Molecular relaxation in cross-linked poly(ethylene glycol) and poly(propylene glycol) diacrylate networks by dielectric spectroscopy

The molecular relaxation characteristics of rubbery amorphous crosslinked networks based on poly(ethylene glycol) diacrylate [PEGDA] and poly(propylene glycol) diacrylate [PPGDA] have been investigated using broadband dielectric spectroscopy. Dielectric spectra measured across the sub-glass transition region indicate the emergence of an intermediate “fast” relaxation in the highly crosslinked networks that appears to correspond to a subset of segmental motions that are more local and less cooperative as compared to those associated with the glass transition. This process, which is similar to a distinct sub-T_g relaxation detected in poly(ethylene oxide) [PEO], may be a general feature in systems with a sufficient level of chemical or physical constraint, as it is observed in the crosslinked networks, crystalline PEO, and PEO-based nanocomposites.     

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.     

Crosslinked poly(vinyl alcohol) hydrogels as swollen elastic networks

Transparent crosslinked PVA hydrogels were prepared by electron beam irradiation of aqueous solutions under nitrogen. These weak hydrogels, upon swelling at 30°C in water, showed low elastic moduli (up to 50 psi), low ultimate tensile strength (up to 4 psi), and low extensibility to break (not higher than 85%). Values of the molecular weight between crosslinks M_c were calculated from swelling and from tensile experiments. In fact, two values of M_c were calculated for each swelling experiment, (a) allowing for observed variation in the polymer–solvent interaction parameter χ₁ with concentration, and (b) fixing χ₁ = 0.494 according to literature data. The correlation of the M_c obtained from tensile data with the M_c obtained from swelling data, by (a) or (b), was approximately linear and gave the same per cent agreement.     

Structure-property relationships in novel poly(imide-amide)-poly(ethylene glycol) hybrid networks

Broadband dielectric relaxation spectroscopy (DRS), thermally stimulated depolarisation currents (TSDC), differential scanning calorimetry (DSC) and to a lesser extent water uptake measurements, were employed to investigate molecular mobility, morphology and crystallization/melting events of PEG in poly(imide-amide)-polyethylene glycol hybrid networks (PIA-PEG) with short (M_n=1000 g/mol) and long (M_n=3400 g/mol) PEG crosslinks. The results obtained suggest long range connectivity of the PEG component in the hybrids with short PEG crosslinks at PEG content higher than 40 wt% and in these with long PEG crosslinks at PEG content higher than 20 wt%. Crystallization of the PEG component is observed by DSC in the hybrids with the longer crosslinks at sufficiently high content of PEG, only. The glass transition temperature, T_g, of PEG component in the hybrids with the shorter PEG crosslinks is shifted to higher temperatures compared to that of the hybrids with longer PEG crosslinks, while suppression of the glass transition of the PEG component is observed in the hybrids with the shorter PEG crosslinks at PEG content lower than 40 wt%. The results are discussed in terms of constraints to segmental motion of the PEG crosslinks, imposed by fixed PEG chain ends on the rigid PI chains.     

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     

Complexation of pepsin poly(ethylene glycol)

Summary Complexation of porcine pepsin (or pepsin A) (EC.3.4.23.1) with poly(ethylene glycol) (PEG) in an aqueous solution was studied as a function of pH and PEG concentration. The addition of PEG increased the reduced viscosity of the enzyme solution at pH 3 but not at pH 4.5. An increase in pH was observed by mixing both PEG and enzyme solutions which were previously adjusted to pH 3. Under conditions of pH 2.5–3 and 50°C, PEG contributed to an increase in the hydrolyzing activity of pepsin towardN-acetyl-l-phenylalanyl-3,5-diiodo-l-tyrosine. These results indicate that pepsin forms a water-soluble complex with PEG mainly through hydrogen bonds between the carboxyl groups in the enzyme and the ether groups in PEG.     

Thermoresponsive poly(oligo ethylene glycol acrylates)

Thermoresponsive polymers have been the subject of numerous publications and research topics in the last few decades mostly driven by their easily controllable temperature stimulus and high potential for in vitro and in vivo applications. P(NIPAAm) is the most studied amongst these polymers, but recently other types of polymers are increasingly being investigated for their thermoresponsive behavior. In particular, polymers bearing a short oligo ethylene glycol (OEG) side chain have been shown to combine the biocompatibility of polyethylene glycol (PEG) with a versatile and controllable LCST behavior. These polymers can be synthesized via controlled radical polymerization techniques from various monomers consisting of an OEG chain and a polymerizable group like a (meth)acrylate, styrene or acrylamide. OEG acrylates offer significant advantages over, e.g., OEG methacrylates as the lower hydrophilicity of the backbone facilitates thermoresponsive behavior with smaller, more defined side chains. Furthermore, PEG acrylates can be polymerized using all major controlled radical polymerization techniques, unlike OEG methacrylates. This review will focus on OEG acrylate based (co)polymers and will provide a comprehensive overview of their reported thermoresponsive properties. The combination and comparison of this data will not only highlight the potential of these monomers, but will also serve as a starting point for future studies.     

End-group effect on chain conformation of poly(propylene glycol) and poly(ethylene glycol)

A comparison is made of the chain conformational distribution of hydroxy-terminated poly(propylene glycol) (PPG) and poly(ethylene glycol) (PEG) with their methoxy-terminated derivatives. The significant end-group dependence on the glass transition temperature in PPG was observed by differential scanning calorimetry. Raman active skeletal vibrations in the low-frequency region indicated a significant difference in chain conformation distribution between methoxy- and hydroxy-terminated PPGs, yet almost no difference between MPEG and HPEG. The increased chain stiffness in HPPG in comparison to MPPG has been attributed to the hydrogen-bonding interaction associated with the hydroxy end group in HPPG. Furthermore, the structural differences observed between PPG and PEG have been attributed to the differences in the interaction of the hydroxy end group to the ether oxygen in the two polymers. The interaction between the hydroxy end group and ether oxygen differs because the —CH₃ side group is present for one and not for the other. These structural differences are reflected in the glass transitions temperatures measured. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 197–202, 1997     

Pressure-volume-temperature properties for binary and ternary polymer solutions of poly(ethylene glycol), poly(propylene glycol), and poly(ethylene glycol methyl ether) with anisole

Pressure-volume-temperature properties were measured for polymer solutions of poly(propylene glycol) (PPG)+anisole, polymer blends of PPG+poly(ethylene glycol methyl ether) (PEGME), and the blends of PPG+PEGME and poly(ethylene glycol) (PEG)+PPG with anisole at temperatures from 298.15 to 348.15 K and pressures up to 50 MPa. The Tait equation represents accurately the pressure effect on the liquid densities over the entire pressure range. The excess volumes change from positive to negative as increasing the mole fraction of PPG in the binary systems of PPG+anisole and PPG+PEGME. The volumetric data of the related binary systems were correlated with the Flory-Orwoll-Vrij and the Schotte equations of state to determine the binary parameters. By using these determined binary parameters, both equations predicted the specific volumes of the polymer blends with anisole to average absolute deviations of better than 0.13%.     

Inhibition of bovine serum albumin adsorption by poly(ethylene glycol) soft segment in biodegradable poly(ethylene glycol)/poly(L-lactide) copolymers

The objective of this study was to investigate the effects of the incorporation of ether linkages into polylactide (PLLA) chains and the time of biodegradation on the behavior of protein adsorption. The content of poly(ethylene glycol) (PEG) in PLLA/PEG copolymers is from 4.4 to 18.3 wt %, and the length of the PEG soft segment is 1000, 2000, and 6000 daltons. The bovine serum albumin (BSA) adsorption onto the biodegradable PLLA/PEG copolymers was carried out using ultraviolet spectroscopy. The surface tension of PLLA and PLLA/PEG was measured using a contact angle. The data show that the incorporation of PEG segments makes the copolymer more polar and, therefore, leads to a reduction of protein adsorption. As the hydrolysis of polymers proceeds, both PLLA and PLLA/PEG turn out to be more polar. However, the initial compositions of degraded PLLA/PEG have a weak influence on the protein adsorption onto its hydrolyzed surface with a substantially long duration of hydrolysis. This phenomenon is attributed to the hydrophobic interaction between polar PLLA/PEG and BSA. © 1993 John Wiley & Sons, Inc.     

Unsaturated polyester based on poly(ethylene glycol)

Unsaturated polyesters were prepared by one-stage melt condensation of maleic anhydride, phthalic anhydride, propylene glycol, and poly(ethylene glycol)s with different molecular weight, and the properties of their castings from styrenated resins were investigated. Tensile and flexural properties decrease with the increase of molecular weight of poly(ethylene glycol), but impact strength, elongation, and water absorption have an inverse effect. This study improves the understanding of the effect of chain length of poly(ethylene glycol) in unsaturated polyester on the properties of its castings.     

Phase separation of poly(ethylene glycol)-water-salt systems

Phase separation temperatures, each corresponding to lower critical solution temperature (LCST) for solutions of poly(ethylene glycol) (PEG) in water-sodium chloride (NaCl) and in water-propionic acid-sodium salt (Pro-Na), have been determined for PEG with molecular weights of M_η = 2.18 × 10³, 8 × 10³ and 719 × 10³ over concentration ranges from 0–1.09 M (mol/1000 g solvent) NaCl and 1.02 M Pro-Na. The phase separation temperature decreases with an increase of salt concentration and depends on polymer molecular weight. The thermal pressure coefficient, thermal expansion coefficient, and density have been determined from 20° to approximately 60°C for ethylene glycol-water solutions over the entire concentration range and also for aqueous salt solutions over the concentration ranges from 0–1.7 M NaCl and 0–0.5 MPro-Na. The excess thermal pressure coefficient, γ^E_V, excess thermal expansion coefficient, α^E, and excess of temperature dependence of γ_V, [$\text{(}\text{?}{}_{\mathrm{\gamma V}}\text{?T}\text{)}{}^{\mathrm{E}}{}_{\mathrm{?}}$], for the EG-water system are all positive, while the excess volume of mixing V^E is negative. The thermal pressure coefficient and thermal expansion coefficient for aqueous salt solutions water-Pro-Na and water-NaCl increase with an increase of salt concentration. The behaviour of the two polymer-salt-water solutions is discussed in terms of a thermodynamic equation of state, and a shortcoming of the usual formulation of the corresponding states theory of polymer solutions is pointed out.     

聚乙二醇增塑聚乳酸的非等温结晶动力学研究

采用DSC方法对聚乙二醇(PEG)增塑聚乳酸的非等温结晶动力学进行了研究。结果表明,PEG的加入明显提高了聚乳酸的结晶速度。对所得数据分别用Ozawa方程和莫志深方法进行了处理,发现在给定温度范围里非等温结晶时,PLA/PEG主要是以均相成核的三维生长方式结晶;PLA的结晶速度随着PEG分子质量的增加而升高。     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997     

Crosslinked poly(acryloylmorpholines) as matrices for gel permeation chromatography

Crosslinked poly(acryloylmorpholines) have been prepared in bead form by suspension polymerization of N-acryloylmorpholine and N,N′-methylenediacrylamide, respective molar ratios 10/1, in aqueous solution dispersed in liquid paraffin. The swelling properties of beads of two porosities, designated Enzacryl Gel K1 and Enzacryl Gel K2, were measured in a range of common solvents. Gels derived by swelling in both chloroform and tetrahydrofuran were evaluated as column packings for gel permeation chromatography. For Enzacryl Gel K1 and polystyrene solutes, molecular weight exclusion limits of approximately 4 × 10³ and 6 × 10² were observed in chloroform and tetrahydrofuran, respectively. In the case of Enzacryl Gel K2, the corresponding exclusion limits were 10⁴ and 5 × 10³. Molecular weight fractionation ranges for both polystyrenes and polyethylene glycols are discussed in terms of gel structure.     

Thermo-oxidative degradation of poly(ethylene glycol)/poly( -lactic acid) blends

The thermo-oxidative degradation of poly(ethylene glycol)/poly( -lactic acid) (PEG/PLLA) blends was studied by infra-red spectroscopy (IR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and thermogravimetry (TGA). The thermo-oxidative degradation of PEG occurred after a period time of aging in air at 80 °C. The mechanism of thermo-oxidative degradation of PEG was found to be the random chain scission of the main chain. As PEG blending with PLLA, the existence of PLLA appeared to enhance the thermo-oxidative degradation of PEG. The enhancement of thermo-oxidative degradation increased first and then decreased with the increase of PLLA. The results could be attributed to the ease of abstraction of the carboxylic hydrogen (–COOH) of PLLA, which enhanced the thermo-oxidative degradation of PEG. Also, the dilution effect of PLLA on the concentration of free radicals was an important factor of the thermo-oxidative degradation.     

New thermogelling poly(organophosphazenes) with methoxypoly(ethylene glycol) and oligopeptide as side groups

A new class of thermogelling poly(organophosphazenes) bearing a hydrophilic methoxypoly(ethylene glycol) (MPEG) and a hydrophobic tri or tetrapeptide such as GlyPheLeuEt, GlyPheIleEt, GlyLeuPheEt, and GlyPheLeuGlyEt have been synthesized and characterized by means of multinuclear (¹H, ³¹P) NMR spectroscopy, gel permeation chromatography, viscometry, and elemental analysis. The gelation of the present polymers is presumed to be attributed to the intermolecular interaction between the hydrophobic oligopeptide side groups, which can form strong physical junction zones in the polymer aqueous solution. The gelation properties of the polymer were affected by the subtle change in the nature of the hydrophobic oligopeptide, composition of the hydrophilic to hydrophobic side groups, and the concentration of the polymer solutions. Among the present thermogels, the copolymer with equimolar MPEG and GlyPheIleEt as side groups showed the excellent gel phase persisting over 35-43 °C, which indicates that it is a new promising material for drug delivery and tissue engineering.     

Polyurethane networks based on poly(ethylene oxide)

A wide range of infinite urethane polymer networks were prepared from poly(ethylene glycol) (PEG) and hexamethylene diisocyanate (HMDI) using 1,1,1-tris-(hydroxymethyl) ethane (THME) as the cross-linking agent. The influence of temperature, cross-linking, and crystallinity on the swelling character of the hydrogel has been discussed. The toxicity of the network polymer by intravaginal implants in rats was studied. Implantation of the polymer did not result in alteration in behavior and feed intake or any pathological changes in the tissue. Vaginal fluids from the polymer-implanted rats or the polymer extract when inoculated on a listeria monocytogene culture plate were unable to inhibit the bacterial growth. © 1993 John Wiley & Sons, Inc.