Preparation and characterization of poly(ethylene glycol) crosslinked chitosan films

Poly(ethylene glycol) (PEG) crosslinked chitosan films with various PEG to chitosan ratio and PEG molecular weight were successfully prepared via the epoxy‐amine reaction between chitosan and PEG‐epoxy. The thermal and mechanical properties and swelling behavior were studied for the PEG crosslinked chitosan films. The mechanical strength of chitosan films were greatly enforced by the introduction of PEG‐epoxy, achieving an elongation of about 80%. It was found that the crosslinked chitosan films form hydrogel in water, achieving a swelling ratio higher than 20 times of original weight. The swelling behavior of chitosan films relied greatly on the molecular weight of the crosslinker PEG‐epoxy and the weight percent of PEG‐epoxy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis,characterization, and enzymatic degradation of chitosan/PEG hydrogel films

Poly(ethyleneglycol) (PEG)/tartaric acid (TA)‐crosslinked chitosan hydrogel (CPT) films were prepared, and the formation of the PEG/TA‐crosslinked structure was confirmed by Fourier transformed infrared (FTIR), nuclear magnetic resonance (NMR), and scanning electron microscope (SEM) measurements. The thermal properties of the crosslinked films were also determined with thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) analysis. The swelling properties of the films were investigated at different temperature and pH values. It was found that the swelling ratio increased with the decrease of pH value of the surrounding buffer solutions, amount of PEG, and with the increase of temperature. Swelling behavior of the PEG/TA‐crosslinked chitosan hydrogel films depended on pH and reversible with the temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tensile,Swelling, and Oxidative Degradation Properties of Crosslinked Polyvinyl Alcohol/Chitosan/Halloysite Nanotube Composites

Glutaraldehyde (GA) crosslinked polyvinyl alcohol (PVA)/chitosan (CS)/halloysite nanotube (HNT) composite films were prepared using a wet casting method. The tensile, morphology, thermal degradation, swelling, moisture, and oxidative degradation properties of crosslinked composite films were carried out. The presences of crosslinking in the composite films were confirmed by FTIR result. The tensile strength of the crosslinked composite films increased up to 0.5 wt% of HNTs loading. Increasing HNTs reduced the thermal degradation, swelling, and moisture properties of crosslinked composite films reduced with the increase of HNTs content. Results also indicated that the crosslinked composite films were degraded using Fenton reagent.     

Dielectric,thermal, and swelling properties of calcium ion‐crosslinked sodium alginate film

In this study, Ca²⁺‐crosslinked sodium alginate (SA) gel films (SA‐Ca/SA2‐Ca) have been prepared, and their structural and thermal characterizations were investigated using fourier transform infrared spectroscopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis, respectively. Dielectric characterization was performed at room temperature in the frequency range of 12 Hz–100 kHz. The equilibrium swelling value (ESV) of gel films was determined both in distilled water and in 0.1 M sodium chloride (NaCl) solution at room temperature. Sodium alginate films (SA/SA2) were also prepared for use as reference. The effect of the crosslinking of sodium alginate on the dielectric and thermal properties of gel films was investigated by comparing the properties of gel films with those of SA/SA2 films. Although ESV of Ca²⁺‐crosslinked SA film in distilled water is about 350 /g_polymer, it decreased into one third in 0.1 M NaCl solution. The crosslinking of SA did not significantly affect the thermal properties, but it decreased the β‐relaxation associated with the polar side groups. Frequency spectra of electric modulus, impedance and Cole‐Cole plots confirmed the higher conductance values of SA‐Ca films at low frequencies than those of SA film due to the presence of by‐product of crosslinking. POLYM. ENG. SCI., 54:1372–1382, 2014. © 2013 Society of Plastics Engineers     

Improvement of physical properties of crosslinked alginate and carboxymethyl konjac glucomannan blend films

Blend films from carboxymethyl konjac glucomannan and sodium alginate in different ratios were prepared by blending 4 wt % sodium alginate aqueous solution with 2 wt % konjac glucomannan aqueous solution. After crosslinking with 5 wt % calcium chloride aqueous solution, the blend films formed a structure of semi‐interpenetrating networks. The structure and physical properties of both uncrosslinked and crosslinked films were characterized by Fourier transformed infrared spectra (FTIR), differential thermal analysis (DTA), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and tensile tests. The results indicated that the mechanical properties and the thermal stability of the films were improved by blending sodium alginate with carboxymethyl konjac glucomannan due to the intermolecular hydrogen bonds between sodium alginate and carboxymethyl konjac glucomannan. The crosslinked blend films with Ca²⁺, compared with uncrosslinked blend films, exhibited further improved physical properties due to the formation of a semi‐IPN structure. Furthermore, the degree of swelling of the crosslinked films was also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2554–2560, 2002     

Barrier properties and abrasion resistance of biopolymer‐based coatings on biodegradable poly(lactic acid) films

Coated polylactic acid (PLA) films consisting of crosslinked‐chitosan/beeswax layer were prepared to improve barrier properties and abrasion resistance of the base substrate. The effect of crosslinking the chitosan layer on durability and barrier properties of the coatings was investigated. Crosslinked samples exhibited lower degree of swelling compared to uncrosslinked samples and 50% reduction in water vapor transmission rate (WVTR) compared to neat PLA films. The beeswax coating decreased the WVTR of chitosan‐coated PLA films significantly (by 100%). However, it had a marginal effect on the oxygen transmission rate. Water vapor transmission was less affected by abrasion than oxygen transmission for both uncrosslinked and crosslinked samples. The WVTR of crosslinked samples were retained even after being subjected to abrasion, whereas WVTR of uncrosslinked samples dropped by 50%. Results obtained using the Taber test method also show that the weight loss of crosslinked coatings are about 75% less than that of uncrosslinked samples and can withstand a greater number of cycles before rupture. These translucent‐coated films retained good barrier and mechanical properties along with providing improved abrasion resistance after crosslinking. This approach provides exciting new possibilities for expanding the use of biodegradable polymers in packaging applications. POLYM. ENG. SCI., 59:1874–1881, 2019. © 2019 Society of Plastics Engineers     

Synthesis and swelling properties of crosslinked poly(orthosilicate)s from cyclohexanedimethanols

Condensations of cyclohexanedimethanol derivatives with tetraethyl orthosilicate in the proper stoichiometric ratio produce crosslinked poly(orthosilicate)s. Synthesized crosslinked polymers have swelling abilities in common organic solvents such as tetrahydrofuran (THF), dichloromethane, benzene and acetone. All these polymers are moderately thermally stable and possess solvent uptake abilities that are not only good and fast but are also regenerable. FTIR, solid‐state ¹³C, ²⁹Si‐NMR and thermal methods were used to characterize these synthesized polymers. The effects of different cyclohexanedimethanol derivatives on the properties of polymers were also examined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122:1182–1189, 2011     

Synthesis and characterization of photo-crosslinkable hydrogel membranes based on modified chitosan

In order to develop a non toxic and biocompatible hydrogel system with potential ability in biotechnology, modified photo-crosslinkable hydrogel membranes based on chitosan were prepared. Using an EDC/NHS conjugation method, chitosan was chemically modified to incorporate a photosensitive α-cyano-4-hydroxycinnamic acid moiety with various degrees of substitutions. Fourier transform infrared spectra (FTIR), proton nuclear magnetic resonance (¹H NMR) and ultraviolet-visible light spectra (UV-vis) were used for structural characterization of modified chitosan, The obtained membranes were crosslinked by irradiation in the ultraviolet region, where the photosensitive monomers showed maximum sensitivity. The prepared photo-crosslinked hydrogel membranes were investigated by thermal gravimetric analysis (TGA) and wide angle X-ray diffraction (WAXD). The swelling behaviors were investigated in terms of pH, time of swelling, and degree of substitution. Also, mechanical properties of the different photo-crosslinked hydrogel membranes were studied in both dry and wet conditions.     

Adsorptive removal kinetics of anionic dye onto chitosan films doped with graphene oxide: An in situ fluorescence monitoring

The aqueous adsorption of a fluorescent dye (pyranine) onto crosslinked chitosan-graphene oxide composite films was studied. In situ fluorescence monitoring technique is introduced as easy and fast experimental technique to select optimal adsorbent conditions. The effect of ionic crosslinker on adsorption was studied with sodium tripolyphosphate, trisodium citrate, and sodium sulfate, respectively. Among the crosslinkers, it was realized that sodium sulfate crosslinked films showed a greater adsorption rate for pyranine than the other two types of crosslinked films. Recently, graphene oxide is of interest as a filler compound for many biopolymer applications due to its favorable thermal, mechanical and surficial properties. In the present study, graphene oxide incorporation increased adsorption rate of the dye and the mechanical strength of ionically crosslinked chitosan films. The adsorption behavior of the adsorbent was explained by a kinetic model. Samples were characterized using scanning electron microscopy, thermogravimetric analysis, swelling experiments and tensile testing method.     

Semi‐interpenetrating polymer network hydrogels based on aspen hemicellulose and chitosan: Effect of crosslinking sequence on hydrogel properties

Semi‐interpenetrating network hydrogel films were prepared using hemicellulose and chemically crosslinked chitosan. Hemicellulose was extracted from aspen by using a novel alkaline treatment and characterized by HPSEC, and consisted of a mixture of high and low molecular weight polymeric fractions. HPLC analysis of the acid hydrolysate of the hemicellulose showed that its major constituent sugar was xylose. X‐ray analysis showed that the relative crystallinity of hydrogels increased with increasing hemicellulose content up to 31.3%. Strong intermolecular interactions between chitosan and hemicellulose were evidenced by FT‐IR analysis. Quantitative analysis of free amino groups showed that hemicellulose could interrupt the chemical crosslinking of chitosan macromolecules. Mechanical testing and swelling experiments were used to define the effective network crosslink density and average molecular weight between crosslinks. Swelling ratios increased with increasing hemicellulose content and mainly consisted of H‐bonded bound water. Results revealed that by altering the hydrogel preparation steps and hemicellulose content, crosslink density and swelling behavior of semi‐IPN hydrogels could be controlled without deteriorating their mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel poly‐bridged‐naphthalene with blue‐light‐emitting property via electropolymerization

Relatively scant work was related to polynaphthalene (PN) and its derivatives because of the unique nonlinear optical properties which make PN and its derivatives owning potential applications in various domains. According to relevant studies, the pursuit for the synthesis of high quality PN films is a great challenge for the applications of PN. To achieve high quality polymer films, three bridged naphthalene derivatives were designed, and finally two crosslinked PN exhibiting space network were electrosynthesized, respectively, by direct anodic oxidation from 1,6‐bis(naphthalen‐2‐yloxy)hexane and 1,4‐bis((naphthalen‐2‐yloxy)methyl)benzene in mixed electrolyte of dichloromethane containing boron trifluoride diethyl etherate. Furthermore, as‐formed conducting films were characterized by cyclic voltammetry, spectroscopic analysis, thermal analysis, and scanning electron microscopy. And the series of characterizations indicated that films hold high stability and good blue‐light‐emitting property. Meanwhile, these polymer films were smooth, shiny, and flexible easily being processed into various shapes by conventional mechanical methods. Consequently, these high quality PN films will facilitate their potential applications as blue‐light‐emitting materials in organic light‐emitting diode. Because di(naphthalen‐2‐yl) terephthalate was difficult to electropolymerize, the effects of bridged spacers to polymerization were also discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Examining the Impact of Squaric Acid as a Crosslinking Agent on the Properties of Chitosan-Based Films

Hydrogels based on chitosan are very versatile materials which can be used for tissue engineering as well as in controlled drug delivery systems. One of the methods for obtaining a chitosan-based hydrogel is crosslinking by applying different components. The objective of the present study was to obtain a series of new crosslinked chitosan-based films by means of solvent casting method. Squaric acid—3,4-dihydroxy-3-cyclobutene-1,2-dione—was used as a safe crosslinking agent. The effect of the squaric acid on the structural, mechanical, thermal, and swelling properties of the formed films was determined. It was established that the addition of the squaric acid significantly improved Young’s modulus, tensile strength, and thermal stability of the obtained materials. Moreover, it should be stressed that the samples consisting of chitosan and squaric acid were characterized by a higher swelling than pure chitosan. The detailed characterization proved that squaric acid could be used as a new effective crosslinking agent.     

Preparation and adsorption properties of metal ions of crosslinked chitosan azacrown ethers

The novel azacrown ether chitosan derivatives (CCAE‐I, CCAE‐II) were prepared by reaction between crosslinked chitosan with epoxy‐activated azacrown ethers. Their structures were confirmed by elemental FTIR spectra analysis and X‐ray diffraction analysis. The adsorption and selectivity properties of the crosslinked chitosan azacrown ethers for Pb²⁺, Cu²⁺, Cr³⁺, Cd²⁺, and Hg²⁺ were also investigated. The experimental results showed that they have high adsorption capacity for Cu²⁺, Cd²⁺, and Hg²⁺. The adsorption capacity of CCAE‐II is higher than CCAE‐I for Cd²⁺ and Hg²⁺. The selectivity properties of CCAE are better than chitosan and crosslinked chitosan. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3053–3058, 1999     

Preparation and characterization of pH‐sensitive hydrogels based on chitosan,itaconic acid and methacrylic acid

Novel pH‐sensitive hydrogels based on chitosan, itaconic acid and methacrylic acid were prepared in two steps. Chitosan was first ionically crosslinked with itaconic acid, after which a free radical polymerization and crosslinking of the chitosan/itaconic acid network was performed by adding methacrylic acid and a crosslinker in order to achieve better mechanical properties and tunable swelling. The samples were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, X‐ray diffraction, dynamic mechanical analysis and the swelling ratios of the hydrogels at various pH values (2.0–8.0). The hydrogel composition is found to have a great impact on the hydrogel structure, mechanical and thermal properties, morphology and swelling kinetics. The highly porous morphology of the gels is probably connected with the bulky chitosan/itaconic acid network which reduces the degree of crosslinking in the second step of the synthesis due to steric hindrances. The gels demonstrate substantial change in buffer absorbency with change of pH, low for acid buffers and the higher for pH values above 6 where the swelling is considerably slow, thus suggesting their strong candidature for use as oral drug‐delivery systems in the lower parts of the gastrointestinal tract and for drugs that require longer release times. Copyright © 2010 Society of Chemical Industry     

Crosslinking of low‐density polyethylene by diisocyanates for superior barrier properties

The chemical modification of low‐density polyethylene (LDPE) resins with hexamethylene diisocyanate and toluene diisocyanate was achieved. The reaction of LDPE with diisocyanate was monitored by Fourier transform infrared spectroscopy, wherein the appearance of new peaks at 3326, 1620, and 1572 cm^?1 corresponding to ? N? H stretching, ? (C?O)? NH₂ stretching, and ? N? H bending in an amide moiety, respectively, was observed. Modified films of excellent clarity and uniform thickness were obtained by the solution casting of crosslinked polyethylene. The oxygen transmission rate (OTR), water vapor transmission rate (WVTR), grease resistance, and thermal properties of the modified films were studied. The results clearly indicate that the OTR was improved by 35% and that grease resistance was improved by 90–125% in the crosslinked LDPE films with little change in their strengths. The heat seal characteristics, however, showed that relatively higher temperatures were needed to achieve efficient sealing in these films. Differential scanning calorimetry showed a decrease in the melting temperature from 104°C for LDPE to 101°C for both of the crosslinked LDPE films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1193–1199, 2005     

Advanced materials based on new structurally designed poly(naphthylimide‐amide)s

This work reports the synthesis and characterization of novel six‐membered poly(imide‐amide)s based on a naphthalene‐N,N′‐bis(imido‐amine) and various dicarboxylic acids containing flexible units such as ether, hexafluoroisopropylidene and diphenylsilane. A new design is proposed for aromatic poly(imide‐amide)s, in which the imide and amide units are directly connected through a N? N bond. These highly thermostable polymers were successfully synthesized using Yamazaki–Higashi reaction conditions. The poly(imide‐amide)s were processed into thin hydrophobic films having self‐assembled micellar structures. The presence of aggregates in solutions with concentrations below 1% was evidenced and is discussed in relation to the chemical structure. The photoluminescence properties of polymer solutions and films showed their ability to produce white and blue light emission. The lowest unoccupied molecular orbital energy level was calculated using cyclic voltammetry data, showing good electron injection and transport characteristics. The properties of these polymers make them attractive for applications in advanced optoelectronics and related fields. © 2014 Society of Chemical Industry     

In situ preparation of lithographic resists containing glutarimide groups

Poly(acrylic acid) and poly(methacrylic acid) homopolymers, copolymers, and 1-μ-thick films have been converted in high yield to their corresponding cyclic imide derivatives by an in situ gas–solid phase reaction at 200°C with ammonia, methylamine, and ethylamine, respectively. Under similar reaction conditions with H₂S or CH₃SH as the reactive gas, sulfur was incorporated into the polymers in low yield. Under UV and electron beam irradiation, these cyclic derivatives degraded with main chain scission to eliminate isocyanic acid or alkyl isocyanate and to form olefins and ketenes. Poly(diacrylimide) was the exception and crosslinked. The poor solubility in organic solvents and the very high solubility in aqueous solutions of base limited the use of these films as positive resists. However, poly(methyl methacrylate) copolymers, containing 20%–25% cyclic groups, exhibited adequate solubility and sensitivity to be utilized as lithographic resists.     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Synergistic effects of crosslinking and chitosan molecular weight on the microstructure,molecular mobility,thermal and sorption properties of porous chitosan/gelatin/hyaluronic acid scaffolds

In this study, synergistic effects of crosslinking and chitosan molecular weight on the microstructure, molecular mobility, thermal, and sorption properties of porous chitosan/gelatin/hyaluronic acid hybrid foams are reported. Fourier transform infrared spectroscopy has been utilized to confirm the covalent attachment of hyaluronic acid to gelatin and chitosan, and covalent chemical crosslinking between gelatin and chitosan. Detailed image analysis of scanning electron microscopy images of the porous scaffold hydrids reveal that the pore size of the materials formulated using either low‐ or high‐molecular‐weight chitosan increases significantly upon crosslinking using ethyl(dimethylaminopropyl) carbodiimide/N‐Hydroxysuccinimide. These microstructural changes are even more pronounced for the crosslinked hybrid scaffolds formulated using low‐molecular‐weight chitosan, highlighting a synergistic effect between crosslinking and the use of low‐molecular‐weight chitosan. Results obtained using differential scanning calorimetry demonstrate a significant reduction in molecular mobility reduction in molecular mobility for crosslinked scaffolds formed using high‐molecular‐weight chitosan compared to non‐crosslinked hybrids and crosslinked hybrids formulated using low‐molecular‐weight chitosan. Correspondingly, dynamic vapor sorption evidenced significantly lower water vapor sorption for crosslinked scaffolds formulated using high‐molecular‐weight chitosan. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44772.     

Ketone derivatives of diels‐alder adducts of levopimaric acid with acrylic acid and maleic anhydride: Synthesis,characterization, and polymerization

Two new ketone‐type derivatives were synthesized by the dehydrodecarboxylation of levopimaric acid acrylic acid adduct and of levopimaric acid maleic anhydride adduct in the presence of sulfonic catalysts. The two compounds were also synthesized by coupling of acrylic acid or maleic anhydride with dipimaryl ketone. These ketones, or rather ketone‐diacids, were condensed with polyalkylenepolyamines to give poly(amide)s or poly(imide)s with good thermal properties. New crosslinked polymers were obtained when these poly(amide)s or poly(imide)s were substituted with epichlorohydrin. The structures of the resulted ketone‐diacids and polymers were investigated by the usual physical and chemical methods. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2240–2252, 2004