Preparation and structural characterization of water‐soluble O‐hydroxypropyl chitin derivatives

Water‐soluble hydroxypropyl chitin (HPC) derivatives were prepared by the reaction of chitin with propylene oxide in homogeneous conditions using a dimethylacetamide/5% lithium chloride solvent system. The reaction conditions for a proper substitution of the hydroxypropyl group were an 80°C reaction temperature, 24‐h reaction time, and 48‐h aging time. ¹H‐NMR and ¹³C‐cross‐polarization/magic angle spinning NMR spectroscopy were used for determining the substitution value and reaction site of substitution. It was found that the substitution reaction occurred mainly at the C₆? OH group in the chitin molecules and water‐soluble chitin derivatives could be obtained at a substitution value higher than 0.35, which is known as a critical substitution value. X‐ray diffraction analysis and FTIR spectroscopy showed that the structural characteristics of HPC derivatives were dependent on the substitution value. As the substitution value of the HPC derivative increased the α‐chitin crystal structure changed to the water‐soluble β‐chitin form in higher substitution values. Differences in the interchenic hydrogen bonding, interplanar spacing of the crystal lattice plane, and crystallinity can explain the structural changes upon substitution. The thermal decomposition temperature was also related to the characteristics of the crystalline structure, depending on a critical substitution value. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2624–2632, 2001     

Fluorescence quenching of phenanthrene and anthracene by maleic anhydride and n‐octadecenylsuccinic anhydride in solution and in bulk polypropylene

Fluorescence quenching of phenanthrene (Ph) and anthracene (An) fluorophores by maleic anhydride (MAH) and n‐octadecenylsuccinic anhydride (ODSA) quenchers in solid polypropylene (PP) films were studied. Results were compared with fluorescence quenching of the same fluorophores by MAH and ODSA quenchers in chloroform solution. Contrary to the results obtained in solution, it was observed that fluorescence emission of Ph fluorophore in PP films was more efficiently quenched by ODSA than by MAH. This was due to the better miscibility of Ph with ODSA than with MAH. When An fluorophore was used instead of Ph, it was observed that its fluorescence intensity in PP films was notably reduced by the addition of MAH. This was mainly due to the Diels–Alder reaction, which consumed a part of the An molecule. However, fluorescence intensity of An strangely increased with the addition of ODSA instead of MAH. Because of short lifetime of An (around 6 ns), ODSA had no quenching effect on An. POLYM. ENG. SCI., 47:192–199, 2007. © 2007 Society of Plastics Engineers     

Preparation and properties of water‐swellable elastomer

A series of water‐swellable elastomers were prepared by blending chlorinated polyethylene (CPE) with poly(acrylic acid–acrylic amide) [P(AA–AM)]. The effect of component on its water‐absorbent properties such as degree of swelling, swelling ratio, and weight loss ratio was discussed. Mechanical behavior of blends was also investigated. The results indicate that swelling rate of CPE/P(AA–AM) was very quick; the blend reached its equilibrium state in only 30 min. The equilibrium swelling ratio increased with increasing amounts of water‐absorbent resin, the greater the amount of P(AA–AM), the higher the swelling degree. The effect of temperature on swelling ratio was very interesting, below 30°C, with an increase of temperature, the swelling ratio of blend increased, but above 30°C, with an increase of temperature, the swelling ratio decreased, indicating that this is a temperature‐sensitive water‐swellable elastomer. The effect of pH of solutions on the swelling behavior showed that water absorption of blends was heavily influenced by pH. The effect of different metal ions on the swelling behavior were also studied and the results showed that the absorption of blends was decreased dramatically with increasing the charge number of the cation, but was not influenced by radius and valence state of the anion. Owing to the compatibility of the amphiphilic graft copolymer (CPE‐g‐PEG), the equilibrium swelling ratio of the blends increased and the weight loss ratio decreased. Adding CPE‐g‐PEG can improve the mechanical behavior of blends. But too much grafted copolymer can worsen the tensile strength of blends. Tensile strength of blends decreased with an increase in P(AA‐AM). After absorbing water, the material's strength is greater than in the dry state. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1719–1723, 2004     

Preparation and characterization of water‐swellable natural rubbers

Water‐swellable rubbers were prepared by dispersing the superabsorbent polymer particles, sodium polyacrylate particles, in natural rubber, and their water absorption properties were investigated. Sodium polyacrylate particles were synthesized using the inverse suspension polymerization technique, and their thermal and water absorption properties were characterized. The equilibrium water uptake in sodium polyacrylate particles was strongly dependent on both the salt concentration of aqueous media and crosslinking density of polymer. The dynamic and equilibrium water‐swelling behavior of the prepared rubbers were significantly affected by addition of carbon black, hydrophilic polymer, and coupling agent. Those effects were well explained by microphotographic morphologies obtained using a scanning electron microscope. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 115–121, 2001     

Preparation of water‐swollen hydrogel membranes for gas separation

Water‐swollen hydrogel (WSH) membranes for gas separation were prepared by the dip‐coating of asymmetric porous polyetherimide (PEI) membrane supports with poly(vinyl alcohol) (PVA)–glutaraldehyde (GA), followed by the crosslinking of the active layer by a solution method. Crosslinked PVA/GA film of different blend compositions (PVA/GA = 1/0.04, 0.06, 0.08, 0.10, 0.12 mol %) were characterized by differential scanning calorimetry (DSC) and their water‐swelling ratio. The swelling behavior of PVA/GA films of different blend compositions was dependent on the crosslinking density and chemical functional groups created by the reaction between PVA and GA, such as the acetal group, ether linkage, and unreacted pendent aldehydes in PVA. The permeation performances of the membranes swollen by the water vapor contained in a feed gas were investigated. The behavior of gas permeation through a WSH membrane was parallel to the swelling behavior of the PVA/GA film in water. The permeation rate of carbon dioxide through the WSH membranes was 10⁵ (cm³ cm^?2 s^?1 cmHg) and a CO₂/N₂ separation factor was about 80 at room temperature. The effect of the additive (potassium bicarbonate, KHCO₃) and catalyst (sodium arsenite, NaASO₂) on the permeation of gases through these WSH membranes was also studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1785–1791, 2001     

Preparation and characterization of water‐soluble polyacrylate sodium modified by organomontmorillonite

Water‐soluble high intrinsic viscosity organomontmorillonite modified polyacrylate sodium (OMMT‐modified PNaA) was prepared via an in situ intercalation adiabatic polymerization of sodium acrylate in the presence of OMMT. The FTIR and XRD analyses correspond to the OMMT‐modified PNaA with exfoliated structure of OMMT. The influences of prepared conditions on intrinsic viscosity and dissolving time of the modified polymers had been investigated in this study. It was found that the incorporation of as little as 0.1 wt % of OMMT added to PNaA matrix could be effective to enhance intrinsic viscosity of the modified PNaA. TGA and DSC studies confirmed the enhancement of the thermal stability of the OMMT‐modified PNaA when compared with PNaA. Furthermore, the solution behavior studies of the modified PNaA showed the “antipolyelectrolyte” effect and high “antishearing” property. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characteristics of a water‐soluble chitosan–heparin complex

To improve the wound‐healing ability of chitosan, heparin, known to be effective in wound healing, was complexed with water‐soluble chitosan (WSC) by chemical reaction. The chemical structure of the water‐soluble chitosan–heparin (CH) complex was analyzed, and CH complex formation was confirmed with an FTIR spectrometer. The mechanical and thermal properties of the CH complex were measured by a tensile tester and thermal analyzers (DSC and TGA). Within the heparin content up to ≈470 IU/g in the aqueous CH complex solution, the intrinsic viscosity and tensile strength of the water‐soluble CH complex gradually increased, but thermal stability slightly decreased by introducing the heparin into the WSC. When the heparin content was greater than these values (470 IU/g), the water‐insoluble CH complex, which is supposed to have a multisubstituted or crosslinked structure, precipitated in the aqueous water‐soluble CH complex solution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1784–1789, 2003     

Comparative evaluation of fluorinated and unfluorinated acrylic copolymers as water‐repellent coating materials for stone

An investigation on the influence of side‐chain fluorination on the performance of a series of acrylic‐based copolymers as protective coating materials for stones has been carried out by comparing them with unfluorinated polymeric analogues. For this purpose, a series of copolymers of 1H,1H,2H,2H‐perfluorodecyl methacrylate (XFDM) and 2,2,2 trifluoroethyl methacrylate (TFEM) with unfluorinated vinyl ether or acrylic comonomers have been synthesized, as well as their not fluorinated analogues, and applied to limestone and marble substrates. A silicone‐type commercial product, widely employed in the protection of stones in buildings and other artifacts, has also been tested as a reference material. Their protection efficiencies were then comparatively evaluated in terms of surface properties, water permeability, and appearance. It is shown that the presence of fluorine always has, as expected, a positive influence on the protective action of the polymer, increasing the water repellency of the coated stone. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 962–977, 2000     

Preparation of water‐soluble chitosan

An improved method of preparing water soluble chitosan was studied by N‐acetylation with acetic anhydride. Its merits were a simple processing technique, very short reaction time, little agent, high molecular weight of the product, and good water solubility. This article not only discusses the effect of several factors, such as the amount of reactants, concentration of hydrogen ions in the solution, and solvent system, on N‐acetylation but also some influential factors on the water solubility of N‐acetylated chitosan. Experiments showed that the amount of acetic anhydride was the most important factor affecting the N‐acetylation degree of the chitosan. The effect of the means of adding materials and the amount of solvent on the reaction could not be ignored. The solubility of half N‐acetylated chitosan was not changed with an increase in the molecular weight in water, and the water solubility decreased with increasing molecular weight in the alkaline region. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3497–3503, 2004     

Preparation and properties of water‐borne polyurethane with branched straight aliphatic chains

Water‐borne polyurethane with branched straight aliphatic chains (CWPU) was prepared and characterized by FTIR and TEM. The relationship between structure and water‐resistance of CWPU was studied. The results showed that the particle size of CWPU emulsion increases and the round particle turns into the spindle‐shaped particle with increasing of content of branched straight aliphatic chains. However, the particle size of CWPU emulsion is not sensitive to the increases of length of branched straight aliphatic chains. The water‐resistance and hydrophobic property of CWPU film increase with the increase of content and length of branched straight aliphatic chains. It is attributed to the hydrophobic layer of aliphatic chains enriched on the surface of CWPU film. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of poly[(butylene succinate)‐co‐(butylene adipate)]/carbon nanotube‐coated silk fiber composites

Biodegradable composites consisting of aliphatic polyesters (poly[(butylenes succinate)‐co‐(butylenes adipate)] (PBSA)) and Bombyx mori silk fibers coated with carbon nanotubes (CNTs) were prepared by melt compression molding. The mechanical properties of PBSA were enhanced by the incorporation of a small amount (3 wt%) of CNT‐coated silk fibers, while allowing its potential biodegradability to be retained, which could make these composites good candidates for commodity materials such as general‐purpose plastics. This improvement is attributed to the interactions between PBSA and CNT‐coated silk fibers in the composites. The average interfacial shear strength of the composites consisting of CNT‐coated silk fibers and PBSA matrix was 1.7 MPa, as measured by the microbond droplet test, while that of composites consisting of pure silk fibers and PBSA was only 1.1 MPa. The morphology of the CNT‐coated silk fiber‐reinforced composites was observed using scanning electron microscopy. Copyright © 2007 Society of Chemical Industry     

Polymer hybrids from self‐emulsified PU anionomer and water‐reducible acrylate copolymer via a postcuring reaction

Water‐reducible acrylate copolymer is obtained from a free‐radical copolymerization of n‐butyl acrylate, acrylic acid, and methacrylic acid. Self‐emulsified aqueous‐based polyurethane (PU) anionomer is prepared by the conventional method. The latent curing agents (di‐ and triaziridinyl compounds, HDDA‐AZ and TMPTA‐AZ) are synthesized from the reaction of aziridine with hexandiol diacrylate and trimethylolpropane triacrylate, respectively. These two polymers and the latent curing agent are miscible in each other and become a single component and self‐curable polymer dispersion. The carboxyl ions of polymers not only stabilize the aqueous polymer dispersions but also serve the curing site toward latent curing agent in the drying process. These two polymers blend with a curing agent, which results in new polymer hybrid formation. These polymer hybrids have the improvements on performance properties and the cost/performance benefits. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3578–3587, 2003     

Preparation and evaluation of some water‐soluble polyester surfactants

A novel series of water‐soluble polyester surfactants were prepared by the polymerization of bis‐1,4‐(dicarboxymethoxy) benzene, maleic anhydride, and oxypropylated 1,4‐butane diol (IP₁–IP₅) or oxypropylated 1,6‐hexane diol (IIP₁–IIP₅). The unique structural features of these surfactants were confirmed by IR and ¹H‐NMR spectra. These water‐soluble polyester surfactants exhibited excellent surface tension, interfacial tension, low foaming, good emulsifier capability, and good biodegradability in river water, solubilization, wetting, and dispersant properties for applied dyes. The antimicrobial and antifungal properties of the prepared polyester surfactants were measured and found to be highly active. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3413–3424, 2001     

Microencapsulation of water‐soluble herbicide by interfacial reaction. I. Characterization of microencapsulation

A new microencapsulation was established in which small microcapsules with a hydrophilic polymeric wall could be fabricated, capsulizing the water‐soluble content. The new microencapsulation is based on an emulsion interfacial reaction technique that combines the characteristics of an interfacial reaction and conventional emulsion processes. In this technique, hydrophilic polymers [poly(vinyl alcohol) and chitosan] were used as the wall material of the microcapsules. The microencapsulation process was composed mainly of the following steps: preparation of a water/oil (w/o) emulsion 1 containing hydrophilic polymers and a water‐soluble core material and w/o emulsion 2 containing a water‐soluble crosslinking agent and catalyst; the formation of microcapsules by mixing emulsion 1 and emulsion 2; and washing and drying the formed microcapsules. In the new technique an insoluble polymer film was formed easily by the fast crosslinking reaction on the surface of tiny emulsified polymer solution particles in contact with the emulsified crosslinking agent solution particles under mixing with high speed agitation. Thereby, small stable microcapsules were formed. The emphasis in this study was on the establishment of the microencapsulation process by which microcapsules were formed and controlled. The microencapsulation was characterized by analysis of the size distribution of microcapsules fabricated with process conditions. The clarification of the effect of the preparation conditions was also made on the morphology and diameter of the microcapsules. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1645–1655, 2000     

Preparation of superhydrophobic silica‐based films by using polyethylene glycol and tetraethoxysilane

Preparation of superhydrophobic silica‐based films via sol‐gel process by adding polyethylene glycol (PEG4000) in the silica sol precursor solution has been developed. The casting films were prepared by casting the above solution on the glass and adding poor solvent on it or not. Surface roughness of the films was obtained by removing polymer from the films at high temperature. Then, the hydrophobic group on the surfaces was obtained by reaction with hexamethyldisilazane (HMDS). Characteristic properties of the as‐prepared surface of the films were analyzed by contact angle measurement, scanning electron microscopy (SEM), atomic force microscope (AFM), Fourier transform infrared (FT‐IR) spectrophotometer, and X‐ray photoelectron spectrometer (XPS). The results showed that the contact angles of the films were varied with the PEG weight fraction of the films, the solvent for the PEG solution, the reaction temperature and time, and adding poor solvent (n‐hexane) or not. However, the surface roughness has been controlled by adjusting the experimental parameters during the early period. The contact angle of the film that prepared by spraying the poor solvent (n‐hexane) onto each coating layer for four times after casting process was greater than 150°. It was difficult to obtain superhydrophobic surface without adding n‐hexane onto any coating layer in this system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fluorinated segmented polyurethane anionomers for water–oil repellent surface treatments of cellulosic substrates

Three model structures of linear segmented anionomeric polyurethanes based on perfluoropolyether dimethylol‐terminated oligomers, isophorone diisocyanate, and dimethylol propionic acid were synthesized and obtained in the form of aqueous dispersions. The structures differed from each other in the chemical nature of the chain extender (diol or diamine) and in the content of carboxylic acid. Dispersions and polymer films were characterized by dynamic light scattering, dynamic mechanical analysis, differential scanning calorimetry, and contact angle measurements. Diluted aqueous dispersions were also evaluated as protective sizing agents in paper treatment, both as bulk modifiers and as surface treatments. Paper sheets characterized by high water and oil repellence were obtained. The results showed that performance is mainly related to the ionic group content of the polymer and to its molecular architecture. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1364–1372, 2005     

Wood–polymer composites made with acrylic monomers,isocyanate, and maleic anhydride

Wood could provide better service in some applications if it were harder and more dimensionally stable. In this study, wood–polymer composites (WPC) made with different chemical combinations were evaluated for dimensional stability, ability to exclude water vapor and liquid water, and hardness. Pine, maple, and oak solid wood were combined with different combinations of hexanediol diacrylate, hydroxyethyl methacrylate, hexamethylene diisocyanate, and maleic anhydride. Treatment slowed the rates of water vapor and liquid water absorption. Although the resultant dimensional stability was not permanent, the rate of swelling of WPC specimens was less than that of unmodified wood specimens. In addition, WPC were harder than unmodified wood. The chemical combination of hexanediol diacrylate, hydroxyethyl methacrylate, and hexamethylene diisocyanate greatly decreased wetting and penetration of water into the wood. This chemical combination also gave the hardest and most dimensionally stable WPC. In general, WPC prepared using hydroxyethyl methacrylate were harder than specimens made without hydroxyethyl methacrylate and excluded water and moisture more effectively. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2493–2505, 1999     

Synthesis and application of water‐soluble hyperbranched poly(ester)s from maleic anhydride and glycerol

A water‐soluble hyperbranched polyester with a considerable number of hydroxyl terminal groups was synthesized by reacting maleic anhydride and glycerol in the absence of a solvent. The synthesized intermediate product was converted to the hyperbranched polyester by condensation polymerization, and the water by‐product produced during the esterification reaction may be removed by vacuum distillation. In the synthesis process, the crosslinking reaction occurs readily if maleic anhydride is in excess. The result shows that the product synthesized by this one‐step method is insoluble in water at room temperature, whereas the product of a quasi one‐step method, in which pentaerythritol was added as a core molecule, has good water solubility when pentaerythritol and the raw material have a molar ratio of 1 : 100 or 1 : 150. The resulting hyperbranched polyester was purified by column chromatography and characterized by infrared spectrometry. The synthetic hyperbranched polyester was used at 0.5% as a crosslinking agent for acrylic ester to inform acrylic ester latex film; the water absorption of the film was decreased significantly, the viscosity was increased, and some mechanical properties were improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Retention properties of arsenate anions of water‐soluble polymers by a liquid‐phase polymer‐based retention technique

The retention properties of arsenic ions from an aqueous solution by water‐soluble cationic polymers and cationic–anionic copolymers were investigated. Poly[(3‐methacryloylamine)propyl]trimethylammonium chloride [P(ClMPTA)] and poly[(3‐methacryloylamine)propyl]trimethylammonium chloride–co–acrylic acid [P(ClMPTA‐co‐AA] were synthesized by radical polymerization. The copolymers were prepared with feed mole ratios of ClMPTA to AA of 1 : 1, 1 : 2, and 2 : 1. The copolymer compositions were evaluated by FTIR spectroscopy, TG‐DSC, and elemental analysis. The liquid‐phase polymer‐based retention (LPR) technique was used. This technique consists of retention of arsenate anions by the quaternary ammonium salt of a water‐soluble polymer in a filtration membrane cell. It was shown that the polymers could bind H₂AsO species from an aqueous solution more selectively at pHs of 6 and 8, than at a pH of 4. An increase in the polymer concentration was associated with increased retention capacity but not linearly. At the highest concentration the influence of pH was better observed. Investigation of copolymers showed the concerted action of polycations and polyanions on the ability to retain arsenic. At the lowest pH, the role of ionic strength of the media had a remarkable effect on the retention ability, independently of copolymer composition. At a pH of 6 a copolymer polycation/polyanion composition of 2 : 1 had the highest selective effect. At a pH of 8, a nonequimolar copolymer composition showed the same efficiency for the retention of arsenate species. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2677–2684, 2006     

Study of P(AM‐NVP‐DMDA) hydrophobically associating water‐soluble terpolymer

A new kind of hydrophobically associating water‐soluble terpolymer P(AM‐NVP‐DMDA) was synthesized by free radical terpolymerization. Compared with micellar terpolymerization, this terpolymerization can be conducted in aqueous solution in absence of external surfactant, because the hydrophobic monomer is surface active. Synthesis, structure, and solution properties of P(AM‐NVP‐DMDA) terpolymer were studied, including its electrolyte effect, rheological behavior, temperature dependence of viscosity, dilute solution property, and the polymer–alkali, polymer–surfactant interaction. The terpolymer shows strong hydrophobic effect, and the terpolymer aqueous brine solution exhibits high viscosity at low polymer concentration. Incorporation of N‐vinyl‐pyrrolidone into the terpolymer causes an improvement in thermal stability of the terpolymer. The transmission electron photomicrograph analysis of the terpolymer indicates that the presence of the microphase separation of the terpolymer in aqueous solution plays an important role in the viscosification efficiency of the terpolymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 211–217, 1999