Dynamic relaxation characteristics of crosslinked poly(ethylene oxide) copolymer networks: Influence of short chain pendant groups

The dynamic relaxation characteristics of short-branch rubbery amorphous networks prepared by the photopolymerization of poly(ethylene glycol) diacrylate [PEGDA] crosslinker have been investigated using dynamic mechanical analysis and broadband dielectric spectroscopy. Copolymerization with low molecular weight acrylates was used to control effective crosslink density in the networks and led to the insertion of ethylene oxide pendant groups along the network backbone. Substantial differences in the sub-glass and glass-rubber relaxation properties of the copolymers were observed as a function of pendant length and the nature of the pendant terminal group (e.g., -OH vs. -OCH₃); the results are compared with prior studies on model copolymers containing longer, more flexible side branches.     

Glass‐transition and gas‐transport characteristics of polymer nanocomposites based on crosslinked poly(ethylene oxide)

The glass‐transition and gas‐transport properties of rubbery polymer nanocomposites based on crosslinked poly(ethylene oxide) and metal oxide nanoparticles were studied. Nanocomposite samples were prepared by the UV photopolymerization of poly(ethylene glycol) diacrylate (n ～ 14) in the presence of magnesium oxide or silica nanoparticles. The thermomechanical properties of the composites were investigated with dynamic mechanical and dielectric spectroscopy methods. The inclusion of nanoparticles in the crosslinked poly(ethylene glycol) diacrylate network led to a systematic increase in rubbery modulus and a modest positive offset (～6°C) in the measured glass‐transition temperature for both systems. Bulk density measurements indicated only minimal void volume fraction in the composites, and CO₂ and light gas permeability decreased with particle loading; for example, the CO₂ infinite dilution permeability at 35°C decreased from 106 barrer in the unfilled polymer to 55 barrer in a nanocomposite containing 30 wt % magnesium oxide nanoparticles. The inclusion of toluene diluent in the prepolymerization mixtures produced a limited enhancement in sample permeability, but the sizeable increases in gas transport with particle loading reported for certain other rubbery nanocomposite systems were not realized in the crosslinked poly(ethylene glycol) diacrylate composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphological, mechanical and gas-transport characteristics of crosslinked poly(propylene glycol): homopolymers, nanocomposites and blends

Linear polyethers possess unusually high CO₂ solubility and, hence, selectivity due to the presence of accessible ether linkages that can interact with the quadrupolar moment of CO₂ molecules. In this work, membranes derived from crosslinked poly(propylene glycol) diacrylate (PPGda) oligomers differing in molecular weight (M), as well as PPGda nanocomposites containing either an organically-modified montmorillonite clay or a methacrylate-terminated fumed silica are investigated and compared with highly CO₂-selective poly(ethylene glycol) diacrylate (PEGda) homopolymer and nanocomposite membranes previously reported. The rheological and permeation properties of PPGda depend sensitively on M, with the elastic modulus decreasing, but CO₂ permeability and CO₂/H₂ selectivity increasing, with increasing M. Incorporation of either nanofiller into PPGda enhances the elastic modulus and reduces the gas permeability in the resultant nanocomposites without strongly affecting CO₂/H₂ selectivity. Blending PPGda and PEGda prior to chemical crosslinking yields binary membranes that exhibit intermediate gas-transport properties accurately described by a linear rule of mixtures.     

Relation between structure and gas transport properties of polyethylene oxide networks based on crosslinked bisphenol A ethoxylate diacrylate

Poly(ethylene oxide) (PEO) networks prepared from the photopolymerization of bisphenol A ethoxylate diacrylate (BPA-EDA) have been investigated as a function of crosslinker molecular weight and copolymer composition. Dynamic mechanical and dielectric methods have been used to elucidate the thermal relaxation characteristics of the polymers as a function of network composition and architecture, and these properties were related to measured gas transport for CO₂ separations. Copolymerization strategies involving the insertion of flexible PEG side chains along the network backbone proved effective in enhancing network free volume and increasing permeability. The gas transport performance of rubbery amorphous membranes based on the n=15 BPA-EDA crosslinker (i.e., crosslinker encompassing 30 ethylene oxide repeat units between crosslinks) compared favorably to model polymers synthesized from poly(ethylene glycol) diacrylate.     

Miscibility of polystyrene with poly(ethylene oxide) and poly(ethylene glycol)

The intrinsic viscosity of polystyrene–poly(ethylene oxide) (PS–PEO) and PS–poly(ethylene glycol) (PEG) blends have been measured in benzene as a function of blend composition for various molecular weights of PEO and PEG at 303.15 K. The compatibility of polymer pairs in solution were determined on the basis of the interaction parameter term, Δb, and the difference between the experimental and theoretical weight-average intrinsic viscosities of the two polymers, Δ[η]. The theoretical weight-average intrinsic viscosities were calculated by interpolation of the individual intrinsic viscosities of the blend components. The compatibility data based on [η] determined by a single specific viscosity measurement, as a quick method for the determination of the intrinsic viscosity, were compared with that obtained from [η] determined via the Huggins equation. The effect of molecular weights of the blend components and the polymer structure on the extent of compatibility was studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1471–1482, 1998     

Shape memory polymer system of semi-interpenetrating network structure composed of crosslinked poly (methyl methacrylate) and poly (ethylene oxide)

Shape memory semi-interpenetrating polymer networks (semi-IPNs) composed of crystalline poly (ethylene oxide) (PEO) and crosslinked poly (methyl methacrylate) (x-PMMA) have been investigated. The selected compositions show shape memory property with a reasonable fast recovery (recovery time ∼1 min) and shape recovery ratio of 99%. Effects of composition (x-PMMA/PEO = 80/20…60/40) and crosslinker (triethyleneglycol dimethacrylate) concentration (up to 6 wt.%) on the creep property were also studied. The recovery time of the semi-IPNs increased and the creep compliance decreased with increasing crosslinker concentration. The network structure containing PEO crystal was characterized by scanning electron microscopy (SEM). Differential scanning calorimetry (DSC) indicated that the PEO, present confined in the semi-IPN, melts at a lower temperature compared to the pure PEO. Dynamic mechanical analysis (DMA) showed a decrease in the glass transition (T_g) of the semi-IPN due to the phase mixing of amorphous PEO and PMMA. Both the glassy and rubbery moduli (E_g and E_r, respectively) were lower for the semi-IPNs than for the x-PMMA network. On the other hand, the E_g/E_r ratio was markedly increased for the semi-IPNs supporting an easy shaping along with a good shape fixing.     

Surface modification of silicone rubber with poly(ethylene glycol) hydrogel coatings

Hydrogel coatings of monoacrylated poly(ethylene glycol) (PEG) methyl ethers of different molecular weights were attached to silicon rubber surfaces and crosslinked with hexanediol diacrylate or ethoxylated trimethylolpropane diacrylate by UV polymerization. The wetting, evaluated with the water contact angles, correlated with the surface oxyethylene chain density, which was evaluated with the ESCA >C? O? /? CH₂? ratio obtained from the C(1s) peak. As measured by the ESCA N(1s) peak, bovine serum albumin formed very thin protein adsorbates on the PEG‐coated surfaces. A strong correlation was found between low protein adsorption and a high >C? O? /? CH₂? ratio of the PEG‐coated substrate. The PEG‐coated silicon rubber also demonstrated very low cell and platelet adhesion. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1486–1492, 2004     

Gelation and crosslinking characteristics of photopolymerized poly(ethylene glycol) hydrogels

The gelation and crosslinking features of poly(ethylene glycol) (PEG) hydrogels were scrutinized through the UV polymerization processes of poly(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) mixtures. The real‐time evolutions of the elastic moduli of the prepolymerized mixtures with different crosslinking ratios of PEGMA and PEGDMA and the photoinitiator concentrations were measured during photopolymerization. The rheological properties were compared with other properties of the PEG hydrogels, including the relative changes in the C?C amounts in the mixtures before and after UV irradiation, water swelling ratio, gel fraction, mesh size, and mechanical hardness. As the portion of PEGDMA as a crosslinker increased, the final elastic modulus and gel fraction increased, whereas the swelling ratio and scratch penetration depth at the hydrogel film surface decreased because of the formation of compact networks inside the hydrogels. These results indicate that there was a good correlation between the rheological analysis for predicting the crosslinking transition during photopolymerization and the macroscopic properties of the crosslinked hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41939.     

Synthesis,extraction, and adsorption properties of calix[4]arene‐poly(ethylene‐glycol) crosslinked polymer

Novel calix[4]arene‐poly(ethylene glycol) crosslinked polymer (CCP) has been synthesized by the polycondensation reaction between a p‐tert‐butylcalix[4]arene derivative and dihydroxyl capped poly(ethylene glycol) (DHPEG, M_n = 1000) catalyzed by neodymium tosylate. The hydrogel, consisted of 66.9% water and 33.1% CCP, can selectively extract aromatic organic molecules from aqueous solution according to the diameter of the guest molecules, which infers that the diameter of the calix[4]arene cavity is about 5.4 Å and the conformation of calix[4]arene units altered from cone conformation to 1,3‐alternate conformation during the polycondensation reaction. Furthermore, CCP can also adsorb naphthalene from gas phase, showing much higher capacity than active carbon does, which may have some potential applications in the field of separation and environment protection. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Change in the molecular weight distribution of poly(ethylene oxide) caused by the complexation with poly(acrylic acid)

The complexation between poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) was made by using double the molar quantity of either polymer component at pH 2 where the resulting complex completely precipitates. After the removal of the precipitate, PEO or PAA remaining in the supernatant was subjected to gel permeation chromatography to investigate the change in the molecular weight distribution (MWD) caused by the complexation. No remarkable difference is observed in the MWD curves for PEO[1] (M_w=1.37 × 10⁴) before and after the complexation with PAA[1] (M_w=1.10 × 10³) and PAA[2] (M_w=4.16 × 10⁵). However, the MWD curves of PEO[2] (M_w=1.26 × 10⁵) and PAA[2] become shortened and shift to the low molecular weight side after the complexation with PAA[1] or [2] and PEO[2], respectively. This tendency is enhanced by increasing the complexation temperature. From these results, it is indicated that the complexation between PEO and PAA deals with an equilibrium reaction, and the equilibrium constant is dependent on the chain length of both polymer components and also on the complexation temperature.     

Photocuring kinetic studies of new dental restorative resins based on poly(ethylene glycol) diacrylate and tris[2-(acryloyloxy)-ethyl]isocyanurate

A new kinetic process for photocuring that is based on the mixture of poly(ethylene glycol) diacrylate and tris[2(acryloyloxy)ethyl]isocyanurate in the presence of the photoinitiator hybrid system camphorquinone/2-(dimethylamino)ethyl methacrylate has been investigated at different component concentrations. The final product is highly crosslinked, showing up to 80% of monomer conversion. The hardness of this photocured product, with 50 wt.-% of inorganic filler added, is similar to the hardness of a widely used commercial product (Restorative Z100MP resin from 3M). This new photocured product may be used for a broad range of applications in dentistry.     

Tetracycline release from bioerodible hydrogels based on semiinterpenetrating polymer networks composed of poly(ε-caprolactone) and poly(ethylene glycol) macromer in vitro

Poly(ethylene glycol) (PEG) macromers terminated with acrylate groups and semiinter-penetrating polymer networks (SIPNs) composed of poly(ε-caprolactone) (PCL) and PEG macromer were synthesized and characterized with the aim of obtaining a bioerodible hydrogel that could be used to release tetracycline HCl for local antibiotic therapy administered peroperatively. Polymerization of PEG macromer resulted in the formation of crosslinked gels due to the multifunctionality of macromer. Noncrosslinked PCL chains were interpenetrated into the crosslinked three-dimensional networks of PEG. Glass transition temperature (T_g) and melting temperature (T_m) of PCL in the SIPNs were inner shifted, indicating interpenetration of PCL and PEG chains. It was found that water content increased with increasing PEG weight fraction due to the hydrophilicity of PEG. Drug release can be controlled by weight fraction of PEG in the PCL/PEG SIPNs, concentration of PEG macromer in the SIPNs preparation, and the nature of PEG. © 1996 John Wiley & Sons, Inc.     

Correlation between interactions, miscibility, and spherulite growth in crystalline/crystalline blends of poly(ethylene oxide) and polyesters

Crystalline/crystalline blend systems of poly(ethylene oxide) (PEO) and a homologous series of polyesters, from poly(ethylene adipate) to poly(hexamethylene sebacate), of different CH₂/CO ratios (from 3.0 to 7.0) were examined. Correlation between interactions, miscibility, and spherulite growth rate was discussed. Owing to proximity of blend constituents' T_g's, the miscibility in the crystalline/crystalline blends was mainly justified by thermodynamic and kinetic evidence extracted from characterization of the PEO crystals grown from mixtures of PEO and polyesters at melt state. By overcoming experimental difficulty in assessing the phase behavior of two crystalline polymers with closely spaced T_g's, this work has further extended the range of polyesters that can be miscible with PEO. The interaction parameters (χ₁₂) for miscible blends of PEO with polyesters [poly(ethylene adipate), poly(propylene adipate), poly(butylene adipate), and poly(ethylene azelate) with CH₂/CO = 3.0-4.5] are all negative but the values vary with the polyester structures, with a maximum for the blend of PEO/poly(propylene adipate) (CH₂/CO = 3.5). The values of interactions are apparently dependent on the structures of the polyester constituent in the blends; interaction strength for the miscible PEO/polyester systems correlate in the same trend with the PEO crystal growth rates in the blends.     

Preparation and characterization of novel crosslinked poly[glycidyl methacrylate–poly(ethylene glycol) methyl ether methacrylate] as gel polymer electrolytes

In this study, glycidyl methacrylate was copolymerized with poly(ethylene glycol) methyl ether methacrylate to obtain a copolymer {poly[glycidyl methacrylate–poly(ethylene glycol) methyl ether methacrylate] [P(GMA–PEGMA)]}, which was crosslinked with α,ω‐diamino poly(propylene oxide) (Jeffamine) at various weight ratios and molecular weights to form novel gel polymer electrolytes (GPEs). The crosslinked copolymers were characterized by Fourier transform infrared spectroscopy and thermal analysis. The crosslinked polymers were amorphous in the pristine state and became crystallized after they were doped with lithium electrolyte. Furthermore, the crosslinking degree of the crosslinked polymers increased with increasing weight ratio of Jeffamine, and both the swelling properties and mechanical behaviors of the crosslinked polymers were heavily affected by the weight ratio and molecular weight of Jeffamine. The ionic conductivity (σ) of the GPEs from the crosslinked copolymers was determined by alternating‐current impedance spectroscopy. A higher molecular weight and increased weight ratio of Jeffamine resulted in a higher σ. The GPE based on P(GMA–PEGMA) crosslinked with an equal weight of Jeffamine D2000 exhibited the highest σ of 8.29 × 10⁻⁴ S/cm at 25°C and had a moderate mechanical strength. These crosslinked copolymers could be potential candidates for the construction of rechargeable lithium batteries. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Shape memory behavior of poly(methyl methacrylate)-graft-poly(ethylene glycol) copolymers

This paper describes a shape memory behavior of graft copolymers poly(methyl methacrylate)-graft-poly(ethylene glycol) (PMMA-g-PEG). In shape memory test, the sample was deformed from its original shape to a temporary shape above glass transition temperature (T_g), cooled below T_g to fix the temporary shape, and subsequently heated above T_g for spontaneous recovery to the original shape. By grafting PEG onto PMMA backbone, shape memory ability was drastically enhanced than PMMA homopolymer. The shape recovery ratio was decreased with the increase in the shape deformation temperature. With considering a good miscibility of backbone and side chain in PMMA-g-PEG, this shape memory ability may be related to a physically cross-linked network structure by chain entanglement of the comb-like graft copolymer. Stress relaxation measurements were investigated in order to confirm the effect of the graft chains on the shape memory behavior.     

Preparation and microstructural analysis of poly(ethylene oxide) comb‐type grafted poly(N‐isopropyl acrylamide) hydrogels crosslinked by poly(ϵ‐caprolactone)

Poly(N‐isopropyl acrylamide) (PNIPAAm)‐graft‐poly(ethylene oxide) (PEO) hydrogels crosslinked by poly(?‐caprolactone) diacrylate were prepared, and their microstructures were investigated. The swelling/deswelling kinetics and compression strength were measured. The relationship between the structure and properties of hydrogel are discussed. It was found that the PEO comb‐type grafted structure reduced the thermosensitivity and increased the compression strength. The addition of poly(?‐caprolactone) (PCL) accelerated the deswelling rate of the hydrogels. Meanwhile, the entanglement of PCL chains restrained the further swelling of the network of gels. The PCL crosslinking agent and PEO comb‐type grafted structure made the behavior of the hydrogels deviate from the rubber elasticity equations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of interpenetrating polymer networks from polyurethane and poly(ethylene glycol) diacrylate

Interpenetrating polymer networks (IPNs) combining polyurethane (PU) and poly(ethylene glycol) diacrylate (PEGDA) networks were prepared with simultaneous polymerization. PU was synthesized from biocompatible and biodegradable poly(ε-caprolactone) diol, and the hydroxyl group of poly(ethylene glycol) was substituted with a crosslinkable acrylate group. The effects of the PU/PEGDA compositions and the crosslink density of PU and PEGDA on the thermal properties, swelling ratio, surface energy, mechanical properties, and morphologies were investigated. The mechanical properties of PEGDA networks were improved by the presence of PU networks, particularly in the 75% PU/25% PEGDA IPNs. All PU/PEGDA IPNs showed a microphase-separated structure with cocontinuous morphology, as observed by atomic force microscopy, which was in agreement with the results of swelling ratio and dynamic mechanical thermal analysis measurements. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal degradation characteristics of poly[poly(ethylene glycol)] phosphates

Thermal degradation characteristics of some poly[poly(ethylene glycol)] phosphates (PPEGP) based on ethylene glycol (PEGP), an equimolar mixture of ethylene glycol and trigol (PETP), digol (PDGP), and trigol (PTGP) have been studied by combined differential thermal and thermogravimetric analyses (DTA/TGA). It has been shown that, in spite of their structural similarities, the PPEGPs do not conform to any generalized degradation pattern. Local strains in the crosslinked network and the possible intranetwork topographic interferences due to crossovers, entanglements, and varying lengths of polyoxyethylene link units are believed to play a pivotal role in the thermal degradation of individual PPEGPs. © 1995 John Wiley & Sons, Inc.     

Miscibility of C60-end-capped poly(ethylene oxide) with poly(vinyl chloride)

The miscibility of blends of single [60]fullerene (C₆₀)-end-capped poly(ethylene oxide) (FPEO) or double C₆₀-end-capped poly(ethylene oxide) (FPEOF) with poly(vinyl chloride) (PVC) has been studied. Similar to poly(ethylene oxide) (PEO), both FPEO and FPEOF are also miscible with PVC over the entire composition range. X-ray photoelectron spectroscopy showed the development of a new low-binding-energy Cl2p doublet and a new high-binding-energy O1s peak in FPEO/PVC blends. The results show that the miscibility between FPEO and PVC arises from hydrogen bonding interaction between the α-hydrogen of PVC and the ether oxygen of FPEO. From the melting point depression of PEO, FPEO or FPEOF in the blends, the Flory-Huggins interaction parameters were found to be −0.169, −0.142, −0.093 for PVC/PEO, PVC/FPEO and PVC/FPEOF, respectively, demonstrating that all the three blend systems are miscible in the melt. However, the incorporation of C₆₀ slightly impairs the interaction between PEO and PVC.     

Biodegradability of poly(ethylene terephthalate) copolymers with poly(ethylene glycol)s and poly(tetramethylene glycol)

Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10–40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200–7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (T_m), cold crystallization and glass transition (T_g) decreased with the copolymerization. T_m depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. T_g was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.