NaCl aqueous solutions with the apparent aggregation number (N_ap) of about 27. There were three kinds of aggregates corresponding to different cohesive energies, the aggregates with low cohesive energy were first dissociated at 60°C, the aggregates with middle cohesive energy were then dissociated at 80 to 90°C, and the aggregates with high cohesive energy were difficult to be disrupted by heating. Decreasing polysaccharide concentration (c_p) or increasing NaCl concentration (c_s) reduced the content of the aggregates. At the critical c_p of 2.5 × 10^?5 g/mL, the aggregates were dissociated into single chains completely. The change of aggregation and disaggregation of 3,6‐O‐CM‐chitin in water–cadoxen mixtures occurred from 0.1 to 0.4 of v_cad, and were irreversible. Intermolecular hydrogen bonding can be ascribed as main driving force for aggregation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1838–1843, 2002     

Effect of the miscibility between a silane and a sizing agent on silanol condensation

The miscibility between a hydrolyzed silane coupling agent, which had chemically nonreactive organofunctional groups such as propyl groups, and a film‐forming polymer [poly(vinyl acetate) PVAc] and its effect on silanol condensation were studied. A mixture consisting of a silane hydrolyzate and PVAc obtained from an alcoholic aqueous solution was investigated with Fourier transform infrared spectroscopy and size exclusion chromatography. Hydrogen bonding between the SiOH groups of the silane and the C?O groups of PVAc and silanol condensation affected by PVAc were examined. The hydrogen bonding and condensation reaction were influenced by the miscibility between the organofunctional group of the silane and PVAc. The miscibility of each system was estimated from the calculated Hildebrand solubility parameter of the organofunctional group. A correlation between the miscibility and the integrated absorbance of the hydrogen‐bonded C?O, obtained by least‐squares curve fitting, was established. On the basis of the molecular weight of the silane and the number of hydrogen‐bonded C?O groups, a micellelike phase was proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 589–598, 2003     

High molecular weight hydrophilic functional copolymers by free‐radical copolymerization of acrylamide and of N‐acryloylmorpholine with N‐acryloxysuccinimide: Application to the synthesis of a graft copolymer

Free‐radical solution copolymerization of acrylamide (AAm) and of a disubstituted acrylamide derivative, N‐acryloylmorpholine (NAM), with N‐acryloxysuccinimide (NAS) was investigated with the aim to obtain a copolymer of at least 100,000 g mol^?1. Different polymerization conditions likely to increase the molecular weight were studied such as monomer and initiator concentrations, temperature, and nature of the solvent. The molecular weights were determined by SEC using a light‐scattering detector. The grafting of end‐functionalized polysaccharide chains onto such high molecular weight poly(NAM‐co‐NAS) was performed and a graft copolymer bearing a high number of saccharidic branches was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1808–1816, 2003     

Comparison of styrene reversible addition–fragmentation chain‐transfer polymerization in a miniemulsion system stabilized by ammonlysis poly(styrene‐alt‐maleic anhydride) and sodium dodecyl sulfate

In this study, we conducted the reversible addition–fragmentation chain‐transfer (RAFT) polymerization of styrene (St) in a miniemulsion system stabilized by two different stabilizers, ammonlysis poly(styrene‐alt‐maleic anhydride) (SMA) and sodium dodecyl sulfate (SDS), with identical reaction conditions. The main objective was to compare the polymerization kinetics, living character, latex stability, and particle morphology. The macro‐RAFT agent used in both systems was SMA, which was obtained by RAFT solution polymerization mediated by 1‐phenylethyl phenyldithioacetate. The experimental results show that the St RAFT miniemulsion polymerization stabilized by SDS exhibited a better living character than that stabilized by ammonlysis SMA. The final latices were very stable in two systems, but different stabilizers had an obvious effect on the polymerization kinetics, living character, and particle morphology. All of the particles obtained by RAFT miniemulsion polymerization stabilized by SDS were solid, but an obvious core–shell structure was observed in the miniemulsion system stabilized by ammonlysis SMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Carbon dioxide switchable polymer surfactant copolymerized with 2‐(dimethylamino)ethyl methacrylate and butyl methacrylate as a heavy‐oil emulsifier

A CO₂‐switchable polymer surfactant was synthesized with 2‐(dimethylamino)ethyl methacrylate and butyl methacrylate. The conductivity, ζ potential, and particle size change illustrated the switchability of the surfactant, and this change could be repeated. Its surface tension decreased sharply when the sample was bubbled with CO₂; this indicated the enhancement of the surface activity. In the heavy‐oil emulsion with a surfactant concentration of 8 g/L, the viscosity almost reached the highest stability. When CO₂ overflowed the emulsion, it became unstable when the temperature beyond 40°C. The emulsion had a nice resistance to inorganic salt, which was maintained stably even when the concentration of NaCl was as high as 90,000 ppm. The emulsion could later be broken by the removal of CO₂. Its hydration rate was over 22 times faster than that in the presence of CO₂. The amount of residual oil in water was only about 53.84 ppm; this showed a good demulsification ability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41307.     

EWOD‐Driven translational movement of a liquid polyelectrolyte droplet

Controlled transportation of air‐ and electrochemically stable materials is of interest in many areas of science. Herein, we report the synthesis and characterization of an ionic liquid monomer and its corresponding polyelectrolyte. The translational movement of these ionic liquid droplets across a substrate using the mechanism of electrowetting on a dielectric (EWOD) is demonstrated with emphasis given to electrode design and selective switching in the device construction. Directional control of a 2 mm sized polyelectrolyte droplet is shown to laterally move across the substrate surface on the order of 10s of minutes due to its increased viscosity, whereas its ionic liquid monomer also transverses but at a much faster pace‐on the order of 10s of seconds. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dissolution of softwood kraft pulps by direct derivatization in lithium chloride/N,N‐dimethylacetamide

A method for the characterization of the molar mass distributions (MMDs) of softwood kraft pulps dissolved in 0.5% lithium chloride (LiCl)/N,N‐dimethylacetamide (DMAc) by size exclusion chromatography is presented. The method is based on derivatization with ethyl isocyanate and the dissolution of samples in 8% LiCl/DMAc. In this study, the derivatization of hardwood kraft pulps did not influence the MMD. In the case of softwood pulps, however, the derivatization decreased the proportion of the high‐molecular‐mass material and increased the proportion of the low‐molecular‐mass material, which resulted in a distribution similar to the MMD of a hardwood kraft pulp. The results suggest that associations between hemicellulose and cellulose in the softwood kraft pulp were ruptured during derivatization. This led to a more correct estimation of the MMD of derivatized softwood kraft pulps than obtained by the dissolution of nonderivatized samples. This new method offers several advantages over derivatization with phenyl isocyanate: a precipitation step is not necessary, it is possible to follow the lignin distribution in the samples, and the method allows very high levels of dissolution of softwood kraft pulps up to a κ number of around 50. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 424–431, 2004     

Micropatterning of polydiacetylene based on a photoinduced chromatic transition and mechanism study

A photoinduced chromatic transition from blue to red for the polydiacetylene 10,12‐pentacosadiynoic acid has been studied. This transition produces an obvious change in the ultraviolet–visible absorption and fluorescence emission spectra. A two‐dimensional micropattern has been realized on the basis of this change and imaged with a confocal fluorescence microscope. Detailed information on the mechanism of the chromatic transition has been obtained by the application of resonance Raman and Fourier transform infrared methods. The results indicate that the conformational change of alkyl side chains constricted by hydrogen‐bonded head groups imposes strain on the polymer backbone and finally leads to a drastic decrease in the π‐electron‐conjugation length. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 942–946, 2007     

Burning‐rate enhancement of a high‐energy rocket composite solid propellant based on ferrocene‐grafted hydroxyl‐terminated polybutadiene binder

Four different samples of ferrocene‐grafted hydroxyl‐terminated polybutadiene (Fc‐HTPB), containing 0.20, 0.52, 0.90, and 1.50 wt % iron, were synthesized by the Friedel–Crafts alkylation of ferrocene with hydroxyl‐terminated polybutadiene (HTPB) in the presence of AlCl₃ as a (Lewis acid) catalyst. The effects of the reaction conditions on the extent of ferrocene substitution were investigated. The Fc‐HTPBs were characterized by IR, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectra. The iron content and number of hydroxyl groups were estimated, and the properties, including thermal degradation, viscosity, and propellant burning rates (BRs), were also studied. The thermogravimetric data indicated two major weight loss stages around 395 and 500°C. These two weight losses were due to the depolymerization and decomposition of the cyclized product, respectively, with increasing temperature. The Fc‐HTPB was cured with toluene diisocyanate and isophorone diisocyanate separately with butanediol–trimethylolpropane crosslinker to study their mechanical properties. Better mechanical properties were obtained for the gumstock of Fc‐HTPB polyurethanes with higher NCO/OH ratios. The BRs of the ammonium perchlorate (AP)‐based propellant compositions having these Fc‐HTPBs (without dilution) as a binder were much higher (8.66 mm/s) than those achieved with the HTPB/AP propellant (5.4 mm/s). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Evolutionary computing approach for evaluating flory distribution curves in gel permeation chromatography: Study of the poly(1‐octene) system

We carried out deconvolution of the molecular weight distribution curves from gel permeation chromatography for polyolefins into individual active sites considering Flory distribution by an evolutionary‐computing‐based real‐coded genetic algorithm, a nonlinear multivariate optimization algorithm. We applied the deconvolution to homopolymers of 1‐octene synthesized using heterogeneous Ziegler–Natta catalysts with different amounts of hydrogen. The molecular weight distribution was deconvoluted in to five Flory distributions, which showed a sensitivity to hydrogen amounts. With no hydrogen presence, the peaks corresponding to high‐molecular‐weight fractions were intense. As the amount of hydrogen was increased, not only did the intensities of the high‐molecular‐weight peaks decrease, but also peaks corresponding to low‐molecular‐weight fractions were observed. The method allowed us to determine the active site distribution of the polymer molecular weight distribution obtained from gel permeation chromatography. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Emulsifier‐free poly[2‐(diethylamino)ethyl methacrylate] microgels with cationic quaternary ammonium monomers

Although poly[2‐(diethylamino)ethyl methacrylate] (PDEA) microgels are biocompatible and show potential in drug delivery, little research exists with respect to their preparation. Therefore, emulsifier‐free PDEA microgels were synthesized in the presence of cationic ammonium salts of 2‐(dimethylamino)ethyl methacrylate (DMA) that were quaternized with 1‐bromohexadecane, 1‐bromooctadecane, 1‐bromopentane, or benzyl chloride. These served as both comonomers and polymerizable surfactants, providing colloidal stability to the DEA droplets during polymerization. The stability of the microgel particles in different pH values between 4 and 11 was investigated by turbidity–wavelength measurements. The benzyl group containing monomer was the most stabilizing. The pH‐responsive behavior of the microgels in dilute aqueous solution was examined with respect to the amount of DEA, amount of copolymer, type of copolymer, and water content. Most of the microgels remain colloidally stable up to a pH of 9.0, while particles are less than 300 nm in size at pH 8.0. The isoelectric points of the microgels are higher than 8.5 in most cases. In fact, this value exceeds 12.0 by modifying the amount of copolymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43196.