Thermal properties and crystallization behaviour of blends of poly(ε‐caprolactone) with chitin and chitosan

Blend films of poly(ε‐caprolactone) (PCL) with chitin and chitosan were prepared as completely biodegradable polyester/polysaccharide composites. Differential scanning calorimetry and Fourier‐transform infrared (FTIR) spectroscopy revealed that the crystallization of PCL, which had been suppressed by blending with chitin and chitosan, progressed with the elapse of time after film preparation. The suppression of crystallization of PCL by blending with polysaccharides was also observed by solid‐state ¹³C NMR spectroscopy. Furthermore, FTIR spectra indicated that the extent of hydrogen bonding between PCL and polysaccharides, which suppressed the crystallization of PCL, decreased with elapse of time after film preparation. Wide‐angle X‐ray diffraction indicated that the polysaccharides affected the crystallization of PCL and slightly deformed its crystalline lattice. Copyright © 2003 Society of Chemical Industry     

Chitosan/silk fibroin composite scaffolds for wound dressing

Three‐dimensional (3D) chitosan/silk fibroin (CS/SF) porous composite scaffolds have been prepared by simply coating a thin layer of CS onto spunlaced SF scaffolds via hydrogen‐bonding assembly technique, and they were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X‐ray diffraction (XRD), and mechanical property measurements. The results show that porous scaffolds have a pore diameter around 50–200 μm, and improved mechanical property compared with SF, resulting from strong intermolecular hydrogen bonding interactions between CS and SF, together with the maintained β‐sheet structure of SF. The medical and biological properties of the composite scaffolds were further evaluated. The results demonstrate that they possess good biocompatibility and a broad spectrum of antimicrobial properties. The in vivo animal experiments show that the composite scaffolds promote skin regeneration of rats without any teratogenic effect and inflection, thus they are very promising in the application of wound dressings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42503.     

Incorporation of 2,3‐Diaminopropionic Acid into Linear Cationic Amphipathic Peptides Produces pH‐Sensitive Vectors

Nonviral vectors that harness the change in pH in endosomes, are increasingly being used to deliver cargoes, including nucleic acids, into mammalian cells. Here we present evidence that the pK_a of the β‐NH₂ in 2,3‐diaminopropionic acid (Dap) is sufficiently lowered, when Dap is incorporated into peptides, that its protonation state is sensitive to the pH changes that occur during endosomal acidification. The lowered pK_a of around 6.3 is stabilized by the increased electron‐withdrawing effect of the peptide bonds, by intermolecular hydrogen bonding and from contributions arising from the peptide conformation. These include mixed polar/apolar environments, Coulombic interactions and intermolecular hydrogen bonding. Changes in the charged state are therefore expected between pH 5 and 7, and large‐scale conformational changes are observed in Dap‐rich peptides, in contrast to analogues containing lysine or ornithine, when the pH is altered through this range. These physical properties confer a robust gene‐delivery capability on designed cationic amphipathic peptides that incorporate Dap.     

Relative strength of H‐bonding groups on biodegradable polymer‐based blends in solution

The intermolecular hydrogen bonding interactions between poly(3‐hydroxybutyrate) and poly(styrene‐co‐vinyl phenol) copolymers with mutual solvent epichlorohydrin were thoroughly investigated by steady‐state fluorescence and viscosity techniques. Fluorescence spectroscopy along with viscosity technique was used to asses the intermolecular hydrogen bonding between poly‐(3‐hydroxybutyrate) and its blends with five copolymer samples of styrene–vinyl phenol, containing different proportions of vinyl phenol but similar average molecular weight and polydispersity index. In the case of very low OH contents (2–4 mol %), as expected, both components of poly(3‐hydroxybutyrate) and poly(styrene‐co‐4‐vinylphenol) chains are well separated and remain so independently of the mixed polymer ratio and overall polymer concentration as well. Conversely, when the OH content reaches 5.8 mol % or more, a significant decrease of the intrinsic fluorescence intensity emitted by the copolymer is detected upon addition of aliquots of poly(3‐hydroxybutyrate). In these cases, an average value for the interassociation equilibrium constant, K_A = 8.7, was obtained using a binding model formalism. A good agreement of these results with those obtained from complementary viscosity measurements, through the interaction parameter, Δb, was found. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 900–910, 2006     

Effect of intermolecular and intramolecular forces on hydrodynamic diameters of poly(N‐isopropylacrylamide) copolymers in aqueous solutions

A novel copolymer, poly(N‐isopropylacrylamide‐co‐hydroxypropyl methacrylate‐co‐3‐trimethoxysilypropyl methacrylate) has been synthesized and the hydrodynamic diameters in various aqueous solutions under different temperatures are determined by dynamic light scattering. The results show that the hydrodynamic diameters of copolymers have no obvious change in each working solution below lower critical solution temperature (LCST); across LCST, the diameters increased suddenly at different initial temperature in various aqueous solutions; above LCST, they decreased slightly as the temperature increased in UHQ water, and increased continuously with increasing temperature or salt concentration in saline solutions, and reduced with the rising of pH value in pH buffer. These are attributed to different intermolecular and intramolecular forces leading to disparity in dimension, conformation, and LCST of copolymers. The hydrogen bonding between water molecules and copolymer chains could maintain size and conformation of copolymer single chain; the hydrogen bonding between amide linkages and hydrophobic interactions between isopropyl groups result in intramolecular collapse and intermolecular aggregation; the electrostatic repulsion weakens aggregation extent of copolymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effects of Temperature on Morphology and Properties of Films Prepared from Poly(ester‐urethane) and Nitrochitosan

Summary: Novel elastic materials were prepared by mixing semicrystalline polyester‐based polyurethane (PU) synthesized at 100 °C with nitrochitosan (NCH) and 1,1,1‐tris(hydroxylmethyl)propane as crosslinker, and then by curing the mixture at 18, 25, 40, 60, and 80 °C. The effects of cure temperature on the crystallization behavior, miscibility, and mechanical properties of the PUNCH materials were studied by attenuated total reflection Fourier transform IR, wide‐angle X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis, X‐ray photoelectron spectroscopy, and tensile test. The results indicated that the crystalline structure of the blend films was more easily interrupted as the cure temperature increased, leading to a decrease of the degree of crystallinity. With an increase of cure temperature, the blend films exhibited high crosslinking density and tensile strength, and the phase separation between hard and soft segments of PU enhanced, resulting in a decrease in the glass transition temperature (T_g) of soft segment. Interestingly, the composite films keeping high elongation at break possessed tensile strength higher than that of the native poly(ester‐urethane). The enhanced mechanical properties of the blend films can be attributed to the relatively dense crosslinking network and strong intermolecular hydrogen bonding between NCH and PU. Therefore, this study not only provided a novel way by adding NCH into PU matrix to prepare elastic materials, which would remain functional characteristic of chitosan, but also expanded the application field of chitosan.

The cure temperature dependence of the tensile strength and elongation at break for the PEPU‐100 and PUNCH‐100 films.     

Fractionated crystallization of dispersed PA6 phase of PP/PP‐g‐MAH/PA6 blends

Fractionated crystallization behavior of dispersed PA6 phase in PP/PA6 blends compatibilized with PP‐g‐MAH was investigated by scanning electron microscopy (SEM), differential scanning calorimeter (DSC), polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD) in this work. The lack of usual active heterogeneities in the dispersed droplet was the key factor for the fractionated crystallization of PA6. The crystals formed with less efficient nuclei might contain more defects in the crystal structures than those crystallized with the usual active nuclei. The lower the crystallization temperature, the lesser the perfection of the crystals and the lower crystallinity would be. The fractionated crystallization of PP droplets encapsulated by PA6 domains was also observed. The effect of existing PP‐g‐MAH‐g‐PA6 copolymer located at the interface on the fractionated crystallization could not be detected in this work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3742–3755, 2004     

Miscibility enhancement through hydrogen bonding interaction of biodegradable poly(3‐hydroxybutyrate) blending with poly(styrene‐co‐vinyl phenol) copolymer

Differential scanning calorimetry, one‐ and two‐dimensional Fourier transform infrared (FTIR), and solid state nuclear magnetic resonance (NMR) spectroscopy have been used to investigate the miscibility of and specific interactions between poly(styrene‐co‐vinyl phenol) (PSOH) and poly(3‐hydroxybutyrate) (PHB) upon varying the vinyl phenol content of the PSOH copolymer. The FTIR and solid state NMR spectra revealed that the phenol units of PVPh interact with the carbonyl groups of PHB through intermolecular hydrogen bonding. A miscibility window exists when the vinyl phenol fraction in the copolymer is greater than 22 mol % in the PSOH/PHB blend system, as predicted using the Painter–Coleman association model. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Functional copolymer/organo‐montmorillonite nanoarchitectures. IX. Synthesis and nanostructure–morphology–thermal behaviour relationships of poly[(maleic anhydride)‐alt‐(acrylic acid)]/organo‐ montmorillonite nanocomposites

Functional copolymer/clay hybrids were synthesized by radical‐initiated interlamellar copolymerization of maleic anhydride/maleic acid and acrylic acid with 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride as a water‐soluble ionizable radical initiator in the presence of reactive (octadecylamine‐montmorillonite (ODA‐MMT)) and non‐reactive (dimethyldodecylammonium‐montmorillonite) organoclays at 60 °C in aqueous medium under nitrogen atmosphere. The monomers were dissolved in aqueous medium, and the two types of clay particles used were easily dissolved and dispersed partially swollen, respectively, in deionized water. Structure, thermal behaviour and morphology of the synthesized nanocomposites were investigated using Fourier transform infrared spectroscopy, X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and scanning and transmission electron microscopy. It is demonstrated that intercalative copolymerization proceeds via ion exchange between organoclays and carboxylic groups of monomers/polymers, which essentially improves interfacial interactions of polymer matrix and clay layers through strong hydrogen bonding. In the case of intercalative copolymerization in the presence of ODA‐MMT clay, a similar improvement is provided by in situ hydrogen bonding and amidolysis of carboxylic/anhydride groups from copolymer chains with primary amine groups of ODA‐MMT. The nanocomposites exhibit higher degree of intercalation/exfoliation of copolymer chains, improved thermal properties and fine dispersed morphology. Copyright © 2011 Society of Chemical Industry     

Crystallization behavior and crystallite morphology control of poly(L‐lactic acid) through N,N′‐bis(benzoyl)sebacic acid dihydrazide

Adding a nucleating agent is one of the best ways to accelerate the crystallization rate of poly(L ‐lactic acid) (PLLA) so as to obtain a high degree of crystallinity during the process, which will improve the heat distortion temperature of final products. In the work reported, N, N′‐bis(benzoyl)sebacic acid dihydrazide (BSAD) was synthesized and used as a nucleating agent for PLLA. Isothermal and non‐isothermal crystallization behaviors were investigated using differential scanning calorimetry (DSC). The addition of BSAD successfully enhances the crystallization rate of PLLA. A unique phase separation behavior of PLLA/BSAD blends is found from DSC as well as from polarized optical microscopy, which explains the difference of optimal BSAD concentration between isothermal and non‐isothermal crystallization. This is the first recording of a phase separation peak in PLLA/nucleating agent blends using DSC. In thermogravimetric analysis, the enhanced thermal stability indicates that there are strong hydrogen bonds between BSAD and PLLA matrix. BSAD can dissolve in PLLA melt below its melting point through intermolecular hydrogen bonding with PLLA and self‐assemble upon cooling, leading to the surface being capable of nucleating PLLA. Different phase separation temperatures can be used to control the morphology of BSAD, which finally determines the crystallite morphology of PLLA. © 2012 Society of Chemical Industry     

Effect of graphene oxide on the molecules of a sodium alginate–krill protein composite system and characterization of the system's composite fiber morphology and mechanical properties

Graphene oxide (GO), sodium alginate (SA), and Antarctic krill protein (AKP) were blended to get functional fibers. These GO–SA–AKP composite fibers were obtained by conventional wet spinning with 5% calcium chloride as a coagulation solution. The intermolecular interactions of the GO–SA–AKP composite system were characterized by Fourier transform infrared spectroscopy. The morphology, crystallinity, thermal stability, and mechanical properties of the GO–SA–AKP composites were investigated with scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry. The results show that the number of GO layers decreased gradually during the process of wet spinning. The addition of GO promoted an increase in intramolecular hydrogen bonding and a decrease in intermolecular hydrogen bonding in the composite system. With increasing GO mass fraction, the intermolecular hydrogen‐bond content, crystallinity, breaking strength, and thermal stability in the composite system increased first and then decreased. At the same time, the mass fraction of GO and the draw ratio had significant effects on the surface morphologies of the composite fibers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46642.     

Transcrystalline morphology of nylon 6 on the surface of aramid fibers

In this paper, the isothermal crystallization of nylon 6 in the presence of Kevlar 129 fiber was investigated by polarized optical microscopy (POM). The formation of a transcrystalline domain was found to be mainly controlled by crystallization conditions, such as the temperature of the isothermal crystallization, residual time at melting temperature and the cooling rate of the melt. The nucleation rate of nylon 6 on the fibers was mainly affected by the crystallization temperature. The interfacial transcrystallinity of nylon 6 occurred on the surface of Kevlar 129 fiber in the temperature range 130–190 °C. The reason for the formation of interfacial transcrystalline morphology is discussed from the molecular level, based on the understanding of the packing mode of nylon 6 chains around fibers and the interaction between matrix and fibers. It was found that the lattice matching and hydrogen‐bonding between nylon 6 and poly(p‐phenylene terephthalamide) (PPTA) crystals play an important role in the epitaxial crystallization. Copyright © 2004 Society of Chemical Industry     

Effect of hydrogen bonding on the crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/silica hybrid composites

Biodegradable poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHB-HHx)/hydrophobically modified silica hybrid composites were prepared using simple melt compounding and the effect of hydrogen bonding on their crystallization behavior was observed. The intermolecular hydrogen bonding between PHB-HHx and silica increased gradually with the increase of silica content of the hybrid composites. However, the extent of intermolecular hydrogen bonding was not directly proportional to the silica content. Although, the crystallization rates of the PHB-HHx/silica hybrids decreased as the strength of intermolecular hydrogen bonding increased, the constant value of the Avrami exponent indicates that the presence of silica does not alter the nucleation mechanism or the geometry of the crystal growth of the PHB-HHx hybrids. The calculated crystallization activation energy increased with the addition of silica, suggesting that silica retards the overall crystallization rate of the PHB-HHx hybrid composites as a result of the existence of intermolecular hydrogen bonding. The relationship between the extent of intermolecular hydrogen bond and crystallization rate is described by the empirical second-order equation.     

Studies on electrospun nylon-6/chitosan complex nanofiber interactions

Composite membranes of nylon-6/chitosan nanofibers with different weight ratio of nylon-6 to chitosan were fabricated successfully using electrospinning. Morphologies of the nanofibers were investigated by scanning electron microscopy (SEM) and the intermolecular interactions of the nylon-6/chitosan complex were evaluated by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) as well as mechanical testing. We found that morphology and diameter of the nanofibers were influenced by the concentration of the solution and weight ratio of the blending component materials. Furthermore FT-IR analyses on interactions between components demonstrated an IR band frequency shift that appeared to be dependent on the amount of chitosan in the complex. Observations from XRD and DSC suggested that a new fraction of γ phase crystals appeared and increased with the increasing content of chitosan in blends, this indicated that intermolecular interactions occurred between nylon-6 and chitosan. Results from performance data in mechanical showed that intermolecular interactions varied with varying chitosan content in the fibers. It was concluded that a new composite product was created and the stability of this system was attributed to strong new interactions such as hydrogen bond formation between the nylon-6 polymers and chitosan structures.     

Selective hydrogen bonding and hierarchical nanostructures in poly(hydroxyether of bisphenol A)/poly(?-caprolactone)-block-poly(2-vinyl pyridine) blends

The phase behavior, hydrogen bonding interactions and morphology of poly(hydroxyether of bisphenol A) (phenoxy) and poly(?-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP) were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy and atomic force microscopy (AFM). In this A-b-B/C type block copolymer/homopolymer system, both P2VP and PCL blocks have favorable intermolecular interaction towards phenoxy via hydrogen bonding. However, the hydrogen bonding between P2VP and phenoxy is significantly stronger than that between PCL and phenoxy. Selective hydrogen bonding between phenoxy/P2VP pair at lower phenoxy contents and co-existence of two competitive hydrogen bonding interactions between phenoxy/P2VP and phenoxy/PCL pairs at higher phenoxy contents were observed in the blends. This leads to the formation of a variety of composition dependent nanostructures including wormlike, hierarchical and core-shell morphologies. The blends became homogeneous at 95 wt% phenoxy where both blocks of the PCL-b-P2VP were miscible with phenoxy due to hydrogen bonding. In the end, a model was proposed to explain the microphase morphology of blends based on the experimental results obtained. The swelling of the PCL-b-P2VP block copolymer by phenoxy due to selective hydrogen bonding causes formation of different microphases.     

The synthesis of a physically crosslinked NVP based hydrogel

Complexes of polyvinyl pyrrolidinone–polyacrylic acid (PVP–PAA) were prepared by photopolymerisation from a mixture of the monomers NVP and AA. The complexes were characterised by means of differential scanning calorimetry, Fourier transform infrared spectroscopy (Ftir), potentiometric titration, swelling studies and gel permeation chromatography. The Ftir spectra of PVP–PAA copolymer complexes indicates hydrogen bonding between the carbonyl group in the PVP and the carboxylic acid group in the PAA moiety. As the percentage of AA increases in the copolymer there is evidence of increased intermolecular hydrogen bonding between the carboxylic acid groups of the AA segments. Swelling of the PVP–PAA complex in a higher pH medium is significantly different from results in low pH solutions. The critical pH range was found to be between 4.07 and 4.49. Above a pH of 4.49, there is a progressive break up of the polymer chain due to a reduction in the amount of intermolecular hydrogen bonding. There is also a significant increase in the solubility of the copolymer complex at higher pHs. The low solubility of the copolymer at low pH may make the complex suitable for gastric drug delivery systems.     

Functionalization of chitosan via single electron transfer living radical polymerization in an ionic liquid and its antimicrobial activity

In this work, single electron transfer living radical polymerization (SET‐LRP) was used to functionalize chitosan in a well‐controlled manner. The chitosan‐based macroinitiator was first synthesized and then initiated the SET‐LRP of methacryloyloxyethyl trimethylammonium chloride (DMC) in ionic liquid system, using Cu⁰/N,N,N′,N′,N′′‐pentamethyldiethylenetriamine as a catalyst. The grafting of PDMC brushes on chitosan was confirmed and analyzed by Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. Transmission electron microscopy reveals that the chitosan copolymer showed self‐assembled behavior in acetone. Surface properties of the copolymer have been investigated by environment scanning electron microscopy analysis. The linear relationship between the ln([M]₀/[M]_t) and time, the linear increase of number‐average molecular mass with conversion as well as the low polydispersity index of the polymer confirmed the “living/controlled” features of the polymerization of DMC through SET‐LRP. Finally, the chitosan copolymer demonstrates its potential antibacterial application, showing excellent inhibitive capability against Escherichia coli. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42754.     

Hydrogen bonding,miscibility, crystallization,and thermal stability in blends of biodegradable polyhydroxyalkanoates and polar small molecules of 4‐tert‐butylphenol

The hydrogen bonding, miscibility, crystallization, and thermal stability of poly(3‐hydroxybutyrate) (PHB)/4‐tert‐butylphenol (BOH) blends and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐3HHx)]/BOH blends were investigated by Fourier transform infrared (FTIR) spectroscopy, solid‐state¹³C‐NMR, differential scanning calorimetry, wide‐angle X‐ray diffraction (WAXD), and thermogravimetric analysis. The results of FTIR spectroscopy and solid‐state¹³C‐NMR show that intermolecular hydrogen bonds existed between the two components in the blends and that the interaction was caused by the carbonyl groups in the amorphous phase of both polyesters and the hydroxyl groups of BOH. With increasing BOH content, the chain mobility of both the PHB and P(3HB‐3HHx) components was improved. After the samples were quenched, the detected single glass‐transition temperatures decreased with composition, indicating that both PHB/BOH and P(3HB‐3HHx)/BOH were miscible blends in the melt. Moreover, as BOH content increased, the melting temperatures of PHB and P(3HB‐3HHx) clearly decreased, which implied that their crystallization was suppressed by the addition of BOH. Although the crystallinity of PHB and P(3HB‐3HHx) components decreased with increasing BOH content in the blends, their crystal structures were hardly affected after they were blended with BOH, which was further proven by WAXD results. In addition, the thermal stability of PHB was improved by a smaller amount of BOH.     

The totally miscible in ternary hydrogen‐bonded polymer blend of poly(vinyl phenol)/phenoxy/phenolic

The individual binary polymer blends of phenolic/phenoxy, phenolic/poly(vinyl phenol) (PVPh), and phenoxy/PVPh have specific interaction through intermolecular hydrogen bonding of hydroxyl–hydroxyl group to form homogeneous miscible phase. In addition, the miscibility and hydrogen bonding behaviors of ternary hydrogen bond blends of phenolic/phenoxy/PVPh were investigated by using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy, and optical microscopy. According to the DSC analysis, every composition of the ternary blend shows single glass transition temperature (T_g), indicating that this ternary hydrogen‐bonded blend is totally miscible. The interassociation equilibrium constant between each binary blend was calculated from the appropriate model compounds. The interassociation equilibrium constant (K_A) of each individually binary blend is higher than any self‐association equilibrium constant (K_B), resulting in the hydroxyl group tending to form interassociation hydrogen bond. Photographs of optical microscopy show this ternary blend possess lower critical solution temperature (LCST) phase diagram. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility,crystallization behavior and specific intermolecular interactions in thermosetting polymer blends of novolac epoxy resin and polyethylene glycol

Thermosetting polymer blends of novolac epoxy resin (EPN) and polyethylene glycol (PEG) were studied. The miscibility and crystallization behavior of the blends before curing reaction were investigated by polarized optical microscopy and differential scanning calorimetry (DSC). Overall uncured blend compositions were homogeneous in amorphous state. Single composition‐dependent glass‐transition temperature (T_g) for each blend could be observed, and the experimental T_g's of blends with EPN content ≥40 wt% could be explained well by the Gordon–Taylor equation. Thermal properties of blends cured with 4,4′‐diaminodiphenylmethane were also determined by DSC. The capability of PEG to crystallize in cured blends was different from that in uncured ones because of the topological effect of highly crosslinking structure. On the basis of Fourier transform infrared spectroscopy results, it was judged that there were intermolecular hydrogen‐bonding interactions between EPN and PEG in both cured and uncured blends. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers