Effect of silicone dioxide and poly(ethylene glycol) on the conductivity and relaxation dynamics of poly(ethylene oxide)–silver triflate solid polymer electrolyte

The conducting and relaxation dynamics of Ag⁺ ions in poly(ethylene oxide) (PEO)–silver triflate (AgCF₃SO₃) solid polymer electrolytes (SPEs) containing nanosize SiO₂ filler and poly(ethylene glycol) (PEG) as a plasticizer were studied in the frequency range 10 Hz to 10 MHz and in the temperature range 303–328 K. The comparatively lower conductivity of the plasticized (PEG) PEO–AgCF₃SO₃–SiO₂ nanocomposite electrolyte system was examined by analysis of the Fourier transform infrared (FTIR) spectroscopy and conductivity data. The electric modulus (M″) properties of the SPE systems were investigated. A shift of the M″ peak spectra with frequency was found to depend on the translation ion dynamics and the conductivity relaxation of the mobile ions. The value of the conductivity relaxation time was observed to be lower for the PEO–AgCF₃SO₃ system only with nanofiller SiO₂. The scaling behavior of the M″ spectra showed that the dynamical relaxation processes was temperature-independent in the PEO–AgCF₃SO₃ and PEO–AgCF₃SO₃–SiO₂–PEG polymer systems, whereas they were temperature-dependent for the PEO–AgCF₃SO₃–SiO₂ system. However, the relaxation processes of all of theses systems were found to be dependent on their respective compositions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Crystallization and morphology of poly(ethylene succinate) and poly(β-hydroxybutyrate) blends

Summary The melting and crystallization behavior of poly(β-hydroxybutyrate) (PHB) and poly(ethylene succinate) blends has been studied by differential scanning calorimetry and optical microscopy. The results indicate that PHB and PES are miscible in the melt. Consequently the blend exhibits a depression of the melting temperature of both PHB and PES. In addition, a depression of the equilibrium melting temperature of PHB is observed. The Flory-Huggins interaction parameter (χ₁₂ ), obtained from melting point depression data, is composition dependent, and its value is always negative. Isothermal crystallization in the miscible blend system PES/PHB is examined by polarized optical microscope. The presence of the PES component gives a wide variety of morphologies. The spherulites exhibit a banded structure and the band spacing decreases with increase PES content. Received: 29 June 1998/Revised version: 31 August 1998/Accepted: 10 September 1998     

Impact of organoclays on the phase morphology and the compatibilization efficiency of immiscible poly(ethylene terephthalate)/poly(ε-caprolactone) blends

Adding nanofillers Cloisite 30B (C30B) and Cloisite 15A (C15A) to poly(ethylene terephthalate) (PET)/poly(ε-caprolactone) (PCL) (70/30, wt/wt) blends via melt blending can improve their phase morphology and change their interface properties. The effects of the different selective localization of clay on the structure and the morphologies are studied and evaluated by theoretical and experimental methods. It is found that C30B is selectively localized in PET and at the PET-PCL interface, whereas C15A is mainly localized at the interface. Moreover, the changes in the rheological behavior of the blends are attributed to the formation of clay network-like structures. X-ray diffraction, scanning electron microscope, and transmission electron micrograph observations also evidenced an exfoliated and/or intercalated structure of C30B, and intercalated structure of C15A in the blend, together with significant morphology changes of the initially immiscible blend. The relative permeability to PET/PCL of the nanocomposites decreased with the increasing of nanoclays content. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48812.     

Prevention of poly(vinyl chloride) degradation through organic terephthalamides generated from poly(ethylene terephthalate) waste

The use of organic compounds as thermal stabilizers for poly(vinyl chloride) (PVC) stabilization is the current state of art worldwide owing to their high efficiency and nontoxic residues after degradation. Terephthalamide, N,N′-dimethylterephthalamide and N,N′-dibutylterephthalamide have been prepared via depolymerization of poly(ethylene terephthalate) through an economical and environmentally friendly approach. These compounds have been examined as thermal stabilizers for PVC formulations and found to exhibit high thermal stabilizing effects. Thermal stability measurements were performed using conventional Congo red test method. Color change experiments were conducted by heating the samples at 200 °C in air, and the colored compounds formed were extracted and compared with the help of UV–visible spectroscopy. Fourier transform infrared spectroscopic studies of organic terephthalamides incorporated PVC samples have been performed in order to insight the probable mechanistic aspects involved in thermal stabilization process. Thermogravimetric analysis (TGA) thermograms of PVC sheets loaded with 10 wt % organic terephthalamides have been recorded and were found stable below 200 °C. SEM and energy dispersive X-ray analysis of char residues of TGA samples were performed supporting the proposed thermal stabilizing action of the organic terephthalamides. Furthermore, specific gravity and mechanical performance of the PVC sheets have also been reported assisting in finding suitable commercial applications of PVC formulations. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48022.     

Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

A series of amphiphilic graft copolymers PEO-g-PCL with different poly (ε-caprolactone) (PCL) molecular weight were successfully synthesized by a combination of anionic ring-opening polymerization (AROP) and coordination-insertion ring-opening polymerization. The linear PEO was produced by AROP of ethylene oxide (EO) and ethoxyethyl glycidyl ether initiated by 2-(2-methoxyethoxy) ethoxide potassium, and the hydroxyl groups on the backbone were deprotected after hydrolysis. The ring-opening polymerization of CL was initiated using the linear poly (ethylene oxide) (PEO) with hydroxyl group on repeated monomer as macroinitiator and Sn(Oct)₂ as catalyst, then amphiphilic graft copolymers PEO-g-PCL were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO-g-PCL with well-defined structure, molecular weight control, and narrow molecular weight distribution were prepared. The expected intermediates and final products were confirmed by ¹H NMR and GPC analyzes. In addition, these amphiphilic graft copolymers could form spherical aggregates in aqueous solution by self-assemble, which were characterized by transmission electron microscopy, and the critical micelle concentration values of graft copolymers PEO-g-PCL were also examined in this article.     

Structure–property evolution of poly(ethylene terephthalate)/poly(trimethylene terephthalate) side-by-side self-crimp filament

To investigate the microstructure and mechanical properties of self-crimping two-component side-by-side bicomponent filament, this paper focuses on systematically investigating the structure–property evolution of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) side-by-side bicomponent filament prepared via melt spinning with various component ratios, drawing and heating treatment. The investigation was operated upon the combination of morphology analysis, thermal analysis, crystallization, and orientation analysis. The variation of cross section and curl-morphology, crystallization, and microstructures mainly containing lamellar and microfibrillar crystals as well as their effects on the mechanical and self-crimping properties were discussed. As the draft ratio (DR) increases, the crystallinity, sonic orientation factor, tensile strength, and crimp-recovery rate of the filaments were increased. The sonic orientation factor in the crystalline region decreases from 0.923 to 0.777 but increases from 0.677 to 0.903 in the amorphous region. In contrast to the variation of the DR, heating temperature has a limited effect on the tensile strength of the PET/PTT hybrid filaments. Crimp-recovery rate, however, first increases to 11.8 and then decreases to 9.8 with an increasing heating temperature from 144 to 168°C. Most of these behaviors have been attributed to changes in the ratio of contractile stress for both PTT and PET components, originating from microstructural evolution in hybrid filaments, including crystal growth, breakage, deflection, and deformation of chains along the axial direction. As a summary, an interpretive diagrammatic sketch has been proposed to clarify the structure–property relationships of the commercial PET/PTT filaments.     

Biodegradable nanoparticles of methoxy poly(ethylene glycol)-b-poly( d, l-lactide)/methoxy poly(ethylene glycol)- b-poly(ϵ-caprolactone) blends for drug delivery

The effects of blend weight ratio and polyester block length of methoxy poly(ethylene glycol)-b-poly( d, l-lactide) (MPEG- b-PDLL)/methoxy poly(ethylene glycol)- b-poly(ϵ-caprolactone) (MPEG- b-PCL) blends on nanoparticle characteristics and drug release behaviors were evaluated. The blend nanoparticles were prepared by nanoprecipitation method for controlled release of a poorly water-soluble model drug, indomethacin. The drug-loaded nanoparticles were nearly spherical in shape. The particle size and drug loading efficiency slightly decreased with increasing MPEG- b-PCL blend weight ratio. Two distinct thermal decomposition steps from thermogravimetric analysis suggested different blend weight ratios. Thermal transition changes from differential scanning calorimetry revealed miscible blending between MPEG- b-PDLL and MPEG- b-PCL in an amorphous phase. An in vitro drug release study demonstrated that the drug release behaviors depended upon the PDLL block length and the blend weight ratios but not on PCL block length.     

Effects of liquid–liquid phase separation on crystallization of poly(ethylene glycol) in blends with isotactic poly(methyl methacrylate)

To analyze the interplay between crystallization and liquid–liquid phase separation (LLPS), isothermal crystallization behavior of poly(ethylene glycol) (PEG) in blends with isotactic poly(methyl methacrylate) (i-PMMA) was investigated by differential scanning calorimetry (DSC). The blend system had an upper critical solution temperature (UCST) type phase diagram. When the crystallization occurred simultaneously with LLPS, the overall crystallization rate was enhanced at high crystallization temperatures T_c, relatively compared with that of neat PEG. This behavior was interpreted by the combination of the effects of spinodal quench depth ?T_s and usual supercooling degree ?T_c, according to the theory of Mitra and Muthukumar, namely, the crystallization rate is enhanced by the concentration fluctuation-assisted nucleation at high T_c. In the crystallization after LLPS proceeded, on the other hand, the overall crystallization rate was slow and less dependent on the blend composition. In addition, it was revealed by small-angle X-ray scattering measurements that amorphous i-PMMA was excluded from the interlamellar region of PEG crystals in SQ as well as WQ.     

High-efficiency synthesis of dendrimer-like poly(ethylene oxide) via “arm-first” approach

In this study, a dendrimer-like polymer based on poly(ethylene oxide) (PEO) was synthesized through a combination of anionic ring-opening polymerization (AROP) and click reaction via arm-first method. Firstly, the polymeric arm, a linear PEO with one alkynyl group and two bromo groups, was synthesized by AROP of ethylene oxide followed by functionalization with propargyl bromide and esterified with 2-bromopropionic bromide. Second, a star PEO carrying three azide groups was synthesized though AROP of ethylene oxide used 1,1,1-tris(hydrosymethyl) ethane as initiator followed esterificated with 2-bromopropionic acid and azidation. By azide–alkyne click reactions between the azide-terminated PEO star polymer and linear PEO with functionalization alkynyl group, a three generation dendrimer-like PEO, G3-PEO-24Br, was successfully synthesized. The resulting polymers were observed to have precisely controlled molecular weights and compositions with narrow molecular weight distributions.     

Synthesis and characterization of polymers from β-propiolactone and poly(ethylene glycol)s

Uncatalysed polymerizations of β-propiolactone with low-molecular-weight poly(ethylene glycol)s were carried out in bulk, at temperatures in the range of 70 to 120°C. ¹H nuclear magnetic resonance (n.m.r.) and differential scanning calorimetry (d.s.c.) measurements on the resulting products indicated a block copolymer structure. Gel permeation chromatography (g.p.c.) and d.s.c. analyses showed that in some cases the copolymerization is accompanied by homopolymerization of β-propiolactone, probably due to the presence of residual water in the poly(ethylene glycol). N.m.r. and infra-red (i.r.) spectra of copolymers revealed the presence of hydroxyl and carboxyl end groups. The copolymerization reaction may be visualized as a two-step process, in which the ring opening of β-propiolactone takes place on both the hydroxyl groups of poly(ethylene glycol), followed by repetitive monomer addition forming an ester-ether-ester triblock copolymer.     

Synthesis of amphiphilic polycyclooctene-graft–poly(ethylene glycol) copolymers by ring-opening metathesis polymerization

In this paper, a novel monomer of 4-methyl-3-(carbamate)–carbanilic acid-4-cyclooctene ester (MCCCE) was synthesized and characterized by FTIR, NMR and ESI-MS. Polycyclooctene-graft-blocked isocyanate copolymers were prepared by the copolymerization of MCCCE and cyclooctene via ring-opening metathesis polymerization (ROMP). Amphiphilic polycyclooctene-graft–PEG copolymers were prepared by melt mixing the polycyclooctene-graft-blocked isocyanate copolymers with poly(ethylene glycol) (PEG) at 200 °C. The blocked isocyanate group on MCCCE can be dissociated to produce free isocyanate group, which will react with the end hydroxyl groups on PEG molecules. The effects of monomer-to-catalyst, monomer-to-chain transfer agent ratios on molecular weight of the copolymer were detailedly studied. The water contact angle of polycyclooctene-graft–PEG copolymer is much smaller than that of polycyclooctene.     

Molecular weight effect on theta-gel formation in poly(vinyl alcohol)–poly(ethylene glycol) mixtures

Injectable hydrogel formulations that undergo in situ gelation at body temperature are promising for minimally invasive tissue repair. This work focuses on the investigation of injectable poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG) mixtures. The injectable PVA–PEG aqueous solutions form a hydrogel as temperature is reduced to near body temperature, while filling a defect in the injection site. Gamma sterilization of these solutions compromises injectability presumably due to crosslinking of PVA. We hypothesized that by modifying the PEG molecular weight and its concentration, injectability of radiation sterilized PVA–PEG hydrogels can be optimized without compromising the mechanical properties of the resulting gel. The use of a bimodal mixture of higher and lower molecular weight PEG (600 and 200 g/mol) resulted in lower PVA/PEG solution viscosity, better injectability, and higher gel mechanical strength. The PVA/bimodal-PEG had a lower viscosity at 2733 ± 149 cP versus a viscosity of 5560 ± 278 cP for PVA/unimodal-PEG (400 g/mol). The gel formed with the bimodal PEG mixture had higher creep resistance (61% total creep strain under 0.5 MPa) than that formed with unimodal PEG (84%). These hydrogel formulations are promising candidates for minimally invasive tissue repair. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Correlation of the morphology and thermooxidative degradation behavior of poly(ethylene terephthalate)–nitrile butadiene rubber–polycarbonate ternary blends

In this study, we prepared ternary poly(ethylene terephthalate) (PET)–nitrile butadiene rubber (NBR)–polycarbonate (PC) blends through a molten mixing procedure, and with a corotating extruder, we studied the morphology and thermodynamic properties of each purified polymer and the binary and ternary blends with different compositions. Dynamic mechanical analysis of both the PET–PC and PET–NBR samples showed individual loss peaks for each component, but in different ternary samples, the effects of different percentages of components (PC–PC and PET–NBR) were observed; this revealed changes in the loss peak locations. Individual loss peaks of PET and PC in the ternary PET–NBR–PC blends (81/9/10 and 63/30/7)—proof of the miscibility of the samples—were also observed in this study. The thermal properties of the samples were measured and examined with the thermogravimetric analysis and differential thermogravimetry testing methods. The activation energy and order of reaction values for the samples under an air atmosphere with single-rate methods of heating were studied. Finally, the relation between the type of morphology and the thermal degradation behavior was investigated. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47171.     

Controlled release of doxycycline within core/shell poly(ε-caprolactone)/poly(ethylene oxide) fibers via coaxial electrospinning

The development of fibers with desired drug release properties has gained a high research interest for water-soluble drugs with controlled drug delivery systems obtained by coaxial electrospinning technique. The objective of this study is to achieve the controlled-release of doxycycline hyclate (DOXH) from the fabricated electrospun fibers. In this case, three different electrospun core/shell fibers have been successfully fabricated using this technique and the model drug, DOXH, has been entrapped in the core layers. The results of the structural properties and in vitro release studies have been compared with electrospun monostructural fibers fabricated by conventional electrospinning technique. Scanning electron microscopy and transmission electron microscopy images have proved that the fabricated electrospun fibers have core/shell structures. Fourier transform infrared spectroscopy has shown convenient interaction and compatibility between polymers and the model drug. X-ray diffraction analysis has revealed that all the encapsulated DOXH are transferred into amorphous physical state and lost its crystalline state in the fibers. Moreover, drug release studies have demonstrated that the electrospun core/shell fibers show a better-controlled release than the monostructural fibers. It can be concluded that the fibers obtained by blending hydrophilic and hydrophobic polymers such as poly(ε-caprolactone) and poly(ethylene oxide) in both shell and core sides are promising candidate for controlled drug release.     

High-surface-area SBA-15–SO3H with enhanced catalytic activity by the addition of poly(ethylene glycol)

The influence of poly(ethylene glycol) (PEG) and synthesis temperature in the synthesis of SBA-15–SO₃H was investigated to evaluate the catalytic activity in the esterification of propionic acid with methanol. The catalysts were characterized by means of surface and structure analyses; X-ray diffraction, FT-IR, scanning electron microscopy, Thermo-gravimetric and N₂ adsorption/desorption techniques. It was found that, by the addition of PEG, the surface area and porosity of SBA-15–SO₃H increased, while the structure and size of mesopores remained unchanged. Nitrogen sorption measurements indicate that PEG introduces additional pores into the pore walls of SBA-15–SO₃H. Thus, a simple way of improving the porosity of mesoporous SBA-15–SO₃H was presented that could enhance transport of substrates through the porous system and allow the generation of stable mesoporous replicas, important for catalytic applications and also beneficial for replication and nanocasting purposes.     

Shape-memory behavior of poly (methyl methacrylate-co –N-vinyl-2-pyrrolidone) / poly (ethylene glycol) semi-interpenetrating polymer networks based on hydrogen bonding

Based on hydrogen bonding interactions, Poly(methyl methacrylate-co-N-vinyl-2-pynolidone) (P(MMA-co-VP)) networks and linear poly(ethylene glycol) (PEG) can form semi-interpenetrating polymer networks (semi-IPNs), i.e. P(MMA-co-VP)/PEG semi-IPNs, which has shape memory behaviour; its maximum storage modulus ratio can be more than 400, and its shape recovery ratio could reach 99%. The morphology, thermal behaviors and dynamic mechanical properties of P(MMA-co-VP)/PEG semi-IPNs were studied by FTIR, TEM, DSC and DMA. When PEG with higher molecular weight was introduced into P(MMA-co-VP) networks, they possess higher glassy state modulus and higher recovering rate. In such a system, the maximum molecular weight of PEG required for the semi-IPN formation reaches 1000.     

Phase behavior of LiClO4-doped poly(ε-caprolactone)-b-poly(ethylene oxide) hybrids in the presence of competitive interactions

The phase behavior of a series of LiClO₄-doped poly(ε-caprolactone)-b-poly(ethylene oxide) (PCL-b-PEO) was studied as a function of PEO volume fraction (f_PEO), doping ratio (r) and temperature (T). It is found that the morphology of the hybrids changes from disordered structure (DIS) to hexagonally packed cylindrical (HEX) structure and then to lamellar (LAM) structure as the volume fraction of the PEO/salt phase (f_PEO/salt) increases at f_PEO/salt < 0.5. Order–order transitions are observed upon heating some hybrids. An approximate phase diagram of the PCL-b-PEO/LiClO₄ hybrids with f_PEO/salt < 0.5 was constructed in terms of f_PEO/salt and the segregation strength (χ_effN). As compared with the phase diagram of the weakly segregated diblock copolymers, the phase diagram of the hybrids has two features: the boundaries of the LAM and HEX structures shifts to lower f_PEO/salt and body-centered cubic spherical (BCC) structure is not observed for the samples studied. This can be attributed to the weaker ability of the salt inducing microphase separation at low f_PEO and the conformational change of the PEO block induced by the salt. Some unexpected phase behaviors were observed for the hybrids with f_PEO/salt > 0.5, including the hexagonally perforated layers (HPL) to LAM transition upon heating the same hybrid and HEX to gyroid (GYR) transition with the increase of doping ratio at the same temperature. These unexpected phase behaviors are qualitatively interpreted based on the competitive association of the PCL block with Li⁺ ions at elevated temperatures and higher doping ratios, which leads to re-distribution of the Li⁺ ions in different phases and the inconsistency between the calculated f_PEO/salt and the real volume fraction of the PEO/salt phase.     

Polystyrene–poly(ethylene oxide) diblock copolymers micelles in water

Micellization in water of polystyrene–poly(ethylene oxide) diblock copolymers is achieved by the stepwise dialysis technique in order to prepare micellar solutions for copolymers with a wide range of molecular parameters. Hydrodynamic radii, determined by quasielastic light scattering, are correlated with the molecular parameters, e.g. molecular weight and composition, and compared with the theory. Two couples of phenanthrene and anthracene labelled copolymers are used to prepare micellar solutions by mixing them before and after dialysis. The non radiative energy transfer is determined on these solutions to prove that polystyrene-poly(ethylene oxide) diblock copolymers micelles in water are "frozen" micelles even when heated near the Tg of polystyrene. Received: 3 November 1997/Revised version: 1 December 1997/Accepted: 2 December 1997     

Magnetite nanoparticles stabilized with polymeric bilayer of poly(ethylene glycol) methyl ether-poly(?-caprolactone) copolymers

In this work, we report a synthetic method of water dispersible magnetite nanoparticles having oleic acid and poly(ethylene glycol) methyl ether-poly(?-caprolactone) (mPEG-PCL) amphiphilic block copolymer as polymeric stabilizers. The particles were prepared by coprecipitation of Fe(II) and Fe(III) in NH₄OH and had bilayer surface with hydrophobic inner layer and hydrophilic corona. mPEG-PCL copolymer was synthesized by a ring-opening polymerization of ?-caprolactone using mPEG as a macroinitiator in the presence of stannous octoate catalyst. FTIR and thermogravimetric analysis (TGA) indicated the presence of the copolymer on the particle surface. Roles of reaction parameters, such as stabilizer concentrations and time of ultrasonicating treatment, on percent of magnetite in the complex and its magnetic properties were investigated. Transmission electron microscopy (TEM) showed the average particle size about 9.0 ± 1.1 nm in diameter. Vibrating sample magnetometry (VSM) measurement indicated that the magnetite nanoparticles were superparamagnetic at room temperature. Approximately 6.8 ± 0.5% of indomethacin model drug (68 μg/mg of magnetite) was effectively entrapped on the particles.     

The crystallization behavior of poly(ethylene glycol)-poly(ε-caprolactone) diblock copolymers with asymmetric block compositions

Crystallization behavior, structural development and morphology evolution of a series of poly (ethylene glycol)-poly(ε-caprolactone) diblock copolymers (PEG-b-PCL) were investigated via differential scanning calorimetry (DSC), X-ray diffraction (XRD) and atomic force microscopy (AFM). In these copolymers, both blocks were crystallizable and biocompatible. The mutual effects between the PEG and PCL blocks were significant, leading to the obvious block composition dependence of the crystallization behavior and morphology of the PEG-b-PCL copolymers. The relative block length determined which block crystallized first. The temperature-dependent XRD measurements confirmed which block crystallized first from the copolymer during the cooling procedure. Single crystals of the PCL and PEG homopolymers and the PEG-b-PCL copolymers were obtained and observed by AFM. The block (PCL or PEG) crystallized first would determine the crystal morphology. The block crystallized later acted as a solvent, which was advantageous to forming perfect single crystals of the whole block copolymers.