Synthesis and characterization of poly(ethylene oxide)/polylactide/poly(ethylene oxide) triblock copolymer

Poly(ethylene oxide/polylactide/poly(ethylene oxide) (PEO/PL/PEO) triblock copolymers, in which each block is connected by an ester bond, were synthesized by a coupling reaction between PL and PEO. Hydroxyl‐terminated PLs with various molecular weights were synthesized and used as hard segments. Hydroxyl‐terminated PEOs were converted to the corresponding acid halides via their acid group and used as a soft segment. Triblock copolymers were identified by Fourier transform infrared spectroscopy, ¹H NMR, and gel permeation chromatography. Differential scanning calorimetry (DSC) and X‐ray diffractometry of PEO/PL/PEO triblock copolymers suggested that PL and PEO blocks were phase‐separated and that the crystallization behavior of the PL block was markedly affected by the presence of the PEO block. PEO/PL/PEO triblock copolymers with PEO 0.75k had two exothermic peaks (by DSC), and both peaks were related to the crystallization of PL. According to thermogravimetric analysis, PEO/PL/PEO triblock copolymer showed a higher thermal stability than PL or PEO. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2545–2555, 2002     

Electrokinetic characterization of poly(acrylic acid) and poly(ethylene oxide) brushes in aqueous electrolyte solutions

Surfaces carrying hydrophilic polymer brushes were prepared from poly(styrene)-poly(acrylic acid) and poly(styrene)-poly(ethylene oxide) diblock copolymers, respectively, using a Langmuir-Blodgett technique and employing poly(styrene)-coated planar glass as substrates. The electrical properties of these surfaces in aqueous electrolyte were analyzed as a function of pH and KCl concentration using streaming potential/streaming current measurements. From these data, both the zeta potential and the surface conductivity could be obtained. The poly(acrylic acid) brushes are charged due to the dissociation of carboxylic acid groups and give theoretical surface potentials of -160 mV at full dissociation in 10(-)(3) M solutions. The surface conductivity of these brushes is enormous under these conditions, accounting for more than 93% of the total measured surface conductivity. However, the mobility of the ions within the brush was estimated from the density of the carboxylic acid groups and the surface conductivity data to be only about 14% of that of free ions. The poly(ethylene oxide) (PEO) brushes effectively screen the charge of the underlying substrate, giving a very low zeta potential except when the ionic strength is very low. From the data, a hydrodynamic layer thickness of the PEO brushes could be estimated which is in good agreement with independent experiments (neutron reflectivity) and theoretical estimates. The surface conductivity in this system was slightly lower than that of the polystyren substrate. This also indicates that no significant amount of preferentially, i.e., nonelectrostatically attracted, ions taken up in the brush.     

Solid state NMR study of intercalate complexes of poly(ethylene oxide) and small molecules

From solid state NMR spectra, a lower shielding of poly(ethylene oxide) (PEO) protons, in contrast to higher shielding of PEO carbons, has been found for PEO/hydroxybenzene and PEO/LiCF₃SO₃ complexes in comparison with neat PEO. The same PEO chemical shifts were found both for crystalline and amorphous phase of PEO/LiCF₃SO₃ polymer electrolyte, confirming the same interaction in both phases. Measurements of 2D ¹H CRAMPS exchange NMR spectra have been used to characterize proton distances in complexes of PEO and benzene derivatives. A close contact (∼ 0.3 nm) between aromatic and PEO protons was detected in some cases. From the measurements of the cross polarization ¹H → ¹³C, using Lee-Goldburg irradiation of ¹H nuclei, the distance between LiCF₃SO₃ carbon and the nearest PEO protons in the PEO/LiCF₃SO₃ complex was determined.     

Flocculation with poly(ethylene oxide)/tyrosine-rich polypeptide complexes

New insights into the mechanism for the flocculation of aqueous colloids by the sequential addition of a water-borne phenolic polymer, called cofactor, followed by very high molecular poly(ethylene oxide) (PEO) are presented. It is proposed that PEO/cofactor complexes form in the aqueous phase and adsorb onto the surfaces of the target colloidal particles. Flocculation will occur if PEO/cofactor complex on one particle will bind to adsorbed complex on a second particle; i.e., if the complexes are sticky. The proposed mechanism was illustrated by flocculation experiments with precipitated calcium carbonate, very high molecular weight PEO, and a polypeptide cofactor called PEY1 which was a 1:1 random copolymer of l-glycine and l-tyrosine. Independent measurements of the PEO/PEY1 complex properties, in the absence of calcium carbonate, were used to support the mechanism. In order for PEO/PEY1 complexes to be sticky, they must simultaneously have unbound PEY1 and polymer segments. With time the complexes deactivate (i.e., lose their stickiness) by a reconfiguration process which results in elimination of either unbound PEY1 or PEO segments.     

Nitroxide spin probe study of probe size,hydrogen bonding and polymer matrix rigidity effects on poly(acrylic acid)/poly(ethylene oxide) complexes

An electron spin resonance (ESR) spin probe study was performed on 1 : 1 by weight poly(acrylic acid) (PAA)/poly(ethylene oxide) (PEO) complex over the 100–450 K temperature range with a series of tetramethylpiperidyloxy‐based spin probes. Measurements of the parameters T_5mT, Ta and Td demonstrated the effects of probe size and the strength of hydrogen bonding. The probes in the series Tempone, Tempo, Tempol and Tamine (respectively 4‐oxo‐, unsubstituted, 4‐hydroxy‐ and 4‐amino‐2,2,6,6,‐tetramethylpiperidine ‐1‐oxyl) displayed noticeable increases in the hydrogen‐bonding effect, as indicated by Ta and Td. These increases correlated with increasing hydrogen bond acceptor strength. On the other hand, as the probe size became larger, T_5mT gradually increased due to the free volume decrease. These effects were analyzed using the established theoretical relationship of T_5mT to probe volume expressed by f. Meanwhile, in order to investigate the effect of polymer matrix rigidity, a similar study was performed with a nitroxide spin probe, 2,2,6,6‐tetramethyl‐1‐piperidine‐1‐oxyl (Tempo), on PAA/PEO complexes of different weight compositions. The quantitative fast motion fraction in the composite ESR spectrum was calculated. The influence of changes in the composition of PAA on the molecular mobility was characterized by changes of the spectral parameters and τ_c. The molecular mobility was shown to diminish with increasing content of PAA in PAA/PEO blends duo to the restriction of the polymer matrix rigidity increase. Copyright © 2003 John Wiley & Sons, Ltd.     

Solid state NMR studies of syndiotactic polystyrene/ethylbenzene and poly(ethylene oxide)/LiCF3SO3 molecular complexes

Solvent dynamics and polymer-solvent interactions in syndiotactic (s) polystyrene (PS)/ethylbenzene (PhEt) clathrates, as well as polymer-salt interactions in the poly(ethylene oxide) (PEO)/LiCF₃SO₃ complex, were characterized by solid state ¹H and ¹³C NMR. ¹H static and ¹H MAS NMR spectra have shown that PhEt molecules in s-PS clathrates retain relatively large, but spatially anisotropic mobility. ¹³C CP/MAS (cross polarization/magic angle spinning) spectra and CP dynamics measured for s-PS-dg/PhEt system indicate that at least a part of PhEt molecules are intercalated between phenyl rings of s-PS. ¹³C CP/MAS NMR spectra show that PEO carbons in complex with LiCF₃SO₃ are more shielded in comparison to neat crystalline PEO. The results (distances) obtained from CP dynamics are in agreement with the published crystal structure of the PEO/LiCF₃SO₃ complex. ¹³C spin-lattice relaxation time measurements have shown that the mobility of PEO in the complex is lower than that in neat crystalline PEO.     

Polymorphism of the poly(ethylene oxide)/Li triflate complexes

We hereafter present the study of the high concentration zone of the PEO/Li triflate phase diagram. This system was found to form three different molecular complexes. Their thermal behaviour was elucidated by use of three complementary techniques: Calorimetry, X-ray diffraction and optical microscopy.     

Voltammetric and waveguide spectroelectrochemical characterization of ultrathin poly(aniline)/poly(acrylic acid) films self-assembled on indium-tin oxide

We report on the spectroelectrochemical characterization of conducting polymer (CP) films, composed of alternating layers of poly(aniline) (PANI) and poly(acrylic acid) (PAA), deposited on ITO-coated, planar glass substrates using layer-by-layer self-assembly. Absorbance changes associated with voltammetrically induced redox changes in ultrathin films composed of only two bilayers (ITO/PANI/PAA/PANI/PAA) were monitored in real time using a unique multiple reflection, broadband attenuated total reflection (ATR) spectrometer. CP films in contact with pH 7 buffer undergo a single oxidation/reduction process, with ca. 12.5% of the aniline centers in the film being oxidized and reduced. The ATR spectra indicate that during an anodic sweep, the leucoemeraldine form of PANI in these films is oxidized to generate both the emeraldine and pernigraniline forms simultaneously. A comparison of the behavior observed during anodic and cathodic sweeps suggests that the rate of oxidation is limited by structural changes in the polymer film originating in electrostatic repulsion between positively charged PANI chains.     

Molecular structure and dynamics of poly(methacrylic acid) and poly(acrylic acid) complexes with dodecyl-substituted poly(ethylene glycol)

The molecular dynamics and the structure of molecular complexes formed by micelles of dodecyl-substituted poly(ethylene glycol) with poly(methacrylic acid) and poly(acrylic acid) in aqueous solutions were studied by viscosimetry, pH measurement, and electron spin resonance spin-probe techniques. At low surfactant concentrations, the conformation of the complex is a compact globule. The local mobility of surfactant molecules in such a complex is much slower than that in the free micelle. At high surfactant concentration, the nonionic micelles and polyacids form hydrophilic associates. The associates have the conformation of extended coils. In an associate, a major part of the micellar poly(ethylene glycol) groups is free. The local mobility of the micellar phase depends on the number of micelles involved in an associate. The mobility of surfactant molecules is slower in the complexes of poly(methacrylic acid) than in the complexes of poly(acrylic acid).     

Morphology of poly(ethylene oxide)/poly(vinyl acetate) blends

The morphology of poly(ethylene oxide)/poly(vinyl acetate) (PEO/PVAc) blends was examined using small angle X-ray scattering (SAXS) and optical microscopy. The morphological and structural parameters of the blends are dependent on both composition and crystallization conditions. Optical microscopy revealed that blend samples prepared by solution casting crystallized with volume-filling crystals up to a composition of 30/70 wt% PEO/PVAc; at higher PVAc content there was no evidence of crystallization in the temperature range studied. Pure PEO always crystallized with a spherulite-hedrite morphology. The formation of spherulites was relatively favoured at lower crystallization temperatures and by addition of PVAc to PEO. Small angle X-ray intensity profiles were analyzed using a recently developed methodology and it was found that, for a given crystallization temperature, the amorphous and interphase thicknesses increased with increasing PVAc content but that the average crystalline thickness was independent of composition. The morphological and structural properties of the PEO/PVAc blends were attributed to the presence of non-crystallizable material in both the interlamellar and interfibrillar regions.     

Complexation of poly(acrylic acid) and poly(ethylene oxide) investigated by enhanced Rayleigh scattering method

The method of enhanced Rayleigh scattering spectroscopy (ERS) was developed to investigate the complexation of poly(acrylic acid) (PAA) and poly(ethylene oxide) (PEO) in semidilute polymer solutions. Based on the Ornstein‐Zernike equation, the relationship between macromolecular static correlation length and ERS intensity was presented. Moreover, the ERS spectra were calculated by the moving window two‐dimensional (MW2D) correlation spectroscopy to get detailed information of the polymer complexation. The results indicated that the ERS spectroscopy characteristics of the polymer mixtures have similar trend, and the ERS intensity promptly increases as the macromolecular chains contract. The increase of ERS intensity showed that the degree of complexation between PAA and PEO increases when the pH value decreases. The complexation results from the collapse of macromolecular chains, which is induced by the PAA chains contracting and the enhanced association between PAA and PEO chains because of the hydrogen bond formation. In addition, the association resulting from the complexation of PAA and PEO in solution was demonstrated by the MW2D correlation spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1847–1852, 2010     

PH effects in the complex formation and blending of poly(acrylic acid) with poly(ethylene oxide)

The effect of pH on the complex formation between poly(acrylic acid) (PAA) and poly(ethylene oxide) (PEO) has been studied in aqueous solutions by turbidimetric and fluorescent methods. It was shown that the formation of insoluble interpolymer complexes is observed below a certain critical pH of complexation (pH(crit1)). The formation of hydrophilic interpolymer associates is possible above pH(crit1) and below a certain pH(crit2). The effects of polymer concentrations in solution and PEO molecular weight as well as inorganic salt addition on these critical pH values were studied. The polymeric films based on blends of PAA and PEO were prepared by casting from aqueous solutions with different pHs. These films were characterized by light transmittance measurements and differential scanning calorimetry. The existence of the pH value above which the polymers form an immiscible blend was demonstrated. The transitions between the interpolymer complex, miscible blend, and immiscible blend caused by pH changes are discussed. The recommendations for preparation of homogeneous miscible films based on compositions of poly(carboxylic acids) and various nonionic water-soluble polymers are presented.     

Conformational changes of poly(ethylene oxide) in poly(ethylene oxide)/poly(methyl methacrylate) blends by supercritical carbon dioxide

The effects of supercritical carbon dioxide (SC CO₂) fluids on the morphology and/or conformation of poly(ethylene oxide) (PEO) in PEO/poly(methyl methacrylate) (PMMA) blends were investigated by means of differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and Fourier transform infrared (FTIR). According to DSC data for a given blend, the melting enthalpy and, therefore, degree of crystallinity of PEO were increased, whereas the melting temperature of PEO was decreased, with SC CO₂ treatment. The enhancement of PEO crystallization with SC CO₂ treatment, as demonstrated by DSC data, was supported by WAXD data. According to FTIR quantitative analyses, before SC CO₂ treatments, the conformation of PEO was transformed from helix to trans planar zigzag via blending with PMMA. This helix‐to‐trans transformation of PEO increased proportionally with increasing PMMA content, with around 0.7% helix‐to‐trans transformation per 1% PMMA incorporation into the blend. For a given blend upon SC CO₂ treatments, the conformation of PEO was transformed from trans to helix. This trans‐to‐helix transformation of PEO decreased with increasing PMMA contents in the blends because of the presence of interactions between the two polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2479–2489, 2004     

Copper sols stabilized by poly(ethylene glycol-600-monolaurate) and its complexes with poly(acrylic acid)

Copper sols stabilized by a polymer-colloid complex are studied via dynamic light scattering and transmission electron microscopy. It is shown that the polymer-colloid complex including poly(acrylic acid) and the nonionogenic polymeric surfactant poly(ethylene glycol-600-monolaurate) is an effective protector of copper nanoparticles formed via the reduction of Cu²⁺ ions in an aqueous medium. The sizes of sol particles of the nanocomposite consisting of the polymer-colloid complex and copper nanoparticles depend on the method of preparation of the nanocomposite. The incorporation of the copper nanoparticles being formed (an average diameter of 5 nm) into particles of the polymer-colloid complex leads to an insignificant change in the sizes of the complex particles. The same sizes are typical for particles of the nanocomposite formed during the introduction of surfactant micelles in the copper sol formed in the solution of poly(acrylic acid). The interaction of copper nanoparticles formed in an aqueous medium with surfactant micelles entails their aggregation; as a result, these nanoparticles turn out to be incorporated into large aggregates with equivalent radii of up to 100 nm. When poly(acrylic acid) is incorporated into this sol, the sizes of its particles insignificantly change apparently because of the low rate of structural rearrangements accompanying the formation of the polymer-colloid complex.     

Thermal ageing of poly(ethylene oxide)/poly(3,4-ethylenedioxythiophene) semi-IPNs

The thermal stability study of a conducting semi-IPN has been reported. The thermo-oxidation of poly(ethylene oxide) (PEO)/poly(3,4-ethylenedioxythiophene) (PEDOT) semi-Interpenetrating Polymer Network (semi-IPN) was studied at 80 °C in open air. The degradation was followed by spectrophotometry in the visible and near infrared range, cyclic voltamperometry and thermogravimetric analysis. Fluorescence spectrophotometry allowed for the identification of OH by-product originated in the PEO network degradation by the use of a chemiluminescent probe, typically terephthalic acid. The formation of hydroxyl radicals damaged the PEDOT chains as checked by infrared spectroscopy. The mechanism of degradation is further confirmed (i) by introducing a radical scavenger or (ii) by performing a thermal ageing under inert atmosphere; in both cases the semi-IPN life-time is tremendously increased.     

Lamellar structure of poly(ethylene oxide) molecular complexes

The phase diagrams of some binary systems such as poly(ethy lene oxide)-p-dihalogenobenzene, poly(ethylene oxide)-resorcinol and poly(ethylene oxide)-p-nitrophenol show the existence of molecular complexes with a well definite stoichiometry. The crystal structure of these molecular complexes has been determined by wide-angle X-ray diffraction. The morphology of these molecular complexes crystallized from the melt is investigated by differential scanning calorimetry and small angle X-ray scattering. PEO-p-dichlorobenzene and PEO-resorcinol complexes crystallize from the melt as extended chains (EC) or integral folded chain (IFC) lamellar crystals. As observed for PEO oligomers, the fraction of EC crystals of PEO-resorcinol increases with the crystallization temperature. However EC crystals are present in a larger range of crystallization temperatures than for pure PEO. On the other hand, the PEO-p-nitrophenol complex crystallizes over all the studied crystallization temperature range as stable non integral folded chain (NIFC) crystals. Explanations related to the crystal structure of these complexes and to their mode of growth are invoked to explain these two deeply different lamellar morphologies.     

Antimicrobial loading into and release from poly(ethylene glycol)/poly(acrylic acid) semi‐interpenetrating hydrogels

Electrostatic interactions within a semi‐interpenetrating network (semi‐IPN) gel can control the postsynthesis loading, long‐term retention, and subsequent release of small‐molecule cationic antibiotics. Here, electrostatic charge is introduced into an otherwise neutral gel [poly(ethylene glycol) (PEG)] by physically entrapping high‐molecular‐weight poly(acrylic acid) (PAA). The network structure is characterized by small‐angle neutron scattering. PEG/PAA semi‐IPN gels absorb over 40 times more antibiotic than PAA‐free PEG gels. Subsequent soaking in physiological buffer (pH 7.4; 0.15 M NaCl) releases the loaded antibiotics for periods as long as 30 days. The loaded gels elute antibiotics with diffusivities of 4.46 × 10^?8 cm²/s (amikacin) and 2.08 × 10^?8 cm²/s (colistin), which are two orders of magnitude less than those in pure PEG gels where diffusion is controlled purely by gel tortuosity. The release and hindered diffusion can be understood based on the partial shielding of the charged groups within the loaded gel, and they have a significant effect on the antimicrobial properties of these gels. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 64–72     

Nanosized amorphous calcium carbonate stabilized by poly(ethylene oxide)-b-poly(acrylic acid) block copolymers

Particles of amorphous calcium carbonate (ACC), formed in situ from calcium chloride by the slow release of carbon dioxide by alkaline hydrolysis of dimethyl carbonate in water, are stabilized against coalescence in the presence of very small amounts of double hydrophilic block copolymers (DHBCs) composed of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blocks. Under optimized conditions, spherical particles of ACC with diameters less than 100 nm and narrow size distribution are obtained at a concentration of only 3 ppm of PEO-b-PAA as additive. Equivalent triblock or star DHBCs are compared to diblock copolymers. The results are interpreted assuming an interaction of the PAA blocks with the surface of the liquid droplets of the concentrated CaCO3 phase, formed by phase separation from the initially homogeneous reaction mixture. The adsorption layer of the block copolymer protects the liquid precursor of ACC from coalescence and/or coagulation.     

Synthesis and pH-sensitive micellization of doubly hydrophilic poly(acrylic acid)-b-poly(ethylene oxide)-b-poly(acrylic acid) triblock copolymer in aqueous solutions

A doubly hydrophilic triblock copolymer poly(acrylic acid)-b-poly(ethylene glycol)-b-poly(acrylic acid) (PAA-b-PEO-b-PAA) with M _w/M _n = 1.15 was synthesized by atom transfer radical polymerization of t-butyl acrylate (tBA), followed by acidolysis of the PtBA blocks. The pH-sensitive micellization of PAA-b-PEO-b-PAA in acidic solution was investigated by potentiometric titration, fluorescence spectrum, dynamic light scattering and zeta potential. The pK _a was 6.6 and 6.0 in deionized water and in 0.1 mol/L NaCl solution, respectively. The copolymer formed micelles composed of a weakly hydrophobic core of complexed PAA and PEO and a hydrophilic PEO shell in 1 mg/mL solution at pH < 5.5 due to hydrogen bonding. The critical micelle concentration was 0.168 mg/mL at pH 2.0. At pH < 4.5, steady and narrow distributed micelles were formed. Increasing pH to 5.0, unsteady and broad distributed micelles were observed. At pH > 5.5, the micelle was destroyed owing to the ionization of the PAA blocks.